JP2006079731A - Optical information recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical information recording medium hardly sticking dust and dirt onto the surface of its hard coat layer and stably recording and reproduction information. <P>SOLUTION: The optical information recording medium is formed by providing a recording layer, a light transmission layer and the hard coat layer on a substrate. The ratio (F/C)<SB>surface</SB>of the peak intensity of F to the peak intensity of C respectively obtained when the surface of the hard coat layer is measured by an X-ray photoelectron spectroscopy is 0.01 to 1.0. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an optical information recording medium, and more particularly to a heat mode type optical information recording medium.

  There is an increasing demand for high-density optical information recording media (DVDs) for recording and reproducing large amounts of character information, image information, and audio information. In particular, in order to cope with recording of digital high-vision TV broadcasting, research on higher density recording has been made. Among them, since the blue-violet laser was released, development of an optical disk system using this blue-violet laser and a high NA pickup has been studied. At ISO 2000, Sony Corporation announced the DVR-Blue system, which is a phase change medium using a blue-violet laser.

  The characteristics of the layer structure of the DVR-Blue system are as follows: (1) a 0.1 mm transparent layer called a cover layer is provided on the laser incident side; and (2) a pickup with a high NA pickup is used. The distance from the disk surface is short, and the pickup may hit the disk surface and damage the surface of the transparent layer due to disk surface blurring.

  As a method of forming a transparent layer having a thickness of 0.1 mm, a method in which a transparent sheet is bonded through an adhesive layer made of an ultraviolet curable resin and a pressure-sensitive adhesive has been proposed (for example, see Patent Documents 1 and 2). . It has also been proposed to provide a hard coat layer and an anti-scratch layer on the disk surface to prevent the disk surface from being scratched (see, for example, Patent Documents 2 and 3).

However, in general, it is possible to prevent scratches only by providing a hard coat layer, but it is not effective in preventing dust adhesion and dirt, and depending on the type of hard coat layer, the chargeability and water absorption increase, and There was a problem that it became easy to get dirty. Dust and dirt on the surface of the hard coat layer cause an error that makes information recording and reproduction impossible. In particular, when the transparent layer that transmits laser light is as thin as 0.1 mm, the influence of dirt attached to the transparent layer becomes significant.
JP 2000-285520 A JP 2000-67468 A Japanese Patent No. 311467

  In view of the above, an object of the present invention is to solve the above conventional problems. That is, an object of the present invention is to provide an optical information recording medium that can prevent dust and dirt from adhering to the surface of a hard coat layer and can stably record and reproduce information.

As a result of intensive studies to solve the above problems, the present inventors have found that the problems can be solved by the present invention described below.
That is, the present invention is an optical information recording medium in which a recording layer, a light transmission layer, and a hard coat layer are provided on a substrate,
A ratio of F peak intensity to C peak intensity when the hard coat layer surface is measured by X-ray photoelectron spectroscopy (F / C) _surface is 0.01 to 1.0. An optical information recording medium.

After measuring the (F / C) _surface by X-ray photoelectron spectroscopy, the peak intensity of F on the hard coat layer surface after sputter etching (12 keV) with Ar ⁺ ion beam for 5 to 500 seconds, Ratio to peak intensity (F / C) _Ar is preferably 1/20 or more of (F / C) _surface .
Moreover, it is preferable that F content in the additive contained in a hard-coat layer is 30-60 mass%.

  In the optical information recording medium of the present invention, dust and dirt are hardly attached to the surface of the hard coat layer, and stable information recording / reproduction can be realized.

In the optical information recording medium of the present invention, the recording layer, the light transmission layer, and the hard coat layer on the substrate have an F peak intensity and a C peak intensity when the surface of the hard coat layer is measured by X-ray photoelectron spectroscopy. (F / C) The _surface ratio is 0.01 to 1.0.

  F present in the hard coat layer is caused by F contained in the additive. That is, the inclusion of F-containing additive in the hard coat layer makes it difficult for dust and dirt to adhere to the surface of the optical information recording medium.

In addition, by controlling the ratio of F on the surface of the hard coat layer, not only the antifouling property but also the surface hardness can be improved. Specifically, the ratio of F peak intensity to C peak intensity when the surface is measured by X-ray photoelectron spectroscopy (F / C) _surface is 0.01 to 1.0. (F / C) If the _surface is less than 0.01, the amount of F on the surface is reduced, so that sufficient antifouling properties cannot be obtained. On the other hand, if the (F / C) _surface exceeds 1.0, the surface of the hard coat layer is plasticized and the surface hardness is lowered.
(F / C) _surface is preferably 0.03 to 0.5, and more preferably 0.05 to 0.1.

(F / C) In order to set the _surface to 0.01 to 1.0, for example, the F content in the additive described later is set to 30 to 60% by mass, and the additive content in the hard coat layer is set to 0.00. What is necessary is just to set it as 5-10 mass%.

  As the solvent for forming the hard coat layer, a solvent having a relatively low boiling point and high volatility may be used, or the temperature during drying may be adjusted to control the surface composition. In addition, after drying, as an annealing treatment, the surface fluorine content may be adjusted by leaving at 40 to 80 ° C. for a certain period of time. Further, the surface of the optical information recording medium may be wiped with a non-woven fabric such as Vilene (CV-685CP manufactured by Nippon Vilene).

In addition, after measuring the (F / C) _surface by X-ray photoelectron spectroscopy, the peak intensity of F on the surface of the hard coat layer after sputter etching (12 keV) with an Ar ⁺ ion beam for 5 to 500 seconds, Ratio of C to peak intensity (F / C) _Ar is preferably 1/20 or more of (F / C) _surface .
By setting the sputter etching (12 keV) for 5 to 500 seconds (preferably 40 to 50 seconds), a composition having a depth of about 1 to 100 nm from the hard coat layer surface can be confirmed. (F / C) When _Ar is 1/20 or more of the above (F / C) _surface , the effect of maintaining the antifouling effect and eliminating the surface repellency of the additive is exhibited. The (F / C) _Ar is preferably 1/10 or more of the above (F / C) _surface .

In order to set the (F / C) _Ar as described above to 1/20 or more of the above (F / C) _surface , the additive used is a radiation-curable functional group in the same manner as the resin used for the hard coat layer. It is only necessary to provide a group, or to have a substituent having the same structure in the resin and additive used in the hard coat layer to improve the affinity with the resin.

