WO2002077047A1 - Ultraviolet-curable composition for optical disk and optical disk - Google Patents

Ultraviolet-curable composition for optical disk and optical disk Download PDF

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Publication number
WO2002077047A1
WO2002077047A1 PCT/JP2002/002754 JP0202754W WO02077047A1 WO 2002077047 A1 WO2002077047 A1 WO 2002077047A1 JP 0202754 W JP0202754 W JP 0202754W WO 02077047 A1 WO02077047 A1 WO 02077047A1
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Prior art keywords
ultraviolet
curable composition
optical disk
parts
mass
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PCT/JP2002/002754
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French (fr)
Japanese (ja)
Inventor
Hirokazu Saito
Kazuo Murakami
Haruhiko Takahashi
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Dainippon Ink And Chemicals, Inc.
Zeon Corporation
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Publication of WO2002077047A1 publication Critical patent/WO2002077047A1/en

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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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • G11B7/256—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers improving adhesion between layers
    • 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
    • G11B7/253—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 substrates
    • G11B7/2533—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 substrates comprising resins

Definitions

  • the present invention relates to an ultraviolet-curable composition for an optical disc, and more particularly, to an ultraviolet-curable composition having excellent adhesion to an optical disc using an amorphous polyolefin resin substrate.
  • Amorphous polyolefin resins have attracted attention as heat-resistant transparent thermoplastic resins.
  • Amorphous polyolefin resin has excellent mechanical and optical properties such as high transparency, low birefringence, heat resistance, and low moisture absorption. Taking advantage of these properties, it can be used as a substitute for polymethyl methacrylate (PMMA) and polycarbonate (PC), which are typical representative transparent thermoplastic resins, for use in various industrial applications, such as use as optical disc substrates. Is being considered.
  • PMMA polymethyl methacrylate
  • PC polycarbonate
  • the adhesion of the UV-curable protective coating agent to the amorphous polyolefin resin surface there is a method of activating the resin surface.
  • pretreatment methods such as a flame treatment method, a corona treatment method, an oxidation treatment method, and a sandblast method.
  • these treatment methods are effective in improving the adhesion, they cause problems such as coloring and surface roughness, which impair optical characteristics, and increase in production costs due to an increase in production processes. There was a lack of practicality as a means of improving adhesion.
  • the adhesive When using polyolefin resin for optical disc substrate, The adhesive must have excellent adhesion to both the amorphous polyrefin resin substrate itself, on which the metal reflection film is not formed, and the metal reflection film formed on the substrate, on the inner and outer circumferences of the disk. .
  • existing UV-curable protective coating agents for optical discs have insufficient adhesion to amorphous polyolefin substrates and examples of UV-curable resin compositions that have good adhesion to amorphous polyolefin substrates
  • Japanese Patent No. 0303053 the composition does not consider adhesion to a metal reflective film formed on an optical disk substrate at all, and the composition is made of amorphous polyolefin.
  • An ultraviolet curable protective coating agent for optical discs having good adhesion to both the substrate and the metal reflective film has not yet been put to practical use.
  • the present invention has been made in view of the above-mentioned problems of the related art, and is applied to an optical disk using an amorphous polyolefin resin without special pretreatment, thereby being ultraviolet-cured in a short time, and forming an amorphous polyolefin resin substrate. It is an object of the present invention to provide an ultraviolet-curable composition for optical disks having excellent adhesion to both metal reflection films. Disclosure of the invention
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by using an ultraviolet-curable composition having a specific blend of a monomer and a polymerization initiator, both the amorphous polyolefin substrate and the metal reflective film can be used. They have found that good adhesion can be obtained, and have completed the present invention.
  • the present invention provides a chemical formula
  • UV curable composition for optical discs characterized by containing 0.01 to 5% by mass of a (meth) acrylate having a phosphate group and a phosphoric acid group, and an optical disk using the cured coating film as a protective layer I will provide a.
  • the optical disk of the present invention can make full use of the excellent mechanical and optical characteristics of the amorphous polyolefin resin.
  • the reason that the ultraviolet curable composition for an optical disk of the present invention has excellent adhesion to an amorphous polyolefin resin is considered as follows.
  • Amorphous polyolefin resin has a main chain composed of a saturated aliphatic group and contains an aliphatic polycyclic ring structure in the main chain.
  • Specific examples include a repeating unit derived from a monomer having a norpolenene skeleton in a repeating unit. It has a unit. Since the polarity of the amorphous polyolefin resin is considered to be low as a whole resin, the lower the polarity of the protective coating agent of this resin, the higher the adhesion.
  • the monomer used in the ultraviolet-curable composition has a polar group such as an atalyloyl group and has high polarity, so that sufficient adhesion cannot be obtained. Chemical formula used in the present invention
  • the compound represented by (1) is indispensable for improving the compatibility between the amorphous polyolefin resin and the ultraviolet-curable composition, and ensuring the adhesion between the resin and the coating composition.
  • the compounding amount of the compound represented by the chemical formula (1) is 55 to 85% by mass in the composition of the present invention.
  • thioxanthone compound used in the present invention means a compound represented by the following chemical formula (2).
  • R represents any one of hydrogen, an alkyl group, and nodogen, and n represents 1 or 2.
  • the mixing amount of thioxanthone is 3 to 10 mass in the composition of the present invention. /. Preferably, it is 4 to 8% by mass. If the amount of thioxanthone is less than 3% by mass, the adhesion of the coating film is reduced. If the amount is more than 10% by mass, the curing speed is reduced, which is not preferable.
  • thioxanthone examples include isopropyl thioxanthone and 2,4-dimethylthioxanthone.
  • thioxanthone alone as an initiator may not have a sufficient surface hardening speed.
  • the surface curing speed can be adjusted by using thioxanthone and another initiator in combination.
  • the initiator to be used in combination include acetophenone-based initiators such as 2-hydroxy-2-methyl-1-phenylprono-1-one, 1-hydroxycyclohexynolefenenoleketone, benzophenone, and benzoyl.
  • acetophenone-based initiators such as 2-hydroxy-2-methyl-1-phenylprono-1-one, 1-hydroxycyclohexynolefenenoleketone, benzophenone, and benzoyl.
  • Benzophenone-based initiators such as methyl benzoate are exemplified.
  • the (meth) acrylate which has a phosphate group used in the present invention includes: 2-methacryloylic acid phosphate, tris-acrylo-leoxy-shethyl phosphate, bis (methacryloxy-shethyl) phosphate, and the like. Such compounds are commercially available as light esters P-1M, Biscoat 3PA, KAY AME RPM-2, etc., and are readily available.
  • the amount of the (meth) acrylate having a phosphate group is 0.01 to 5 mass in the composition of the present invention. / 0 , preferably 0.05 to 3% by mass. If the amount is less than 0.01% by mass, a sufficient adhesive force with the metal reflection film cannot be obtained. On the other hand, if the content exceeds 5% by mass, signal characteristics are degraded during a high-temperature and constant-humidity durability test, which is not preferable.
