CN103534758A - Ultraviolet-ray-curable resin composition - Google Patents

Ultraviolet-ray-curable resin composition Download PDF

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Publication number
CN103534758A
CN103534758A CN201280023346.2A CN201280023346A CN103534758A CN 103534758 A CN103534758 A CN 103534758A CN 201280023346 A CN201280023346 A CN 201280023346A CN 103534758 A CN103534758 A CN 103534758A
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methyl
ultraviolet
resin composition
curing resin
acrylate
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CN103534758B (en
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木户场润
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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    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)

Abstract

The present invention relates to an ultraviolet-ray-curable resin composition for BDs, which comprises: (A) 5-15 parts by weight of a compound represented by formula (1) (wherein R1 represents a linear alkylene group having 4-10 carbon atoms, an alkylene group having 4-10 carbon atoms and having an ether bond, or an alkylene group having 4-10 carbon atoms and having a branched chain; and R11 represents a hydrogen atom or a methyl group); (B) 10-60 parts by weight of a compound represented by formula (2) (wherein R21 represents a hydrogen atom or a methyl group; and n represents an integer of 1-10); (C) 30-60 parts by weight of a urethane (meth)acrylate which is a reaction product of polytetramethylene glycol, polyisocyanate and a hydroxyl-C2-C4-alkyl(meth)acrylate; and (D) 2-8 parts by weight of a photopolymerization initiator. This ultraviolet-ray-curable resin composition enables the production of a light-permeable layer that rarely undergoes warpage upon curing and has excellent durability under high-temperature high-humidity environments, and enables the provision of a BD that is deteriorated in a light reflectance to a lesser extent under high-temperature high-humidity environments.

Description

Ultraviolet-curing resin composition
Technical field
The present invention relates to the ultraviolet-curing resin composition using in the light-transmitting layer of Blu-ray Disc and use this ultraviolet-curing resin composition as the CD of light-transmitting layer, this Blu-ray Disc is at least formed with reflection layer and light-transmitting layer, and utilizes the blue laser within the scope of 370nm～430nm with oscillation wavelength see through described light-transmitting layer and record or regenerate (regeneration).
Background technology
In recent years, due to the development of infotech and Information Network, carry out continually the transmission of large capacity information record.Thereupon, the requirement high density huge capacity compact discs of jumbo image, music, computer data etc. that can record and regenerate.For as high-density recording media and universal DVD (Digital Versatile Disc, digital versatile disc), in order to realize densification, use wavelength ratio CD (Compact Disc, compact disk) laser of shorter 650nm, optical system has also realized high-NA.But, in order to record or the HDTV that regenerates (high definition television, high-definition television) corresponding high image quality image etc., need further densification, therefore, the next generation at DVD has carried out the method for further high density recording and the research of CD thereof, and has proposed to utilize the high density recording mode of the new compact disk structure of the optical system of using the blue laser that wavelength ratio DVD is shorter.
This new CD be on the transparent or opaque substrate being formed by plastics such as polycarbonate, form the information recording positions such as pit or information recording layer, then on upper strata, information recording position the light-transmitting layer of folded approximately 100 μ m, make recording light or reproduced light or the two see through this light-transmitting layer and the CD of the structure of incident.From the viewpoint of throughput rate, special in using ultraviolet-curing resin composition to be studied in the light-transmitting layer of this CD.
This CD (the Blu-ray Disc that utilizes blue laser to record or regenerate, below also referred to as BD) in, the light-transmitting layer that light-transmitting layer and DVD are used is in a ratio of thick film, in addition, situation about using from the middle layer as DVD-9 structure is different, near top layer or top layer, light-transmitting layer is set.Therefore,, even if directly conversion was suitable for the CD ultraviolet-curing resin composition of DVD in the past, compare the reliability reduction that sometimes also can obviously produce the record regenerating causing because of the corrosion of distortion or reflection layer etc. with DVD.In addition, need to have transmitance and the high rigidity in order to use of the light transmission steady in a long-term that makes short wavelength near top layer or top layer, in addition, from the problem of throughput rate, also requiring is the composition that can be applicable to making thick film.
As the ultraviolet-curing resin composition that can alleviate disc tilt, for example, disclose and contained by making lactone compound and the resulting monomer of (methyl) acrylate reactions of hydroxyl react the ultraviolet-curing resin composition (referring to Patent Document 1) of carbamate (methyl) acrylate obtaining with polyisocyanate compound.This ultraviolet-curing resin composition is as low cure shrinkage and the useful ultraviolet-curing resin composition of low viscous protective finish agent by using better carbamate (methyl) acrylate of flexibility.But viscosity is low when said composition is made BD with light-transmitting layer, be therefore difficult to form thick film.In addition, when the content that increases carbamate (methyl) acrylate in order to improve viscosity forms the light-transmitting layer of CD, exist under hot and humid environment and to produce deteriorated problem because of the corrosion of metal film etc.
In addition, as the composition of the few resin molding of the corrosion of metal film that can obtain recording medium, disclose and contained the resin combination (referring to Patent Document 2) that proportion is the more than 1.10 liquid oligomer of high specific gravity.Said composition reduces the effect of the variable color of recording medium by the burn into that uses the hyperbaric solution state oligomer such as epoxy acrylate of epoxy acrylate, particularly bisphenol A-type that moisture-penetrability is low to have inhibition metallic film, but this oligomer has the skeleton of rigidity, therefore, in the top layer of recording medium, situation about particularly using with light-transmitting layer as BD, produce warpage sometimes and cause the reliability of recording medium to reduce.
On the other hand; the active-energy solidification compound using as the optical article with prismatic action or lensing, discloses to contain and in molecule, has had the composition (referring to Patent Document 3) in carbamate (methyl) acrylate of 3 (methyl) acryloyl groups and molecule with (methyl) acrylate of 3 (methyl) acryloyl groups.Said composition is to provide the composition of the curing overlay film that crimpiness when stacked with resin film, shape retention properties, the transparency, skin hardness etc. are good; but use, in molecule, have while having composition that (methyl) acrylate of 3 (methyl) acryloyl groups forms as the light-transmitting layer of CD in carbamate (methyl) acrylate of 3 (methyl) acryloyl groups and molecule, to have the low problem of tackiness of the metallic reflector to using as reflection layer.In addition; although there is the modifier through EO or PO modification in (methyl) acrylate of 3 (methyl) acryloyl groups, metallic reflector is had to tackiness, owing to thering are a large amount of hydrophilic structures, make the permanance existing problems under hot and humid environment.
Up to now, in order to meet the desired characteristic of CD, the various ultraviolet-curing resin compositions (patent documentation 4～10) that are conceived to permanance or the so specific physical property of adhesive power and prepare have been proposed.But, in ultraviolet-curing resin composition, the relation that when warpage while having found to solidify when required hardness has the tendency that becomes large to improve specific physical property like this, other physical property can variation, therefore strong expectation is developed and is met the resin that requires characteristic that all market is sought.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 11-12495 communique
Patent documentation 2: Japanese kokai publication hei 11-302309 communique
Patent documentation 3: TOHKEMY 2002-69139 communique
Patent documentation 4: TOHKEMY 2005-243109 communique
Patent documentation 5: TOHKEMY 2006-249228 communique
Patent documentation 6: TOHKEMY 2009-32302 communique
Patent documentation 7: TOHKEMY 2009-32303 communique
Patent documentation 8: No. 2008/099666 pamphlet of International Publication
Patent documentation 9: TOHKEMY 2000-345073 communique
Patent documentation 10: No. 2009/144926 pamphlet of International Publication
Summary of the invention
Invent problem to be solved
The ultraviolet-curing resin composition that warpage while solidifying is few even if problem to be solved by this invention is to provide, the permanance under hot and humid environment is good and under hot and humid environment the also few CD of reduction of light reflectivity.
For the means of dealing with problems
In the present invention, find, by using, using specific ratio and contain as the compound shown in the following formula (1) of difunctionality (methyl) acrylate, as the compound shown in the following formula (2) of simple function (methyl) acrylate and as the curing overlay film of the composition of the polytetramethylene glycol of carbamate (methyl) acrylate and reaction product carbamate (methyl) acrylate of polyisocyanates and (methyl) acrylic acid hydroxyl C2～C4 Arrcostab as light-transmitting layer, can suppress the variable color (xanthochromia etc.) of the light-transmitting layer under hot and humid environment, the reduction of reflectivity, the albefaction causing because of corrosion or the oxidation of metallic film, and can reduce the generation of the warpage that causes characteristic variation,
Thereby completed the present invention.
Figure BDA0000414287510000041
(in formula, R 1the alkylidene with side chain that represents the straight-chain alkyl-sub-of carbon number 4～10, the alkylidene with ehter bond of carbon number 4～10 or carbon number 4～10, R 11represent hydrogen atom or methyl)
Figure BDA0000414287510000042
(in formula, R 21represent hydrogen atom or methyl, n represents 1～10 integer)
And, there is curing overlay film that this permanance is good as the CD of the present invention of light-transmitting layer, even if be also difficult for the reduction that produces light reflectivity because of variable color and warpage under hot and humid environment, characteristics of signals deteriorated few, therefore, recording of information/regeneration that the long blue laser of radiothermy carries out is good, therefore useful.
The present invention relates to the ultraviolet-curing resin composition using in the light-transmitting layer of BD, this BD is at least laminated with reflection layer and light-transmitting layer on substrate, and from above-mentioned light-transmitting layer side incident blue laser and the regeneration of the information of carrying out.
That is, the present invention relates to following ultraviolet-curing resin composition, its solidfied material and the BD with its solidfied material for BD.
1. a Blu-ray Disc has the solidfied material layer of following ultraviolet-curing resin composition as light-transmitting layer on substrate,
Described ultraviolet-curing resin composition is following Blu-ray Disc ultraviolet-curing resin composition,
In total amount 100 weight portions of ultraviolet-curing resin composition, with following ratio, contain following (A)～(D) composition,
(A) compound 5～15 weight portions shown in following formula (1),
Figure BDA0000414287510000051
In formula (1), R 1the alkylidene with side chain that represents the straight-chain alkyl-sub-of carbon number 4～10, the alkylidene with ehter bond of carbon number 4～10 or carbon number 4～10, R 11represent hydrogen atom or methyl;
(B) compound 10～60 weight portions shown in following formula (2),
Figure BDA0000414287510000061
In formula (2), R 21represent hydrogen atom or methyl, n represents 1～10 integer;
(C) reaction product carbamate (methyl) acrylate 30～60 weight portions of polytetramethylene glycol and polyisocyanates and (methyl) acrylic acid hydroxyl C2～C4 Arrcostab; And
(D) Photoepolymerizationinitiater initiater 2～8 weight portions.
2. the Blu-ray Disc as described in above-mentioned 1 wherein, is at least formed with reflection layer and light-transmitting layer on substrate, and utilizes the blue laser within the scope of 370nm～430nm with oscillation wavelength see through this light-transmitting layer and record or regenerate.
3. a Blu-ray Disc ultraviolet-curing resin composition, wherein, in total amount 100 weight portions of ultraviolet-curing resin composition, contains following (A)～(D) composition with following ratio,
(A) compound 5～15 weight portions shown in following formula (1),
Figure BDA0000414287510000062
In formula (1), R 1the alkylidene with side chain that represents the straight-chain alkyl-sub-of carbon number 4～10, the alkylidene with ehter bond of carbon number 4～10 or carbon number 4～10, R 11represent hydrogen atom or methyl;
(B) compound 10～60 weight portions shown in following formula (2),
Figure BDA0000414287510000071
In formula (2), R 21represent hydrogen atom or methyl, n represents 1～10 integer;
(C) reaction product carbamate (methyl) acrylate 30～60 weight portions of polytetramethylene glycol and polyisocyanates and (methyl) acrylic acid hydroxyl C2～C4 Arrcostab; And
(D) Photoepolymerizationinitiater initiater 2～8 weight portions.
