CN104395961A - Ultraviolet curable resin composition and blue-ray disc - Google Patents

Ultraviolet curable resin composition and blue-ray disc Download PDF

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Publication number
CN104395961A
CN104395961A CN201380026648.XA CN201380026648A CN104395961A CN 104395961 A CN104395961 A CN 104395961A CN 201380026648 A CN201380026648 A CN 201380026648A CN 104395961 A CN104395961 A CN 104395961A
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methyl
acrylate
resin composition
ultraviolet
curing resin
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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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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
    • G11B7/254—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B2007/24302—Metals or metalloids
    • G11B2007/24306—Metals or metalloids transition metal elements of groups 3-10
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B2007/24302—Metals or metalloids
    • G11B2007/24312—Metals or metalloids group 14 elements (e.g. Si, Ge, Sn)
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B2007/24318—Non-metallic elements
    • G11B2007/2432—Oxygen
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/254—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers
    • G11B2007/25402—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers consisting essentially of organic resins

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  • Macromonomer-Based Addition Polymer (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)

Abstract

The present invention relates to an ultraviolet curable resin composition for blue-ray discs and a blue-ray disc having a layer of a cured product formed from the composition. The resin composition contains an epoxy (meta) acrylate (A) obtained by reacting a glycidyl ether epoxy compound with a (meta) acrylate compound having a carboxy group, such as a (meta) acrylic acid, a monofunctional (meta) acrylate compound (B), and a photoinitiator (C). The content of the (A) is greater than or equal to 30 parts by weight based on 100 parts by weight of the total resin composition, and when the content for the (A) is regarded as A and the content for the (B) is regarded as B, A/B ranges from 0.8 to 1.45. A cured product produced from the resin composition has both a high glass transition temperature and a high modulus of elasticity at 50 DEG C, and the restoring property after pressing is good. A blue-ray disc having a layer of the cured product has small variation in both warping from curing and warping after an endurance test.

Description

Ultraviolet-curing resin composition and Blu-ray Disc
Technical field
The resin solidification nitride layer that the present invention relates to CD, the ultraviolet-curing resin composition being preferred for light-transmitting layer and use the solidification nitride layer of this ultraviolet-curing resin composition preferably as the CD of light-transmitting layer, this CD 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 to carry out recording or regenerating through described light-transmitting layer.
Background technology
In recent years, the transmission of jumbo information record is carried out continually due to the development of infotech, Information Network.Accompany therewith, the high density huge capacity compact discs of jumbo image, music, computer data etc. can be recorded and regenerate to requirement.For DVD (the Digital Versatile Disc universal as high-density recording media, digital versatile disc), wavelength ratio CD (Compact Disc is used in order to realize densification, compact disk) laser of shorter 650nm, optical system also carries out high-NA.But, in order to record or regenerate the high image quality image etc. corresponding to HDTV (HighDefinition Television, high-definition television), need further densification.Therefore, the method for further high density recording and the research of CD thereof has been carried out the next generation of DVD.Propose such as utilization and use the high density recording mode of the new compact disk structure of the optical system of the blue laser that wavelength ratio DVD is shorter.
This new CD has on the transparent or opaque substrate formed by plastics such as polycarbonate, to form the information recording part such as pit, information recording layer position, the then structure of light-transmitting layer of stacked about 100 μm on information recording part position.In this CD, form the structure that recording light or reproduced light or both incide this light-transmitting layer.From the view point of throughput rate, ultraviolet-curing resin composition is used to be studied in the light-transmitting layer of this CD specially.
This CD utilizing blue laser to carry out recording or regenerating (in this manual, also referred to as Blu-ray Disc or BD) in, compared with the light-transmitting layer used with DVD, the light-transmitting layer of BD is thick film, in addition, different from the situation that the middle layer as DVD-9 structure uses, near top layer or top layer, light-transmitting layer is set.Therefore, even if directly conversion was suitable for the CD ultraviolet-curing resin composition of DVD in the past, the reliability that sometimes also obviously can produce the record regenerating caused by the corrosion etc. of distortion, reflection layer compared with DVD reduced.In addition, needs have makes the light of the short wavelength transmitance of transmission steady in a long-term and the high rigidity in order to use near top layer or top layer, in addition, considers from the problem of throughput rate, also requires it is the composition that can be applicable to making thick film.
As the ultraviolet-curing resin composition that can reduce disc tilt, disclose the ultraviolet-curing resin composition (see patent documentation 1) of carbamate (methyl) acrylate such as reacting containing the monomer by making lactone compound and hydroxyl (methyl) acrylate reactions obtain and polyisocyanate compound and obtain.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 more excellent carbamate (methyl) acrylate of flexibility.But said composition viscosity for formation BD light-transmitting layer is low, is therefore difficult to form thick film.In addition, during in order to improve content that viscosity increases carbamate (methyl) acrylate to form the light-transmitting layer of CD, there is the problem producing deterioration under hot and humid environment due to the corrosion of metal film etc.
In addition, as being out of shape little, toughness, excellent heat resistance composition, the resin combination (see patent documentation 2) containing carbamate (methyl) acrylate, epoxy (methyl) acrylate is disclosed.Said composition by ultraviolet-curing resin composition containing carbamate (methyl) acrylate more than a certain amount of, thus and suppress solidification time distortion, and give toughness, but, carbamate (methyl) acrylate is easily subject to the impact being changed the change of the warpage caused by temperature variation, humidity, when therefore there is humidity or temperature variation in the environment of keeping records medium, there is the problem causing the reliability of recording medium to reduce.
In addition, in the optical recording media of solidfied material with ultraviolet-curing resin composition in the past, by suppressing distortion containing a certain amount of above carbamate (methyl) acrylate, therefore there is restriction for the environment preserved.Namely, the recording medium of what the variable quantity due to warpage was little the have solidfied material of ultraviolet-curing resin composition is easily subject to the impact of temperature variation, therefore under the hot environment in summer etc. (30 DEG C ~ 40 DEG C), the problem that the change quantitative change of warpage is large can be produced.In addition, when not possessing hard conating, during preservation/management under the hot environment in summer, optical recording media each other likely can be gluing by ultraviolet-curing resin composition.
On the other hand, as the ultraviolet-curing resin composition that elastic modulus is high, disclose the resin combination (see patent documentation 3) containing epoxy (methyl) acrylate.But warpage during epoxy (methyl) acrylate cures is very big, if do not add the composition giving flexibility, then the excellent recording medium of reliability can not be obtained.But, use carbamate (methyl) acrylate as when giving the composition of flexibility, the drawback that cause the reduction of reliability, hot environment due to above-mentioned problem under, (30 DEG C ~ 40 DEG C) are preserved.Therefore, when using ultraviolet-curing resin composition in the past, the ultraviolet curing resin with thick film being solidified to the CD of nitride layer, being difficult to reduce warpage and do not reduce reliability.
Up to the present, in order to meet the requirement characteristic of CD, proposing and being variously conceived to the specific physical property such as permanance, adhesive power and the ultraviolet-curing resin composition (patent documentation 4 ~ 8) regulated; But also do not find warpage during solidification to suppress low, and as the ultraviolet curing resin that variable quantity is little, reliability is excellent being changed the warpage caused by temperature variation, humidity of solidfied material, even and if there is the Blu-ray Disc of solidfied material of the ultraviolet-curable composition also can stablizing preservation in high temperature environments.Therefore, strongly expect to meet the resin that this requires characteristic required by developing target market.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 11-12495 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2007-169450 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2009-266355 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2005-243109 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2006-249228 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2009-32302 publication
Patent documentation 7: Japanese Unexamined Patent Publication 2009-32303 publication
Patent documentation 8: No. 2008/099666th, International Publication
Summary of the invention
Invent problem to be solved
Problem to be solved by this invention is to provide a kind of ultraviolet-curing resin composition, glass transition temperature (Tg) can be obtained up to more than certain numerical value and the high solidfied material of elastic modulus after its solidification, and when being applied to CD, warpage during solidification is few, in addition, even if can be formed when occur humidity change or temperature variation, namely preserve under hot and humid environment when, the variable quantity solidification nitride layer that also little, reliability is excellent of warpage; Even and if provide a kind of solidification nitride layer, excellent durability with this resin combination also can stablize preservation in high temperature environments, the CD that warpage variable quantity is little, reliability is excellent, preferred Blu-ray Disc.
For the means of dealing with problems
Find in the present invention to contain as epoxy (methyl) acrylate using specific ratio, by epoxy (methyl) acrylate that (methyl) acrylate compounds and diglycidyl ether type epoxy compound that make to have carboxyl react and obtain, and the curing overlay film of the composition of simple function (methyl) acrylate compounds is applied in CD (preferred Blu-ray Disc) as such as light-transmitting layer etc., can provide thus to be changed by humidity or the variable quantity of warpage that temperature variation causes little, even and if also can stablize the CD of preservation in high temperature environments, thus complete the present invention.
And, thisly to be changed by humidity or CD that the variable quantity of warpage that temperature variation causes is little is not easy to produce the reduction of the light reflectivity caused by warpage, the deterioration of characteristics of signals is few, therefore, the recording/reproducing of the information that the long blue laser of radiothermy carries out is good, is therefore useful as Blu-ray Disc.
In addition, in this manual, term " has (methyl) acrylate compounds of carboxyl " with the meaning same with (methyl) acrylic compounds comprising carboxyl and (methyl) acryloyl group and uses.Therefore, in this manual, (methyl) acrylic acid is also comprised in " there is (methyl) acrylate compounds of carboxyl ".
In addition, term " (methyl) acrylic acid " uses with the meaning of any one or both of acrylic acid and methacrylic acid, and term " (methyl) acrylate " uses with the meaning of any one or both of acrylate and methacrylate too.
The preferred mode of the present invention relates to, on substrate at least stacked reflection layer and light-transmitting layer, from described light-transmitting layer side incident blue laser and carry out the ultraviolet-curing resin composition of the use resin solidification nitride layer (preferred light transmission layer) of the CD of information regeneration, its solidfied material, and the Blu-ray Disc of solidification nitride layer with this resin combination.
That is, the present invention relates to following (1) ~ (18).