  • the ultraviolet-curable composition for an optical disk of the present invention comprises a monofunctional monomer having an alkyl group or a monofunctional monomer having an alicyclic structure composed of at least two types of atoms among carbon, hydrogen and oxygen. ⁇ 30 mass. / 0 is preferably contained.
  • monofunctional monomers include (meth) acrylate having a linear alkyl group, (meth) atalylate having an alkyl group having a side chain, (meth) atalylate having a cyclohexane ring, and dicyclopentanyl ring.
  • this monofunctional methacrylate examples include n-lauryl methacrylate, stearyl methacrylate, isodecyl methacrylate, cyclohexyl methacrylate, dicyclopentenyl methacrylate, isopornino methacrylate, and tetrahydrofurfuryl methacrylate.
  • Photopolymerizable monomers are exemplified.
  • the compounding amount of the monofunctional monomer is 3 to 30% by mass, preferably 5 to 25% by mass in the composition of the present invention.
  • This component not only increases the adhesiveness between the cured coating and the amorphous polyolefin, but also has the effect of eliminating residual distortion during curing of the UV-curable composition.However, excessive use of this component reduces the pencil hardness and curing speed of the cured coating. This is undesired because it lowers it.
  • an aromatic amine as a starting aid.
  • aromatic amine activates thioxanthone upon irradiation with ultraviolet light, and as a result, between amorphous polyolefin and cured coating It is considered that a strong adhesion is formed on the substrate.
  • initiation aid examples include p-dimethylaminoacetophenone, 4-dimethylaminoethyl benzoate, p-dimethylaminoacetophenone, and the like.
  • the compounding amount of the starting aid is 0.5 to 5% by mass, preferably 1 to 3% by mass. Initiating aids can be used in combination of two or more if necessary.
  • the above-mentioned components alone can sufficiently achieve the initial purpose.
  • a photopolymerizable monomer and a photopolymerizable oligomer are used as long as the original characteristics are not changed. Can be blended.
  • additives such as a polymerization inhibitor can be added as long as the effects of the present invention are not impaired.
  • polymerization inhibitor examples include hydroquinone monomethyl ether, t-butynole, p-benzoquinone, 2,5-t-butynole-dihydroquinone, and phenothiazine.
  • the use amount of these additives is preferably in the range of 0.1 to 5% by mass of the composition of the present invention.
  • a disk is prepared in which pits corresponding to signals are formed on a circular transparent substrate made of amorphous polyolefin and a light reflection layer is provided. Further, instead of the pits, a disk in which a recording layer made of an organic dye, a phase change recording material, or the like is provided, and a light reflection layer is laminated thereon may be used.
  • the organic dye that can be used in the recording layer is not particularly limited as long as it can form pits by a laser beam used for recording, and examples thereof include a cyamine-based, phthalocyanine-based, azo-based, and naphthalocyanine-based dye. And anthraquinone, triphenylmethane, pyrylium or thiapyrylium salts, squarium, croconium, formazan, and metal complex dyes.
  • metal complexes such as acetyl acetonate-based, bisdithio- ⁇ -diketone-based and bispheninolethiol-based, such as bisdithiol-based, thiocateconole-based, salicylaldehyde hydroxyxime-based, and thiobisphenolate-based metal complexes are preferable.
  • amine-based compounds having a radical cation of nitrogen and amine-based quenchers such as hindered amines are suitable.
  • phase change recording material examples include chalcogen alloys such as GeSbTe and AgInSbTe.
  • the light reflecting layer can be obtained by forming a thin film of a metal such as aluminum, silver, gold, and the like or an alloy thereof, or a silicon compound by a method such as sputtering or vapor deposition.
  • the ultraviolet curable composition according to the present invention is applied on the light reflecting layer, and a coating film is formed by a spin coating method or the like so that the film thickness after curing becomes 3 to 20 ⁇ .
  • the optical disk of the present invention can be obtained by irradiating ultraviolet rays and curing the coating film.
  • a continuous irradiation type ultraviolet irradiation apparatus such as a high pressure mercury lamp and a metal halide lamp, or a flash irradiation type ultraviolet irradiation apparatus such as a xenon flash can be used.
  • the optical disk of the present invention may be a conventional one in which information is reproduced and recorded by a laser beam through a substrate or through a cured film of the ultraviolet curable composition according to the present invention. Is also good.
  • an ultraviolet-curable composition was prepared in the same manner as in Example 1.
  • an ultraviolet-curable composition was prepared in the same manner as in Example 1.
  • Trimethylonolepropane ethoxy triatalylate 4. parts
  • Noninolephenoxy polyethylene glycol acrylate 5 parts Trimethylolpropane ethoxytriatalylate 4. parts Bis (methacryloxyshethyl) phosphate 0.1 parts
  • Trimethylolpropane ethoxy triatalylate 4.2 parts 1-Hydroxycyclohexyl phenyl ketone 3.5 ⁇ (5 2, 4-getylthioxanthone 4.5 parts
  • the ultraviolet-curable compositions prepared in the above Examples and Comparative Examples were applied to an amorphous polyolefin substrate and an amorphous polyolefin substrate having an aluminum reflective film on an aluminum surface so that the film thickness after curing was 7 to 10 ⁇ .
  • the composition was applied by a spin coating method, and was cured by a curing apparatus having a condensing high-pressure mercury lamp (120 W / cm) at an irradiation amount of 1 jZcm 2 .
  • the sample using an amorphous polyolefin substrate was disk A, and the sample using an amorphous polyolefin substrate with an aluminum reflective film was disk B.
  • the adhesiveness of the cured films on the disk A and the disk B was evaluated according to the X-cut tape method of JIS K5400 (ISO 24 ⁇ 9).
  • the case where the coating film did not peel off from the contact surface was indicated by ⁇
  • the case where the coating film was peeled was indicated by X
  • the results and overall evaluation are shown in Table 1 by OK and NG.
  • Comparative Example 1 using a polymerization initiator other than the thioxanthone compound, the compounding amount of the thioxanthone compound was 3 mass. /.
  • Comparative Example 2 the coating film peeled off from the surface of the amorphous polyolefin substrate, and in Comparative Example 3 containing no (meth) atalylate having a phosphoric acid group, the coating film peeled off from the aluminum reflective film surface. Good adhesion to both the substrate and the metal reflective film was not obtained.
  • the ultraviolet-curable composition for an optical disc of the present invention exhibits good adhesion to both the amorphous polyolefin resin and the metal reflective film without impairing the excellent optical properties of the amorphous polyolefin resin, and is highly transparent.
  • the present invention can provide an optical disk using an amorphous polyolefin resin having excellent mechanical properties and optical properties such as low refractive index, low birefringence, heat resistance, and low moisture absorption as a substrate.