4. the Blu-ray Disc ultraviolet-curing resin composition as described in above-mentioned 3, wherein, the compound (A) shown in above-mentioned formula (1) is any one or two kinds in dipropylene glycol two (methyl) acrylate and hexanediol two (methyl) acrylate.
5. the Blu-ray Disc ultraviolet-curing resin composition as described in above-mentioned 3 or 4, wherein, in reaction product carbamate (methyl) acrylate (C) of polytetramethylene glycol and polyisocyanates and (methyl) acrylic acid hydroxyl C2～C4 Arrcostab, 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 described in any one in above-mentioned 3～5, wherein, in total amount 100 weight portions of ultraviolet-curing resin composition, with the ratio of 15～53 weight portions, contain (E) through bisphenol A-type two (methyl) acrylate of 4～12 moles of ethylene oxide modifications.
7. the Blu-ray Disc ultraviolet-curing resin composition as described in any one in above-mentioned 3～6, wherein, contains the compound shown in following formula (3) as antioxidant,
Figure BDA0000414287510000081
In formula (3), R 2, R 3, R 4independent existence separately, R 2the alkyl that represents carbon number 1～3, R 3the alkylidene that represents carbon number 1～6, R 4the alkyl that represents carbon number 5～20.
8. the Blu-ray Disc ultraviolet-curing resin composition as described in any one in above-mentioned 3～7, wherein, contains the compound shown in following formula (4) as silane coupling agent,
Figure BDA0000414287510000082
In formula (4), R 5and R 6independent existence separately, R 5the alkyl that represents carbon number 1～3, R 6the alkylidene that represents carbon number 1～6.
9. the BD ultraviolet-curing resin composition as described in any one in above-mentioned 3～8, wherein, contains the compound that (F) has hindered piperidine skeleton.
10. the BD ultraviolet-curing resin composition as described in above-mentioned 9, wherein, has the compound (F) of hindered piperidine skeleton for have the compound of hindered piperidine skeleton and (methyl) acryloyl group simultaneously.
11. Blu-ray Disc ultraviolet-curing resin compositions as described in any one in above-mentioned 3～6, wherein, at least contain TMDPO as Photoepolymerizationinitiater initiater (D).
12. Blu-ray Disc ultraviolet-curing resin compositions as described in above-mentioned 6, wherein, contain at least one in the group of selecting freedom (F) to there is the antioxidant composition shown in the silane coupling agent shown in the compound of hindered piperidine skeleton, aforementioned formula (4) and aforementioned formula (3).
13. Blu-ray Disc ultraviolet-curing resin compositions as described in any one in above-mentioned 6～12, wherein, at least contain bisphenol A-type two (methyl) acrylate through 9～11 moles of ethylene oxide modifications as (E) composition, its content is 35～90 weight portions with respect to content 100 weight portions of (C) composition.
The application of the light-transmitting layer that is used to form the Blu-ray Disc with recording layer of the ultraviolet-curing resin composition in 14. above-mentioned 3～13 described in any one.
15. 1 kinds of solidfied materials, it irradiates active energy beam by the ultraviolet-curing resin composition to described in any one in above-mentioned 3～13 and obtains.
16. 1 kinds of manufacture methods with the BD of recording layer, wherein, are applied to the ultraviolet-curing resin composition described in any one in above-mentioned 3～13 on BD substrate, and make coated film be solidified to form light-transmitting layer by irradiating active energy beam.
Invention effect
BD of the present invention can form curability, permanance and the curing overlay film good with the adhesiveness of reflection horizon or contact bed with ultraviolet-curing resin composition.In addition, ultraviolet-curing resin composition of the present invention when solidifying and under cryogenic conditions or hot conditions the shrinkage factor after long preservation also few, therefore, can reduce the generation of warpage in the BD of the curing overlay film with this resin combination.And, even the curing overlay film with ultraviolet-curing resin composition of the present invention as the BD of light-transmitting layer under hot and humid environment after long-time use, also can suppress the variable color (xanthochromia etc.) of light-transmitting layer, the reduction of reflectivity and the albefaction that causes because of corrosion or the oxidation of metallic film, therefore, can the long blue laser of radiothermy recording/reproducing information well.In addition, there is the curing overlay film of ultraviolet-curing resin composition of the present invention good as the nerve of the BD of light-transmitting layer.
Embodiment
Reaction product carbamate (methyl) acrylate 30～60 weight portions that ultraviolet-curing resin composition of the present invention contains compound 10～60 weight portions, (C) polytetramethylene glycol and the polyisocyanates shown in compound 5～15 weight portions shown in (A) following formula (1), (B) following formula (2) and (methyl) acrylic acid hydroxyl C2～C4 Arrcostab and (D) Photoepolymerizationinitiater initiater 2～8 weight portions.
(in formula, R 1the alkylidene with side chain that represents the straight-chain alkyl-sub-of carbon number 4～10, the alkylidene with ehter bond of carbon number 4～10 or carbon number 4～10, R 11represent hydrogen atom or methyl)
Figure BDA0000414287510000102
(in formula, R 21represent hydrogen atom or methyl, n represents 1～10 integer)
In addition, in this instructions, " (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) (below also referred to as " (A) composition ").
Figure BDA0000414287510000111
(in formula, R 1the alkylidene with side chain that represents the straight-chain alkyl-sub-of carbon number 4～10, the alkylidene with ehter bond of carbon number 4～10 or carbon number 4～10, R 11represent hydrogen atom or methyl)
At this, " alkylidene with ehter bond of carbon number 4～10 " refers to that a plurality of alkylidenes form by least one ehter bond (O-) bonding and the carbon number of a plurality of alkylidenes adds up to 4～10 group.
In compound (A) shown in above-mentioned formula (1), can preferably use R 1compound for the alkylidene with side chain of the straight-chain alkyl-sub-of carbon number 4～6, the alkylidene with ehter bond of carbon number 4～6 or carbon number 4～10.
As the concrete example of the compound (A) shown in above-mentioned formula (1), can enumerate for example dipropylene glycol two (methyl) acrylate, 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, particularly, can enumerate Photomer4226 (propylene glycol diacrylate, the manufacture of Ke Ning Co., Ltd.), TPGDA (tripropylene glycol diacrylate, for example Daicel-Qing Te Co., Ltd. manufacture), Photomer4017 (1,6-hexanediyl ester ，Ke Ning Co., Ltd. manufactures) etc.
From improving the viewpoint of nerve, as the compound (A) shown in above-mentioned formula (1), more preferably R in above-mentioned formula (1) 1for the compound of the straight-chain alkyl-sub-of carbon number 4～10, particularly preferably hexanediyl ester.
The viewpoint of warpage when also minimizing is solidified from raising adhesiveness, as the compound (A) shown in above-mentioned formula (1), R in preferred above-mentioned formula (1) 1compound for the alkylidene with ehter bond of carbon number 4～10 or the alkylidene with side chain of carbon number 4～10, more preferably dipropylene glycol two (methyl) acrylate or tripropylene glycol two (methyl) acrylate, particularly preferably propylene glycol diacrylate.
In the present invention, by contain the compound (A) shown in above-mentioned formula (1) with specific ratio, cross-linking density can be improved, the curing overlay film that hardness is suitable for protecting BD can be formed.
From obtaining the viewpoint of the solidfied material that has adhesiveness, nerve and hardness as target concurrently, the content of the compound (A) shown in the formula in ultraviolet-curing resin composition of the present invention (1) is generally 5～15 weight portions with respect to total amount 100 weight portions of ultraviolet-curing resin composition, be preferably 5～12 weight portions, more preferably 5～7 weight portions.(A), when composition is less than 5 weight portion with respect to total amount 100 weight portions of this resin combination, curability, difference of hardness, be therefore difficult to obtain the curing overlay film with target capabilities.(A) when composition surpasses 15 weight portion with respect to total amount 100 weight portions of this resin combination, easily produce warpage, adhesiveness reduces, and therefore can not be applicable to BD.
In ultraviolet-curing resin composition of the present invention, as being applicable to and (A) difunctionality (methyl) acrylate of composition use, can enumerate bisphenol A-type two (methyl) acrylate (E) (below also referred to as " (E) composition ") through 4～12 moles of ethylene oxide modifications.As this bisphenol A-type two (methyl) acrylate (E), so long as known bisphenol A-type two (methyl) acrylate can be not particularly limited to use, preferably enumerate bisphenol A-type two (methyl) acrylate through 6～11 moles of ethylene oxide modifications, more preferably enumerate bisphenol A-type two (methyl) acrylate through 9～11 moles of ethylene oxide modifications.
As bisphenol A-type two (methyl) acrylate (E) through 4～12 moles of ethylene oxide modifications, can use such as bisphenol A-type two (methyl) acrylate through 4 moles of ethylene oxide modifications (BPE-4A manufacturing such as Di-ichi Kogyo Seiyaku Co., Ltd. etc.), through bisphenol A-type two (methyl) acrylate (BPE-10 manufacturing such as Di-ichi Kogyo Seiyaku Co., Ltd. etc.) of 10 moles of ethylene oxide modifications.
Use in the situation of above-mentioned bisphenol A-type two (methyl) acrylate (E) through 4～12 moles of ethylene oxide modifications (also referred to as BPE4～12 (E) or referred to as (E) composition), this two (methyl) acrylate (E) that contains 15～53 weight portions by total amount 100 weight portions with respect to ultraviolet-curing resin composition of the present invention, can improve cross-linking density and flexibility the two.From improving the viewpoint of permanance, the content of this bisphenol A-type two (methyl) acrylate (E) is preferably 15～50 weight portions, more preferably 15～40 weight portions.
Should can use separately or can be used together 2～3 kinds by (E) composition.According to circumstances different, sometimes preferably also with 2 kinds.And in the situation of use, preferably and use through bisphenol A-type two (methyl) acrylate of 4～8 moles of ethylene oxide modifications and bisphenol A-type two (methyl) acrylate through 9～12 moles of ethylene oxide modifications.One of preferred mode for use a kind of or and with two kinds should (E) composition modes, be for example with respect to bisphenol A-type two (methyl) acrylate 100 weight portions through 9～11 moles of ethylene oxide modifications with the ratio use of 0～100 weight portion the mode through bisphenol A-type two (methyl) acrylate of 4～8 moles of ethylene oxide modifications.In this case, particularly preferably with respect to total amount 100 weight portions of aforementioned resin, with the ratio of 15～30 weight portions, contain 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 the corrosion of CD metal film.In addition, the content of this two (methyl) acrylate (E) is 15 weight portions when above with respect to total amount 100 weight portions of resin combination, can give sufficient flexibility, therefore preferably.
When the content of aforementioned carbamate (methyl) acrylate (C) is made as to 100 weight portion, should (E) composition with respect to this, be preferably the ratio of approximately 40 weight portions～approximately 120 weight portions.In should (E) composition, through bisphenol A-type two (methyl) acrylate of 9～11 moles of ethylene oxide modifications, with respect to content 100 weight portions of this (C) composition, be preferably 35～90 weight portions, the more preferably ratio of 40～80 weight portions.