(1) a kind of Blu-ray Disc, it has the solidification nitride layer of Blu-ray Disc ultraviolet-curing resin composition, in this Blu-ray Disc ultraviolet-curing resin composition, contain epoxy (methyl) acrylate (A) that (i) is reacted by (methyl) acrylate compounds and diglycidyl ether type epoxy compound making to have carboxyl and obtained, (ii) simple function (methyl) acrylate compounds (B) and (iii) Photoepolymerizationinitiater initiater (C), relative to total amount 100 weight portion of this resin combination, described epoxy (methyl) acrylate (A) containing proportional be more than 30 weight portions, described epoxy (methyl) acrylate (A) is set to A weight portion containing proportional, by described simple function (methyl) acrylate compounds (B) containing proportional be set to B weight portion time, A/B is 0.8 ~ 1.45.
(2) a kind of Blu-ray Disc ultraviolet-curing resin composition, contain epoxy (methyl) acrylate (A) that (methyl) acrylate compounds and diglycidyl ether type epoxy compound by making to have carboxyl react and obtain, simple function (methyl) acrylate compounds (B) and Photoepolymerizationinitiater initiater (C), wherein, relative to total amount 100 weight portion of this resin combination, described epoxy (methyl) acrylate (A) containing proportional be more than 30 weight portions, described epoxy (methyl) acrylate (A) is set to A weight portion containing proportional, by described simple function (methyl) acrylate compounds (B) containing proportional be set to B weight portion time, A/B is 0.8 ~ 1.45.
(3) the Blu-ray Disc ultraviolet-curing resin composition as described in above-mentioned (2), it is characterized in that, (methyl) acrylate compounds with carboxyl is the compound that (a) unsaturated carboxylic acid or derivatives thereof or (b) are obtained with multi-anhydride (b2) by the lactone addition product (b1) of hydroxyl (methyl) acrylate compounds.
(4) the Blu-ray Disc ultraviolet-curing resin composition as described in above-mentioned (2) or (3), it is characterized in that, diglycidyl ether type epoxy compound is to be represented by following formula (2) and epoxide equivalent is the liquid diglycidyl ether type epoxy compound of 180g/ equivalent ~ 200g/ equivalent
In formula, n represents the integer of 0 ~ 20.
(5) the Blu-ray Disc ultraviolet-curing resin composition according to any one of above-mentioned (2) ~ (4), wherein, simple function (methyl) acrylate compounds (B) is for having (methyl) acrylate compounds of phenyl ring or having (methyl) acrylate compounds of dihydro dicyclopentadiene base or dicyclopentadiene base.
(6) ultraviolet-curing resin composition according to any one of above-mentioned (2) ~ (5), it is characterized in that, as described simple function (methyl) acrylate compounds (B), containing the compound that following formula (1) represents
In formula, n represents the integer of 1 ~ 10.
(7) the Blu-ray Disc ultraviolet-curing resin composition as described in above-mentioned (6), wherein, in described formula (1), n is 2.
(8) the Blu-ray Disc ultraviolet-curing resin composition as described in above-mentioned (6) or (7), wherein, relative to total amount 100 weight portion of Blu-ray Disc ultraviolet-curing resin composition, the compound that formula (1) is represented containing proportional be set to B1 weight portion time, or when also containing (methyl) acrylic acid dihydro dicyclopentadiene oxygen base ethyl ester as simple function (methyl) acrylate compounds (B) together with the compound that formula (1) represents, by the total both them containing proportional be set to B1 weight portion time, A/B1 is 0.8 ~ 1.45.
(9) the Blu-ray Disc ultraviolet-curing resin composition according to any one of above-mentioned (2) ~ (8), it is characterized in that, relative to total amount 100 weight portion of described ultraviolet-curing resin composition, with the ratio below 20 weight portions also containing carbamate (methyl) acrylate.
(10) the Blu-ray Disc ultraviolet-curing resin composition according to any one of above-mentioned (2) ~ (9), wherein, epoxy (methyl) acrylate (A) is epoxy (methyl) acrylate (A) that the diglycidyl ether type epoxy compound by making (methyl) acrylic acid and following formula (2) represent reacts and obtain
In formula, n represents the integer of 1 ~ 10.
(11) the Blu-ray Disc ultraviolet-curing resin composition according to any one of above-mentioned (2) ~ (10), wherein, relative to weight 100 weight portion of described ultraviolet-curing resin composition, the content ratio A weight portion of epoxy (methyl) acrylate (A) and described simple function (methyl) acrylate compounds (B) add up at least 80 weight portions containing proportional B weight portion.
(12) the Blu-ray Disc ultraviolet-curing resin composition according to any one of above-mentioned (2) ~ (11), wherein, the glass transition temperature Tg of the solidfied material of Blu-ray Disc ultraviolet-curing resin composition is at least 40 DEG C.
(13) the Blu-ray Disc ultraviolet-curing resin composition according to any one of above-mentioned (2) ~ (12), wherein, to Blu-ray Disc ultraviolet-curing resin composition irradiation ultraviolet radiation, the elastic modulus of 50 DEG C of the solidfied material formed after Ultraviolet radiation is 450 ~ 1500MPa.
(14) solidfied material, it is by obtaining the Blu-ray Disc ultraviolet-curing resin composition solidification according to any one of above-mentioned (1) ~ (13).
(15) solidfied material, it obtains by irradiating active energy beam to the ultraviolet-curing resin composition according to any one of above-mentioned (1) ~ (13).
(16) a kind of Blu-ray Disc, it has light-transmitting layer, the ultraviolet-curing resin composition of this light-transmitting layer by being coated with on optic disc base board according to any one of above-mentioned (1) ~ (13), and irradiate active energy beam and obtain.
(17) Blu-ray Disc as described in above-mentioned (16), wherein, optic disc base board is the optic disc base board with reflection horizon.
(18) Blu-ray Disc as described in above-mentioned (16) or (17), wherein, the glass transition temperature Tg of the solidfied material described in above-mentioned (14) is at least 40 DEG C, have the initial warpage of the Blu-ray Disc of the layer of this solidfied material variable quantity and 80 DEG C, expose 250 hours under the environment of relative humidity 85% after long duration test after the value of both variable quantities of warpage be all less than ± 0.6 degree.
Invention effect
Blu-ray Disc ultraviolet-curing resin composition of the present invention (hereinafter also referred to ultraviolet-curing resin composition of the present invention or resin combination of the present invention) can obtain having high glass-transition temperature (Tg), high elastic modulus after hardening, and the solidfied material that nerve is also good.In addition, when this resin combination is applied to Blu-ray Disc, warpage when can form solidification is little, there is excellent curability and inhibit changed by humidity, the curing overlay film of the variable quantity of warpage that temperature variation causes.In addition, the CD (preferred Blu-ray Disc) with the solidification nitride layer of ultraviolet-curing resin composition of the present invention is the CD that variable quantity is little, reliability is high of the warpage when solidifying and after long duration test, is easy to the preservation carrying out in high temperature environments (30 DEG C ~ 40 DEG C).
Embodiment
Ultraviolet-curing resin composition of the present invention contains simple function (methyl) acrylate (B) with special ratios, and in epoxy (methyl) acrylate (A) reacting and obtain by (methyl) acrylate compounds and diglycidyl ether type epoxy compound making to have carboxyl at least both.Namely, relative to total amount 100 weight portion of ultraviolet-curing resin composition of the present invention, more than epoxy (methyl) acrylate (A) 30 weight portion, and, the content ratio of epoxy (methyl) acrylate (A) is set to A weight portion, when the content of simple function (methyl) acrylate (B) is set to B weight portion, the scope being 0.8 ~ 1.45 with A/B contain above-mentioned both.The preferable range of this A/B is 0.8 ~ 1.3, is more preferably 0.8 ~ 1.1.
As the simple function used in ultraviolet-curing resin composition of the present invention (methyl) acrylate, be not particularly limited, specifically preferably following simple function (methyl) acrylate.
As simple function (methyl) acrylate, can enumerate: (methyl) acrylic acid C5 ~ C20 (preferred C7 ~ C18) Arrcostabs such as (methyl) Isooctyl acrylate monomer, (methyl) isoamyl acrylate, (methyl) lauryl acrylate, (methyl) isodecyl acrylate, (methyl) stearyl acrylate ester, (methyl) acrylic acid cetyl, the different myristin of (methyl) acrylic acid, (methyl) tridecyl acrylate, (methyl) benzyl acrylate, (methyl) phenylethyl ethylene oxidic ester, polypropylene oxide (methyl) nonylphenol acrylate phenyl ester, the acrylate etc. shown in previously described formula (1) have (methyl) acrylate compounds of phenyl ring, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) acrylic acid morpholine ester etc. have (methyl) acrylate of heterocycle, (methyl) acrylic acid 2-hydroxypropyl acrylate etc. has (methyl) acrylic acid C2 ~ C8 Arrcostab of hydroxyl, poly alkylene glycol (methyl) acrylate such as ethoxydiglycol (methyl) acrylate, 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 (such as, the FANCRYL FA-511A that Hitachi Chemical Co., Ltd. manufactures), acrylic acid dihydro dicyclopentadiene oxygen base ethyl ester (such as, the FANCRYL FA-512A that Hitachi Chemical Co., Ltd. manufactures), metering system acid dihydride dicyclopentadiene oxygen base ethyl ester (such as, the FANCRYL FA-512M that Hitachi Chemical Co., Ltd. manufactures), acrylic acid tetrahydrochysene dicyclopentadiene base ester (such as, the FANCRYL FA-513A that Hitachi Chemical Co., Ltd. manufactures), methacrylic acid tetrahydrochysene dicyclopentadiene base ester (such as, the FANCRYL FA-513M that Hitachi Chemical Co., Ltd. manufactures), acrylic acid 1-adamantane esters (such as, the Adamantate AA that Idemitsu Kosen Co., Ltd. manufactures), acrylic acid 2-methyl-2-adamantane esters (such as, the Adamantate MA that Idemitsu Kosen Co., Ltd. manufactures), acrylic acid 2-ethyl-2-adamantane esters (such as, the Adamantate EA that Idemitsu Kosen Co., Ltd. manufactures), methacrylic acid 1-adamantane esters (such as, the Adamantate AM that Idemitsu Kosen Co., Ltd. manufactures) etc. there is (methyl) acrylate compounds of C7 ~ C10 aliphatics ring, phosphoric acid (methyl) acrylate such as ethylene-oxide-modified phenoxylation phosphoric acid (methyl) acrylate, ethylene-oxide-modified butoxylated phosphoric acid (methyl) acrylate and ethylene-oxide-modified octyloxy phosphoric acid (methyl) acrylate, Deng.