Abstract

An ultraviolet-curable composition for optical disks which has excellent adhesion to amorphous polyolefin substrates and with which an optical disk having excellent durability is realized. The composition contains 55 to 85 wt.% compound represented by the chemical formula (1) and 3 to 10 wt.% thioxanthone compound.

Description

光ディスク用紫外線硬化型組成物及び光ディスク 技術分野  UV curable composition for optical disk and optical disk
本発明は、 光ディスク用紫外線硬化型組成物に関し、 更に詳しくはァモルファ スポリオレフィン榭脂基板を使用した光ディスクとの密着性に優れた紫外線硬化 型組成物に関する。  The present invention relates to an ultraviolet-curable composition for an optical disc, and more particularly, to an ultraviolet-curable composition having excellent adhesion to an optical disc using an amorphous polyolefin resin substrate.
本出願は、 日本国特許出願第 2 0 0 1— 0 8 9 6 3 1号を基礎としており、 そ の内容を本明細書に組み込む。 背景技術  This application is based on Japanese Patent Application No. 201-096931, the contents of which are incorporated herein. Background art
近年、 耐熱性透明熱可塑性樹脂として、 アモルファスポリオレフィン樹脂が注 目されている。 アモルファスポリオレブイン樹脂は、 高透明性、 低複屈折率、 耐 熱性、 低吸湿性等の優れた力学的、 光学的性質を持つ。 このような性質を生かし て、 従来の代表的な透明熱可塑性樹脂であるポリメチルメタクリレート （P MM A) やポリカーボネート （P C) の代替として、 例えば光ディスク基板としての 使用等、 各種産業用途への展開が検討されている。  In recent years, amorphous polyolefin resins have attracted attention as heat-resistant transparent thermoplastic resins. Amorphous polyolefin resin has excellent mechanical and optical properties such as high transparency, low birefringence, heat resistance, and low moisture absorption. Taking advantage of these properties, it can be used as a substitute for polymethyl methacrylate (PMMA) and polycarbonate (PC), which are typical representative transparent thermoplastic resins, for use in various industrial applications, such as use as optical disc substrates. Is being considered.
し力 し、 アモルファスポリオレフイン樹脂と良好な密着性を有する保護コート 剤がなかったために、 P MMAや P Cの代替として産業上利用される機会が少な かった。  However, since there was no protective coating agent with good adhesion to the amorphous polyolefin resin, there were few opportunities for industrial use as a substitute for PMMA and PC.
アモルファスポリオレフィン樹脂表面に対する紫外線硬化型保護コート剤の密 着性を向上させる手段として、 樹脂表面を活性化させる方法がある。 例えば、 火 炎処理法、 コロナ処理法、 酸化処理法、 サンドブラスト法等の前処理法がある。 これらの処理方法は、 密着性を向上させる点では有効であるが、 着色や表面の荒 れを引き起こし光学的特性を損なう問題、 あるいは、 生産プロセスが増えること による設備費用の増加等の問題等があり、 密着性向上の手段としては実用性に乏 しいものであった。  As a means for improving the adhesion of the UV-curable protective coating agent to the amorphous polyolefin resin surface, there is a method of activating the resin surface. For example, there are pretreatment methods such as a flame treatment method, a corona treatment method, an oxidation treatment method, and a sandblast method. Although these treatment methods are effective in improving the adhesion, they cause problems such as coloring and surface roughness, which impair optical characteristics, and increase in production costs due to an increase in production processes. There was a lack of practicality as a means of improving adhesion.
.ポリオレフイン樹脂を光ディスク用基板に応用する場合、 保護コ 一ト剤にはディスク内外周部の、 金属反射膜が形成されていないアモルファスポ リォレフィン樹脂基板それ自体と、 基板上に形成される金属反射膜との両方に優 れた密着性が必要となる。 し力 し、 既存の光ディスク用紫外線硬化型保護コート 剤ではアモルファスポリオレフイン基板への密着性が不十分であり、 また、 ァモ ルファスポリオレフィン基板への密着性が良い紫外線硬化型樹脂組成物の例が日 本国特許第 3 0 3 0 9 5 3号に開示されているが、 該組成物は光ディスク基板上 に形成される金属反射膜との密着性に関しては全く考慮されておらず、 ァモルフ ァスポリオレフィン基板と金属反射膜の両方に対し良好な密着性を有する光ディ スク用紫外線硬化型保護コート剤は未だ実用化に至っていない。 When using polyolefin resin for optical disc substrate, The adhesive must have excellent adhesion to both the amorphous polyrefin resin substrate itself, on which the metal reflection film is not formed, and the metal reflection film formed on the substrate, on the inner and outer circumferences of the disk. . However, existing UV-curable protective coating agents for optical discs have insufficient adhesion to amorphous polyolefin substrates and examples of UV-curable resin compositions that have good adhesion to amorphous polyolefin substrates Although disclosed in Japanese Patent No. 0303053, the composition does not consider adhesion to a metal reflective film formed on an optical disk substrate at all, and the composition is made of amorphous polyolefin. An ultraviolet curable protective coating agent for optical discs having good adhesion to both the substrate and the metal reflective film has not yet been put to practical use.
本発明は、 前記従来技術の課題を背景になされたもので、 特別な前処理をせず にアモルファスポリオレフィン樹脂を使用した光ディスクに塗布することにより 、 短時間で紫外線硬化し、 アモルファスポリオレフィン樹脂基板と金属反射膜の 両方に対し密着性に優れた光ディスク用紫外線硬化型組成物を提供することを目 白勺とする。 発明の開示  The present invention has been made in view of the above-mentioned problems of the related art, and is applied to an optical disk using an amorphous polyolefin resin without special pretreatment, thereby being ultraviolet-cured in a short time, and forming an amorphous polyolefin resin substrate. It is an object of the present invention to provide an ultraviolet-curable composition for optical disks having excellent adhesion to both metal reflection films. Disclosure of the invention
本発明者らは上記課題を解決するために鋭意検討した結果、 特定の配合のモノ マーと重合開始剤を有する紫外線硬化型組成物を用いることにより、 ァモルファ スポリオレフィン基板と金属反射膜の両方に対する良好な密着性が得られること を見出し、 本発明を完成するに至ったものである。  The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by using an ultraviolet-curable composition having a specific blend of a monomer and a polymerization initiator, both the amorphous polyolefin substrate and the metal reflective film can be used. They have found that good adhesion can be obtained, and have completed the present invention.