Measurement of (F / C) _Ar and (F / C) _surface by X-ray photoelectron spectroscopy (ESCA) can be performed using, for example, ESCA-3400 manufactured by Shimadzu Corporation under the following conditions. .
(1) Irradiation X-ray: Monochrome Al / Kα, 12 kV, 10 mA
(2) Measurement spectrum: C 1s peak, F 1s peak (3) Vacuum degree in sample chamber: 1 × 10 ⁻⁸ Torr
(4) Ar ⁺ ion beam output and time for sputter etching: 12 keV), 5 to 500 seconds

The hard coat layer is formed by applying and curing an additive-containing hard coat layer coating solution on the light transmission layer of the optical information recording medium or on the substrate on which the recording layer or the like is not formed.
The additive-containing hard coat layer coating solution includes at least a curable composition for forming a hard coat layer, and a curable resin (for example, an antifouling agent) containing a fluorine atom (F) and having a group capable of polymerization. And can be prepared by mixing. The curing method may be active energy ray polymerization or thermal polymerization, but active energy ray polymerization is preferred from the viewpoint of productivity.

Hereinafter, the details of the hard coat layer will be described.
The pencil hardness on the surface of the hard cord layer is preferably B or more, more preferably H or more, and further preferably 3H or more.
Furthermore, the contact angle with respect to water on the surface is preferably 90 ° or more, more preferably 97 ° or more, from the viewpoint of antifouling properties. Moreover, as an upper limit, 150 degree | times is preferable and 130 degree | times is more preferable.

The curable resin as an additive containing a fluorine atom and having a group that is polymerized by active energy rays (for example, radiation) has a known fluorine-curable resin that is polymerized by active energy rays and a skeleton containing fluorine atoms. A curable resin (for example, a compound used in Examples) is used. From the viewpoint of further improving the antifouling property, a silicon curable resin or a curable resin having a skeleton containing a silicon atom may be used in combination.
Furthermore, an active energy ray polymerizable resin having a skeleton having a good compatibility with the cured resin mainly constituting the hard coat layer or a metal oxide dispersed in the resin, and a skeleton containing a fluorine atom is preferable.
By curing such a curable resin, fluorine can be present on the surface of the hard coat layer.

  Specific examples of the curable resin as an additive used in the hard coat layer include a monomer containing a fluorine atom, a copolymer of a monomer containing a fluorine atom, a block copolymer, or a graft copolymer. Examples thereof include polymers in which an acrylic group is incorporated into the coalescence. Moreover, when using together the cured resin containing silicon, the monomer containing silicon can be used like the case of the said fluorine.

  As an arbitrary silicon-containing monomer, a monomer having a siloxane group by a reaction such as polydimethylsiloxane and (meth) acrylic acid may be mentioned. Specific examples of the terminal (meth) acrylate siloxane compound include X-22-164A, X-22-164B, X-22-164C, X-22-2404, X-22-174D, X-22-8201, X-22-2426 (manufactured by Shin-Etsu Chemical Co., Ltd.), UMS182 (manufactured by Chisso Corporation), and the like.

  Examples of fluorine-containing monomers include perfluoroalkyl group-containing (meth) acrylic acid esters represented by hexafluoroisopropyl acrylate, heptade force fluorodecyl acrylate, perfluoroalkylsulfonamidoethyl acrylate, perfluoroalkylamidoethyl acrylate, and the like. Can be mentioned.

  Specifically, acrylate compounds such as 2-perfluorooctylethyl methacrylate, 2-perfluorooctylethyl acrylate (manufactured by Nippon Mektron Co., Ltd.), M-3633, M-3833, R-3633, R-3833 and the like ( Contains polymerizable groups such as Daikin Fine Chemical Laboratory Co., Ltd., AFC-1000, AFC-2000, FA-16, etc. (manufactured by Kyoeisha Chemical Co., Ltd.), MegaFuck 531A (manufactured by Dainippon Ink Co., Ltd.) The compound to be mentioned is mentioned.

  As the copolymer containing fluorine, there is a copolymer having a main chain composed only of carbon atoms and a fluorine-containing vinyl monomer polymer unit and a polymer unit having a (meth) acryloyl group in the side chain. Specific examples include a copolymer represented by the following general formula (1).

  In general formula (1), Mf represents a fluorine-containing vinyl monomer, L represents a linking group having 1 to 10 carbon atoms, and m represents 0 or 1. X represents a hydrogen atom or a methyl group. A represents a polymerization unit of any vinyl monomer, and may be a single component or a plurality of components. x ′, y, and z represent the mol% of each constituent component, and represent values satisfying 30 ≦ x ′ ≦ 60, 40 ≦ y ≦ 80, and 0 ≦ z ≦ 65.

  As the fluorine-containing vinyl monomer represented by Mf in the general formula (1), fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, etc.), partially (meth) acrylic acid or completely fluorinated Alkyl ester derivatives (for example, Biscoat 6FM (trade name, manufactured by Osaka Organic Chemical Co., Ltd.) and M-2020 (trade name, manufactured by Daikin)), perfluoroalkylsulfonic acid methacrylamide, fully or partially fluorinated vinylethyls and the like can be mentioned. However, perfluoroolefins are preferred, and hexafluoropropylene is particularly preferred from the viewpoints of solubility, transparency, availability, and the like.

  The copolymer has a polymer unit having a (meth) acryloyl group in the side chain as an essential component. The method for introducing the (meth) acryloyl group into the copolymer is not particularly limited. For example, (1) after synthesizing a polymer having a nucleophilic group such as a hydroxyl group or an amino group, (meth) acrylic acid is used. A method in which chloride, (meth) acrylic anhydride, (meth) acrylic acid and methanesulfonic acid mixed acid anhydride, etc. are allowed to act; (2) the polymer having the nucleophilic group in the presence of a catalyst such as sulfuric acid ( (3) a method of allowing a methacrylic acid to act, (3) a method of causing a compound having both an isocyanate group such as methacryloyloxypropyl isocyanate and a (meth) acryloyl group to act on the polymer having the nucleophilic group, and (4) a polymer having an epoxy group. (5) A method in which (meth) acrylic acid is allowed to act after the synthesis of (5) a polymer having a carboxyl group, Method of reacting a compound having both a carboxy group and a (meth) acryloyl group, and a method of performing dehydrochlorination after obtained by polymerizing a vinyl monomer having a (6) 3-chloropropionic acid ester moiety. Among these, it is preferable to introduce a (meth) acryloyl group by the method (1) or (2) with respect to a polymer containing a hydroxyl group.