In above-mentioned material, as preferred simple function (methyl) acrylate, acrylate shown in preferred previously described formula (1), (methyl) benzyl acrylate, (methyl) phenylethyl ethylene oxidic ester, polypropylene oxide (methyl) nonylphenol acrylate phenyl ester etc. has (methyl) acrylate compounds of phenyl ring, (methyl) acrylic acid dicyclopentadiene oxygen base ethyl ester, acrylic acid dihydro dicyclopentadiene base ester (such as, the FANCRYL FA-511A that Hitachi Chemical Co., Ltd. manufactures), acrylic acid dihydro dicyclopentadiene oxygen base ethyl ester (such as, the FANCRYL FA-512A that Hitachi Chemical Co., Ltd. manufactures), metering system acid dihydride dicyclopentadiene oxygen base ethyl ester (such as, the FANCRYL FA-512M that Hitachi Chemical Co., Ltd. manufactures) etc. there is (methyl) acrylate compounds of dihydro dicyclopentadiene base or dicyclopentadiene base.Wherein, especially preferred (methyl) acrylate compounds of representing of acrylic acid dihydro dicyclopentadiene oxygen base ethyl ester or following formula (1).
Simple function (methyl) acrylate compounds with 1 (methyl) acryloyl group has the function of the mechanical property (suppressing warpage, distortion etc.) improving the CD formed as light-transmitting layer by ultraviolet-curing resin composition of the present invention.
Therefore, as optimal way of the present invention, as this simple function (methyl) acrylate compounds, can enumerate: comprise the compound shown in following formula (1) and any one in (methyl) acrylic acid dihydro dicyclopentadiene oxygen base ethyl ester or both situations.In addition, as preferred mode, can enumerate: the mode comprising the compound shown in following formula (1).In this case, relative to total amount 100 weight portion of resin combination of the present invention, when the content ratio of any one in the compound shown in following formula (1) and (methyl) acrylic acid dihydro dicyclopentadiene oxygen base ethyl ester or both totals is set to B1 weight portion, A/B1 is more preferably 0.8 ~ 1.45, more preferably 0.8 ~ 1.3, be particularly preferably 0.8 ~ 1.1.In this case, the effect of the compound shown in following formula (1) and/or (methyl) acrylic acid dihydro dicyclopentadiene oxygen base ethyl ester composition can be given full play to.
In these cases, as simple function (methyl) acrylate (B), can not containing other simple function (methyl) acrylate that also can contain as required beyond the compound shown in following formula (1) and/or (methyl) acrylic acid dihydro dicyclopentadiene oxygen base ethyl ester.Relative to total amount 100 weight portion of simple function (methyl) acrylate (B), the preferred content of the compound shown in formula (1) and/or (methyl) acrylic acid dihydro dicyclopentadiene oxygen base ethyl ester is 50 ~ 100 weight portions, be preferably 80 ~ 100 weight portions, be more preferably 90 ~ 100 weight portions, more preferably 95 ~ 100 weight portions.All the other are this other simple function (methyl) acrylate.
When containing this other simple function (methyl) acrylate, even if according to circumstances A/B is beyond the scope of 0.8 ~ 1.45, sometimes also can realize the effect of the present application, these situations fall within the scope of the present invention.
In simple function (methyl) acrylate (B) that can use in the present invention, as particularly preferred compound, the compound shown in following formula (1) can be used.
In formula, n represents the integer of 1 ~ 10.
Wherein, in above-mentioned formula (1), n is preferably 1 ~ 3.As the compound shown in the above-mentioned formula (1) used, specifically can enumerate: ethylene-oxide-modified phenol (methyl) acrylate.This compound can obtain from the market.As goods, Photomer4035 (such as Ke Ning Co., Ltd. manufactures), EBECRYL110 (such as Daicel-Cytec Co., Ltd. manufactures) etc. specifically can be enumerated.
At this, from the view point of warpage when raising nerve, reduction solidification, more preferably in above-mentioned formula (1), n is the compound of 1 or 2, and preferred n is the compound of 2 further.In addition, in the compound of above-mentioned formula (1), in order to give warpage when high nerve, reduction solidification, preferred mode is used alone the compound of n=2 or also uses the mode of the compound of n=1 with the amount same with n=2 Compound Phase below, is preferably used alone the mode of the compound of n=2 further.That is, the compound of n=2 in the compound represented relative to formula (1) above-mentioned in UV resin composition, by the compound of n=1 containing proportional be shown below be set as 0 ~ 1 scope in be preferred.
Formula: (compound of the middle n=1 of above-mentioned formula (1))/(compound of the middle n=2 of above-mentioned formula (1))=0 ~ 1.0.
The content of simple function (methyl) acrylate compounds (B) in ultraviolet-curing resin composition of the present invention, usually, relative to total amount 100 weight portion of ultraviolet-curing resin composition, be generally 10 ~ 60 weight portions, be preferably 15 ~ 50 weight portions, from the view point of raising adhesiveness and flexibility, nerve, described epoxy (methyl) acrylate (A) preferably meets the scope of condition of more than 30 weight portions, A/B=0.8 ~ 1.45, preferably more than 20.7 weight portions.In the content of simple function (methyl) acrylate compounds (B) scope particularly preferably in 20 ~ 40 weight portions, and meeting with in the scope of the above-mentioned relation of described epoxy (methyl) acrylate (A).When being less than 10 weight portion, likely adhesiveness, flexibility, nerve can not be realized, during more than 60 weight portion, likely enough hardness can not be obtained.
In the present invention, epoxy (methyl) acrylate (A) is used.Epoxy (methyl) acrylate (A) has the hardness, the curing rate that improve curability, improve solidfied material, improve the function of curability when solidifying, there is the function of tackiness when suppressing softening compared with carbamate (methyl) acrylate.In addition, as epoxy (methyl) acrylate (A), as long as make to have the product that (methyl) acrylate compounds of carboxyl and diglycidyl ether type epoxy compound react and obtain, just can use.As the preferred diglycidyl ether type epoxy compound for obtaining epoxy (methyl) acrylate (A), can enumerate: the diglycidyl ether of bisphenol-A or its alkylene oxide addition product, the diglycidyl ether of Bisphenol F or its alkylene oxide addition product, the diglycidyl ether of hydrogenated bisphenol A or its alkylene oxide addition product, the diglycidyl ether of A Hydrogenated Bisphenol A F or its alkylene oxide addition product, ethylene glycol diglycidylether, propylene glycol diglycidylether, neopentylglycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cyclohexanedimethanodiglycidyl diglycidyl ether, polypropylene glycol diglycidyl ether etc.
As the epoxy that can preferably use in the present invention (methyl) acrylate (A), it is the bisphenol-a epoxy acrylate obtained by bisphenol A type epoxy compound.
As bisphenol-a epoxy acrylate, can enumerate such as: reacted by the diglycidyl ether type epoxy compound of (methyl) acrylate compounds and bisphenol-A that make to have carboxyl and epoxy (methyl) acrylate obtained.More specifically, can preferably use: react and epoxy (methyl) acrylate obtained by making to have the liquid diglycidyl ether type epoxy compound shown in (methyl) acrylate compounds of carboxyl and following formula (2).
In formula, n represents the integer of 0 ~ 20.In the compound of above-mentioned formula (2), preferred epoxide equivalent is 150g/ equivalent ~ 550g/ equivalent, is more preferably 180g/ equivalent ~ 200g/ equivalent.Reason is, when epoxide equivalent is lower than 150g/ equivalent, the warpage after being solidified by ultraviolet-curing resin composition likely becomes excessive, during more than 550g/ equivalent, is easily subject to the impact of the temperature variation in summer, likely preserves and becomes difficulty.
As (methyl) acrylate compounds with carboxyl, can enumerate: the compound that (a) unsaturated carboxylic acid or derivatives thereof and (b) are obtained by lactone addition product (b1) and the multi-anhydride (b2) of hydroxyl (methyl) acrylate compounds.
As the unsaturated carboxylic acid or derivatives thereof of above-mentioned (a), can use such as: the derivants such as unsaturated carboxylic acid and their carboxylic acid halides, acid amides, acid imide, acid anhydride, ester such as (methyl) acrylic acid (acrylic acid or methacrylic acid), maleic acid, α-ethylacrylate, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, tetrahydrophthalic acid methyl esters.In the middle of them, preferably (methyl) acrylic acid.
As the compound of above-mentioned (b), namely, the compound obtained by lactone addition product (b1) and the multi-anhydride (b2) of hydroxyl (methyl) acrylate compounds, can enumerate such as: make the lactone addition product of hydroxyl (methyl) acrylate compounds and multi-anhydride with mol ratio be 0.9 ~ 1.1, preferred etc. mole carry out reacting the compound obtained.
Above-mentioned reaction is preferably reacted under the existence of polymerization inhibitor, under the condition of temperature of reaction 50 ~ 150 DEG C, preferably 60 DEG C ~ 120 DEG C.
The lactone addition product (b1) of hydroxyl (methyl) acrylate compounds can carry out open loop addition by making lactone and hydroxyl (methyl) acrylate compounds and obtain.
As hydroxyl (methyl) acrylate compounds, can enumerate: (methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, dihydroxymethyl cyclohexyl list (methyl) acrylate, hydroxyl caprolactone (methyl) acrylate etc.Wherein, preferably (methyl) Hydroxyethyl Acrylate is used.
As lactone, beta-propiolactone, beta-butyrolactone, gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, Beta-methyl-gamma-valerolactone, γ-hexalactone, 6-caprolactone etc. can be used.
The preferably 6-caprolactone of 2 moles and hydroxyl (methyl) the acrylate compounds addition of 1 mole and the compound obtained.
As multi-anhydride (b2), can enumerate: phthalic anhydride, 1, 2, 3, 6-tetrabydrophthalic anhydride and derivant thereof, 3, 4, 5, 6-tetrabydrophthalic anhydride and derivant thereof, 1, 2, 3, 4-tetrabydrophthalic anhydride and derivant thereof, 2, 3, 4, 5-tetrabydrophthalic anhydride and derivant thereof, hexahydrophthalic anhydride and derivant thereof, succinic anhydride and derivant thereof, mono-alkyl succinic acid acid anhydride and derivant thereof, dialkyl group succinic anhydride and derivant thereof, maleic anhydride and derivant thereof, monoalkyl maleic anhydride and derivant thereof, dialkyl group maleic anhydride and derivant thereof.Wherein, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride is preferably used.
Epoxy (methyl) acrylate (A) can be carried out reacting by (methyl) acrylate compounds and these diglycidyl ether type epoxy compounds making to have carboxyl and is obtained under following condition.