即ち、 本発明は、 化学式
Figure imgf000004_0001
That is, the present invention provides a chemical formula
Figure imgf000004_0001
( 1 ) で示される化合物を、 5 5〜8 5質量％、 チォキサントン系化合物を 3 ~ 1 0質 量。 /。、 及びリン酸基を有する （メタ） ァクリレートを 0 . 0 1〜5質量％含有す ることを特徴とする光デイスク用紫外線硬化型組成物、 及ぴこの硬化塗膜を保護 層として用いた光ディスクを提供する。 本発明の光ディスクは、 アモルファスポリオレフイン樹脂からなる基板を用い ることにより、 前記のアモルファスポリオレフイン樹脂の優れた力学的、 光学的 特性を充分に利用することが可能となる。 55 to 85% by mass of the compound represented by (1), and 3 to 10% by mass of the thioxanthone compound. /. UV curable composition for optical discs, characterized by containing 0.01 to 5% by mass of a (meth) acrylate having a phosphate group and a phosphoric acid group, and an optical disk using the cured coating film as a protective layer I will provide a. By using the substrate made of the amorphous polyolefin resin, the optical disk of the present invention can make full use of the excellent mechanical and optical characteristics of the amorphous polyolefin resin.
本発明の光ディスク用紫外線硬化型組成物が、 アモルファスポリオレフイン樹 脂に対して優れた密着性を有する理由は以下のように考えられる。  The reason that the ultraviolet curable composition for an optical disk of the present invention has excellent adhesion to an amorphous polyolefin resin is considered as follows.
アモルファスポリオレフイン樹脂は、 飽和脂肪族よりなる主鎖を持ち、 その主 鎖中に脂肪族多環環状構造を含むものであって、 具体例としては、 繰り返し単位 中にノルポルネン骨格を有するモノマー由来の繰り返し単位を有するものである 。 アモルファスポリオレフイン樹脂は樹脂全体として極性は低いと考えられるた め、 この樹脂の保護コート剤も、 極性が低い方が密着性は上がると考えられる。 通常、 紫外線硬化型組成物に用いられるモノマーは、 アタリロイル基等の極性基 を有しており、 極性が高いため充分な密着性が得られない。 しカゝし、 本発明に用 いる化学式
Figure imgf000005_0001
Amorphous polyolefin resin has a main chain composed of a saturated aliphatic group and contains an aliphatic polycyclic ring structure in the main chain.Specific examples include a repeating unit derived from a monomer having a norpolenene skeleton in a repeating unit. It has a unit. Since the polarity of the amorphous polyolefin resin is considered to be low as a whole resin, the lower the polarity of the protective coating agent of this resin, the higher the adhesion. Usually, the monomer used in the ultraviolet-curable composition has a polar group such as an atalyloyl group and has high polarity, so that sufficient adhesion cannot be obtained. Chemical formula used in the present invention
Figure imgf000005_0001
( 1 ) で示される化合物のように分子内にアルキル鎖、 環構造が存在し、 これにチォキ サントン系化合物を重合開始剤として用いることにより、 それらコンフオメーシ ヨンによる極性緩和効果により、 硬化後の塗膜は極性が低くなり、 その結果、 了 モルファスポリオレフィン樹脂との良好な密着性が発現するものと考えられる。 更に接着助剤としてリン酸基を有する （メタ） アタリレートを併用することに より、 金属反射膜との密着性を上げることができる。 発明を実施するための最良の形態 As in the compound shown in (1), an alkyl chain and a ring structure are present in the molecule, and by using a thioxanthone compound as a polymerization initiator, the conformational relaxation effect of these conformations causes the coating after curing. It is considered that the film has low polarity, and as a result, good adhesion to the morphous polyolefin resin is exhibited. Furthermore, by using (meth) acrylate which has a phosphate group together as an adhesion assistant, the adhesion to the metal reflection film can be improved. BEST MODE FOR CARRYING OUT THE INVENTION
本発明に用いられる化学式  Chemical formula used in the present invention
H2C=CHCOOCH2 CHフ OCOCH=CH2 ( 1 ) で示される化合物は、 アモルファスポリォレフィン樹脂と紫外線硬化型組成物の 相溶性を向上させ、 樹脂と被膜組成物間の密着性を確保するのに不可欠である。 化学式 （1 ) で示される化合物の配合量は、 本発明の組成物中に 5 5〜 8 5質量 %である。 H 2 C = CHCOOCH 2 CH OCOCH = CH 2 The compound represented by (1) is indispensable for improving the compatibility between the amorphous polyolefin resin and the ultraviolet-curable composition, and ensuring the adhesion between the resin and the coating composition. The compounding amount of the compound represented by the chemical formula (1) is 55 to 85% by mass in the composition of the present invention.
また、 本発明に用いられるチォキサントン系化合物とは下記化学式 （2 ) で表 される化合物を意味する。  In addition, the thioxanthone compound used in the present invention means a compound represented by the following chemical formula (2).
Figure imgf000006_0001
Figure imgf000006_0001
( 2 ) (2)
ここで、 Rは水素、 アルキル基、 ノヽロゲンの何れかを表し、 nは 1または 2を 表す。  Here, R represents any one of hydrogen, an alkyl group, and nodogen, and n represents 1 or 2.
チォキサントンの配合量は、 本発明の組成物中に 3〜 1 0質量。/。、 好ましくは 4〜 8質量％である。 チォキサントンの配合量が 3質量％未満では塗膜の密着性 が低下し、 逆に 1 0質量％越えると、 硬化スピードが遅くなつてしまい、 好まし くない。  The mixing amount of thioxanthone is 3 to 10 mass in the composition of the present invention. /. Preferably, it is 4 to 8% by mass. If the amount of thioxanthone is less than 3% by mass, the adhesion of the coating film is reduced. If the amount is more than 10% by mass, the curing speed is reduced, which is not preferable.
チォキサントンの具体例としては、 イソプロピルチォキサントン、 2 , 4—ジ ェチルチオキサントン等が挙げられる。  Specific examples of thioxanthone include isopropyl thioxanthone and 2,4-dimethylthioxanthone.
組成物の配合組成によっては、 開始剤として、 チォキサントン単独では表面硬 化スピードが不十分な場合がある。 その場合は、 チォキサントンと他の開始剤を 併用することにより、 表面硬化スピードを調整することができる。  Depending on the composition of the composition, thioxanthone alone as an initiator may not have a sufficient surface hardening speed. In that case, the surface curing speed can be adjusted by using thioxanthone and another initiator in combination.
併用する開始剤の具体例としては、 2—ヒ ドロキシー 2—メチルー 1一フエ二 ルプロノくンー 1一オン、 1—ヒ ドロキシシクロへキシノレフエニノレケトン等のァセ トフエノン系開始剤、 ベンゾフエノン、 ベンゾィル安息香酸メチル等のベンゾフ エノン系開始剤が挙げられる。  Specific examples of the initiator to be used in combination include acetophenone-based initiators such as 2-hydroxy-2-methyl-1-phenylprono-1-one, 1-hydroxycyclohexynolefenenoleketone, benzophenone, and benzoyl. Benzophenone-based initiators such as methyl benzoate are exemplified.