  If the composition ratio of these (meth) acryloyl group-containing polymer units is increased, the film strength will be improved, and depending on the type of the fluorine-containing vinyl monomer polymer units, generally the (meth) acryloyl group-containing polymer units are 40 to 80 mol%. Preferably 45 to 75 mol%, more preferably 50 to 70 mol%.

  Useful copolymers contain any vinyl monomer unit represented by A in the general formula (1) in addition to the above-mentioned fluorine-containing vinyl monomer polymer units and polymer units having a (meth) acryloyl group in the side chain. Vinyl monomer is selected from various viewpoints such as adhesion to film, adjustment of polymer Tg (contributes to film hardness), solubility in solvent, transparency, slipperiness, dustproof / antifouling property, etc. These vinyl monomers can also be copolymerized. A plurality of these vinyl monomers may be combined depending on the purpose, and are preferably introduced in the range of 0 to 65 mol% in the copolymer in total, and in the range of 0 to 40 mol%. More preferably, it is particularly preferably in the range of 0 to 30 mol%.

The vinyl monomer unit that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, ethyl acrylate, butyl acrylate, acrylic) 2-ethylhexyl acid, 2-hydroxyethyl acrylate, glycidyl acrylate, allyl acrylate, trimethoxysilylpropyl acrylate, etc.), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid) 2-ethylhexyl, 2-hydroxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate, trimethoxysilylpropyl methacrylate, etc.), styrene derivatives (styrene, p-hydroxymethylstyrene, p-methoxystyrene) Vinyl ethers (methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether, allyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate) , Vinyl butyrate, vinyl cinnamate, etc.), unsaturated rubonic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.), acrylamides (N, N-dimethylacrylamide, N-tertbutylacrylamide, N -Cyclohexyl acrylamide etc.), methacrylamides (N, N-dimethylmethacrylamide), acrylonitrile and the like.
Preferred are vinyl ethyl derivatives and vinyl ester derivatives, and particularly preferred are vinyl ethyl derivatives.

In the general formula (1), L represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, particularly preferably a linking group having 2 to 4 carbon atoms, which is linear. Alternatively, it may have a branched structure, may have a ring structure, and may have a heteroatom selected from O, N, and S.
Preferred ^{_{examples, * - (CH 2) 2}} -O- **, * - (CH 2) 2 -NH- **, * - (CH 2) 4 -O- **, * - (CH 2) ^{_{6 -O- **, * - (CH}} 2) 2 -O- (CH 2) 2 -O- **, -CONH- (CH 2) 3 -O- **, * -CH 2 CH (OH) CH ₂ —O— ^* , ^* —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — ^** (“ ^* ” represents a connecting portion on the polymer main chain side, and “ ^** ” represents the (meth) acryloyl group side. For example). m represents 0 or 1;

  In general formula (1), X represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, a hydrogen atom is more preferable.

  x ′, y, and z represent mol% of each constituent component, and represent values satisfying 30 ≦ x ′ ≦ 60, 40 ≦ y ≦ 80, and 0 ≦ z ≦ 65. Preferably, 35 ≦ x ′ ≦ 55, 30 ≦ y ≦ 60, 0 ≦ z ≦ 20, particularly preferably 40 ≦ x ′ ≦ 55, 50 ≦ y ≦ 70, 0 ≦ z ≦ 10. is there.

  A group that is polymerized by irradiation with active energy rays is imparted, for example, by introducing a radical polymerizable double bond such as an acrylic group or a cationic polymerizable group such as an epoxy group. The content of fluorine, silicon and the compound having an active energy ray polymerizable group contained in these curable compositions is preferably 0.001 to 0.2% by mass of the total curable resin, and 0.005 to 0.15% by mass. % Is more preferable.

In order for the hard coat layer to have excellent scratch resistance, it is preferable that the hardness of the hard coat layer is large to some extent. From the viewpoint of hardness, the surface elastic modulus of the hard coat layer is preferably about 4.0 GPa or more, more preferably 4.5 GPa or more. When the surface elastic modulus is 4.0 GPa or more, sufficient pencil hardness and scratch resistance can be obtained. When the surface elastic modulus is expressed in universal hardness, the value is preferably about 250 N / mm ² or more, and more preferably 300 N / mm ² or more.

  The surface elastic modulus can be increased by adding inorganic fine particles. When the amount of inorganic fine particles added is increased, the brittleness deteriorates, so the upper limit of the surface elastic modulus is 10 GPa, preferably 9.0 GPa. Therefore, the preferable range of the surface elastic modulus is 4.0 to 10 GPa, and particularly preferably 4.5 to 9.0 GPa.

The surface elastic modulus is a value determined using a micro surface hardness tester (manufactured by Fischer Instruments: Fischer Scope H100VP-HCU). Specifically, using a diamond pyramid indenter (tip-to-face angle: 136 °), the indentation depth is measured under an appropriate test load within a range where the indentation depth does not exceed 1 μm. This is the elastic modulus obtained from the change in load and displacement over time.
Further, the surface hardness can be obtained as a universal hardness by using the above-mentioned micro surface hardness tester. The universal hardness is a value obtained by measuring the indentation depth of a quadrangular pyramid indenter under a test load and dividing the test load by the surface area of the indent calculated from the geometric shape of the indent generated by the test load.
It is known that there is a positive correlation between the surface elastic modulus and the universal hardness.

  The thickness of the hard coat layer is preferably 0.1 μm or more, and more preferably 1 μm or more. If the thickness of the hard coat layer is too thick, the pencil hardness is improved, but it becomes difficult to bend the film, and cracks due to bending tend to occur. Therefore, the thickness of the hard coat layer is preferably 20 μm or less, preferably 10 μm or less. More preferred. Therefore, the thickness of the hard coat layer is preferably 0.1 to 20 μm, more preferably 1 to 10 μm.

  The hard coat layer may be composed of a single layer or a plurality of layers, but is preferably a single layer that is simple in the production process. In this case, the single layer refers to a hard coat layer formed by curing from the same curable composition. If the composition after application and drying is the same composition, it is cured after being applied multiple times. It may be formed. On the other hand, the term “multiple layers” refers to layers that are cured and formed from a plurality of curable compositions having different compositions.