In ultraviolet-curing resin composition of the present invention, as simple function (methyl) acrylate, use the compound (B) shown in following formula (2) (below also referred to as " (B) composition ").
Figure BDA0000414287510000141
(in formula, R 21represent hydrogen atom or methyl, n represents 1～10 integer)
In above-mentioned formula (2), the compound that preferably n is 1～3.As the compound (B) shown in used above-mentioned formula (2), specifically can enumerate phenol (methyl) acrylate of ethane via epoxyethane modification, more preferably through phenol (methyl) acrylate of 1～3 moles of ethylene oxide modification, more preferably through phenol (methyl) acrylate of 1 mole or 2 moles of ethylene oxide modifications.The phenol of this ethane via epoxyethane modification (methyl) acrylate (B) can be obtained by market, as goods, specifically can enumerate Photomer4035 (manufacture of acrylic acid phenoxy ethyl ,n=1, Ke Ning Co., Ltd.), EBECRYL110 (phenol acrylate, n=2, Daicel-Qing Te Co., Ltd. through 2 moles of ethylene oxide modifications manufacture) etc.
At this, from improving the viewpoint of nerve, the phenol through 2 moles of ethylene oxide modifications (methyl) acrylate that in preferred above-mentioned formula (2), n is 2.
In addition, acrylic acid phenoxy ethyl (n=1) is also because cheap and can obtain suitable characteristic and preferably.
The content that is somebody's turn to do (B) composition is conventionally preferably many than the content of (A) composition, for example, while the content of (A) composition being made as to 100 weight portion, (B) content of composition with respect to this more than 100 weight portions, be for example approximately 102 weight portions～approximately 600 weight portions, approximately 105 weight portions～approximately 500 weight portion more preferably.
In addition, when the content of aforementioned carbamate (methyl) acrylate (C) is made as to 100 weight portion, the content that is somebody's turn to do (B) composition is preferably the ratio of approximately 20 weight portions～approximately 100 weight portions with respect to this, the more preferably ratio of approximately 30 weight portions～approximately 90 weight portions, the more preferably ratio of approximately 30 weight portions～approximately 80 weight portions.
From improving the viewpoint of adhesiveness, flexibility and nerve, the content of the compound (B) shown in the above-mentioned formula (2) in ultraviolet-curing resin composition of the present invention is generally 10～60 weight portions with respect to total amount 100 weight portions of ultraviolet-curing resin composition, be preferably 15～50 weight portions, sometimes be preferably 10～40 weight portions, be particularly preferably 20～40 weight portions.When the content of this compound (B) is very few, adhesiveness, flexibility, nerve as target cannot be brought into play, in addition, in the time of too much, the problem that cannot obtain sufficient hardness can be produced.
In ultraviolet-curing resin composition of the present invention, as carbamate (methyl) acrylate (C), use reaction product carbamate (methyl) acrylate (below also referred to as " (C) composition ") of polytetramethylene glycol and polyisocyanates and (methyl) acrylic acid hydroxyl C2～C4 Arrcostab.While using this carbamate (methyl) acrylate (C) with appropriate amount, be improved the function of the mechanical property (warpage, distortion etc.) of BD.
The carbamate using in the present invention (methyl) acrylate (C) can be by making polytetramethylene glycol (a) react and obtain with polyisocyanates (b) and (methyl) acrylic acid hydroxyl C2～C4 Arrcostab (c).
As polytetramethylene glycol (a), in order to obtain good carbamate (methyl) acrylate of balance of flexibility and hardness, preferred number average molecular weight is 400～2000, from viscosity, cost, the adhering viewpoint of raising, more preferably using number-average molecular weight is 500～1000 polytetramethylene glycol (a), the polytetramethylene glycol (a) that particularly preferably number-average molecular weight is 500～750.According to circumstances, preferably using number-average molecular weight is 400～750 polytetramethylene glycol (a).
When the number-average molecular weight of the polytetramethylene glycol of using (a) is excessive, can make the hardness of solidfied material of resin combination deteriorated, therefore not preferred.In addition, when this number-average molecular weight is too small, cannot give good flexibility, and be difficult to improve the mechanical property (warpage, distortion etc.) of BD, therefore not preferred.
As polyisocyanates (b), so long as there is the compound of 2 above isocyanate group, do not limit, can enumerate for example isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, Xylene Diisocyanate, diphenyl methane-4,4 '-diisocyanate or tetrahydrochysene dicyclopentadiene based isocyanate etc.
In this case, as polyisocyanates (b), preferably use isophorone diisocyanate or toluene diisocyanate.
As (methyl) acrylic acid hydroxyl C2～C4 Arrcostab (c), can enumerate such as (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid hydroxy butyl ester etc.Wherein, preferably use (methyl) hydroxy-ethyl acrylate.
As this carbamate (methyl) acrylate (C), more preferably make polytetramethylene glycol (a) take the isocyanate group equivalent of polyisocyanates (b) with polyisocyanates (b) and react and synthesize the oligourethane that two ends are isocyanate group and make resulting oligourethane react carbamate (methyl) acrylate obtaining with (methyl) acrylic acid hydroxyl C2～C4 Arrcostab (c) as superfluous amount with respect to the hydroxyl equivalent of polytetramethylene glycol (a).
The synthetic reaction of carbamate (methyl) acrylate (C) for example can be carried out as follows.; the mode that polytetramethylene glycol (a) and polyisocyanates (b) are preferably to 1.1～2.0 equivalents with this isocyanate group with respect to the hydroxyl of every 1 equivalent is mixed, preferably reaction and synthesis of carbamates oligomer under the temperature of reaction of 70～90 ℃.Then, the mode that resulting oligourethane and (methyl) acrylic acid hydroxyl C2～C4 Arrcostab (c) are preferably to 1～1.5 equivalent with the hydroxyl of (methyl) crylic acid hydroxy ester (c) with respect to every 1 equivalent of isocyanate group of oligourethane is mixed, and reaction at 70～90 ℃, can access thus carbamate (methyl) acrylate as target.
Molecular weight as the carbamate using in ultraviolet-curing resin composition of the present invention (methyl) acrylate (C), is preferably approximately 400～approximately 10000 in number-average molecular weight.
From improving the viewpoint of adhesiveness, flexibility and nerve, the content of the carbamate in ultraviolet-curing resin composition of the present invention (methyl) acrylate (C) is generally 30～60 weight portions with respect to the total amount of ultraviolet-curing resin composition, is preferably 30～50 weight portions.When content is very few, cannot bring into play adhesiveness, flexibility, nerve as target, in the time of too much, can produce the problem that cannot obtain sufficient hardness, therefore cannot bring into play target effect of the present invention, therefore not preferred.
In the present invention, can be used together above-mentioned carbamate (methyl) acrylate (C) carbamate (methyl) acrylate in addition.
Can be applicable to and carbamate (methyl) acrylate of use can be by making polyvalent alcohol (d) react and obtain with polyisocyanates (b) and (methyl) crylic acid hydroxy ester compound (e).
At this, polyisocyanates (b) can be used above-mentioned polyisocyanates.
As operable polyvalent alcohol (d), can enumerate routine polyvalent alcohol described as follows.
(i) neopentyl glycol, 3-methyl isophthalic acid, 5-pentanediol, propylene glycol, BDO, 1, the aliphatic alcohols such as 6-hexanediol, trimethylolpropane, pentaerythrite, dihydroxymethyl tristane, two [methylol] cyclohexane;
(ii) a kind of polyester polyol obtaining that reacts with polyprotonic acid in the aliphatic polyol described in above-mentioned by making (i).
In addition, as above-mentioned polyprotonic acid, can enumerate such as succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid (TPA), hexane diacid, azelaic acid, tetrabydrophthalic anhydride etc.
(iii) the caprolactone alcohol obtaining with reacting of 6-caprolactone by polyvalent alcohol.
(iv) polycarbonate polyol.The PCDL for example obtaining with reacting of diphenyl carbonate by 1,6-hexanediol etc.
(v) polyether glycol.Such as the poly-C2～C3 such as polyglycol or polypropylene glycol aklylene glycol, oxirane modified bisphenol A etc.
The number-average molecular weight of the polyvalent alcohol in above-mentioned (ii)～(v) is preferably approximately 200～approximately 8000, and more preferably approximately 200～approximately 3000.
As operable (methyl) crylic acid hydroxy ester compound (e), can enumerate (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid hydroxy butyl ester, list (methyl) acrylic acid dihydroxymethyl cyclohexyl, (methyl) acrylic acid hydroxyl caprolactone etc.Wherein, preferably use (methyl) hydroxy-ethyl acrylate.
Above-mentioned carbamate (methyl) acrylate (C) carbamate (methyl) acrylate in addition can be used the method identical with the method for recording in above-mentioned carbamate (methyl) acrylate (C) to synthesize.
And in the situation with above-mentioned carbamate (methyl) acrylate (C) carbamate (methyl) acrylate in addition, in whole carbamates (methyl) acrylate composition that both merge, more than the content of carbamate (methyl) acrylate (C) is preferably 80 % by weight, more preferably more than 90 % by weight.
In addition, conventionally do not need and use above-mentioned carbamate (methyl) acrylate (C) carbamate (methyl) acrylate in addition, preferably using separately the mode of aforementioned carbamate (methyl) acrylate (C).
In total amount 100 weight portions of resin combination of the present invention, the total amount of above-mentioned (A)～(C) is generally 45～98 weight portions, is preferably 50～80 weight portions, more preferably 55～75 weight portions.Remainder is (D) composition and optional member, more preferably contains aforementioned (E) composition as the mode of one of optional member.
In ultraviolet-curing resin composition of the present invention, use Photoepolymerizationinitiater initiater (D) (below also referred to as " (D) composition ").As operable Photoepolymerizationinitiater initiater (D) in the present invention, so long as known Photoepolymerizationinitiater initiater all can be used, for example can enumerate: benzoin isobutyl ether, 2, 4-diethyl thioxanthone, ITX, dibenzoyl, 1-hydroxy-cyclohexyl 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 and 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide equimolecular open ring type Photoepolymerizationinitiater initiater, and the dehydrogenation type Photoepolymerizationinitiater initiater such as benzophenone, 4-phenyl benzophenone, isophthalic benzophenone, 4-benzoyl-4 '-methyldiphenyl base sulfide etc.As preferred Photoepolymerizationinitiater initiater, can enumerate 1-hydroxy-cyclohexyl phenyl ketone and TMDPO equimolecular open ring type Photoepolymerizationinitiater initiater.These Photoepolymerizationinitiater initiaters can use a kind of or and with two or more.
One of particularly from improving the viewpoint of inside solidification, and be preferred mode by the mode of TMDPO.One of preferred mode is for for example and with above-mentioned molecule open ring type Photoepolymerizationinitiater initiater, preferred 1-hydroxy-cyclohexyl phenyl ketone and TMDPO.
While using TMDPO as Photoepolymerizationinitiater initiater (D), its content is preferably 3～50 % by weight with respect to the total amount of this (D) composition.
The content of Photoepolymerizationinitiater initiater (D) in ultraviolet-curing resin composition is generally 1～10 weight portion with respect to total amount 100 weight portions of ultraviolet-curing resin composition, is preferably 2～8 weight portions, more preferably 3～8 weight portions.
Ultraviolet-curing resin composition of the present invention contains (A)～(D) composition with aforementioned ratio, also can contain (A)～(D) composition is in addition as remainder.