Relative to epoxy radicals 1 equivalent of diglycidyl ether type epoxy compound, be 0.9 ~ 1.5 equivalent with the carboxyl of (methyl) acrylate compounds with carboxyl, be more preferably the ratio of 0.95 ~ 1.1 equivalent and react.Temperature of reaction is preferably 80 ~ 120 DEG C, and the reaction time is about 10 ~ about 35 hours.In order to promote reaction, preferably use such as: the catalyzer such as triphenylphosphine, TAP (trialkyl phosphine), triethanolamine, etamon chloride.In addition, in order to prevent polymerization in reaction, such as p methoxy phenol, methyl hydroquinone etc. also can be used as polymerization inhibitor.
In ultraviolet-curing resin composition of the present invention, the content of epoxy (methyl) acrylate (A) is generally more than 30 weight portions relative to total amount 100 weight portion of ultraviolet-curing resin composition of the present invention, be preferably more than 40 weight portions, be more preferably more than 50 weight portions.The upper limit is not particularly limited, but is generally below 80 weight portions, is preferably below 70 weight portions, is more preferably below 60 weight portions.
Reason is, when being less than 30 weight portion, likely changes the change quantitative change of the warpage caused greatly by temperature variation or humidity, surface cure deterioration, and then when High temperature storage as sticky flux.
In the optimal way of ultraviolet-curing resin composition of the present invention, as epoxy (methyl) acrylate (A), containing epoxy (methyl) acrylate (A1) by making (methyl) acrylic acid and diglycidyl ether type epoxy compound react and obtain.
In above-mentioned preferred mode, in the CD ultraviolet-curing resin composition containing above-mentioned epoxy (methyl) acrylate (A1) and simple function (methyl) acrylate (B), relative to total amount 100 weight portion of ultraviolet-curing resin composition, contain proportional (weight portion relative to (A1) composition of total amount 100 weight portion of ultraviolet-curing resin composition) of above-mentioned epoxy (methyl) acrylate (A1) is set to A1 weight portion, by described simple function (methyl) acrylate compounds (B) containing proportional (weight portion relative to (B) composition of total amount 100 weight portion of ultraviolet-curing resin composition) be set to B weight portion time, A1/B is preferably the scope of 0.8 ~ 1.45.If this ratio is less than 0.8, then stability degradation during High temperature storage, if more than 1.45, then warpage when solidifying becomes large.At this, as simple function (methyl) acrylate (B), containing the compound shown in previously described formula (1) or (methyl) acrylic acid dihydro dicyclopentadiene base ester, its containing proportional be B1 weight portion time, more preferably the scope of A1/B1 is identical value with the scope of above-mentioned A1/B, that is, A1/B1 is the scope of 0.8 ~ 1.45.
In addition, in above-mentioned, as simple function (methyl) acrylate (B), the compound represented containing above-mentioned formula (1) or (methyl) acrylic acid dihydro dicyclopentadiene base ester, and when A1/B1 is above-mentioned scope, can not other simple function (methyl) acrylate compounds be contained; But also can contain other simple function (methyl) acrylate compounds as required.When containing this other simple function (methyl) acrylate, even if according to circumstances A/B is beyond the scope of 0.8 ~ 1.45, sometimes also can realize the effect of the present application, these situations fall within the scope of the present invention.
In resin combination of the present invention, by epoxy (methyl) acrylate (A) and contain proportional (A/B) of simple function (methyl) acrylate compounds are set as that containing of the scope of 0.8 ~ 1.45 is proportional, even if when total amount 100 weight portion relative to ultraviolet-curing resin composition of epoxy (methyl) acrylate (A) in ultraviolet-curing resin composition containing proportional up to 30 weight portions more than, also can effectively reduce warpage during solidification, nerve, curability can also be given.
Namely, by in polyfunctional epoxy (methyl) acrylate (A) with above-mentioned ratio in conjunction with simple function (methyl) acrylate (B), simple function (methyl) acrylate is utilized to suppress crosslinked further, prevent from carrying out the three-dimensional cross-linked of height, warpage when solidifying and the conservatory excellent balance under hot environment can be realized.Particularly, when will coordinate with epoxy (methyl) acrylate with above-mentioned ratio as the compound of the above-mentioned formula (1) of simple function (methyl) acrylate, while the characteristic keeping epoxy (methyl) acrylate, low-shrinkage, flexibility can be given especially significantly.
In addition, by coordinating with above-mentioned ratio, can provide being changed by humidity, the variable quantity of warpage after variable quantity, the particularly long duration test of warpage that temperature variation causes suppresses be less than positive and negative 0.6, not exceed the degree of specialized range solidfied material.
In addition, in preferred mode of the present invention, above-mentioned variable quantity all can be controlled, positive and negative less than 0.5, more preferably positive and negative less than 0.4, the reliability of recording characteristic can be improved further.
From the view point of the function of the variable quantity of the warpage after the warpage performance of giving when more excellent reduction is solidified, the variable quantity suppressing the warpage caused by temperature variation or long duration test, above-mentioned A/B is preferably more than 0.8 and is less than 1.41.
In addition, consider other characteristic etc., above-mentioned A/B is more preferably 0.8 ~ 1.3, and more preferably 0.8 ~ 1.1.
In addition, the variable quantity of the warpage after the variable quantity of the variable quantity of warpage during solidification and the warpage of temperature variation or long duration test, with the warpage of the substrate before coating resin for benchmark, for positive and negative more than 0.6 time, recording characteristic be deteriorated, the worry of reliability is increased.
In resin combination of the present invention, epoxy (methyl) acrylate (A) and simple function (methyl) acrylate compounds (B) both content are as previously mentioned, both total content is relative to total amount 100 weight portion of resin combination of the present invention, be generally 80 ~ 99 weight portions, be preferably 90 ~ 99 weight portions, be more preferably 92 ~ 97 weight portions.
In ultraviolet-curing resin composition of the present invention, use Photoepolymerizationinitiater initiater (C).As may be used for Photoepolymerizationinitiater initiater of the present invention (C), such as have: benzoin isobutyl ether, 2,4-diethyl thioxanthones, ITX, dibenzoyl, 1-hydroxycyclohexyl 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 and 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino propane-1-ketone equimolecular cracking type; Benzophenone, 4-phenyl benzophenone, isophthalic benzophenone, 4-benzoyl-4 ' the dehydrogenation type Photoepolymerizationinitiater initiater etc. such as-methyldiphenyl thioether.These Photoepolymerizationinitiater initiaters can use one or and with two or more; Particularly from the view point of raising inside solidification, preferably and use TMDPO.
Photoepolymerizationinitiater initiater (C) content in ultraviolet-curing resin composition, relative to total amount 100 weight portion of ultraviolet-curing resin composition, is generally 1 ~ 10 weight portion, is preferably 3 ~ 8 weight portions.
In ultraviolet-curing resin composition of the present invention, carbamate (methyl) acrylate can be contained as required.Carbamate (methyl) acrylate, by using the amount be applicable to, has mechanical property (warpage, the distortion etc.) function improving CD.
Can be applicable to and carbamate (methyl) acrylate can by make polyvalent alcohol, polyisocyanates and hydroxyl (methyl) acrylate compounds react and obtain.
As operable polyvalent alcohol, example polyvalent alcohol described as follows can be enumerated.
The poly alkylene glycol such as (i) polyglycol, polypropylene glycol, polytetramethylene glycol;
(ii) neopentyl glycol, 3-methyl isophthalic acid, the aliphatic alcohol such as 5-pentanediol, propylene glycol, BDO, 1,6-hexanediol, trimethylolpropane, pentaerythrite, Tricyclodecane Dimethanol, two (methylol) cyclohexane;
(iii) a kind of and polyprotonic acid of the aliphatic polyol recorded by above-mentioned (i) is reacted and the polyester polyol obtained.
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.
(iv) by the reaction of polyvalent alcohol and 6-caprolactone and the caprolactone alcohol obtained;
(v) polycarbonate polyol.Such as, by the reaction of 1,6-hexanediol and diphenyl carbonate and the PCDL etc. obtained.
(vi) polyether glycol.Poly-C2-C3 aklylene glycol such as such as polyglycol or polypropylene glycol etc., ethylene-oxide-modified bisphenol-A etc.
Their number-average molecular weight is preferably about 200 ~ about 8000, is more preferably about 200 ~ about 3000.
As polyisocyanates, can enumerate such as: isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, Xylene Diisocyanate, diphenyl methane-4,4-diisocyanate or isocyanic acid tetrahydrochysene dicyclopentadiene base ester etc.
In this case, preferably isophorone diisocyanate or toluene diisocyanate is used.
As operable hydroxyl (methyl) acrylate compounds, can enumerate: (methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, dihydroxymethyl cyclohexyl list (methyl) acrylate, hydroxyl caprolactone (methyl) acrylate etc.Wherein, preferably (methyl) Hydroxyethyl Acrylate is used.
Previous reaction is such as carried out as follows.That is, organic multiple isocyanate is mixed with polyvalent alcohol make the isocyanate group of the hydroxyl 1 equivalent organic multiple isocyanate relative to polyvalent alcohol be preferably 1.1 ~ 2.0 equivalents, preferably at 70 ~ 90 DEG C, make it react, thus synthesis of carbamates oligomer.Then, hydroxyl (methyl) acrylate compounds is mixed with oligourethane and makes the hydroxyl of isocyanate group 1 equivalent of hydroxyl groups (methyl) acrylate compounds relative to oligourethane be preferably 1 ~ 1.5 equivalent, at 70 ~ 90 DEG C, make it react, obtain desired carbamate (methyl) acrylate thus.As the molecular weight of carbamate (methyl) acrylate, preferably about 400 ~ about 10000.As the weight-average molecular weight of carbamate (methyl) acrylate, preferably about 7000 ~ about 25000, more preferably 10000 ~ 20000.When weight-average molecular weight is less than 7000, shrinks and become large, when weight-average molecular weight is greater than 25000, curability is deteriorated.
The content of carbamate (methyl) acrylate in ultraviolet-curing resin composition of the present invention, from function, the hardness of giving the variable quantity suppressing the warpage caused by humidity change, temperature variation, improve adhesiveness and flexibility simultaneously, the viewpoint of nerve sets out, be 0 ~ 20 weight portion relative to total amount 100 weight portion of ultraviolet-curing resin composition, be preferably 0 ~ 10 weight portion.During more than 20 weight portion, produce and can not obtain enough hardness, suppress the problems such as the function variation of the variable quantity of the warpage caused by humidity change, temperature variation, therefore can not realize target effect of the present invention, therefore not preferred.