The hard coat layer is formed by applying a curable composition that is cured by irradiation with active energy rays and then curing by irradiation with active energy rays. The cure shrinkage ratio of the curable composition by irradiation with active energy rays is 0 to 15%, preferably 0 to 13%, more preferably 0 to 11%.
The curing shrinkage rate is obtained by calculating the density of the curable composition before irradiation with the active energy ray used, for example, UV light, and the density of the curable composition after irradiation curing, and calculating from the values by the following formula A. Value. The density is a value measured (25 ° C.) with MULTIVOLUME PYCNOMETER manufactured by Micrometric.

  Formula A: Volume shrinkage (%) = {1− (density before curing / density after curing)} × 100

  Unlike the curable resin as the additive, the curable composition for forming the hard coat layer avoids confusion with the curable resin that cures by active energy rays or heat (hereinafter referred to as additive). Therefore, it is called “cured resin”) as a main component. A curable composition for forming a hard coat layer (hereinafter, also simply referred to as “curable composition”) includes a cured resin having a ring-opening polymerizable group and / or an ethylenically unsaturated group as the cured resin. It is preferable to contain a cured resin having 3 or more in the same molecule, and it is more preferred to contain both of these two kinds of cured resins. As a result, the surface hardness of the hard coat layer is increased, and a hard coat film having excellent scratch resistance can be obtained. At the same time, the volume shrinkage rate satisfies the above-described range, curling after curing is reduced, and cracks during handling are less likely to occur. Furthermore, the above-described effect becomes more remarkable by setting the hard coat layer to a certain thickness.

Hereinafter, a cured resin containing a ring-opening polymerizable group that is preferably used will be described.
The cured resin containing a ring-opening polymerizable group is a cured resin having a ring structure in which ring-opening polymerization proceeds by the action of a cation, an anion, a radical, etc. Among them, a heterocyclic group-containing cured resin is preferable. Examples of such cured resins include epoxy derivatives, oxetane derivatives, tetrahydrofuran derivatives, cyclic lactone derivatives, cyclic carbonate derivatives, cyclic iminoethyls such as oxazoline derivatives, and the like, and epoxy derivatives, oxetane derivatives, and oxazoline derivatives are particularly preferable.

  The cured resin having a ring-opening polymerizable group preferably has two or more ring-opening polymerizable groups in the same molecule, more preferably three or more. In the present invention, two or more kinds of cured resins having a ring-opening polymerizable group may be used in combination. In this case, a cured resin having one ring-opening polymerizable group in the same molecule may be combined with a cured resin having two or more ring-opening polymerizable groups in the same molecule, or ring-opening polymerization in the same molecule. You may combine 2 or more types only of cured resin which has two or more sex groups.

  Here, the cured resin having a ring-opening polymerizable group is not particularly limited as long as it is a cured resin having a cyclic structure as described above. Preferred examples of such a cured resin include monofunctional glycidyl ethers, monofunctional alicyclic epoxies, bifunctional alicyclic epoxies, diglycidyl ethers (for example, glycidyl ethers such as ethylene glycol diglycidyl ether, bisphenol). A diglycidyl ether), trifunctional or higher glycidyl ethers (trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ethyl, glycerol triglycidyl ether, tris (glycidyloxyethyl) isocyanurate, etc.), tetrafunctional or higher glycidyl ether (Sorbitol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, polyglycidyl ether of cresol novolac resin, polyglycidyl ether of phenol novolac resin) Cydyl ether, etc.), cycloaliphatic epoxies (Celoxide 2021P, Celoxide 2081, Epolide GT-301, Epolide GT-401 (above, Daicel Chemical Industries, Ltd.), EHPE (Daicel Chemical Industries, Ltd.), Phenol novolak resin polycyclohexyl epoxy methyl ether, etc.), oxetanes (OX-SQ, PNOX-1009 (manufactured by Toagosei Co., Ltd.), etc.) and the like, but the present invention is limited to these. is not.

  It is particularly preferable that the cured resin having a ring-opening polymerizable group contains a crosslinkable polymer containing a repeating unit represented by the following general formula (2). These crosslinkable polymers are described in detail below.

In the general formula (2), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group.
L ¹ is a single bond or a divalent or higher-valent linking group, preferably a single bond, —O—, an alkylene group, an arylene group, and a main chain on the “*” side, * —COO—, * —CONH -, * -OCO-, * -NHCO-.
P ¹ is a monovalent ring-opening polymerizable group or a monovalent group having a ring-opening polymerizable group. Preferred examples of P ¹ include an epoxy ring, an oxetane ring, a tetrahydrofuran ring, a lactone ring, a carbonate ring, and an oxapurine ring. And monovalent groups having an iminoethyl ring, and the like. Among these, a monovalent group having an epoxy ring, an oxetane ring, or an oxazoline ring is particularly preferable.

The crosslinkable polymer containing the repeating unit represented by the general formula (2) is preferably synthesized by polymerizing a corresponding monomer. In this case, radical polymerization is the simplest and preferable as the polymerization reaction.
Although the preferable specific example of the repeating unit represented by General formula (2) below is shown, this invention is not limited to these.

  In the present invention, the crosslinkable polymer containing the repeating unit represented by the general formula (2) may be a copolymer composed of a plurality of repeating units represented by the general formula (2). A copolymer containing a repeating unit other than (2) (for example, a repeating unit not containing a ring-opening polymerizable group) may be used. Particularly suitable is a method of controlling the Tg or hydrophilicity / hydrophobicity of the crosslinkable polymer or a copolymer containing a repeating unit other than the general formula (2) for the purpose of controlling the content of the ring-opening polymerizable group of the crosslinkable polymer. It is. As a method for introducing the repeating unit other than the general formula (2), a method of introducing the corresponding monomer by copolymerization is preferable.