Preferred ultraviolet-curing resin composition of the present invention, except containing (A)～(D), contains (E) composition with aforementioned ratio.(A) in ultraviolet-curing resin composition of the present invention～(E) content of composition composition in addition (being its total amount in the situation that contains Multiple components) is generally approximately 0 weight portion～approximately 35 weight portion with respect to total amount 100 weight portions of ultraviolet-curing resin composition of the present invention, is preferably approximately 0 weight portion～approximately 10 weight portion.
In ultraviolet-curing resin composition of the present invention, can use as required epoxy (methyl) acrylate (G) (below also referred to as " (G) composition ").Epoxy (methyl) acrylate (G) has the curability of raising, improves the hardness of solidfied material and the function of curing rate.
In addition, as epoxy (methyl) acrylate (G), so long as all can use by making glycidyl ether type epoxy compound react epoxy (methyl) acrylate obtaining with (methyl) acrylic acid.As for obtaining the glycidyl ether type epoxy compound of preferred epoxy (methyl) acrylate, can enumerate: the diglycidyl ether of bisphenol-A or its alkylene oxide addition product, the diglycidyl ether of Bisphenol F or its alkylene oxide addition product, the diglycidyl ether of hydrogenated bisphenol A or its alkylene oxide addition product, the diglycidyl ether of A Hydrogenated Bisphenol A F or its alkylene oxide addition product, ethylene glycol bisthioglycolate glycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polypropylene glycol diglycidyl ether etc.
Epoxy (methyl) acrylate (G) can be by making these glycidyl ether type epoxy compounds react and obtain under condition as described below with (methyl) acrylic acid.
With respect to epoxy radicals 1 equivalent of glycidyl ether type epoxy compound, make (methyl) acrylic acid with 0.9～1.5 mole, more preferably the ratio of 0.95～1.1 mole reacts.Preferably 80～120 ℃ of temperature of reaction, the reaction time is approximately 10 hours～approximately 35 hours.In order to promote reaction, preferably use catalyzer such as triphenylphosphine, TAP, triethanolamine or etamon chloride.In addition, in order to prevent the polymerization in reaction, also can use such as p methoxy phenol or methylnaphthohydroquinone etc. as polymerization inhibitor.
As epoxy (methyl) acrylate (G) that can be applicable in the present invention using, can enumerate by acrylic acid bisphenol type epoxy (methyl) acrylate obtaining that reacts of bisphenol type epoxy compound and (methyl).In the present invention, the molecular weight of epoxy (methyl) acrylate (G) is preferably 500～10000.
In ultraviolet-curing resin composition of the present invention, can according to circumstances contain epoxy (methyl) acrylate (G).For example, from guaranteeing flexibility, adhering viewpoint, sometimes also preferably with respect to total amount 100 weight portions of ultraviolet-curing resin composition of the present invention conventionally containing 0 weight portion～approximately 20 weight portion of having an appointment, more preferably containing the mode of 0 weight portion～approximately 10 weight portions of having an appointment.Conventionally, the mode that does not preferably contain epoxy (methyl) acrylate (G).
In ultraviolet-curing resin composition of the present invention, can use as required aforementioned (A) composition, aforementioned (B) composition, aforementioned (C) composition, aforementioned (C) composition carbamate (methyl) acrylate, aforementioned (E) composition and above-mentioned (G) composition in addition (methyl) acrylate monomer (H) (below also referred to as " (H) composition ") in addition.In addition, should not comprise the composition that light stabilizer described later and other adjuvants person comprise by (methyl) acrylate monomer (H).
For operable this (methyl) acrylate monomer (H), so long as there is the compound of (methyl) acryloyl group not containing in 1 above aforementioned composition, be not particularly limited.
For example, as the compound with 1 above (methyl) acryloyl group, can enumerate: (methyl) acrylic acid C5～C20 such as (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid isopentyl ester, (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 (preferably C7～C18) Arrcostab, (methyl) acrylate compounds with phenyl ring that compound shown in the aforementioned formulas (2) such as (methyl) benzyl acrylate, (methyl) acrylic acid phenyl glycidyl ester and polypropyleneoxide modification (methyl) acrylic acid nonyl phenyl ester does not comprise, (methyl) acrylic acid tetrahydrofuran ester and (methyl) acrylic acid morpholine ester etc. have (methyl) acrylate of heterocycle, (methyl) acrylic acid such as (methyl) acrylic acid 2-hydroxypropyl acrylate have C2～C8 Arrcostab of hydroxyl, polyalkylene glycol mono (methyl) acrylate such as ethoxy diethylene glycol (methyl) acrylate and polypropylene glycol (methyl) acrylate, (methyl) acrylic acid tristane ester, (methyl) isobornyl acrylate, (methyl) acrylic acid dicyclopentadiene oxygen base ethyl ester, acrylic acid dihydro dicyclopentadiene base ester (for example, the FANCRYL FA-511A that Hitachi Chemical Co., Ltd. manufactures), acrylic acid dihydro dicyclopentadiene base oxygen base ethyl ester (for example, the FANCRYL FA-512A that Hitachi Chemical Co., Ltd. manufactures), metering system acid dihydride dicyclopentadiene base oxygen base ethyl ester (for example, the FANCRYL FA-512M that Hitachi Chemical Co., Ltd. manufactures), acrylic acid tetrahydrochysene dicyclopentadiene base ester (for example, the FANCRYL FA-513A that Hitachi Chemical Co., Ltd. manufactures), methacrylic acid tetrahydrochysene dicyclopentadiene base ester (for example, the FANCRYL FA-513M that Hitachi Chemical Co., Ltd. manufactures), acrylic acid 1-adamantane esters (for example, the Adamantate AA that Idemitsu Kosen Co., Ltd. manufactures), acrylic acid 2-methyl-2-adamantane esters (for example, the Adamantate MA that Idemitsu Kosen Co., Ltd. manufactures), acrylic acid 2-ethyl-2-adamantane esters (for example, the Adamantate EA that Idemitsu Kosen Co., Ltd. manufactures) and methacrylic acid 1-adamantane esters (for example, the Adamantate AM that Idemitsu Kosen Co., Ltd. manufactures) etc. (methyl) acrylate compounds with C7～C10 aliphatics ring, (methyl) acrylic acid phosphates such as oxirane modification (methyl) acrylic acid phenoxylation phosphate, oxirane modification (methyl) acrylic acid butoxy phosphate and oxirane modification (methyl) acrylic acid octyloxy phosphate etc.
This (methyl) acrylate monomer (H) with 1 (methyl) acryloyl group according to circumstances has the function of the mechanical property (suppressing warpage, distortion etc.) of the BD that improves the light-transmitting layer with the solidfied material that comprises ultraviolet-curing resin composition of the present invention sometimes.
About this (methyl) acrylate monomer (H), as (methyl) acrylate monomer with 2 (methyl) acryloyl groups, can enumerate: cyclohexane-1,4-dimethanol two (methyl) acrylate, cyclohexane-1,3-dimethanol two (methyl) acrylate, tristane dihydroxymethyl two (methyl) acrylate (for example, the KAYARAD R-684 (tristane dihydroxymethyl diacrylate) that Nippon Kayaku K. K manufactures etc.) and two (methyl) acrylic acid tetrahydrochysene dicyclopentadiene base ester etc. there is two (methyl) acrylate compounds of C5～C10 aliphatics ring, dioxane glycol two (methyl) acrylate (the KAYARAD R-604 (dioxane glycol diacrylate) that for example, Nippon Kayaku K. K manufactures etc.) etc. has two (methyl) acrylate compounds of heterocycle, aklylene glycol two (methyl) acrylate that compound shown in aforementioned formula (1) does not comprise or its alkylene oxide modifier, for example, (a) C2 or C3 glycol two (methyl) acrylate, through 1 of 3～10 moles of ethylene oxide modifications, 6-hexanediol two (methyl) acrylate, through two (methyl) acrylic acid alkylene ester and the alkylene oxide modifiers thereof such as neopentyl glycol two (methyl) acrylate of 3～10 mol of alkylene oxide modifications, hydroxy new pentane acid neopentyl glycol two (methyl) acrylate, repeat number is that more than 6 polyglycol two (methyl) acrylate and repeat number are poly alkylene glycol two (methyl) acrylate that more than 4 polypropylene glycol two (methyl) acrylate etc. is greater than C10, aforementioned bisphenol A-type two (methyl) acrylate (E) through 4～12 moles of ethylene oxide modifications alkylene oxide modified bisphenol A type two (methyl) acrylate in addition, and oxirane modification two (methyl) acrylic acid phosphate etc.
In this case, from the viewpoint of variable quantity, the viewpoint of permanance of the warpage that suppresses to be caused by temperature variation and improve the viewpoint of hardness, sometimes preferably use two (methyl) acrylic acid alkylene ester or its alkylene oxide modifier beyond the compound that aforementioned formula (1) represents.
About this (methyl) acrylate monomer (H), as (methyl) acrylate monomer with 3 (methyl) acryloyl groups, can enumerate: trihydroxy methyl C2～C10 alkane three (methyl) acrylate such as trimethylolpropane tris (methyl) acrylate and trihydroxy methyl octane three (methyl) acrylate; Trihydroxy methyl C2～C10 many alkoxys three of alkane (methyl) acrylate such as the many ethoxys three of trimethylolpropane (methyl) acrylate, many propoxyl group three (methyl) acrylate of trimethylolpropane and the many propoxyl group three of the many ethoxys of trimethylolpropane (methyl) acrylate; And alkylene oxide modification trimethylolpropane tris (methyl) acrylate such as three [(methyl) acryloxy ethyl] isocyanuric acid ester, pentaerythrite three (methyl) acrylate, oxirane modification trimethylolpropane tris (methyl) acrylate and epoxy pronane modification trimethylolpropane tris (methyl) acrylate etc.
About this (methyl) acrylate monomer (H); as (methyl) acrylate monomer with 4 (methyl) acryloyl groups, can enumerate: the many ethoxys four of pentaerythrite (methyl) acrylate, the many propoxyl group four of pentaerythrite (methyl) acrylate, pentaerythrite four (methyl) acrylate, double trimethylolpropane four (methyl) acrylate and dipentaerythritol four (methyl) acrylate etc.
About this (methyl) acrylate monomer (H), as (methyl) acrylate monomer with 5 (methyl) acryloyl groups, can enumerate dipentaerythritol five (methyl) acrylate etc.
About this (methyl) acrylate monomer (H), as (methyl) acrylate monomer with 6 (methyl) acryloyl groups, can enumerate dipentaerythritol six (methyl) acrylate etc.In addition, operable in the present invention (methyl) acrylate monomer also can be for having multifunctional (methyl) acrylate monomer of 7 above (methyl) acryloyl groups.
In ultraviolet-curing resin composition of the present invention, these (H) compositions can or mix two or more with arbitrary proportion and use with a kind.(H) content of composition in ultraviolet-curing resin composition is generally approximately 0 weight portion～approximately 53 weight portion with respect to total amount 100 weight portions of ultraviolet-curing resin composition, be for example according to circumstances approximately 20 weight portions～approximately 80 weight portion, be preferably approximately 30 weight portions～approximately 70 weight portion.