また、 本発明に用いられるリン酸基を有する （メタ） アタリレートとしては、 2—メタクリロイ口キシェチノレアシッドホスフェイ ト、 トリスァクリロイノレォキ シェチルホスフェート、 ビス （メタクリロキシェチル） ホスフェイ ト等が挙げら れる。 このような化合物はライ トエステル P— 1 M、 ビスコート 3 P A、 KAY AME R P M— 2等として市販されており、 容易に入手可能である。 リン酸基 を有する （メタ） ァクリ レートの配合量は、 本発明の組成物中に 0 . 0 1〜5質 量。 /0、 好ましくは 0 . 0 5〜 3質量％である。 配合量が 0 . 0 1質量％よりも少 ないと金属反射膜との接着力を充分に得られない。 また 5質量％を越すと、 高温 恒湿耐久試験の際信号特性の劣化を招き、 好ましくない。 The (meth) acrylate which has a phosphate group used in the present invention includes: 2-methacryloylic acid phosphate, tris-acrylo-leoxy-shethyl phosphate, bis (methacryloxy-shethyl) phosphate, and the like. Such compounds are commercially available as light esters P-1M, Biscoat 3PA, KAY AME RPM-2, etc., and are readily available. The amount of the (meth) acrylate having a phosphate group is 0.01 to 5 mass in the composition of the present invention. / 0 , preferably 0.05 to 3% by mass. If the amount is less than 0.01% by mass, a sufficient adhesive force with the metal reflection film cannot be obtained. On the other hand, if the content exceeds 5% by mass, signal characteristics are degraded during a high-temperature and constant-humidity durability test, which is not preferable.
本発明の光ディスク用紫外線硬化型組成物には、 アルキル基を有する単官能モ ノマーまたは、 炭素、 水素及ぴ酸素の内、 少なくとも 2種類の原子からなる脂環 式構造を有する単官能モノマーを 3〜3 0質量。 /0含有することが好ましい。 これ ら単官能モノマーとして、 直鎖アルキル基を有する （メタ） ァクリレート、 側鎖 を有するアルキル基を持つ （メタ） アタリレート、 シクロへキサン環を有する （ メタ） アタリレート、 ジシクロペンタニル環を有する （メタ） アタリレート、 ィ ソボル二ル環を有する （メタ） アタリレート、 テトラヒ ドロフラン環構造を有す る （メタ） アタリレートなどが挙げられるが、 特にメタクリレートモノマーがァ モルファスポリオレフイン基板との接着性の面で好ましい。 The ultraviolet-curable composition for an optical disk of the present invention comprises a monofunctional monomer having an alkyl group or a monofunctional monomer having an alicyclic structure composed of at least two types of atoms among carbon, hydrogen and oxygen. ~ 30 mass. / 0 is preferably contained. These monofunctional monomers include (meth) acrylate having a linear alkyl group, (meth) atalylate having an alkyl group having a side chain, (meth) atalylate having a cyclohexane ring, and dicyclopentanyl ring. (Meth) acrylate, (meth) acrylate having a sobornyl ring, and (meth) acrylate having a tetrahydrofuran ring structure. Particularly, methacrylate monomer is bonded to an amorphous polyolefin substrate. It is preferable in terms of properties.
この単官能メタタリ レートの具体例としては、 n—ラウリルメタクリ レート、 ステアリルメタクリ レート、 イソデシルメタクリレート、 シクロへキシルメタク リ レート、 ジシク口ペンテニルメタクリレート、 ィソポルニノレメタクリ レート、 テトラヒ ドロフルフリルメタクリレートなどの光重合性モノマーが挙げられる。 単官能モノマーの配合量は、 本発明の組成物中に 3〜3 0質量％、 好ましくは 5〜2 5質量％でぁる。 この成分は、 硬化塗膜とアモルファスポリオレフイン間 の密着性を上げるだけでなく、 紫外線硬化型組成物硬化時の残留歪みを除く効果 もあるが、 過剰な使用は硬化被膜の鉛筆硬度及び硬化スピードを低下させること になり、 好ましくない。  Specific examples of this monofunctional methacrylate include n-lauryl methacrylate, stearyl methacrylate, isodecyl methacrylate, cyclohexyl methacrylate, dicyclopentenyl methacrylate, isopornino methacrylate, and tetrahydrofurfuryl methacrylate. Photopolymerizable monomers are exemplified. The compounding amount of the monofunctional monomer is 3 to 30% by mass, preferably 5 to 25% by mass in the composition of the present invention. This component not only increases the adhesiveness between the cured coating and the amorphous polyolefin, but also has the effect of eliminating residual distortion during curing of the UV-curable composition.However, excessive use of this component reduces the pencil hardness and curing speed of the cured coating. This is undesired because it lowers it.
更に、 開始助剤として芳香族ァミンを 0 . 5〜5質量％含有することが好まし レ、。 芳香族ァミンをチォキサントンと共存させることにより、 紫外線照射時にチ ォキサントンが活性化され、 その結果アモルファスポリオレフインと硬化塗膜間 に強固な密着性が形成されると考えられる。 Further, it is preferable to contain 0.5 to 5% by mass of an aromatic amine as a starting aid. The coexistence of aromatic amine with thioxanthone activates thioxanthone upon irradiation with ultraviolet light, and as a result, between amorphous polyolefin and cured coating It is considered that a strong adhesion is formed on the substrate.
開始助剤の具体例として、 p—ジメチルアミノアセトフエノン、 4—ジメチル ァミノ安息香酸ェチル、 p—ジメチルアミノアセトフエノン等が挙げられる。 開 始助剤の配合量は、 0 . 5〜5質量％、 好ましくは 1〜3質量％である。 開始助 剤は、 必要に応じて 2種類以上組み合わせて使用することもできる  Specific examples of the initiation aid include p-dimethylaminoacetophenone, 4-dimethylaminoethyl benzoate, p-dimethylaminoacetophenone, and the like. The compounding amount of the starting aid is 0.5 to 5% by mass, preferably 1 to 3% by mass. Initiating aids can be used in combination of two or more if necessary.
本発明の塗料組成物には、 上記の成分のみで十分初期の目的を達成できるもの であるが、 更に性能改良のため、 本来の特性を変えない範囲で光重合性モノマー 及び、 光重合性ォリゴマーを配合することができる。  In the coating composition of the present invention, the above-mentioned components alone can sufficiently achieve the initial purpose. However, in order to further improve the performance, a photopolymerizable monomer and a photopolymerizable oligomer are used as long as the original characteristics are not changed. Can be blended.
また、 更なる性能改良のため、 本発明の効果を損なわない範囲で、 重合禁止剤 等の添加物を添加することもできる。  In order to further improve the performance, additives such as a polymerization inhibitor can be added as long as the effects of the present invention are not impaired.
重合禁止剤としては、 例えば、 ハイ ドロキノンモノメチルエーテル、 tーブチ ノレ力テコ一ノレ、 p一べンゾキノン、 2 , 5— tーブチノレ一ノヽィ ドロキノン、 フエ ノチアジンが挙げられる。  Examples of the polymerization inhibitor include hydroquinone monomethyl ether, t-butynole, p-benzoquinone, 2,5-t-butynole-dihydroquinone, and phenothiazine.