From the view point of the storage stability improving (30 ~ 40 DEG C) under hot environment, carbamate (methyl) acrylate be preferably below 20 weight portions containing proportional.
In resin combination group of the present invention, multifunctional (methyl) acrylate compounds ((methyl) acrylate monomer hereinafter also referred to beyond (B)) can also be contained as required.In addition, in the present invention, (methyl) acrylate monomer beyond this multifunctional (methyl) acrylate compounds of term or (B) refers to multifunctional (methyl) acrylate compounds ((methyl) acrylate monomer beyond (B)) except aforesaid carbamate (methyl) acrylate and epoxy (methyl) acrylate.
As (methyl) acrylate monomer beyond (B); as long as have multiple (methyl) acryloyl group; but be generally multifunctional (methyl) acrylate compounds ((methyl) acrylate monomer hereinafter also referred to having 2 ~ 6 (methyl) acryloyl groups) with 2 ~ 6 (methyl) acryloyl groups, preferably two (methyl) acrylate monomer.
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, Tricyclodecane Dimethanol two (methyl) acrylate (such as, Nippon Kayaku K. K manufactures, KAYARAD R-684, Tricyclodecane Dimethanol diacrylate etc.), tetrahydrochysene dicyclopentadiene base two (methyl) acrylate etc. has two (methyl) acrylate compounds of C5 ~ C10 aliphatics ring, dioxane glycol two (methyl) acrylate (such as, Nippon Kayaku K. K manufactures, KAYARAD R-604, dioxane glycol diacrylate etc.) etc. there is two (methyl) acrylate compounds of heterocycle, ethylene-oxide-modified 1, C2 ~ C10 alkyl two (methyl) acrylate and the alkylene oxide modifiers thereof such as 6-hexanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate etc. of alkylene oxide modification has C2 ~ C10 alkylidene two (methyl) acrylate and the alkylene oxide modifier thereof of side chain, 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, poly alkylene glycol two (methyl) acrylate such as polypropylene glycol two (methyl) acrylate, bisphenol A-type two (methyl) acrylate of alkylene oxide modification and ethylene-oxide-modified di(2-ethylhexyl)phosphate (methyl) acrylate etc.
In this case, using C2 ~ C10 alkylidene two (methyl) acrylate or its alkylene oxide modifier, from the view point of suppressing the viewpoint of variable quantity of the warpage caused by temperature variation, the viewpoint of permanance and improving hardness, is preferred.
About (methyl) acrylate monomer beyond (B), as (methyl) acrylate monomer with 3 (methyl) acryloyl groups, can enumerate: trimethylolpropane tris (methyl) acrylate, trihydroxy methyl C2 ~ C10 alkane three (methyl) acrylate such as trihydroxy methyl octane three (methyl) acrylate, trimethylolpropane polyethoxy three (methyl) acrylate, trimethylolpropane gathers propoxyl group three (methyl) acrylate, trimethylolpropane polyethoxy gathers trihydroxy methyl C2 ~ C10 alkane such as propoxyl group three (methyl) acrylate and gathers alkoxy three (methyl) acrylate, three [(methyl) acryloyl-oxyethyl] isocyanuric acid ester, pentaerythrite three (methyl) acrylate, ethylene-oxide-modified trimethylolpropane tris (methyl) acrylate, trimethylolpropane tris (methyl) acrylate etc. of the alkylene oxide modifications such as trimethylolpropane tris (methyl) acrylate of epoxy pronane modification.
About (methyl) acrylate monomer beyond (B); as (methyl) acrylate monomer with 4 (methyl) acryloyl groups, can enumerate: pentaerythrite polyethoxy four (methyl) acrylate, pentaerythrite gather propoxyl group four (methyl) acrylate, pentaerythrite four (methyl) acrylate, double trimethylolpropane four (methyl) acrylate, dipentaerythritol four (methyl) acrylate etc.
About (methyl) acrylate monomer beyond (B); as (methyl) acrylate monomer with 5 (methyl) acryloyl groups, can enumerate: dipentaerythritol five (methyl) acrylate etc.
About (methyl) acrylate monomer beyond (B); as (methyl) acrylate monomer with 6 (methyl) acryloyl groups, can enumerate: dipentaerythritol six (methyl) acrylate etc.
In addition, (methyl) acrylate monomer that can use in the present invention can be multifunctional (methyl) acrylate monomer with more than 7 (methyl) acryloyl groups.
In ultraviolet-curing resin composition of the present invention, these (methyl) acrylate monomer compositions can use a kind or be mixed with two or more with arbitrary ratio.The content of these (methyl) acrylate monomer compositions in ultraviolet-curing resin composition, relative to total amount 100 weight portion of ultraviolet-curing resin composition, be generally about 0 ~ about 10 weight portion, can be according to circumstances 10 ~ 80 weight portions, be preferably 20 ~ 70 weight portions.
As the adjuvant that may be used in ultraviolet-curing resin composition of the present invention, the light stabilizer such as antioxidant, hindered amine such as sensitizer, silane coupling agent, surfactant, levelling agent, hot polymerization inhibitor, hindered phenol, phosphite ester can also be used.These adjuvants can not be included in resin combination of the present invention, also can use as required.
As sensitizer, can use such as: 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 photopolymerizable compound generation addition reaction.From the view point of operability during making CD, preferably the compound with hindered piperidine skeleton is used to be useful.
As the compound with hindered piperidine skeleton of operable hindered amine compound, as long as known compound, then can use without particular limitation.Specifically, can use and such as be selected from by 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-piperidine ethanol, methacrylic 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, poly-{ [6-(1, 1, 3, 3-tetramethyl butyl) amino-1, 3, 5-triazine-2, 4-bis-base] [(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, 5-di-tert-butyl-4-hydroxyl benzyl)-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 (the 2-hydroxyl-1 of 9-, 1-dimethyl ethyl)-2, 4, 8, 10-tetra-oxaspiro [5.5] undecanoic mixed ester compound, and 1, 2, 3, 4-ethylene-dimalonic acid and 2, 2, 6, 6-tetramethyl-4-piperidine alcohols and 3, two (the 2-hydroxyl-1 of 9-, 1-dimethyl ethyl)-2, 4, 8, at least a kind of hindered amine compound in the group of the undecanoic mixed ester compound composition of 10-tetra-oxaspiro [5.5].Wherein, from the view point of giving excellent permanance, preferably 1 can be used, 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).
In the compound with hindered piperidine skeleton, be obstructed and refer to that alternatively base is bonded with the alkyl with side chain on the compound with piperidine scaffolds; Preferably use, above-mentioned substituting group has the compound of the tert-butyl group.In addition; when forming solidfied material; the compound itself with hindered piperidine skeleton occurs crosslinked; thus seldom to separate out with the form of impurity; and also can not damage the curability of ultraviolet-curing resin composition; therefore, the compound with hindered piperidine skeleton had containing (methyl) acryloyl group can particularly preferably be used.
There is the content of compound in ultraviolet-curing resin composition of hindered piperidine skeleton, relative to total amount 100 weight portion of ultraviolet-curing resin composition, be generally 0.01 ~ 10 weight portion, be preferably 0.03 ~ 8 weight portion, be particularly preferably 0.03 ~ 5 weight portion.
In addition, as silane coupling agent, as long as known silane coupling agent, then can be not particularly limited to use.
In addition, the antioxidant can giving excellent permanance can be added.
Can enumerate particularly: two [2-methyl-4-[3-(dodecyl sulfenyl) propionyloxy]-5-tert-butyl-phenyl] thioether and two [2-methyl-4-[3-(myristyl sulfenyl) propionyloxy]-5-tert-butyl-phenyl] thioether, two { 2-methyl-4-[3-N-alkyl (C12 or C14) sulfenyl propionyloxy]-5-tert-butyl-phenyl } thioether etc.; AO-23 (such as, Asahi Denka Co., Ltd. manufactures) can be obtained from the market.
The content of antioxidant in ultraviolet-curing resin composition, relative to total amount 100 weight portion of ultraviolet-curing resin composition, is generally 0.01 ~ 10 weight portion, is preferably 0.03 ~ 8 weight portion, is particularly preferably 0.03 ~ 5 weight portion.
The optimal way of resin combination of the present invention is as follows.
(I) a Blu-ray Disc ultraviolet-curing resin composition, wherein,
Epoxy (methyl) acrylate (A) is the diglycidyl ether type epoxy compound shown in through type (2) and (methyl) acrylic acid reaction and epoxy (methyl) acrylate that obtains;
Containing simple function (methyl) acrylate compounds (B);
Relative to total amount 100 weight portion of resin combination of the present invention, described epoxy (methyl) acrylate (A) containing proportional be 30 ~ 60 weight portions, by described epoxy (methyl) acrylate (A) containing proportional be set to A weight portion, by described simple function (methyl) acrylate compounds (B) containing proportional for B weight portion time, A/B is 0.8 ~ 1.45;
The content of Photoepolymerizationinitiater initiater (C) is 1 ~ 10 weight portion relative to total amount 100 weight portion of resin combination of the present invention.
(II) the Blu-ray Disc ultraviolet-curing resin composition as described in above-mentioned (I), wherein, as simple function (methyl) acrylate compounds (B), containing the compound that formula (1) represents, its content is 40 ~ 100 weight portions relative to total amount 100 weight portion of simple function (methyl) acrylate compounds (B); Remaining as simple function (methyl) acrylate compounds beyond it.
(III) the Blu-ray Disc ultraviolet-curing resin composition as described in above-mentioned (I) or (II), wherein, as simple function (methyl) acrylate compounds (B), contain (methyl) acrylic acid dihydro dicyclopentadiene oxygen base ethyl ester with the scope being below 100 weight portions relative to total amount 100 weight portion of simple function (methyl) acrylate compounds (B); Remaining as simple function (methyl) acrylate compounds beyond it.
(IV) the Blu-ray Disc ultraviolet-curing resin composition as described in above-mentioned (I) or (II), wherein, the compound that simple function (methyl) acrylate compounds (B) represents for formula (1) separately, or the compound represented for formula (1) and (methyl) acrylic acid dihydro dicyclopentadiene oxygen base ethyl ester.
(V) the Blu-ray Disc ultraviolet-curing resin composition as described in above-mentioned (IV), wherein, compound 100 weight portion that the content of (methyl) acrylic acid dihydro dicyclopentadiene oxygen base ethyl ester represents relative to formula (1) is below 100 weight portions.