As (methyl) acrylate compounds containing in ultraviolet-curing resin composition of the present invention, can use any one in acrylate compounds or methacrylate compound.Common preferred acrylate compound, the total amount of the methacrylate compound containing in this resin combination is preferably less than 10 weight portions with respect to total amount 100 weight portions of this resin combination.In addition, (methyl) acrylate compounds containing in ultraviolet-curing resin composition of the present invention refers to as carbamate (methyl) acrylate, aforementioned (E) composition, aforementioned (G) composition and above-mentioned (H) composition beyond aforementioned (A) composition, aforementioned (B) composition, aforementioned (C) composition, aforementioned (C) composition and contains (methyl) acrylate compounds in this resin combination.
In ultraviolet-curing resin composition of the present invention, as other adjuvants, can use as required the light stabilizers such as the antioxidants such as sensitizer, silane coupling agent, surfactant, levelling agent, hot polymerization inhibitor, hindered phenol and phosphite ester and hindered amine.
Use in the situation of above-mentioned adjuvant, its content is 0.05～10 weight portion with respect to total amount 100 weight portions of ultraviolet-curing resin composition of the present invention, is preferably 0.1～5 weight portion.
As the sensitizer in ultraviolet-curing resin composition of the present invention, for example can use trimethylamine, methyl dimethoxy hydramine, triethanolamine, to dimethylamino benzoylformaldoxime, ESCAROL 507 ethyl ester, ESCAROL 507 isopentyl ester, N, N-dimethyl benzylamine and 4,4 '-bis-(diethylamino) benzophenone etc.In addition also can be used together not with the amine of aforementioned optical polymerism compound generation addition reaction as sensitizer.
The viewpoint of the operability during from making CD, in ultraviolet-curing resin composition of the present invention, preferably use light stabilizer, as this light stabilizer, hindered amine compound, the compound (F) (below also referred to as " (F) composition ") particularly with hindered piperidine skeleton are useful.
Have hindered piperidine skeleton compound (F) so long as known thing can use without particular limitation.
Particularly, for example can use choosing free 2, 2, 6, 6-tetramethyl-4-piperidones, 2, 2, 6, 6-tetramethyl-4-piperidine alcohols, 1, 2, 2, 6, 6-pentamethyl-4-piperidine alcohols, 4-hydroxyl-2, 2, 6, 6-tetramethyl-1-piperidines ethanol, (methyl) acrylic acid 1, 2, 2, 6, 6-pentamethyl-4-piperidine ester, methacrylic acid 2, 2, 6, 6-tetramethyl-4-piperidine ester, decanedioic acid two (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) ester, decanedioic acid two (2, 2, 6, 6-tetramethyl-4-piperidyl) ester, it is poly-that { [6-(1, 1, 3, 3-tetramethyl butyl) amino-1, 3, 5-triazine-2, 4-bis-bases] [(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-hydroxyethyl)-4-hydroxyl-2, 2, 6, the condensed polymer of 6-tetramethyl piperidine, 2-(3, the tertiary acrinyl of 5-bis-)-2-n-butylmalonic acid two (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) ester, 1, 2, 3, 4-ethylene-dimalonic acid four (2, 2, 6, 6-tetramethyl-4-piperidyl) ester, 1, 2, 3, 4-ethylene-dimalonic acid and 1, 2, 2, 6, the mixed ester compound of 6-pentamethyl-4-piperidine alcohols and 1-tridecanol, 1, 2, 3, 4-ethylene-dimalonic acid and 2, 2, 6, the mixed ester compound of 6-tetramethyl-4-piperidine alcohols and 1-tridecanol, 1, 2, 3, 4-ethylene-dimalonic acid and 1, 2, 2, 6, 6-pentamethyl-4-piperidine alcohols and 3, two (2-hydroxyl-1 of 9-, 1-dimethyl ethyl)-2, 4, 8, the undecanoic mixed ester compound of 10-tetra-oxaspiros [5.5], and 1, 2, 3, 4-ethylene-dimalonic acid and 2, 2, 6, 6-tetramethyl-4-piperidine alcohols and 3, two (2-hydroxyl-1 of 9-, 1-dimethyl ethyl)-2, 4, 8, at least a kind of hindered amine compound in the group that the undecanoic mixed ester compound of 10-tetra-oxaspiros [5.5] forms.Wherein, from giving the viewpoint of good permanance, can preferably 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 (LA-82 that Asahi Denka Co., Ltd. manufactures).
Above-mentioned hindered amine compound, preferably there is the compound (F) of hindered piperidine skeleton) in, be obstructed that it is sterically hindered to represent that molecule has, refer to that bonding has the bulky alkyl with side chain on the carbon atom of nitrogen-atoms or its adjacency.Hindered amine compound as preferred use, can enumerate bonding on nitrogen-atoms has the compound of the alkyl with side chains such as the tert-butyl groups, for example have at least 2,26, the compound on 6 position with the piperidines skeleton of C1～C3 alkyl replacement, preferably enumerate and have at least 1,2,2, the compound on 6,6 position with the piperidines skeleton of C1～C3 alkyl replacement.
In addition; while making ultraviolet-curing resin composition of the present invention form solidfied material; the compound itself with hindered piperidine skeleton can occur crosslinked; thereby less form with impurity is separated out; and also can not damage the curability of ultraviolet-curing resin composition; therefore, can particularly preferably use the compound with the hindered piperidine skeleton that contains (methyl) acryloyl group.For example, preferably at least 2,2,6,6 position has (methyl) acrylic acid piperidine ester that C1～C3 alkyl replaces, more preferably (methyl) acrylic acid 1,2,2,6,6-pentamethyl-4-piperidine ester.
Light stabilizer, the content of compound (F) in ultraviolet-curing resin composition preferably with hindered piperidine skeleton are generally 0.01～10 weight portion with respect to total amount 100 weight portions of ultraviolet-curing resin composition, more preferably 0.03～8 weight portion, is particularly preferably 0.03～5 weight portion.
As operable silane coupling agent in ultraviolet-curing resin composition of the present invention, so long as known silane coupling agent can be not particularly limited to use.According to circumstances, from improving the viewpoint of permanance of the cured layer of ultraviolet-curing resin composition of the present invention, preferably use the compound shown in following formula (4).
(in formula, R 5and R 6independent existence separately, R 5the alkyl that represents carbon number 1～3, R 6the alkylidene that represents carbon number 1～6)
At this, as the compound shown in above-mentioned formula (4), R in preferred formula (4) 5be methyl, R 6compound for the alkylidene of carbon number 2～4.Particularly, can enumerate the silane compounds such as 3-sulfydryl propyl trimethoxy silicane.
The content of the silane coupling agent in ultraviolet-curing resin composition of the present invention is generally 0.01～10 weight portion with respect to total amount 100 weight portions of ultraviolet-curing resin composition, is preferably 0.05～3 weight portion.
From giving to the cured layer of ultraviolet-curing resin composition of the present invention the viewpoint of good permanance, can preferably use the compound shown in following formula (3) as antioxidant.
Figure BDA0000414287510000272
(in formula, R 2, R 3and R 4independent existence separately, R 2the alkyl that represents carbon number 1～3, R 3the alkylidene that represents carbon number 1～6, R 4the alkyl that represents carbon number 5～20)
R in preferred above-mentioned formula (3) 2for methyl, R 3alkylidene and R for carbon number 2～5 4compound for the straight chained alkyl of the carbon number 10～15 of straight chain.
As the compound shown in above-mentioned formula (3), specifically can enumerate: two [2-methyl-4-[3-(dodecyl sulfenyl) propionyloxy]-5-tert-butyl-phenyl] sulfide, two [2-methyl-4-[3-(myristyl sulfenyl) propionyloxy]-5-tert-butyl-phenyl] sulfide and two { 2-methyl-4-[3-N-alkyl (C12 or C14) sulfenyl propionyloxy]-5-tert-butyl-phenyl } sulfide etc.For example, can obtain from the market AO-23 (Asahi Denka Co., Ltd. manufactures, two { 2-methyl-4-[3-N-alkyl (C12 or C14) sulfenyl propionyloxy]-5-tert-butyl-phenyl } sulfide).
The content of antioxidant in ultraviolet-curing resin composition is generally 0～10 weight portion with respect to total amount 100 weight portions of ultraviolet-curing resin composition.From permanance aspect, preferably generally contain, its content is 0.01～10 weight portion, is preferably 0.03～8 weight portion, is particularly preferably 0.03～5 weight portion.
Below record the several optimal ways in ultraviolet-curing resin composition for BD of the present invention.Contained content (weight portion) wherein when if not otherwise specified, " part " in each component content represents that the total amount of ultraviolet-curing resin composition is made as to 100 weight portion.
(I) a kind of Blu-ray Disc ultraviolet-curing resin composition, it contains 2～8 parts of 5～15 parts of above-mentioned (A) compositions, above-mentioned (B) composition 10～60 parts (preferably 10～50 parts), 30～60 parts of above-mentioned (C) compositions and above-mentioned (D) compositions, and remainder is (A)～(D) composition in addition.
(II) ultraviolet-curing resin composition as described in above-mentioned (I), wherein, also contains 15～50 parts, more preferably bisphenol A-type two (methyl) acrylate through 4～12 moles of ethylene oxide modifications of 15～40 parts of conducts (E) composition.
(III) ultraviolet-curing resin composition as above-mentioned (I) or (II), wherein, should (C) composition be by carbamate (methyl) acrylate being obtained with reacting of (methyl) acrylic acid hydroxyl C2～C4 Arrcostab (c) by polytetramethylene glycol (a) and the synthetic oligourethane of polyisocyanates (b).
(IV) ultraviolet-curing resin composition as described in above-mentioned (III), wherein, the number-average molecular weight of this polytetramethylene glycol (a) is 400～750.
(V) ultraviolet-curing resin composition as above-mentioned (III) or (IV), wherein, this polyisocyanates (b) is any one or two kinds in isophorone diisocyanate and toluene diisocyanate.
(VI) ultraviolet-curing resin composition as described in any one in above-mentioned (III)～(V) wherein, should (methyl) acrylic acid hydroxyl C2～C4 Arrcostab (c) be (methyl) hydroxy-ethyl acrylate.
(VII) ultraviolet-curing resin composition as described in any one in above-mentioned (I)～(VI), wherein, should (A) composition be any one or two kinds in dipropylene glycol two (methyl) acrylate and hexanediol two (methyl) acrylate.
(VIII) ultraviolet-curing resin composition as described in any one in above-mentioned (I)～(VII) wherein, should (B) composition be phenol (methyl) acrylate through 1 mole or 2 moles of ethylene oxide modifications.
(IX) ultraviolet-curing resin composition as described in any one in above-mentioned (I)～(VIII), wherein, at least contains TMDPO as this (D) composition.
(X) ultraviolet-curing resin composition as described in above-mentioned (IX), wherein, the content of TMDPO is 3～50 % by weight with respect to the total amount of this (D) composition.
(XI) ultraviolet-curing resin composition as described in any one in above-mentioned (I)～(X), wherein, also contains 0.01～10 part, preferred 0.03～5 part of above-mentioned (F) composition.
(XII) ultraviolet-curing resin composition as described in above-mentioned (XI), wherein, is somebody's turn to do (F) composition contains the hindered piperidine skeleton of (methyl) acryloyl group compound for having.
(XIII) ultraviolet-curing resin composition as described in any one in above-mentioned (I)～(XII), wherein, also contains 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 described in any one in above-mentioned (I)～(XIII), wherein, also contains 0.01～10 part, preferably 0.05～3 part as the compound shown in the above-mentioned formula (4) of silane coupling agent.