これらの添加物の使用量は、 本発明組成物の 0 . 1〜 5質量％の範囲が好まし レ、。  The use amount of these additives is preferably in the range of 0.1 to 5% by mass of the composition of the present invention.
次に本発明に係る光ディスクの実施形態の例について説明する。  Next, an example of an embodiment of an optical disk according to the present invention will be described.
まず、 アモルファスポリオレフインからなる円形透明基板上に、 信号に対応する ピットを形成レた上に光反射層を設けたディスクを用意する。 また、 ピットの代 わりに、 有機色素、 相変化記録材料等からなる記録層を設け、 その上に光反射層 を積層したディスクを用いてもよい。 First, a disk is prepared in which pits corresponding to signals are formed on a circular transparent substrate made of amorphous polyolefin and a light reflection layer is provided. Further, instead of the pits, a disk in which a recording layer made of an organic dye, a phase change recording material, or the like is provided, and a light reflection layer is laminated thereon may be used.
上記記録層に用いることができる有機色素としては、 記録に用いるレーザー光 によってピットを形成することができるものであれば、 特に制限なく、 例えばシ ァニン系、 フタロシアニン系、 ァゾ系、 ナフタロシアニン系、 アントラキノン系 、 トリフエニルメタン系、 ピリリウムないしチアピリリウム塩系、 スクヮリ リウ ム系、 クロコニゥム系、 ホルマザン系、 金属錯体色素系等が挙げられる。  The organic dye that can be used in the recording layer is not particularly limited as long as it can form pits by a laser beam used for recording, and examples thereof include a cyamine-based, phthalocyanine-based, azo-based, and naphthalocyanine-based dye. And anthraquinone, triphenylmethane, pyrylium or thiapyrylium salts, squarium, croconium, formazan, and metal complex dyes.
また、 色素に一重項酸素クェンチヤ一を混合して用いるのもよい。  It is also possible to use a mixture of a singlet oxygen quencher and a dye.
クェンチヤ一としては、 ァセチルァセトナート系、 ビスジチォ一 α—ジケトン系 やビスフエニノレジチオール系などのビスジチオール系、 チォカテコーノレ系、 サリ チルアルデヒ ドォキシム系、 チオビスフヱノレート系等の金属錯体が好ましい。 また、 窒素のラジカルカチオンを有するアミン系化合物やヒンダ一ドアミン等の ァミン系のクェンチヤ一も好適である。 ' As the quencher, metal complexes such as acetyl acetonate-based, bisdithio- α -diketone-based and bispheninolethiol-based, such as bisdithiol-based, thiocateconole-based, salicylaldehyde hydroxyxime-based, and thiobisphenolate-based metal complexes are preferable. . Also, amine-based compounds having a radical cation of nitrogen and amine-based quenchers such as hindered amines are suitable. '
上記記録層に用いることができる相変化記録材料としては、 G e S b T e、 A g I n S b T e等のカルコゲン合金が挙げられる。  Examples of the phase change recording material that can be used for the recording layer include chalcogen alloys such as GeSbTe and AgInSbTe.
上記光反射層は、 アルミニウム、 銀、 金、 鲖等の金属又はその合金、 あるいは ケィ素化合物等をスパッタリング、 蒸着等の方法で薄膜形成することにより得る ことができる。  The light reflecting layer can be obtained by forming a thin film of a metal such as aluminum, silver, gold, and the like or an alloy thereof, or a silicon compound by a method such as sputtering or vapor deposition.
次に本発明に係る紫外線硬化型組成物を上記光反射層上に塗布し、 スピンコー ト法等によって硬化後の膜厚が 3〜2 0 μ πιになるように塗膜を形成し、 続いて 、 紫外線を照射して、 塗膜を硬化することによって本発明の光ディスクを得るこ とができる。  Next, the ultraviolet curable composition according to the present invention is applied on the light reflecting layer, and a coating film is formed by a spin coating method or the like so that the film thickness after curing becomes 3 to 20 μπι. The optical disk of the present invention can be obtained by irradiating ultraviolet rays and curing the coating film.
紫外線を照射する手段として、 例えば、 高圧水銀灯、 メタルハライドランプ等 の連続照射方式の紫外線照射装置または、 キセノンフラッシュ等の閃光照射方式 の紫外線照射装置を使用できる。  As means for irradiating the ultraviolet rays, for example, a continuous irradiation type ultraviolet irradiation apparatus such as a high pressure mercury lamp and a metal halide lamp, or a flash irradiation type ultraviolet irradiation apparatus such as a xenon flash can be used.
更に本発明の光ディスクは、 従来のようにレーザー光による情報の再生，記録 を、 基板を通して行うものであっても良いし、 本発明に係る紫外線硬化型組成物 の硬化膜を通して行うものであってもよい。  Furthermore, the optical disk of the present invention may be a conventional one in which information is reproduced and recorded by a laser beam through a substrate or through a cured film of the ultraviolet curable composition according to the present invention. Is also good.
次に実施例を挙げて本発明を説明するが、 本発明はこれら実施例に限定される ものではない。 尚、 以下の実施例中 「部」 は 「質量部」 を表す。  Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In the following examples, “parts” represents “parts by mass”.
実施例 1 Example 1
化学式 （1 ) で示される化合物 8 1 . 5部 81.5 parts of a compound represented by the chemical formula (1)
ラウリルアタリレート 5部 Lauryl Atarilate 5 parts
トリメチロールプロパンエトキシトリアタリ レート 4 . 1部  Trimethylolpropane ethoxy triatalylate 4.1 parts
ビス （メタクリロキシェチル） ホスフェイ ト 0 . 1部 Bis (methacryloxyshethyl) phosphate 0.1 part
1—ヒ ドロキシシクロへキシルフェ二ルケトン 3 . 5部  1—Hydroxycyclohexylphenyl ketone 3.5 parts
2 , 4—ジェチルチオキサントン、 4 . 5部  2, 4-getylthioxanthone, 4.5 parts
p一ジメチルァミノァセトフエノン · 1部 p-dimethylaminoacetophenone1 part
p—ジメチルァミノ安息香酸ェチル ' 0 . 2部 p-dimethylaminoethyl benzoate '0.2 part
メ トキノン 0 . 1部 以上を混合し、 65°C 2時間加熱溶解後、 紫外線硬化型組成物を調製した t 実施例 2 Methoquinone 0.1 parts A mixture of at least, was heated and dissolved 65 ° C 2 hours, t Example 2 was prepared ultraviolet-curable composition
化学式 （1) で示される化合物 '71. 5部 Compound represented by chemical formula (1) '71 .5 parts
テトラヒ ドロフルフリルメタタリ レート 1 5部 Tetrahydrofurfurfuryl metatarylate 1 5 parts
トリメチロールプロパンエトキシトリアタリレート 4 部  Trimethylolpropane ethoxytriatalylate 4 parts
ビス （メタクリ ロキシェチル） ホスフェイ ト 0. 1部 Bis (methacryloxyshethyl) phosphate 0.1 part
1ーヒ ドロキシシクロへキシルフェニルケトン 3. 5部 1-Hydroxycyclohexyl phenyl ketone 3.5 parts
2, 4 -ジェチルチオキサントン 4. 5部 2, 4-Getylthioxanthone 4.5 parts
p—ジメチルアミノアセトフエノン 1部 p-Dimethylaminoacetophenone 1 part
p—ジメチルァミノ安息香酸ェチル 0. 2部 0.2 parts of p-dimethylaminoethyl benzoate
メ トキノン 0. 1部 Methoquinone 0.1 parts
以上を、 実施例 1と同様にして紫外線硬化型組成物を調製した Above, an ultraviolet-curable composition was prepared in the same manner as in Example 1.