  When the repeating unit other than the general formula (2) is introduced by polymerizing the corresponding vinyl monomer, the monomer preferably used is derived from acrylic acid or α-alkylacrylic acid (for example, methacrylic acid). Esters (eg, methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, n-propyl acrylate, 1-propyl acrylate, 2-hydroxypropyl acrylate, 2-methyl-2-nitropropyl acrylate, n-butyl acrylate, i-butyl Acrylate, t-butyl acrylate, t-pentyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-methoxymethoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate Over DOO, 2,2-dimethylbutyl acrylate,

  3-methoxybutyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, n-pentyl acrylate, 3-pentyl acrylate, octafluoropentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, cyclopentyl acrylate, cetyl acrylate, benzyl acrylate, n-octyl Acrylate, 2-ethylhexyl acrylate, 4-methyl-2-propylpentyl acrylate, heptade force fluorodecyl acrylate, n-octadecyl acrylate, methyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl Methacrylate, hydroxyethyl methacrylate, 2-hydroxy Propyl methacrylate, n- butyl methacrylate,

1-butyl methacrylate, sec-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, benzyl methacrylate, heptade force fluorodecyl methacrylate, n-octadecyl methacrylate, 2-isobol Nyl methacrylate, 2-norbornylmethyl methacrylate, 5-norbornen-2-ylmethyl methacrylate, 3-methyl-2-norbornylmethyl methacrylate, dimethylaminoethyl methacrylate),

Amides derived from acrylic acid or α-alkylacrylic acid (for example, methacrylic acid) (for example, Ni-propylacrylamide, Nn-butylacrylamide, Nt-butylacrylamide, N, N-dimethyl) Acrylamide, N-methylmethacrylamide, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, acrylamidopropyltrimethylammonium chloride, methacrylamide, diacetone acrylamide, acryloylmorpholine, N-methylolacrylamide, N-methylolmethacrylamide), acrylic S derived from acids or α-alkyl acrylic acids (acrylic acid, methacrylic acid, itaconic acid, etc.), vinyl esters (eg vinyl acetate), maleic acid or fumaric acid Tellurium (dimethyl maleate, dibutyl maleate, diethyl fumarate, etc.), maleimide (N-phenylmaleimide, etc.), maleic acid, fumaric acid, sodium salt of p-styrenesulfonic acid, acrylonitrile, methacrylonitrile, dienes (For example, butadiene, cyclopentadiene, isoprene), aromatic vinyl compounds (for example, styrene, p-chlorostyrene, t-butylstyrene, α-methylstyrene, sodium styrenesulfonate), N-vinylpyrrolidone, N-vinyloxazolidone, N -Vinyl succinimide, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, 1-vinylimidazole, 4-vinylpyridine, vinylsulfonic acid, vinyl Sodium sulfonic acid, sodium allyl sulfonate, sodium methallyl sulfonate, vinylidene chloride, vinyl alkyl ethyl ethers (e.g. methyl vinyl ethyl), ethylene, propylene, 1-butene, isobutene and the like.

Two or more of these vinyl monomers may be used in combination. Vinyl monomers other than these are listed in Research Disclosure No. Those described in 19551 (1980, July) can be used.
Of these, esters and amides derived from acrylic acid or methacrylic acid, and aromatic vinyl compounds are particularly preferably used.

  As the repeating unit other than the general formula (2), a repeating unit having a reactive group other than the ring-opening polymerizable group can also be introduced. In particular, if you want to increase the hardness of the hard coat layer, or if you want to improve the adhesion between layers when using another functional layer on the hard coat layer, it is a copolymer containing a reactive group other than the ring-opening polymerizable group The technique is preferred. As a method for introducing a repeating unit having a reactive group other than the ring-opening polymerizable group, a method of copolymerizing a corresponding vinyl monomer (hereinafter referred to as a reactive monomer) is simple and preferable.

  Although the preferable specific example of a reactive monomer is shown below, this invention is not limited to these.

  Hydroxyl group-containing vinyl monomers (eg, hydroxyethyl acrylate, hydroxyethyl methacrylate, allyl alcohol, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc.), isocyanate group-containing vinyl monomers (eg, isocyanatoethyl acrylate, isocyanatoethyl methacrylate, etc.), N -Methylol group-containing vinyl monomers (for example, N-methylol acrylamide, N-methylol methacrylamide, etc.), carboxyl group-containing vinyl monomers (for example, acrylic acid, methacrylic acid, itaconic acid, carboxyethyl acrylate, vinyl benzoate), alkyl halides Vinyl monomers (eg chloromethylstyrene, 2-hydroxy-3-chloropropyl methacrylate), acids Water-containing vinyl monomers (eg maleic anhydride), formyl group-containing vinyl monomers (eg acrolein, methacrolein), sulfinic acid group-containing vinyl monomers (eg potassium styrenesulfinate), active methylene-containing vinyl monomers (eg acetoacetoxyethyl) Methacrylate), acid chloride-containing monomers (eg acrylic acid chloride, methacrylic acid chloride), amino group-containing monomers (eg allylamine), alkoxysilyl group-containing monomers (eg methacryloyloxypropyltrimethoxysilane, acryloyloxypropyltrimethoxysilane), etc. Can be mentioned.

  In the crosslinkable polymer containing the repeating unit represented by the general formula (2), the proportion of the repeating unit represented by the general formula (2) is 1% by mass or more and 100% by mass or less, preferably 30% by mass or more. It is 100 mass% or less, Most preferably, it is 50 mass% or more and 100 mass% or less.

  The range of the preferable number weight average molecular weight (measured by gel permeation chromatography, converted to polyethylene glycol) of the crosslinkable polymer containing the repeating unit represented by the general formula (2) is 1,000 to 1,000,000, more preferably 3000. More than 200,000. Most preferably, it is 5000 or more and 100,000 or less.

  Although the preferable example of the crosslinkable polymer containing the repeating unit represented by General formula (2) below is shown in Table 1, this invention is not limited to these. In addition, the repeating unit represented by the general formula (2) mentioned above with the specific example is represented by the number of the specific example given above, and the repeating unit derived from the copolymerizable monomer describes the monomer name. The copolymer composition ratio is indicated by mass%.

As described above, the curable composition that is cured by the active energy ray for forming the hard coat layer has three or more cured resins containing a ring-opening polymerizable group and ethylenically unsaturated groups in the same molecule. It is preferable to contain both the hardening resin to contain.
Hereinafter, the cured resin containing three or more ethylenically unsaturated groups in the same molecule will be described in detail.