In ultraviolet-curing resin composition of the present invention, all good and by the few ultraviolet-curing resin composition of variable quantity of the variable quantity of the curability of ultraviolet-curing resin composition, warpage that temperature variation causes and warpage when curing for the adhesiveness adhesiveness of reflection layer, contact bed (particularly with), nerve, hardness and the permanance that obtain solidfied material, preferred mode is described below.
(i) ultraviolet-curing resin composition as described in any one in above-mentioned (I)～(XV), wherein, total amount 100 weight portions with respect to ultraviolet-curing resin composition, contain 5～15 weight portions as dipropylene glycol two (methyl) acrylate of this (A) composition and one or both in hexanediol two (methyl) acrylate, 12～50 weight portions are as (methyl) acrylate of the phenol through 1 moles of ethylene oxide modification of this (B) composition and one or both in phenol (methyl) acrylate of 2 moles of ethylene oxide modifications, 30～50 weight portions are as polytetramethylene glycol (polytetramethylene glycol that particularly preferably number-average molecular weight is 400～750) and the polyisocyanates (b) and reaction product carbamate (methyl) acrylate of (methyl) acrylic acid 2-hydroxyl ethyl ester and the Photoepolymerizationinitiater initiater (D) of 2～8 weight portions of this (C) composition.
(ii) ultraviolet-curing resin composition as described in any one in above-mentioned (I)～(XIV) and above-mentioned (i), wherein, contains 20～40 weight portions as (methyl) acrylic acid phenoxy ethyl of this (B) composition.
(iii) ultraviolet-curing resin composition as described in any one as above-mentioned (I)～(IV), above-mentioned (i) and (ii), wherein, also contain 15～30 weight portions as bisphenol A-type two (methyl) acrylate through 9～11 moles of ethylene oxide modifications of (E) composition.
(iv) ultraviolet-curing resin composition as described in any one as above-mentioned (I)～(XIV), above-mentioned (i) and (iii), wherein, with respect to the total amount of the carbamate containing in ultraviolet-curing resin composition (methyl) acrylate composition, the content of reaction product carbamate (methyl) acrylate (C) of the polytetramethylene glycol of number-average molecular weight 400～700 and polyisocyanates and (methyl) acrylic acid 2-hydroxyl ethyl ester is 90 % by weight above (particularly preferably 100 % by weight).
(v) ultraviolet-curing resin composition as described in any one in above-mentioned (I)～(XIV) and above-mentioned (i)～(iv), wherein, above-mentioned (A) composition, (B) composition and (C) total content of composition are generally the ratio of 45～98 weight portions in total amount 100 weight portions of resin combination of the present invention, be preferably the ratio of 50～80 weight portions, the ratio of 55～75 weight portions more preferably, remainder is (D) composition and optional member.
(vi) ultraviolet-curing resin composition as described in any one in above-mentioned (I)～(XIV) and above-mentioned (i)～(v), wherein, when the content of (A) composition is made as to 100 weight portion, (B) content of composition with respect to this more than 100 weight portions and be below 600 weight portions, when the content of (C) is made as to 100 weight portion, (B) composition is the ratio of approximately 30 weight portions～approximately 90 weight portions with respect to the content of above-mentioned carbamate (methyl) acrylate (C).
(vii) ultraviolet-curing resin composition as described in any one in above-mentioned (I)～(XIV) and above-mentioned (i)～(vi), wherein, contain bisphenol A-type two (methyl) acrylate through 9～11 moles of ethylene oxide modifications as (E) composition, its content is the ratio of 35～90 weight portions with respect to content 100 weight portions of above-mentioned carbamate (methyl) acrylate (C).
(viii) ultraviolet-curing resin composition as described in any one in above-mentioned (I)～(XIV) and above-mentioned (i)～(vii), the total amount of the methacrylate compound wherein, containing in ultraviolet-curing resin composition is less than 10 weight portions with respect to total amount 100 weight portions of ultraviolet-curing resin composition.
Blu-ray Disc of the present invention can be by obtaining above-mentioned each composition mixed dissolution at normal temperature～80 ℃ with ultraviolet-curing resin composition.Can wait operation that snotter is removed by filtration as required.
Consider coating, Blu-ray Disc of the present invention is preferably 300～2000 (mPas), more preferably 500～1200 (mPas) by the viscosity of ultraviolet-curing resin composition at 25 ℃.By making viscosity easily form thick film at this range content, can shorten and produce apart from the time (the running time of production of units quantity).
BD of the present invention is with using mentioned component solvent in addition in ultraviolet-curing resin composition.In this case, the content of solvent is preferably less than 10 weight portions with respect to total amount 100 weight portions of ultraviolet-curing resin composition, more preferably less than 5 weight portions, does not particularly preferably use the situation of solvent.
BD of the present invention is with in ultraviolet-curing resin composition, and the elastic modulus of the cured layer that ultraviolet ray forms after irradiating at 25 ℃ is preferably 10～3000MPa, and more preferably 50～2000MPa, is particularly preferably 100～1000MPa.
In addition the less person of warpage who produces because of temperature variation in the cured layer of formation, can prevent the mistake of the characteristics of signals that produces because of temperature variation effectively.Therefore,, in the situation that ultraviolet-curing resin composition is used for to the light-transmitting layer of BD, the warpage while preferably preserving at 5 ℃～55 ℃ is less than 0.8 degree with respect to the variable quantity of the warpage when preserving at present for 25 ℃, is particularly preferably less than 0.6 degree.In addition, warp value is near the most peripheral of CD, apart from the warp value (angle) at the position of the 56mm of cd centre.
[BD]
BD of the present invention is at least formed with reflection layer and light-transmitting layer and utilizes blue laser to see through above-mentioned light-transmitting layer and the BD that records or regenerate on substrate, and above-mentioned light-transmitting layer comprises the solidfied material of ultraviolet-curing resin composition for light-transmitting layer of the present invention.Light-transmitting layer in this BD can be the one-sided outermost layer of this BD, also can have hard conating thereon in addition and take this hard conating as outermost layer.Another outermost layer is generally substrate.For BD of the present invention, the light-transmitting layer of the application of the invention uses the solidfied material layer of ultraviolet-curing resin composition as light-transmitting layer, even be also difficult for producing the reduction of adhesive power under hot and humid, good permanance can be accessed, therefore recording of information/regeneration can be carried out well.
Light-transmitting layer in BD of the present invention preferably makes the blue laser transmission efficiently that the oscillation wavelength of laser is 370～430nm, and preferably under 100 μ m thickness, the optical transmission rate of 405nm is more than 85%, to be particularly preferably more than 90%.
The preferred thickness of light-transmitting layer is the scope of 50～150 μ m, more preferably 75～150 μ m.The thickness of light-transmitting layer is set as approximately 100 μ m in the situation that of individual layer.The thickness of light-transmitting layer brings very large impact can to light transmission, signal-obtaining and record, therefore need to control fully.Light-transmitting layer can form with individual layer the cured layer of this thickness, also can stacked a plurality of light-transmitting layers.In the situation of multilayer, preferably the thickness sum of each light-transmitting layer is above-mentioned thickness range.The common preferred single layer of light-transmitting layer of the present invention.
BD of the present invention has reflection layer conventionally.As this reflection layer, if reflection laser, can form can recording/reproducing BD, mineral compounds such as the alloy that can use the metals such as gold, silver, copper, aluminium or contain any one metal wherein, silicon.Wherein, because near light reflectivity 400nm is high, therefore preferably use the alloy that silver or the silver of take are principal ingredient.The thickness of the reflection layer of BD of the present invention is preferably set to about 10nm～about 60nm.
Conventionally, reflection layer forms by evaporation on substrate or the above-mentioned metal of sputter or its alloy.
The ultraviolet-curing resin composition of the application of the invention, can improve permanance and the adhesiveness such as photostability, thermotolerance of this reflection layer.Particularly, comprise silver or take in the reflectance coating of the alloy that silver is principal ingredient and can preferably use ultraviolet-curing resin composition of the present invention.
As the substrate of BD of the present invention, can use the circular resin substrate of optical disc shapes, as this resin, can preferably use polycarbonate.At BD, for regeneration is special-purpose in the situation that, on the one-sided surface of substrate, be to form and undertake the pit of recorded information on the surface of face of stacked reflection layer, and forms reflectance coating thereon and form recording layer.
BD of the present invention is in the situation of writeable BD, between reflection layer and light-transmitting layer, is provided with recording layer.As recording layer, as long as can carry out recording of information/regeneration, can be the random layer in phase change type recording layer, magneto-optical recorder layer or organic pigment type recording layer.
In writeable BD, on the recorded information face of substrate, be provided with recording layer.Recording layer can suitably utilize the existing known material as used by optical recording medium recording layer.Can enumerate such as pigment, amorphous semiconductor, part nitride film, partial oxide film (inoranic membrane) etc.
BD of the present invention can have a plurality of above-mentioned recording layers.In this case, each layer can be formed by identical material, also can form by combination in any other materials.By using other materials to form a plurality of recording layers, can change the optical properties such as transmissivity of each layer.
As the concrete kind of recording layer, can enumerate inorganic type recording layer and organic pigment type recording layer.As the material using in inorganic type recording layer, can enumerate amorphous semiconductor material, part nitride and partial oxide.
As the concrete example of the amorphous semiconductor material using in inorganic type recording layer, can enumerate: the material of SbTe system, GeTe system, GeSbTe system, InSbTe system, AgSbTe system, AgInSbTe system, GeSb system, GeSbSn system, InGeSbTe system and InGeSbSnTe system etc.In amorphous semiconductor material, in order to improve crystallization rate, preferably use and take the composition that Sb is principal ingredient.In addition, these amorphous semiconductor materials can be used separately a kind, also can be to combine arbitrarily and ratio use two or more.
The part nitride film using as inorganic type recording layer and the concrete example of partial oxide film, can enumerate the part nitride film that comprises BiGeN or SnNbN etc. and the partial oxide film that comprises TeOx, BiFOx and TiSixOy etc.
As recording layer, can use organic pigment type recording layer.The material require of organic pigment type recording layer is used sharp light wavelength to have photonasty to record regenerating.And the material require of organic pigment type recording layer is by utilizing the irradiation of laser to cause that physical change or chemical reaction change refractive index.As the material of organic pigment type recording layer, can enumerate for example cyanines pigment, oxonols (oxonol) pigment, azopigment, phthalocyanine dye and porphyrin pigment.Use, by these organic materials and the solution that for example oxytol acetate, tetrafluoropropanol equal solvent mix, forms organic pigment type recording layer by this solution of the coatings such as spin-coating method.More than the thickness of organic pigment type recording layer is preferably 15nm and below 25nm.
In BD of the present invention, can on recording layer, form contact bed.Contact bed has the hot function that cushions recording layer and produce, the function that regulates CD reflection rate.In addition, contact bed has that the recording materials that contain in recording layer while preventing light-transmitting layer film forming diffuse to light-transmitting layer or light-transmitting layer infiltrates into the function of the mixing phenomenas such as recording layer with solvent containing in resin combination etc.
The material that forms this contact bed is used the potpourri of silicon dioxide and zinc sulphide conventionally.In addition can enumerate: monox is the oxide such as silicon dioxide, zinc paste, cerium oxide, yttria, indium oxide, tin indium oxide, gallium oxide and aluminium oxide particularly; Zinc sulphide and yttrium sulfide sulfides; The nitride such as silicon nitride; Silit; The potpourri of above-mentioned oxide and sulphur; The fluoride of magnesium and calcium etc. etc.This contact bed forms by methods such as sputters.