実施例 3 Example 3
化学式 （1) で示される化合物 71. 5部 Compound represented by chemical formula (1) 71.5 parts
シクロへキシノレメタタリ レート 1 5部 Cyclohexinolemethalate 1 5 parts
トリメチロールプロパンエトキシトリアタリ レート 4. 1部  Trimethylolpropane ethoxy triatalylate 4.1 parts
ビス (メタクリ 口キシェチル) ホスフェイ ト 0. 1部 Bis (methacrylic mouth kissil) phosphate 0.1 part
1ーヒ ドロキシシクロへキシルフェニルケトン 3. 5部  1-Hydroxycyclohexyl phenyl ketone 3.5 parts
2, 4—ジェチルチオキサントン 4. 5部 2, 4-getylthioxanthone 4.5 parts
p—ジメチルアミノアセトフエノン 1部 p-Dimethylaminoacetophenone 1 part
p—ジメチルァミノ安息香酸ェチル 0. 2部 0.2 parts of p-dimethylaminoethyl benzoate
メ トキノン 0. 1部 Methoquinone 0.1 parts
以上を、 実施例 1と同様にして紫外線硬化型組成物を調製した Above, an ultraviolet-curable composition was prepared in the same manner as in Example 1.
実施例 4 Example 4
化学式 (1) で示される化合物 6 1. 5部 61.5 parts of the compound represented by the chemical formula (1)
ラウリルメタクリレート、 共栄社 (株) 製） 25部 Lauryl methacrylate, manufactured by Kyoeisha Co., Ltd.) 25 parts
トリメチローノレプロパンエトキシトリアタリ レート 4. 部  Trimethylonolepropane ethoxy triatalylate 4. parts
ビス (メタクリ ロキシェチノレ) ホスフェイ ト 0. 1部 Screw (methacrylic loxyshechnole) phosphate 0.1 part
1ーヒ ドロキシシクロへキシルフェニルケトン 3. 5部 2， 4一ジェチルチオキサントン 4. 5部 1-Hydroxycyclohexyl phenyl ketone 3.5 parts 2,4-I-ethylthioxanthone 4.5 parts
p—ジメチルアミノアセトフエノン 1部 p-Dimethylaminoacetophenone 1 part
p—ジメチルァミノ安息香酸ェチル 0. 2部 0.2 parts of p-dimethylaminoethyl benzoate
メ トキノン 0. 1部 Methoquinone 0.1 parts
以上を、 実施例 1と同様にして紫外線硬化型組成物を調製した。 比較例 1 In the same manner as in Example 1, an ultraviolet-curable composition was prepared. Comparative Example 1
化学式 (1) で示される化合物 87部 87 parts of the compound represented by the chemical formula (1)
トリメチロールプロパンエトキシトリアタリ レート 4. 6部 ビス （メタクリロキシェチル） ホスフェイ ト 0. 1部  Trimethylolpropane ethoxy triatalylate 4.6 parts Bis (methacryloxyshethyl) phosphate 0.1 part
1—ヒ ドロキシシクロへキシルフェニノレケトン 8部 1-Hydroxycyclohexylpheninole ketone 8 parts
p—ジメチルァミノ安息香酸ェチル 0. 2部 0.2 parts of p-dimethylaminoethyl benzoate
メ トキノン 0. 1部 Methoquinone 0.1 parts
以上を、 実施例 1と同様にして紫外線硬化型組成物を調製した。 比較例 2 In the same manner as in Example 1, an ultraviolet-curable composition was prepared. Comparative Example 2
化学式 ( 1) で示される化合物 71. 5部 Compound represented by chemical formula (1) 71.5 parts
ノニノレフエノキシポリエチレングリコールァクリ レート 5部 トリメチロールプロパンエトキシトリアタリ レート 4. 部 ビス （メタクリロキシェチル） ホスフェイ ト 0. 1部 Noninolephenoxy polyethylene glycol acrylate 5 parts Trimethylolpropane ethoxytriatalylate 4. parts Bis (methacryloxyshethyl) phosphate 0.1 parts
1—ヒ ドロキシシクロへキシルフェニルケトン 5. 5部 2, 4一ジェチノレチォキサントン 2. 5部  1-Hydroxycyclohexyl phenyl ketone 5.5 parts 2,4-1,4-Jetinorethioxanthone 2.5 parts
p—ジメチルァミノァセトフエノン 1部 p-Dimethylaminoacetophenone 1 part
p—ジメチルァミノ安息香酸ェチル 0. 2部 0.2 parts of p-dimethylaminoethyl benzoate
メ トキノン 0. 1部 Methoquinone 0.1 parts
以上を、 実施例 1と同様にして紫外線硬化型組成物を調製した。 比較例 3 In the same manner as in Example 1, an ultraviolet-curable composition was prepared. Comparative Example 3
化学式 （1) で示される化合物 71. 5部 Compound represented by chemical formula (1) 71.5 parts
シク口へキシルメタクリ レ一ト 1 5部 Hexyl methacrylate 1 5 parts
トリメチロールプロパンエトキシトリアタリレート 4. 2部 1ーヒ ドロキシシクロへキシルフェニルケトン 3. 5咅 (5 2, 4—ジェチルチオキサントン 4. 5部 Trimethylolpropane ethoxy triatalylate 4.2 parts 1-Hydroxycyclohexyl phenyl ketone 3.5 咅 (5 2, 4-getylthioxanthone 4.5 parts
P—ジメチルァミノァセトフエノン 1部 P-Dimethylaminoacetophenone 1 part
p—ジメチルァミノ安息香酸ェチル 0. 2部 0.2 parts of p-dimethylaminoethyl benzoate
メ トキノン 0. 1部 Methoquinone 0.1 parts
以上を、 実施例 1と同様にして紫外線硬化型組成物を調製した。 In the same manner as in Example 1, an ultraviolet-curable composition was prepared.