Preferred types of ethylenically unsaturated groups are acryloyl group, methacryloyl group, styryl group and vinylethyl group, particularly preferably acryloyl group.
A cured resin (monomer or oligomer) containing one or two ethylenically unsaturated groups may be used in combination with a cured resin containing three or more ethylenically unsaturated groups in the same molecule.
In addition, polyfunctional acrylate monomers having 3-6 acrylate groups in the molecule, and several hundred molecular weights having several acrylate groups in the molecule called urethane acrylate, polyester acrylate, epoxy acrylate. To several thousand oligomers can be preferably used as the cured resin.

  Specific examples of the cured resin having three or more acrylic groups in the same molecule include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Examples thereof include polyol polyacrylates such as dipentaerythritol hexaacrylate, urethane acrylates obtained by the reaction of polyisocyanate salt and hydroxyl group-containing acrylates such as hydroxyethyl acrylate.

  Moreover, the crosslinkable polymer containing the repeating unit represented by following General formula (3) can also be preferably used as a cured resin which has three or more ethylenically unsaturated groups in the same molecule. Hereinafter, the crosslinkable polymer containing the repeating unit represented by the general formula (3) will be described in detail.

In the general formula (3), R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group.
P ² represents a monovalent ethylenically unsaturated group or a monovalent group having an ethylenically unsaturated group.
L ² represents a single bond or a divalent or higher valent linking group, preferably a single bond, —O—, an alkylene group, an arylene group, and * —COO—, * —CONH— which are connected to the main chain on the “*” side. , * -OCO-, * -NHCO-.
P ² is preferably an acryloyl group, a methacryloyl group, a styryl group or a monovalent group containing any of these groups, and most preferably an acryloyl group or a monovalent group containing the same.

The crosslinkable polymer containing the repeating unit represented by the general formula (3) may be synthesized by a method of (i) directly introducing an ethylenically unsaturated group by polymerizing a corresponding monomer, and (ii) You may synthesize | combine by the method of introduce | transducing an ethylenically unsaturated group into a polymer obtained by superposing | polymerizing the monomer which has a functional group by high molecular reaction. Moreover, it can also synthesize | combine combining the method of said (i) and (ii). Examples of the polymerization reaction include radical polymerization, cationic polymerization, and anionic polymerization.
When the method (i) is used, it is possible to utilize the difference in polymerizability between the ethylenically unsaturated group consumed by the polymerization reaction and the ethylenically unsaturated group remaining in the crosslinkable polymer. For example, when P ² in the general formula (3) is an acryloyl group, a methacryloyl group, or a monovalent group containing any one of these, the polymerization reaction for forming a crosslinkable polymer is referred to as cationic polymerization. The crosslinkable polymer of the present invention can be obtained by the method i). On the other hand, when P ² is a styryl group or a monovalent group containing a styryl group, gelation is likely to proceed by any of radical polymerization, cationic polymerization, and anionic polymerization. The crosslinkable polymer of the general formula (3) is synthesized by a technique.

Thus, the method using the polymer reaction of (ii) above is useful because it is possible to obtain a crosslinkable polymer regardless of the type of ethylenically unsaturated group introduced into the general formula (3). It is.
In the polymer reaction, (I) for example, after a polymer containing a functional group obtained by precuring an ethylenically unsaturated group that removes hydrochloric acid from a 2-chloroethyl group is generated, a functional group conversion (elimination reaction, (II) a method in which an ethylenically unsaturated group is derived by oxidation reaction, reduction reaction, etc.) and (II) after a polymer containing an arbitrary functional group is formed, a bond formation reaction proceeds with the functional group in the polymer. The method of reacting the reactive monomer which has both the functional group which can produce | generate a covalent bond, and an ethylenically unsaturated group is mentioned. These methods (I) and (II) may be performed in combination.

  The bond formation reaction referred to here can be used without particular limitation as long as it is a reaction that forms a covalent bond in the bond formation reaction generally used in the field of organic synthesis. On the other hand, since the ethylenically unsaturated group contained in the crosslinkable polymer may be thermally polymerized and gelled during the reaction, the reaction proceeds at the lowest possible temperature (preferably 60 ° C. or less, particularly preferably room temperature or less). Those that do are preferred. A catalyst may be used for the purpose of promoting the progress of the reaction, and a polymerization inhibitor may be used for the purpose of suppressing gelation.

  Although the example of the combination of the functional group in which a preferable polymer bond formation reaction advances below is given, this invention is not limited to these.

As a combination of functional groups that the reaction proceeds at heating or room temperature,
(I) With respect to the hydroxyl group, epoxy group, isocyanate group, N-methylol group, carboxyl group, alkyl halide, acid anhydride, acid chloride, active ester group (for example, sulfate ester), formyl group, acetal group,
(B) Isocyanate group, hydroxyl group, mercapto group, amino group, carboxyl group, N-methylol group,
(C) With respect to the carboxyl group, an epoxy group, an isocyanate group, an amino group, an N-methylol group,
(D) N-methylol group, isocyanate group, N-methylol group, carboxyl group, amino group, hydroxyl group,
(E) An epoxy group, a hydroxyl group, an amino group, a mercapto group, a carboxyl group, an N-methylol group,
(F) A sulfinic acid group, an amino group,
(Ii) hydroxyl group, mercapto group, active methylene group with respect to formyl group,
(H) Formyl group, vinyl group (allyl group, acrylic group, etc.), epoxy group, isocyanate group, N-methylol group, carboxyl group, alkyl halide, acid anhydride chloride, active ester group (for mercapto group) Eg sulfuric ester),
(Li) Amino group, formyl group, vinyl group (allyl group, acrylic group, etc.), epoxy group, isocyanate group, N-methylol group, carboxyl group, alkyl halide, acid anhydride, acid chloride, active ester group (For example, sulfate ester), and the like.

  Although the preferable specific example of a reactive monomer is shown below, this invention is not limited to these.

  Hydroxyl group-containing vinyl monomers (eg, hydroxyethyl acrylate, hydroxyethyl methacrylate, allyl alcohol, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc.), isocyanate group-containing vinyl monomers (eg, isocyanatoethyl acrylate, isocyanatoethyl methacrylate, etc.), N -Methylol group-containing vinyl monomers (for example, N-methylol acrylamide, N-methylol methacrylamide, etc.), epoxy group-containing vinyl monomers (for example, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ethyl, CYCLOMER-M100, A200 (Daicel Chemical Industries ( Etc.)), carboxyl group-containing vinyl monomers (eg acrylic acid, methacrylate) Acid, itaconic acid, carboxyethyl acrylate, vinyl benzoate), alkyl halide-containing vinyl monomers (eg, chloromethylstyrene, 2-hydroxy-3-chloropropyl methacrylate), acid anhydride-containing vinyl monomers (eg, maleic anhydride), Formyl group-containing vinyl monomer (for example, acrolein, methacrolein), sulfinic acid group-containing vinyl monomer (for example, potassium styrenesulfinate), active methylene-containing vinyl monomer (for example, acetoacetoxyethyl methacrylate), vinyl group-containing vinyl monomer (for example, allyl methacrylate, Allyl acrylate), acid chloride-containing monomers (for example, acrylic acid chloride, methacrylic acid chloride), amino group-containing monomers (for example, allylamine), and the like. It is.