The curing overlay film that comprises ultraviolet-curing resin composition of the present invention is to forming the material of contact bed, particularly for silicon dioxide is good with the adhesiveness of potpourri, indium oxide or the tin indium oxide etc. of zinc sulphide, so can preferably use.
BD of the present invention can form plural recording layer (information recording position).For example, in the situation that the special-purpose BD of regeneration, can there is stacked the first reflection layer and the first light-transmitting layer on the substrate of pit, and on this first light-transmitting layer or in the situation that being laminated with other layer as required these other layer on form the second reflection layer and the second light-transmitting layer.In this case, on the first light-transmitting layer or be laminated on the first light-transmitting layer other layer on form pit.In addition, in the situation that BD that can recording/reproducing, can adopt on substrate stacked the first reflection layer, the first recording layer and the first light-transmitting layer and on this first light-transmitting layer, further form the second reflection horizon, the second recording layer and the second light-transmitting layer and there is the formation of two-layer recording layer.Or can adopt and similarly layer be carried out stacked and there is the formation of three layers of above recording layer.The in the situation that of stacked a plurality of layers, so that reaching the mode of above-mentioned thickness, the bed thickness sum of each layer suitably regulates.In addition, can be at sandwiched contact bed between reflection layer and recording layer and/or between recording layer and light-transmitting layer.
Ultraviolet-curing resin composition of the present invention is used in the situation of light-transmitting layer, can suppress to contact the corrosion of the contact bed of light-transmitting layer or recording layer etc. and deteriorated, therefore, ultraviolet-curing resin composition of the present invention also can be suitable for having the BD of recording layer.
In BD of the present invention, light-transmitting layer can be the layer of most surface, but also surface coating (hard conating) can be further set on its top layer.Material as forming hard conating, is not particularly limited so long as can form the material of the solidfied material layer that hardness is high and mar proof is good, conventionally uses ultraviolet-curing resin composition.
BD of the present invention has the special-purpose CD of regeneration and CD that can recording/reproducing.
The special-purpose CD of regenerating can be manufactured by following method.When 1 circular resin substrate is carried out to injection moulding, be provided as the pit of information recording layer, then on this information recording layer, form reflection layer.On reflection layer, after stacked other layers, by methods such as 2P method, rolling method, serigraphy or spin-coating method, be coated with light-transmitting layer ultraviolet-curing resin composition of the present invention as required.From the one-sided or both sides of BD, irradiate near the ultraviolet ray～near ultraviolet ray (wavelength 200～400nm) as active energy beam, make this resin combination be solidified to form light-transmitting layer, obtain thus the special-purpose BD of regeneration of the present invention.
CD that can recording/reproducing can be manufactured by following method.By evaporation or sputter etc., on 1 circular resin substrate, form reflection layer, and recording layer is set thereon.Stacked contact bed on this recording layer as required, further on this recording layer or on contact bed by the coatings such as said method light-transmitting layer ultraviolet-curing resin composition of the present invention.To irradiate active energy beam with above-mentioned same mode to BD, make this resin combination be solidified to form light-transmitting layer, obtain thus BD that can recording/reproducing of the present invention.
Ultraviolet light source when light-transmitting layer is solidified with ultraviolet-curing resin composition, so long as lamp that can near irradiation ultraviolet radiation～near ultraviolet ray (wavelength 200～400nm) is not particularly limited.Such as using (pulse) xenon lamp, electrodeless lamp, metal halide lamp, low pressure mercury lamp, high-pressure sodium lamp or ultrahigh pressure mercury lamp etc.Ultraviolet ray irradiation can be carried out in continuous light irradiation mode, also can carry out in flash irradiation mode.
During irradiation ultraviolet radiation, preferably so that its accumulative total light quantity is 0.05～1J/cm 2mode control.More preferably adding up light quantity is 0.05～0.8J/cm 2, be particularly preferably 0.05～0.6J/cm 2.
The light-transmitting layer using in BD of the present invention is good by the curability of ultraviolet-curing resin composition, therefore, even if accumulative total light quantity, on a small quantity can be fully curing, can not produce adhesion (being clamminess), warpage and the distortion that more can not produce BD at BD end face and surface yet.
[embodiment]
Below, as the concrete example of BD of the present invention, an example of the concrete formation of single-layer type BD and multi-layered type BD (for example double deck type BD) is shown below.
In BD of the present invention, preferred implementation as single-layer type BD, for example, have: stacked reflection layer and light-transmitting layer, the formation of carrying out the formation of recording of information or regeneration and hard conating is further set at light-transmitting layer from light-transmitting layer side incident blue laser on substrate.Light-transmitting layer is the layer of the solidfied material that comprises ultraviolet-curing resin composition of the present invention, and its thickness is for example the scope of 100 ± 10 μ m.Hard conating is preferably the layer that hardness is high and mar proof is good.The thickness of hard conating is preferably 1～10 μ m, more preferably 3～5 μ m.The thickness of substrate is about 1.1mm.Reflection layer is preferably silver or take the film of alloy that silver is principal ingredient etc.
In addition, as the preferred implementation with the single-layer type BD of recording layer, for example, there is the formation that stacks gradually reflection layer, the first contact bed arranging as required, recording layer (inorganic type recording layer, organic pigment type recording layer all can), second contact surface layer, light-transmitting layer and carry out the formation of recording of information or regeneration and hard conating is further set at light-transmitting layer from light-transmitting layer side incident blue laser on substrate.
As the preferred implementation of multi-layered type BD, for example, there are on substrate stacked the first reflection layer and the first light-transmitting layer, further stacked the second reflection layer and the second light-transmitting layer from the second light-transmitting layer side incident blue laser, carry out the formation of the double deck type BD of recording of information or regeneration thereon.The first light-transmitting layer and the second light-transmitting layer are the layer of the solidfied material that comprises ultraviolet-curing resin composition, and one deck is the layer that comprises ultraviolet-curing resin composition of the present invention at least arbitrarily.As the thickness of layer, preferably the thickness sum of the thickness of the first light-transmitting layer and the second light-transmitting layer is the scope of 100 ± 10 μ m.The thickness of substrate is about 1.1mm.Reflection layer is for silver or take the film of alloy that silver is principal ingredient etc.
In addition, as the preferred implementation with the multi-layered type BD of recording layer, for example, have and on substrate, stack gradually the first reflection layer, the first contact bed, the first recording layer (inorganic type recording layer, organic pigment type recording layer all can), second contact surface layer, the first light-transmitting layer, further stacked the second reflection layer, the 3rd contact bed, the second recording layer (inorganic type, organic pigment type all can), the 4th contact bed, the second light-transmitting layer from the second light-transmitting layer side incident blue laser, carry out the formation of the double deck type BD of recording of information or regeneration thereon.
In the double deck type BD of this formation, track record (groove) is also formed at the surface of the first light-transmitting layer, therefore, this first light-transmitting layer can form with the form of following multilayer: the layer upper strata stacked package of the cured film that comprises the ultraviolet-curing resin composition that tackiness is good containing being applicable to forming the layer of cured film of ultraviolet-curing resin composition of track record the multilayer that forms.In addition, during this forms, also can on top layer, be provided with hard conating.
(embodiment)
Below, by embodiment, be described more specifically the present invention, but the present invention is not subject to any restriction of these embodiment.
As embodiment 1～7 and comparative example 1～3, preparation comprises the ultraviolet-curing resin composition forming shown in following table 1.
Use resulting ultraviolet-curing resin composition, by following method, make and there is the Blu-ray Disc of inorganic recording layer, and carry out evaluating characteristics.
(making of Blu-ray Disc)
1. thering is track space, be that the diameter 12cm of the guide channel of 0.32 μ m is, on the polycarbonate substrate of thickness 1.1mm, so that the mode sputtering silver alloy that thickness is 100nm forms reflection horizon.Then, sputtered with Ti SiO and form inorganic recording layer on reflection horizon.And then, so that the mode sputter ZnS-SiO that thickness is about 15nm 2(mol ratio 80:20), forms contact bed thus, makes Blu-ray Disc substrate.
With contact bed mode upward by resulting Blu-ray Disc substrate-placing on universal stage.To be covered to the mode at internal diameter 11.5mm place, to carry out circle and add a cover (cap) and process, then by the present invention or relatively the ultraviolet-curing resin composition 3.0g of use be supplied on the lid of central part.
3. with the velocity range of 900rpm, carry out the spin coating of 4 seconds～7 seconds, so that the mode that coating film thickness is 95 μ m is coated with.When spin coating finishes, with xenon flash lamp, irradiate 2 flashes of light, make it be cured to the degree that surface mobility disappears.
4. use high-pressure sodium lamp, the accumulative total light quantity of take is 400mJ/cm 2mode from upside, irradiate the ultraviolet ray in 3 seconds, make the coated film of ultraviolet-curing resin composition completely curing.
5. in the mode upward of the ultraviolet-curing resin composition after solidifying, optic disc base board is loaded on universal stage.To be covered to the mode at internal diameter 11.5mm place, to carry out circle and add a cover processing, the ultraviolet-curing resin composition of then hard conating being used (HOD3950B, Nippon Kayaku K. K manufactures) 3.0g is supplied on the lid of central part.
6. the spin coating of carrying out 4 seconds～7 seconds with the velocity range of 6000rpm is coated with.When spin coating finishes, with xenon flash lamp, irradiate 2 flashes of light, make it be cured to the degree that surface mobility disappears, making the present invention or the relatively Blu-ray Disc of use.
Use resulting Blu-ray Disc to carry out evaluation of physical property, result obtains the result of following table 1.
Figure BDA0000414287510000411
In addition, as described below with each composition shown in abbreviation in table 1.
UA-1: the urethane acrylate that polytetramethylene glycol (number-average molecular weight 650), toluene diisocyanate and hydroxy-ethyl acrylate are obtained with the molar ratio reaction of 1:2:2
UA-2: the urethane acrylate that polytetramethylene glycol (number-average molecular weight 650), isophorone diisocyanate and hydroxy-ethyl acrylate are obtained with the molar ratio reaction of 1:2:2
UA-3: the urethane acrylate that polypropylene glycol (number-average molecular weight 1000), toluene diisocyanate and hydroxy-ethyl acrylate are obtained with the molar ratio reaction of 1:2:2
Photomer4226: propylene glycol diacrylate ，Ke Ning Co., Ltd. manufactures
Photomer4017:1,6-hexanediyl ester ，Ke Ning Co., Ltd. manufactures
TPGDA: tripropylene glycol diacrylate, Daicel-Qing Te Co., Ltd. manufactures
BPE4A: through the bisphenol A-type diacrylate of 4 moles of ethylene oxide modifications, Di-ichi Kogyo Seiyaku Co., Ltd. manufactures
BPE-10: through the bisphenol A-type diacrylate of 10 moles of ethylene oxide modifications, Di-ichi Kogyo Seiyaku Co., Ltd. manufactures
Photomer4035: acrylic acid phenoxy ethyl ，Ke Ning Co., Ltd. manufactures
EBECRYL110: through the phenol acrylate of 2 moles of ethylene oxide modifications, Daicel-Qing Te Co., Ltd. manufactures
FA-512A: acrylic acid dicyclopentadiene base oxygen base ethyl ester, Hitachi Chemical Co., Ltd. manufactures
IRGACURE184:1-hydroxy-cyclohexyl phenyl ketone, BASF AG manufactures
SPEEDCURE TPO:2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 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-sulfydryl propyl trimethoxy silicane ，Dong Li DOW CORNING Co., Ltd. manufactures
AO-23: two 2-methyl-4-[3-N-alkyl (C12 or C14) sulfenyl propionyloxy] and-5-tert-butyl-phenyl } sulfide, Asahi Denka Co., Ltd. manufactures
(adhesiveness test)
Adhesiveness test is undertaken by using universal tensile testing machine (RTM-250, Japan Baldwin company manufactures) to measure peel strength.As assay method, use has the BD of cured film of the ultraviolet-curing resin composition of resulting each embodiment or each comparative example, on the surface of the curing overlay film side of BD, cut out the otch of wide 10mm, use cutter that the end of the curing overlay film of wide 10mm is peeled off from contact bed, then with universal tensile testing machine, curing overlay film is peeled off with 90 degree directions, measured peel strength (25 ℃, 45%RH).