サンプルディスクの作製 Preparation of sample disk
上記実施例及び比較例で調製した紫外線硬化型組成物を、 アモルファスポリオ レフィン基板上及びアルミ反射膜を有するアモルファスポリオレフィン基板のァ ルミ面上に、 硬化後の膜厚が 7〜10 μπιとなる様スピンコート法により塗布し 、 集光型高圧水銀ランプ （120W/cm) を有する硬化装置により、 照射光量 1 jZcm2で硬化させた。 アモルファスポリオレフイン基板を使用したサンプ ルをディスク A、 アルミ反射膜を有するァモルファスポリオレフィン基板を使用 したサンプルをディスク Bとした。 The ultraviolet-curable compositions prepared in the above Examples and Comparative Examples were applied to an amorphous polyolefin substrate and an amorphous polyolefin substrate having an aluminum reflective film on an aluminum surface so that the film thickness after curing was 7 to 10 μπι. The composition was applied by a spin coating method, and was cured by a curing apparatus having a condensing high-pressure mercury lamp (120 W / cm) at an irradiation amount of 1 jZcm 2 . The sample using an amorphous polyolefin substrate was disk A, and the sample using an amorphous polyolefin substrate with an aluminum reflective film was disk B.
試験方法 Test method
J I S K5400 (I SO 24◦ 9) の Xカットテープ法に準じ、 デイス ク A及びディスク B上の硬化膜の密着性を評価した。 塗膜が密着面から剥離しな かった場合を〇、 剥離した場合を Xとレ、 表 1にその結果及び総合評価を OKと NGで示した。  The adhesiveness of the cured films on the disk A and the disk B was evaluated according to the X-cut tape method of JIS K5400 (ISO 24◦9). The case where the coating film did not peel off from the contact surface was indicated by 〇, the case where the coating film was peeled was indicated by X, and the results and overall evaluation are shown in Table 1 by OK and NG.
(表 1) (table 1)
ディスク A ディスク B || 、 n IFP木  Disk A Disk B ||, n IFP tree
実施例 1 〇 〇 OK Example 1 〇 〇 OK
実施例 2 〇 〇 OK Example 2 〇 〇 OK
実施例 3 〇 〇 OK Example 3 〇 〇 OK
実施例 4 〇 〇 OK Example 4 〇 〇 OK
比較例 1 X 〇 NG Comparative Example 1 X NG NG
比較例 2 X o NG Comparative Example 2 Xo NG
比較例 3 O X NG 表 1から明らかなように、 実施例 1〜 4で得られた本発明の光ディスク用紫外 線硬化型組成物では、 ァモルファスポリオレフィン基板と金属反射膜の両方に対 し良好な密着'性を示した。 Comparative Example 3 OX NG As is clear from Table 1, the ultraviolet-curable compositions for optical discs of the present invention obtained in Examples 1 to 4 exhibited good adhesion to both amorphous polyolefin substrates and metal reflective films. Was.
しかし、 チォキサントン系化合物以外の重合開始剤を用いた比較例 1、 チォキ サントン系化合物の配合量が 3質量。/。未満の比較例 2では、 アモルファスポリオ レフイン基板面から塗膜が剥がれ、 またリン酸基を有する （メタ） アタリレート を含有しない比較例 3では、 アルミ反射膜面から塗膜が剥がれ、 アモルファスポ リオレフイン基板と金属反射膜の両方に対する良好な密着性が得られなかった。 産業上の利用可能性  However, Comparative Example 1 using a polymerization initiator other than the thioxanthone compound, the compounding amount of the thioxanthone compound was 3 mass. /. In Comparative Example 2, the coating film peeled off from the surface of the amorphous polyolefin substrate, and in Comparative Example 3 containing no (meth) atalylate having a phosphoric acid group, the coating film peeled off from the aluminum reflective film surface. Good adhesion to both the substrate and the metal reflective film was not obtained. Industrial applicability
本発明の光ディスク用紫外線硬化型組成物は、 ァモルファスポリオレフイン樹 脂の優れた光学的性質を損なわずに、 該ァモルファスポリオレフイン樹脂と金属 反射膜の両方に対し良好な密着性を示し、 高透明性、 低複屈折率、 耐熱性、 低吸 湿性等の優れた力学的、 光学的性質を持つアモルファスポリオレフイン樹脂を基 板として使用した光ディスクを提供することができる。  The ultraviolet-curable composition for an optical disc of the present invention exhibits good adhesion to both the amorphous polyolefin resin and the metal reflective film without impairing the excellent optical properties of the amorphous polyolefin resin, and is highly transparent. The present invention can provide an optical disk using an amorphous polyolefin resin having excellent mechanical properties and optical properties such as low refractive index, low birefringence, heat resistance, and low moisture absorption as a substrate.

Claims

請求の範囲 The scope of the claims
1 . 化学式
Figure imgf000014_0001
1. Chemical formula
Figure imgf000014_0001
( 1 ) で示される化合物を 5 5〜8 5質量％、 チォキサントン系化合物を 3〜 1 0質量 %、 及びリン酸基を有する （メタ） アタリレートを 0 . 0 1〜5質量％含有する 光ディスク用紫外線硬化型組成物。 An optical disk containing 55 to 85% by mass of the compound represented by (1), 3 to 10% by mass of a thioxanthone-based compound, and 0.01 to 5% by mass of a (meth) atalylate having a phosphate group. UV curable composition for use.
2 . 請求の範囲 1記載の光ディスク用紫外線硬化型組成物であって、 さらに、 ァ ルキル基を有する単官能モノマーまたは、 炭素、 水素及び酸素の内、 少なくとも 2種類の原子からなる脂環式構造を有する単官能モノマーを、 3〜3 0質量％含 有する。 2. The ultraviolet curable composition for an optical disk according to claim 1, further comprising a monofunctional monomer having an alkyl group, or an alicyclic structure comprising at least two kinds of atoms of carbon, hydrogen and oxygen. 3 to 30% by mass of a monofunctional monomer having the formula:
3 . 請求の範囲 2記載の光ディスク用紫外線硬化型組成物であって、 該単官能モ ノマーがメタクリレートモノマーである。 3. The ultraviolet-curable composition for an optical disk according to claim 2, wherein the monofunctional monomer is a methacrylate monomer.
4 . 請求の範囲 1に記載の光ディスク用紫外線硬化型組成物であって、 芳香族ァ ミンを 0 . 5〜 5質量。/。含有する。 4. The ultraviolet-curable composition for an optical disk according to claim 1, wherein the aromatic amine has a content of 0.5 to 5 mass. /. contains.
5 . 請求の範囲 1〜 4に記載の何れかの紫外線硬化型組成物の硬化塗膜を保護層 として有する光ディスク。 5. An optical disc having a cured coating film of the ultraviolet-curable composition according to any one of claims 1 to 4 as a protective layer.
6 . 請求の範囲 5に記載の光ディスクであって、 アモルファスポリオレフイン樹 脂からなる基板を有する。 6. The optical disc according to claim 5, comprising a substrate made of an amorphous polyolefin resin.
PCT/JP2002/002754 2001-03-27 2002-03-22 Ultraviolet-curable composition for optical disk and optical disk WO2002077047A1 (en)

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