CD ultraviolet-curing resin composition of the present invention can by by above-mentioned each composition mixed dissolution and obtaining at normal temperature ~ 80 DEG C.Operation can be waited to be removed by snotter by filtering as required.For resin combination of the present invention, consider coating, the viscosity of ultraviolet-curing resin composition of the present invention is preferably 300 ~ 2000 (mPas) at 25 DEG C, is more preferably 500 ~ 1200 (mPas).By making viscosity within the scope of this, easily forming thick film, can shorten and produce apart from time (タ Network ト タ イ system).
In addition, as ultraviolet-curing resin composition of the present invention, preferably do not use solvent, even if use solvent, relative to total amount 100 weight portion of ultraviolet-curing resin composition, be preferably less than 10 weight portions, be particularly preferably less than 5 weight portions.
For ultraviolet-curing resin composition of the present invention, the elastic modulus of the solidfied material formed after Ultraviolet radiation at 25 DEG C is 1000 ~ 3000MPa, is more preferably 1500 ~ 2500MPa, is particularly preferably 1800 ~ 2200MPa.Reason is, when being less than 1000MPa, can not have enough hardness, and during more than 3000MPa, warpage during solidification likely excessively becomes large.In addition, the elastic modulus at 50 DEG C is generally 35 ~ 1500MPa, is preferably 45 ~ 1500MPa.
In addition, the little mistake that effectively can prevent the characteristics of signals produced by temperature variation of the warpage caused by temperature variation, therefore, compared with the warpage of 25 DEG C, the variable quantity of the warpage of 5 DEG C ~ 55 DEG C is preferably less than 0.8 degree, is particularly preferably less than 0.6 degree.
In addition, when forming solidification nitride layer resin combination of the present invention is applied to CD, particularly when forming the light-transmitting layer of Blu-ray Disc, the variable quantity of the warpage (initial warpage) during solidification is the smaller the better, this variable quantity be with coating before the difference of substrate warp, be preferably less than 0.6 degree.When this variable quantity is more than 0.6 degree, there is the tendency that read error sharply increases.Be preferably less than 0.57 degree, be more preferably less than 0.5 degree, more preferably less than 0.4 degree.
In addition, according to reason same as described above, the variable quantity with the warpage after the long duration test of the CD of solidification nitride layer as light-transmitting layer of resin combination of the present invention, preferably Blu-ray Disc is also preferably less than 0.6 degree, is more preferably less than 0.5 degree, more preferably less than 0.4 degree.
In addition, the glass transition temperature (Tg) of the cured layer formed after Ultraviolet radiation is preferably more than 40 DEG C.Reason is, during lower than 40 DEG C, in high temperature environments (30 ~ 40 DEG C), elastic modulus can sharply reduce, and flexibility can extremely rise, thus as sticky flux, that is, likely can produce tackiness.
[CD]
CD of the present invention on substrate, is at least formed with reflection layer and light-transmitting layer and utilizes the above-mentioned light-transmitting layer of laser light and carry out the CD that records or regenerate, and above-mentioned light-transmitting layer comprises the solidfied material of light-transmitting layer ultraviolet-curing resin composition of the present invention.For CD of the present invention, the CD ultraviolet-curing resin composition of the application of the invention is as light-transmitting layer, due to the solidfied material that the variable quantity that can obtain the warpage caused by humidity change, temperature variation is little, therefore, it is possible to carry out the recording/reproducing of information well.
For the light-transmitting layer of CD of the present invention, preferably make the oscillation wavelength of laser be the blue laser transmission efficiently of 370 ~ 430nm, preferably when 100 μm of thickness, the transmissivity of the light of 405nm is more than 85%, is particularly preferably more than 90%.
The gross thickness of the thickness of light-transmitting layer is the scope of 50 ~ 150 μm, is particularly preferably 75 ~ 150 μm.The thickness of light-transmitting layer is set as about 100 μm when individual layer.Thickness can produce a very large impact light transmission, signal-obtaining and record, therefore needs sufficient control.Light-transmitting layer can be formed with the cured layer of this thickness of individual layer, also can laminated multi-layer.When multilayer, the thickness sum of preferred each light-transmitting layer is above-mentioned thickness range.
As reflection layer, if can reflects laser, can be formed can the CD of recording/reproducing, can use metal or its mineral compounds such as alloy, silicon such as such as gold, silver, copper, aluminium.Wherein, because the light reflectance near 400nm is high, therefore preferably use silver or take silver as the alloy of principal ingredient.The thickness of reflection layer is preferably set to about 10nm ~ about 60nm.
Usually, reflection layer is formed by the above-mentioned metal of evaporation on substrate or its alloy.
As substrate, the circular resin substrate of optical disc shapes can be used, as this resin, preferably can use polycarbonate.When CD be regeneration special, on substrate, the surface of stacked reflection layer is formed and bears the pit of information record.
In addition, when writeable CD, recording layer is set between reflection layer and light-transmitting layer.As recording layer, as long as the recording/reproducing of information can be carried out, can be any one in phase change type recording layer, magneto-optical recorder layer or organic pigment type recording layer.
In writeable CD, the recorded information face of substrate is provided with recording layer.Recording layer suitably can utilize the existing known material as used by optical recording medium recording layer.Can enumerate such as: pigment, amorphous semiconductor, partial nitridation film, partial oxide film (inoranic membrane) etc.
Optical recording media can have multiple above-mentioned recording layer.In this case, each layer can be formed by identical material, also can be formed by other material of combination in any.Thereby, it is possible to change the optical properties such as the 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 concrete example of the amorphous semiconductor material of the inorganic type recording layer used in recording layer, can enumerate: the materials such as SbTe base, GeTe base, GeSbTe base, InSbTe base, AgSbTe base, AgInSbTe base, GeSb base, GeSbSn base, InGeSbTe base and InGeSbSnTe base.In these materials, in order to improve crystallization rate, preferably use take Sb as the composition of principal ingredient.In addition, these amorphous semiconductor materials can be used alone a kind, also can to combine arbitrarily and ratio use two or more.
As the partial nitridation film of the inorganic type recording layer used in the recording layer, the concrete example of partial oxide film, can enumerate: the partial nitridation films such as BiGeN, SnNbN; The partial oxide film of TeOx, BiFOx etc.
In addition, as recording layer, organic pigment type recording layer can be used.The material require of organic pigment type recording layer to record regenerating use the wavelength of laser to have photonasty.And the material require of organic pigment type recording layer makes refractive index change by the physical change or chemical reaction that utilize laser to irradiate to produce.Therefore, as the material of organic pigment type recording layer, such as cyanines pigment, oxonols (oxonol) pigment, azopigment, phthalocyanine dye, porphyrin pigment can be enumerated.Use the solution these organic materials and such as oxytol acetate, tetrafluoropropanol equal solvent mixed, form organic pigment type recording layer by spin-coating method etc.The thickness of organic pigment type recording layer is preferably more than 15nm and below 25nm.
At this, contact bed can be had on the recording layer.Require that contact bed has the function of the heat that buffering recording layer produces, regulates the function of CD reflection rate; And there is the function that solvent etc. that the pigment contained in organic pigment recording layer when preventing light-transmitting layer film forming diffuses to light-transmitting layer or light-transmitting layer formation cured resin infiltrates into the mixing phenomenas such as organic pigment layer.The material forming this contact bed uses silicon dioxide to form with mixing of zinc sulphide usually.In addition, can enumerate: monox is the oxide such as silicon dioxide, zinc paste, cerium oxide, yttria, indium oxide, tin indium oxide, gallium oxide particularly; Zinc sulphide and yttrium sulfide sulfides; The nitride such as silicon nitride; Silit; The potpourri of oxide and sulphur; The fluoride etc. of aluminium oxide, magnesium, calcium etc.This contact bed is formed by methods such as sputterings.
Ultraviolet-curing resin composition of the present invention to contact bed, specifically silicon dioxide and zinc sulphide mix composition, indium oxide, tin indium oxide adhesiveness excellent, therefore can preferably use.
The CD of the present application can form plural recording layer (information recording part position).Such as, when regenerating special CD, can on the substrate with pit stacked first reflection layer, the first light-transmitting layer, and on this first light-transmitting layer other layer stacked, this layer is formed the second reflection layer, the second light-transmitting layer.In this case, on the first light-transmitting layer or on stacked other layer thereon, pit is formed.In addition, when can the CD of recording/reproducing, there is the formation being laminated with recording layer, reflection layer and light-transmitting layer on substrate; Also can adopt and on this light-transmitting layer, form the second reflection layer, the second recording layer and the second light-transmitting layer again and the formation with two-layer recording layer; Or can adopt and similarly carry out stacked above-mentioned layer and the formation with the recording layer of more than three layers.When stacked multiple layers, suitably regulate and make the thickness sum of each layer reach above-mentioned thickness.
When ultraviolet-curing resin composition of the present invention is used for light-transmitting layer, can suppresses to contact the contact bed of light-transmitting layer or the burn into deterioration of recording layer, also can be suitable for the CD with recording layer.
In addition, in CD of the present invention, light-transmitting layer can be the layer of most surface, but also can arrange surface coating further on its top layer.
CD of the present invention comprises the special CD of regeneration and can the CD of recording/reproducing.Regenerate special CD to be manufactured by following method: when by 1 circular resin substrate injection moulding, be provided as the pit of information recording layer, then on this information recording layer, form reflection layer, then (as required after other layer stacked) is by coating light-transmitting layer ultraviolet-curing resin compositions such as such as 2P method, rolling method, serigraphy, spin-coating methods; Then irradiate the ultraviolet ~ near ultraviolet ray (near wavelength 200 ~ 400nm) as active energy beam from one-sided or two sides, make this resin composition thus and form light-transmitting layer.In addition, can the CD of recording/reproducing can be manufactured by following method: on 1 circular resin substrate, form reflection layer, and recording layer is set; Then on this reflection layer, light-transmitting layer ultraviolet-curing resin composition is coated with by spin-coating method etc.; Then make this resin composition by Ultraviolet radiation and form light-transmitting layer.
When the light-transmitting layer ultraviolet-curing resin composition solidification being made coating by Ultraviolet radiation, as long as can the lamp of irradiation ultraviolet radiation ~ near ultraviolet ray (near wavelength 200 ~ 400nm), be not particularly limited.Such as (pulse) xenon lamp, electrodeless lamp, metal halide lamp, low pressure mercury lamp, high-pressure sodium lamp or ultrahigh pressure mercury lamp etc. can be used.Ultraviolet radiation can carry out with continuous light radiation modality, also can carry out in flash irradiation mode.