Adhering evaluation:
◎ ... measured value is more than 0.4g/10mm
Zero ... measured value is more than 0.2g/10mm and is less than 0.4g/10mm
* ... measured value is less than 0.2g/10mm
(nerve test)
Nerve test is used Fei Xier sclerometer (HP100-XYp, Fei Xier instrument company manufactures) to carry out.As assay method, with 1000mN pressurization 60 seconds, then measure the depression (25 ℃, 45%RH) that starts the cured film of formation after 60 seconds from removing pressurization (0mN).
The evaluation of nerve:
◎ ... final tested volume is less than 4mm
Zero ... final tested volume is more than 4mm and is less than 5mm
△ ... final tested volume is more than 5mm and is less than 6mm
* ... final tested volume is more than 6mm
(initial camber test)
Initial warpage be coated with the substrate before the ultraviolet-curing resin composition of embodiment or comparative example warpage by mensurations be coated with this resin combination and make it curing after the difference of warpage of substrate evaluate.For the warpage of BD substrate, (Dr.Schenk company manufactures, ProductName: プ ロ メ テ ウ ス MT-146), measure most peripheral near CD, apart from the angle at the position of the 56mm of cd centre to use the mechanical property determinator of BD.
The warp value of the substrate before warp value-coating ultraviolet-curing resin composition of initial warpage variable quantity=after solidifying
◎ ... be less than ± 0.4 degree
Zero ... ± 0.4 degree is above and be less than ± 0.6 degree
* ... more than ± 0.6 degree
(temperature warping test)
The warpage of the BD substrate after temperature warping is coated with the ultraviolet-curing resin composition of embodiment or comparative example by mensuration and it is solidified is evaluated with the difference of this substrate being placed under low temperature (5 ℃) or high temperature (50 ℃) to the warpage of the substrate after 24 hours.The mensuration of the warpage of BD substrate is undertaken by method same as described above.
The warp value of the substrate of warp value after 24 hours of temperature warping variable quantity=place under low temperature or high temperature-after solidifying
◎ ... be less than ± 0.6 degree
Zero ... ± 0.6 degree is above and be less than ± 0.8 degree
* ... more than ± 0.8 degree
(the tracer signal characteristic after the endurancing of Blu-ray Disc and visual judgement)
After using ODU-1000 that Blu-ray Disc data-signal determinator Pa Lusi company manufactures to record with the condition of linear velocity 4.92m/s, regenerating power 0.30mW, recording power 6.0mW, T continuous recording (long=0.08 μ m of 1T) BD of each embodiment or each comparative example, under 80 ℃, the environment of 85%RH, place 250 hours.
About the Blu-ray Disc after endurancing, use above-mentioned signal measuring device to measure tracer signal characteristic (jitter value (jitter), R8H and RSER), and evaluate with following benchmark.In addition, observe the surface of the Blu-ray Disc after endurancing and carry out visual judgement (ocular estimate), with following benchmark, evaluating.Jitter value, R8H and RSER are electric signal a kind of of BD.
(a) jitter value
The numerical value of jitter value is higher, represents that the signal data of Blu-ray Disc is more deteriorated, more than 10%, is difficult to read and write data if.
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 (reflectivity) is lower, represents that the data of BD are more deteriorated.
The evaluation of R8H:
Zero ... more than 10
* ... be less than 10
(c)RSER
The value of RSER is higher, represents that the data of BD are more deteriorated.
The evaluation of RSER:
Zero ... be less than 2 * 10 -3
* ... 2 * 10 -3above
(d) visual judgement
By the cured film of visualization Blu-ray Disc, be determined with the curing inequality without gonorrhoea or sharkskin shape.
The evaluation of visual judgement:
Zero ... the curing inequality that there is no gonorrhoea or sharkskin shape in cured film
* ... the curing inequality that has gonorrhoea or sharkskin shape in cured film
(comprehensive evaluation)
In comprehensive evaluation, during each of tracer signal characteristic (jitter value, R8H, RSER) after adhesiveness (90 ° of disbonded tests), nerve, initial warpage, temperature warping (5 ℃ and 50 ℃), endurancing and visual judgement evaluated, all ◎ of being evaluated as or comprehensive evaluation is designated as to zero at 1 o'clock, any one be evaluated as △ or * time is designated as comprehensive evaluation *.
As shown in Table 1, for the solidfied material of resin combination of the present invention with embodiment 1～7, as for the BD of light-transmitting layer, after endurancing, also obtained good tracer signal characteristic.Confirmed in addition: the curability of the resin combination of the present invention of embodiment 1～7 is good, its solidfied material is adhesiveness and the good solidfied material of nerve, by using this solidfied material as light-transmitting layer, the few BD of variable quantity of the warpage that can access while solidifying and produce because of temperature variation.
In addition, for the BD of embodiment 4～7, in endurancing, even in the situation that place 500 hours under 80 ℃, the environment of 85%RH, jitter value is also less than 10.0%, has good permanance.

Claims (16)

1. a Blu-ray Disc has the solidfied material layer of following ultraviolet-curing resin composition as light-transmitting layer on substrate,
Described ultraviolet-curing resin composition is following Blu-ray Disc ultraviolet-curing resin composition,
In total amount 100 weight portions of ultraviolet-curing resin composition, with following ratio, contain following (A)～(D) composition,
(A) compound 5～15 weight portions shown in following formula (1),
In formula (1), R 1the alkylidene with side chain that represents the straight-chain alkyl-sub-of carbon number 4～10, the alkylidene with ehter bond of carbon number 4～10 or carbon number 4～10, R 11represent hydrogen atom or methyl;
(B) compound 10～60 weight portions shown in following formula (2),
Figure FDA0000414287500000012
In formula (2), R 21represent hydrogen atom or methyl, n represents 1～10 integer;
(C) reaction product carbamate (methyl) acrylate 30～60 weight portions of polytetramethylene glycol and polyisocyanates and (methyl) acrylic acid hydroxyl C2～C4 Arrcostab; And
(D) Photoepolymerizationinitiater initiater 2～8 weight portions.
2. Blu-ray Disc as claimed in claim 1 wherein, is at least formed with reflection layer and light-transmitting layer on substrate, and utilizes the blue laser within the scope of 370nm～430nm with oscillation wavelength see through this light-transmitting layer and record or regenerate.
3. a Blu-ray Disc ultraviolet-curing resin composition, wherein, in total amount 100 weight portions of ultraviolet-curing resin composition, contains following (A)～(D) composition with following ratio,
(A) compound 5～15 weight portions shown in following formula (1),
Figure FDA0000414287500000021
In formula (1), R 1the alkylidene with side chain that represents the straight-chain alkyl-sub-of carbon number 4～10, the alkylidene with ehter bond of carbon number 4～10 or carbon number 4～10, R 11represent hydrogen atom or methyl;
(B) compound 10～60 weight portions shown in following formula (2),
Figure FDA0000414287500000022
In formula (2), R 21represent hydrogen atom or methyl, n represents 1～10 integer;
(C) reaction product carbamate (methyl) acrylate 30～60 weight portions of polytetramethylene glycol and polyisocyanates and (methyl) acrylic acid hydroxyl C2～C4 Arrcostab; And
(D) Photoepolymerizationinitiater initiater 2～8 weight portions.
4. Blu-ray Disc ultraviolet-curing resin composition as claimed in claim 3, wherein, the compound (A) shown in above-mentioned formula (1) is any one or two kinds in dipropylene glycol two (methyl) acrylate and hexanediol two (methyl) acrylate.
5. Blu-ray Disc ultraviolet-curing resin composition as claimed in claim 3, wherein, in reaction product carbamate (methyl) acrylate (C) of polytetramethylene glycol and polyisocyanates and (methyl) acrylic acid hydroxyl C2～C4 Arrcostab, 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 total amount 100 weight portions of ultraviolet-curing resin composition, with the ratio of 15～53 weight portions, contain (E) through bisphenol A-type two (methyl) acrylate of 4～12 moles of ethylene oxide modifications.
7. the Blu-ray Disc ultraviolet-curing resin composition as described in any one in claim 3～6, wherein, contains the compound shown in following formula (3) as antioxidant,
In formula (3), R 2, R 3, R 4independent existence separately, R 2the alkyl that represents carbon number 1～3, R 3the alkylidene that represents carbon number 1～6, R 4the alkyl that represents carbon number 5～20.
8. the Blu-ray Disc ultraviolet-curing resin composition as described in any one in claim 3～6, wherein, contains the compound shown in following formula (4) as silane coupling agent,
Figure FDA0000414287500000041
In formula (4), R 5and R 6independent existence separately, R 5the alkyl that represents carbon number 1～3, R 6the alkylidene that represents carbon number 1～6.
9. the Blu-ray Disc ultraviolet-curing resin composition as described in any one in claim 3～6, wherein, contains the compound that (F) has hindered piperidine skeleton.
10. Blu-ray Disc ultraviolet-curing resin composition as claimed in claim 9, wherein, has the compound (F) of hindered piperidine skeleton for have the compound of hindered piperidine skeleton and (methyl) acryloyl group simultaneously.
11. Blu-ray Disc ultraviolet-curing resin compositions as described in any one in claim 3～6, wherein, at least contain TMDPO as Photoepolymerizationinitiater initiater (D).
12. Blu-ray Disc ultraviolet-curing resin compositions as claimed in claim 6, wherein, contain at least one in the group of selecting freedom (F) to there is the antioxidant composition shown in the silane coupling agent shown in the compound of hindered piperidine skeleton, aforementioned formula (4) and aforementioned formula (3).
13. Blu-ray Disc ultraviolet-curing resin compositions as claimed in claim 6, wherein, at least contain bisphenol A-type two (methyl) acrylate through 9～11 moles of ethylene oxide modifications as (E) composition, its content is 35～90 weight portions with respect to content 100 weight portions of (C) composition.
The application of the light-transmitting layer that is used to form the Blu-ray Disc with recording layer of the ultraviolet-curing resin composition in 14. claims 3～13 described in any one.
15. 1 kinds of solidfied materials, it irradiates active energy beam by the ultraviolet-curing resin composition to described in any one in claim 3～13 and obtains.
16. 1 kinds of manufacture methods with the Blu-ray Disc of recording layer, wherein, ultraviolet-curing resin composition described in any one in claim 3～13 is applied on Blu-ray Disc substrate, and makes coated film be solidified to form light-transmitting layer by irradiating active energy beam.
CN201280023346.2A 2011-05-13 2012-05-07 Ultraviolet-curing resin composition Expired - Fee Related CN103534758B (en)

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