The polymer containing any functional group described in (II) above can be obtained by polymerizing a reactive monomer having both a reactive functional group and an ethylenically unsaturated group. Moreover, it can also obtain by performing functional group conversion after superposition | polymerization of a precursor monomer with low reactivity like polyvinyl alcohol obtained by modify | denaturating polyvinyl acetate.
As a polymerization method in these cases, radical polymerization is the simplest and preferable.

  Although the preferable specific example of the repeating unit represented by General formula (3) below is shown, this invention is not limited to these.

  The crosslinkable polymer containing the repeating unit represented by the general formula (3) may be a copolymer composed of a plurality of types of repeating units represented by the general formula (3), and other than the general formula (3). The copolymer containing the repeating unit (for example, the repeating unit which does not contain an ethylenically unsaturated group) may be sufficient. In particular, it is preferable to control the Tg or hydrophilicity / hydrophobicity of the crosslinkable polymer, or to prepare a copolymer containing a repeating unit other than the general formula (3) for the purpose of controlling the content of the ethylenically unsaturated group of the crosslinkable polymer. It is. As a method for introducing the repeating unit other than the general formula (3), (a) a method of directly introducing the corresponding monomer by copolymerization may be used, (b) a precursor monomer capable of functional group conversion is polymerized, A technique of introducing by polymer reaction may be used. Further, the methods (a) and (b) can be combined and introduced.

  In the case where the repeating unit other than the general formula (3) is introduced by polymerizing the corresponding vinyl monomer by the method of (a), as the monomer preferably used, in the description of the general formula (2), the general formula ( Examples of the monomer that is preferably used when a repeating unit other than 2) is introduced by polymerizing the corresponding vinyl monomer are the same as those mentioned above. Two or more of these vinyl monomers may be used in combination. Vinyl monomers other than these are listed in Research Disclosure No. Those described in 19551 (1980, July) can be used. Of these, esters and amides derived from acrylic acid or methacrylic acid, and aromatic vinyl compounds are particularly preferably used.

  In addition, when the repeating unit represented by the general formula (3) is introduced by a polymer reaction as in the above (ii) and the reaction is not completed, a functional group or a reactive functional group obtained by precursorizing an ethylenically unsaturated group In the present invention, this can be used without particular limitation.

  Most of the repeating units that do not contain ethylenically unsaturated groups derived from the vinyl monomers listed above can be introduced by polymerizing the above-mentioned (b) functional group-convertable precursor monomers and polymerizing them. It is. On the other hand, the crosslinkable polymer containing the repeating unit represented by the general formula (3) in the present invention may contain a repeating unit other than the general formula (3) that can be introduced only by a polymer reaction. Typical examples include polyvinyl alcohol obtained by modifying polyvinyl acetate, polyvinyl butyral obtained by acetalization reaction of polyvinyl alcohol, and the like. Specific examples of these repeating units are shown below, but the present invention is not limited thereto.

  In the crosslinkable polymer containing the repeating unit represented by the general formula (3), the proportion of the repeating unit represented by the general formula (3) is 1% by mass or more and 100% by mass or less, preferably 30% by mass or more. It is 100 mass% or less, Most preferably, it is 50 mass% or more and 100 mass% or less.

  The range of the preferable number average molecular weight (measured by gel permeation chromatography, converted to polyethylene glycol) of the crosslinkable polymer containing the repeating unit represented by the general formula (3) is 1,000 or more and 1,000,000 or less, more preferably 3000 or more. 200,000 or less. Most preferably, it is 5000 or more and 100,000 or less.

  Although the preferable example of the crosslinkable polymer containing the repeating unit represented by General formula (3) below is shown in Table 2, this invention is not limited to this. In addition, the repeating unit represented by the general formula (3) and the repeating unit such as polyvinyl alcohol described above with specific examples are represented by the numbers of the specific examples given above, and the repeating unit derived from a copolymerizable monomer. Indicates the name of the monomer and the copolymer composition ratio in mass%.

  Examples of the cured resin having a ring-opening polymerizable group that can be used in the present invention also include polymers containing both repeating units represented by the general formulas (2) and (3). In this case, preferred repeating units of the general formulas (2) and (3) are the same as those described above. Further, even a copolymer containing a repeating unit other than the general formulas (2) and (3) is a copolymer containing a repeating unit having a reactive group other than an ethylenically unsaturated group and a ring-opening polymerizable group. Also good.

  In the crosslinkable polymer containing both repeating units represented by the general formulas (2) and (3), the proportion of the repeating unit represented by the general formula (2) is 1% by mass or more and 99% by mass or less, Preferably they are 20 mass% or more and 80 mass% or less, Most preferably, they are 30 mass% or more and 70 mass% or less, and the ratio in which the repeating unit represented by General formula (3) is contained is 1 mass% or more and 99 mass% or less. The content is preferably 20% by mass or more and 80% by mass or less, and particularly preferably 30% by mass or more and 70% by mass or less.

  The range of the preferable weight average molecular weight (measurement by gel permeation chromatography, polystyrene conversion value) of the crosslinkable polymer containing both repeating units represented by the general formulas (2) and (3) is 1,000 to 1,000,000. More preferably, it is 3000 or more and 200,000 or less. Most preferably, it is 5000 or more and 100,000 or less.

  Although the preferable example of the crosslinkable polymer containing both the repeating units represented by General formula (2) and (3) is shown in following Table 3, this invention is not limited to these. It should be noted that the repeating units represented by the general formulas (2) and (3) given above as specific examples and the repeating units such as polyvinyl alcohol are represented by the numbers of the specific examples given above and are derived from a copolymerizable monomer. The repeating unit is described with the monomer name, and the copolymer composition ratio is indicated by mass%.