During irradiation ultraviolet radiation, preferably with accumulative light quantity for 0.05 ~ 1J/cm 2mode control.Accumulative light quantity is more preferably 0.05 ~ 0.8J/cm 2, be particularly preferably 0.05 ~ 0.6J/cm 2.The curability of the light-transmitting layer ultraviolet-curing resin composition used in CD of the present invention is excellent, therefore, even if accumulative light quantity is for also can fully solidify on a small quantity, can not produces and be clamminess, and warpage, the distortion of CD can not be produced on CD end face, surface.
[explanation of the concrete formation of CD]
Below, as the concrete example of CD of the present invention, an example of the concrete formation of single-layer type CD and multi-layered type CD (such as dual-layer type disc) is shown below.
In CD of the present invention, as the preferred implementation of single-layer type CD, such as, have: the formation of stacked reflection layer and light-transmitting layer, the record of incident blue laser and the information of carrying out or regeneration from light-transmitting layer side on substrate, the formation of hard conating is set at light-transmitting layer further.Light-transmitting layer is the layer of the solidfied material comprising ultraviolet-curing resin composition of the present invention, and its thickness is such as the scope of 100 ± 10 μm.Hard conating is preferably the high and layer of high abrasion resistance of hardness.The thickness of hard conating is preferably 1 ~ 10 μm, is more preferably 3 ~ 5 μm.The thickness of substrate is about 1.1mm.Reflection layer is the film of silver etc.
In addition, as the preferred implementation of single-layer type CD with recording layer, such as have and stack gradually reflection layer, the first contact bed, recording layer (inorganic type recording layer, organic pigment type recording layer), second interface layer, light-transmitting layer on substrate, and the formation of the record of incident blue laser and the information of carrying out or regeneration from light-transmitting layer side, the formation of hard conating is set at light-transmitting layer further.
As the preferred implementation of multi-layered type CD, such as to have on substrate stacked first reflection layer and the first light-transmitting layer, further stacked second reflection layer and the second light-transmitting layer thereon, and from the second light-transmitting layer side the formation of incident blue laser and the record of the information of carrying out or the dual-layer type disc of regeneration.First light-transmitting layer and the second light-transmitting layer are the layer of the solidfied material comprising ultraviolet-curing resin composition, and one deck is the layer comprising ultraviolet-curing resin composition of the present invention at least arbitrarily.As the thickness of layer, preferably the thickness of the first light-transmitting layer and the thickness sum of the second light-transmitting layer are the scope of 100 ± 10 μm.The thickness of substrate is about 1.1mm.Reflection layer is the film of silver etc.
In addition, as the preferred implementation of multi-layered type CD with recording layer, such as have and stack gradually the first reflection layer on substrate, first contact bed, first recording layer (inorganic type recording layer, organic pigment type recording layer), second interface layer, first light-transmitting layer, stacked second reflection layer thereon further, 3rd contact bed, second recording layer (inorganic type, organic pigment type), 4th contact bed, second light-transmitting layer, and from the second incident blue laser in light-transmitting layer side the formation of the record of the information of carrying out or the dual-layer type disc of regeneration.
In the dual-layer type disc of this formation, track record (groove) is also formed at the surface of the second light-transmitting layer, therefore, light-transmitting layer can be formed in the mode of following multilayer: comprising the layer upper strata stacked package of cured film of the excellent ultraviolet-curing resin composition of tackiness containing being applicable to the layer of cured film of the ultraviolet-curing resin composition forming track record and the multilayer that formed.In addition, in this formation, also hard conating can be set on most top layer.
Next, as an example the manufacture method of CD is described below.
First, by polycarbonate resin injection moulding is made the substrate with the guide channel for following the trail of laser being called track record (groove).Next, on the surface of the track record side of substrate, sputtering or evaporation silver alloy etc., thus form reflection layer.Be coated with ultraviolet-curing resin composition of the present invention thereon, by making ultraviolet-curing resin composition solidify from the one side of CD or two sides irradiation ultraviolet radiation, thus formation light-transmitting layer, or form hard conating by spin-coating method etc. thereon further.
(embodiment)
Below, further illustrate the present invention by embodiment, but the present invention is not by any restriction of these embodiments.
As embodiment 1 ~ 9, comparative example 1 ~ 4, preparation comprises the ultraviolet-curing resin composition of composition shown in following table 1.
Use the ultraviolet-curing resin composition of the present invention obtained, make the Blu-ray Disc with inorganic recording layer, and carry out evaluating characteristics.
(making of Blu-ray Disc)
1., on the polycarbonate substrate with diameter 12cm that track space is the guide channel of 0.32 μm, thickness 1.1mm, sputtering silver alloy to reach thickness for 100nm, thus forms reflection horizon.Then, sputtered with Ti SiO forms inorganic recording layer.Then, ZnS-SiO is sputtered 2(mol ratio 80:20), to reach thickness for about 15nm, forms contact bed, thus makes Blu-ray Disc substrate.
2. with reflection horizon mode upward by Blu-ray Disc substrate-placing on universal stage, carry out circle in the mode being covered to internal diameter 11.5mm place and add a cover (cap) process, then the present invention or the ultraviolet-curing resin composition 3.0g that compares are supplied on the lid of central part.
3. carry out spin coating in 4 seconds ~ 7 seconds with the velocity range of 900rpm, and to carry out being coated with to reach coating film thickness be 95 μm.At the end of spin coating, irradiate 2 times with xenon flash lamp, make it be cured to degree without surface mobility.
4. use high-pressure sodium lamp, with 400mJ/cm 2irradiated for 3 seconds from upside, thus ultraviolet-curing resin composition of the present invention is solidified completely.
5. be placed on universal stage in the ultraviolet-curing resin composition of the present invention mode upward after solidification, carry out circle in the mode being covered to internal diameter 11.5mm place and add a cover process, then ultraviolet-curing resin composition (HOD3950B, the Nippon Kayaku K. K manufactures) 3.0g of hard conating is supplied on the lid of central part.
6. carry out spin coating in 4 seconds ~ 7 seconds with the velocity range of 6000rpm to be coated with.At the end of spin coating, irradiate 2 times with xenon flash lamp, make it be cured to degree without surface mobility, thus make Blu-ray Disc of the present invention.
Use the Blu-ray Disc obtained to carry out evaluation of physical property, obtain the result of following table 1.
[table 1]
In addition, as described below with shown each composition of abridging in table 1.
EP-1: the epoxy radicals 1 mole by the epoxide equivalent represented relative to above-mentioned formula (2) being the diglycidyl ether type epoxy compound of 187g/ equivalent, makes acrylic acid 1 molar reactive and the epoxy acrylate obtained
EP-2: the epoxy radicals 1 mole by the epoxide equivalent represented relative to above-mentioned formula (2) being the diglycidyl ether type epoxy compound of 193g/ equivalent, makes acrylic acid 1 molar reactive and the epoxy acrylate obtained
UA-1: make the urethane acrylate that polypropylene glycol (number-average molecular weight 850), isophorone diisocyanate and acrylic acid 2-hydroxyl ethyl ester obtain with the molar ratio reaction of 1:1.9:1.9
UA-2: make the urethane acrylate that polytetramethylene glycol (number-average molecular weight 650), isophorone diisocyanate and acrylic acid 2-hydroxyl ethyl ester obtain with the molar ratio reaction of 1:1.8:1.8
FA-321A: the bisphenol A-type diacrylate of oxirane 10 mole, Hitachi Chemical Co., Ltd. manufactures
M-200:1,6-hexanediyl ester, Mei Yuan Co., Ltd. manufactures
THE-330: trimethylolpropane polyethoxy triacrylate, Nippon Kayaku K. K manufactures
Photomer4035: acrylate, Ke Ning Co., Ltd. manufactures
FA-512AS: acrylic acid dihydro dicyclopentadiene oxygen base ethyl ester, Japan changes into Industrial Co., Ltd and manufactures
M-142: the acrylate of oxirane 2 mole, Changxing Co., Ltd. manufactures
LA-82: methacrylic acid 1,2,2,6,6-pentamethyl-4-piperidine ester, Asahi Denka Kogyo K. K's (being now Asahi Denka Co., Ltd.) manufactures
SPEEDCURE TPO:2,4,6-trimethyl benzoyl diphenyl base phosphine oxide, DKSH Amada Co., Ltd. manufactures
IRGACURE184:1-hydroxycyclohexyl phenyl ketone, BASF Co., Ltd. manufactures
(elasticity modulus test)
Glass transition temperature (Tg), elastic modulus at 50 DEG C measure as follows, for the ultraviolet-curing resin composition obtained according to the composition of embodiment, comparative example, irradiate 3 seconds ultraviolet (100mJ/cm 2) and be cured, thus make the sheet of cuboid of longitudinal 4mm, horizontal 1mm, high 2mm, with Measurement of Dynamic Viscoelasticity device (manufacture of Seiko Electronics Co., Ltd) DMS6100, Chi bent げ Try test method is held) by two cantilever bending test method (both, setpoint frequency is 10Hz, programming rate is 4 DEG C/minute, measures the temperature dependency data of-50 DEG C ~ 150 DEG C.
(hardness test)
Hardness test uses Fei Xier sclerometer (manufacture of HP100-XYp, Fei Xier instrument company) to carry out.Working sample, except not arranging except hard conating in the making of the Blu-ray Disc of art heretofore taught, uses the Blu-ray Disc made in the same way.As assay method, the heavy burden of applying 1000mN 60 seconds, then removes heavy burden (0mN), and measures the compression distance (the darkest compression distance) (25 DEG C, 45%RH) after just having removed heavy burden (0mN).Unit is μm.
(nerve test)
Nerve test uses Fei Xier sclerometer (manufacture of HP100-XYp, Fei Xier instrument company) to carry out.Measuring sample except not arranging except hard conating in the making of the Blu-ray Disc of art heretofore taught, using the Blu-ray Disc made in the same way.As assay method, apply the heavy burden 60 seconds of 1000mN, then measure the compression distance after just having removed heavys burden (0mN) and from (0mN) is born a heavy burden in removing after 60 seconds the cup depth (25 DEG C, 45%RH) of the cured film of formation.Nerve is the difference of the former value and the value of the latter, that is, measure by the value that following formula is tried to achieve.Unit is μm.
Compression distance after 60 seconds of nerve=from removing is born a heavy burden-just removed the compression distance after heavy burden (0mN)
(initial camber test)
Initial warpage is evaluated by the difference of the warpage of the warpage of the substrate before the coating that measures the ultraviolet-curing resin composition of coating Examples or the comparative example substrate with this resin combination of coating and after making it solidify.
The warpage of the substrate before the warpage after initial warpage variable quantity=solidification-coated UV line curable resin composition
Zero ... be less than ± 0.6 degree
× ... more than ± 0.6 degree
(Blu-ray Disc endurancing)
Warpage after permanance (to be coated with and after solidifying by warpage after the warpage of the substrate before the ultraviolet-curing resin composition that measures coating Examples or comparative example and environmental test, 80 DEG C, place 250 hours under the environment of 85%RH (relative humidity) after, and at room temperature place the warpage after 3 days) difference (value obtained with following formula) and evaluate.Unit is " degree ".
The warpage of the substrate before the warpage after initial warpage variable quantity=environmental test-ultraviolet-curing resin composition coating
Zero ... be less than ± 0.6 degree
× ... more than ± 0.6
(curability test)
By having the diameter 12cm of the guide channel of track space 0.32 μm, the polycarbonate substrate of thickness 1.1mm is placed on universal stage, carry out circle in the mode being covered to internal diameter 11.5mm place and add a cover process, then the ultraviolet-curing resin composition 3.0g of embodiment or comparative example is supplied on the lid of central part.Carry out spin coating in 4 seconds ~ 7 seconds with the velocity range of 900rpm, carry out coating and make coating film thickness be 95 μm.At the end of spin coating, irradiate 2 flashes of light with xenon flash lamp, make it be cured to degree without surface mobility, then use high-pressure sodium lamp, with 400mJ/cm 2irradiated for 3 seconds from upside, thus ultraviolet-curing resin composition of the present invention is solidified completely.Refluxed 9 hours at 80 DEG C in MEK by the cured coating film (weight: W1) peeled off from polycarbonate substrate, then 80 DEG C of dryings 4 hours, then weigh (weight: W2), measures gel fraction.
Gel fraction=W2 × 100/W1
From the results shown in Table 1, the glass transition temperature Tg of the resin combination of the present invention of embodiment 1 ~ 9 is all more than 40 DEG C, warpage variable quantity after the variable quantity of initial warpage and long duration test is the value being less than 0.6, is all values of the present permissible range required by high level.In addition, under present technical merit, when thinking that the variable quantity of warpage is more than 0.6, mistake can sharply increase.On the other hand, in a comparative example, although meet on the one hand, other side, outside permissible range, for present high request level, goes back residue problem.
In addition, in an embodiment of the present invention, from the viewpoint of reply environment for use, under the normality of particularly preserving under the high temperature period such as summer or the temperature also higher than supposition usually, because temperature is high, therefore preferred Tg temperature height person, compared with embodiment 2, preferred embodiment 1, more preferred embodiment 8, preferably Tg is the embodiment 4 ~ 7 of more than 50 DEG C further, and most preferably Tg is the embodiment 4,5 and 7 of more than 60 DEG C.While meeting the value of Tg, if the elastic modulus at 50 DEG C (50 DEG C of E, MPa) is more than 35MPa, then meet present requirement level, if possible, be preferably more than 45MPa, be more preferably more than 100MPa, more preferably more than 300MPa, most preferably be more than 450MPa.
In addition, if the warpage variable quantity after the variable quantity of initial warpage and long duration test is all in the permissible range of above-mentioned requirements, then present requirement is met for the time being; But in order to tackle be increased sharply requirement level, reduce mistake further, both values are preferably less than 0.5, are more preferably less than 0.4.
In addition, in hardness test, the value of above-mentioned table 1 is preferably less than 54, is more preferably less than 51, most preferably is less than 40.In addition, the value of nerve is preferably more than 4, is more preferably more than 5, and more preferably more than 6.
The curability of the resin combination of the above embodiment of the present invention is excellent, can obtain the solidfied material that high, at 50 DEG C the elastic modulus of Tg is also high, and when being applied to Blu-ray Disc, the variable quantity of warpage during solidification is also little.In addition, the variable quantity with the warpage that Blu-ray Disc is changed by humidity, temperature variation causes of this solidification nitride layer is little, and therefore the inhibit feature of the variable quantity of the warpage of this solidification nitride layer is excellent, and permanance is also excellent.Therefore, curable resin composition of the present invention, by forming its solidification nitride layer (preferred light transmission layer) in Blu-ray Disc, can produce the Blu-ray Disc with above-mentioned advantageous property.

Claims (18)

1. a Blu-ray Disc, it has the solidification nitride layer of Blu-ray Disc ultraviolet-curing resin composition,
In this Blu-ray Disc ultraviolet-curing resin composition, contain epoxy (methyl) acrylate (A), (ii) simple function (methyl) acrylate compounds (B) and (iii) Photoepolymerizationinitiater initiater (C) that (i) is reacted by (methyl) acrylate compounds and diglycidyl ether type epoxy compound making to have carboxyl and obtained
Relative to total amount 100 weight portion of this resin combination, described epoxy (methyl) acrylate (A) containing proportional be more than 30 weight portions,
By described epoxy (methyl) acrylate (A) containing the proportional A of being set to weight portion, by described simple function (methyl) acrylate compounds (B) containing proportional be set to B weight portion time, A/B is 0.8 ~ 1.45.
2. a Blu-ray Disc ultraviolet-curing resin composition, contain epoxy (methyl) acrylate (A), simple function (methyl) acrylate compounds (B) and Photoepolymerizationinitiater initiater (C) that (methyl) acrylate compounds and diglycidyl ether type epoxy compound by making to have carboxyl react and obtain, wherein
Relative to total amount 100 weight portion of this resin combination, described epoxy (methyl) acrylate (A) containing proportional be more than 30 weight portions,
Described epoxy (methyl) acrylate (A) containing the proportional A of being set to weight portion, by described simple function (methyl) acrylate compounds (B) containing proportional be set to B weight portion time, A/B is 0.8 ~ 1.45.
3. Blu-ray Disc ultraviolet-curing resin composition as claimed in claim 2, it is characterized in that, (methyl) acrylate compounds with carboxyl is the compound that (a) unsaturated carboxylic acid or derivatives thereof or (b) are obtained with multi-anhydride (b2) by the lactone addition product (b1) of hydroxyl (methyl) acrylate compounds.
4. Blu-ray Disc ultraviolet-curing resin composition as claimed in claim 2, it is characterized in that, diglycidyl ether type epoxy compound is to be represented by following formula (2) and epoxide equivalent is the liquid diglycidyl ether type epoxy compound of 180g/ equivalent ~ 200g/ equivalent
In formula, n represents the integer of 0 ~ 20.
5. Blu-ray Disc ultraviolet-curing resin composition as claimed in claim 2, wherein, simple function (methyl) acrylate compounds (B) is for having (methyl) acrylate compounds of phenyl ring or having (methyl) acrylate compounds of dihydro dicyclopentadiene base or dicyclopentadiene base.
6. ultraviolet-curing resin composition as claimed in claim 2, is characterized in that, the compound represented containing following formula (1) as described simple function (methyl) acrylate compounds (B),
In formula, n represents the integer of 1 ~ 10.
7. Blu-ray Disc ultraviolet-curing resin composition as claimed in claim 6, wherein, in described formula (1), n is 2.
8. Blu-ray Disc ultraviolet-curing resin composition as claimed in claim 6, wherein, relative to total amount 100 weight portion of Blu-ray Disc ultraviolet-curing resin composition, the compound that formula (1) is represented containing proportional be set to B1 weight portion time, or when together with the compound that formula (1) represents also containing (methyl) acrylic acid dihydro dicyclopentadiene oxygen base ethyl ester as when simple function (methyl) acrylate compounds (B) by the total both them containing proportional be set to B1 weight portion time, A/B1 is 0.8 ~ 1.45.
9. Blu-ray Disc ultraviolet-curing resin composition as claimed in claim 2, it is characterized in that, relative to total amount 100 weight portion of described ultraviolet-curing resin composition, with the ratio below 20 weight portions also containing carbamate (methyl) acrylate.
10. Blu-ray Disc ultraviolet-curing resin composition as claimed in claim 6, wherein, epoxy (methyl) acrylate (A) is epoxy (methyl) acrylate (A) that the diglycidyl ether type epoxy compound by making methacrylic acid and following formula (2) represent reacts and obtain
In formula, n represents the integer of 1 ~ 10.
11. Blu-ray Disc ultraviolet-curing resin compositions as claimed in claim 2, wherein, relative to weight 100 weight portion of described ultraviolet-curing resin composition, the content ratio A weight portion of epoxy (methyl) acrylate (A) and described simple function (methyl) acrylate compounds (B) add up at least 80 weight portions containing proportional B weight portion.
12. Blu-ray Disc ultraviolet-curing resin compositions as claimed in claim 2, wherein, the glass transition temperature Tg of the solidfied material of Blu-ray Disc ultraviolet-curing resin composition is at least 40 DEG C.
13. Blu-ray Disc ultraviolet-curing resin compositions as claimed in claim 2, wherein, to Blu-ray Disc ultraviolet-curing resin composition irradiation ultraviolet radiation, the elastic modulus of 50 DEG C of the solidfied material formed after Ultraviolet radiation is 450 ~ 1500MPa.
14. 1 kinds of solidfied materials, it is by obtaining the Blu-ray Disc ultraviolet-curing resin composition solidification according to any one of claim 1 ~ 13.
15. 1 kinds of solidfied materials, it obtains by irradiating active energy beam to the ultraviolet-curing resin composition according to any one of claim 1 ~ 13.
16. 1 kinds of Blu-ray Discs, it has light-transmitting layer, the ultraviolet-curing resin composition of described light-transmitting layer by being coated with on optic disc base board according to any one of claim 1 ~ 13, and irradiates active energy beam and obtain.
17. Blu-ray Discs as claimed in claim 16, wherein, optic disc base board is the optic disc base board with reflection horizon.
18. Blu-ray Discs as claimed in claim 16, wherein, the glass transition temperature Tg of the solidfied material described in claim 14 is at least 40 DEG C, have the initial warpage of the Blu-ray Disc of the layer of this solidfied material variable quantity and 80 DEG C, expose 250 hours under the environment of relative humidity 85% after long duration test after the value of both variable quantities of warpage be all less than ± 0.6 degree.
CN201380026648.XA 2012-05-22 2013-05-20 Ultraviolet curable resin composition and blue-ray disc Pending CN104395961A (en)

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