  A preferable mixing ratio of a cured resin containing three or more ethylenically unsaturated groups in the same molecule and a cured resin containing a ring-opening polymerizable group, preferably contained in the curable composition for forming the hard coat layer, The ratio of the cured resin containing an ethylenically unsaturated group is preferably 30% by mass or more and 90% by mass or less, more preferably 50%. The mass is 80% by mass or more.

  A curable composition containing a curable resin containing an ethylenically unsaturated group and a curable resin containing a ring-opening polymerizable group (hereinafter, unless otherwise specified, the “curable composition” includes both of these curable resins. When the composition is cured, it is preferable that the crosslinking reaction of both cured resins proceed. A preferable crosslinking reaction of the ethylenically unsaturated group is a radical polymerization reaction, and a preferable crosslinking reaction of the ring-opening polymerizable group is a cationic polymerization reaction. In either case, the polymerization reaction can be advanced by the action of active energy rays. Usually, a small amount of radical generator and cation generator (or acid generator) called polymerization initiators can be added and decomposed by active energy rays to generate radicals and cations to proceed the polymerization. . Although radical polymerization and cationic polymerization may be performed separately, it is preferable to proceed simultaneously.

When the curable composition is cured by irradiation with active energy rays, the crosslinking reaction often proceeds at a low temperature, which is preferable.
In the present invention, radiation, gamma rays, alpha rays, electron beams, ultraviolet rays and the like are used as active energy rays. Among them, a method of adding a polymerization initiator that generates radicals or cations using ultraviolet rays and curing with ultraviolet rays is particularly preferable. Further, there may be a case where curing can be further advanced by heating after irradiation with ultraviolet rays, and this method can be preferably used. A preferable heating temperature in this case is 140 ° C. or lower.

Examples of photoacid generators that generate cations by ultraviolet rays include ionic curable resins such as triarylsulfonium salts and diaryliodonium salts, and nonionic curable resins such as nitrobenzyl esters of sulfonic acids. Various known photoacid generators such as cured resins described in the study group, “Imaging Organic Materials” published by Bunshin Publishing Co., Ltd. (1997) can be used. Among these, a sulfonium salt or an iodonium salt is particularly preferable, and PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ^{− and the} like are preferable as a counter ion.

  Examples of polymerization initiators that generate radicals by ultraviolet rays include known radical generators such as acetophenones, benzophenones, Michler's ketone, benzoylbenzoate, benzoins, α-acyloxime esters, tetramethylthiuram monosulfide, and thioxanthone. Can be used. Further, as mentioned above, since sulfonium salts and iodonium salts that are usually used as photoacid generators also act as radical generators upon irradiation with ultraviolet rays, these may be used alone in the present invention. In addition to a polymerization initiator, a sensitizer may be used for the purpose of increasing sensitivity. Examples of the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, and thioxanthone derivatives.

  The polymerization initiators may be used in combination, or in the case of a cured resin that generates both radicals and cations alone, etc., one kind can be used alone. As addition amount of a polymerization initiator, it is 0.1-15 mass% with respect to the total mass of ethylenically unsaturated group containing cured resin and ring-opening polymerizable group containing cured resin contained in a curable composition. It is preferable to use it, and it is more preferable to use it in the range of 1 to 10% by mass.

When a crosslinkable polymer having a repeating unit represented by the general formula (2) or a crosslinkable polymer having a repeating unit represented by the general formula (3) is used, the polymer is usually a solid or a high-precision liquid. In the case where the polymer is water-soluble or in the form of an aqueous dispersion, it can be applied in an aqueous system, but is usually dissolved in an organic solvent and applied. Any organic solvent can be used without particular limitation as long as it can dissolve such a polymer.
Preferable organic solvents include ketones such as methyl ethyl ketone, alcohols such as isopropanol, esters such as ethyl acetate, and the like. In addition, when the above-mentioned monofunctional or polyfunctional vinyl monomer, or a cured resin having a monofunctional, bifunctional, or trifunctional or higher ring-opening polymerizable group is a low molecular weight curable resin, when these are used in combination, a curable composition It is possible to adjust the viscosity of the product, and it can be applied without using a solvent.

Moreover, you may add microparticles | fine-particles in a curable composition. By adding fine particles, the amount of curing shrinkage of the hard coat layer can be reduced, which is preferable because adhesion with a substrate or a light transmission layer (hereinafter sometimes referred to as “substrate or the like”) can be improved or curling can be reduced. As the fine particles, any of inorganic fine particles, organic fine particles, and organic / inorganic composite fine particles can be used. Examples of the inorganic fine particles include silicon dioxide particles, titanium dioxide particles, zirconium oxide particles, and aluminum oxide particles. Such inorganic fine particles are generally hard, and by filling the hard coat layer, not only the shrinkage during curing can be improved, but also the surface hardness can be increased.
However, since the fine particles generally tend to increase haze, the filling method is adjusted in view of the balance of each necessary characteristic.

In general, inorganic fine particles have a low affinity with organic components such as such polymers and polyfunctional vinyl monomers, so that they may form aggregates or crack the hard coat layer after curing by simply mixing them. Therefore, in order to increase the affinity between the inorganic fine particles and the organic component, the surface of the inorganic fine particles can be treated with a surface modifier containing an organic segment. The surface modifier preferably has a functional group capable of forming a bond with or adsorbing to the inorganic fine particles and a functional group having high affinity with the organic component in the same molecule.
Examples of the surface modifier having a functional group capable of binding or adsorbing to inorganic fine particles include metal alkoxide surface modifiers such as silane, aluminum, titanium, and zirconium, phosphate groups, sulfate groups, sulfonate groups, carboxylic acid groups, and the like. A surface modifier having an anionic group is preferred.
Furthermore, the functional group having a high affinity with the organic component may be simply a combination of the organic component and the hydrophilicity / hydrophobicity, but a functional group that can be chemically bonded to the organic component is preferable, particularly an ethylenically unsaturated group, Or a ring-opening polymerizable group is preferable.
A preferred inorganic fine particle surface modifier in the present invention is a cured resin having a metal alkoxide or an anionic group and an ethylenically unsaturated group or a ring-opening polymerizable group in the same molecule.

Representative examples of these surface modifiers include the following unsaturated double bond-containing coupling agents, phosphate group-containing organic curable resins, sulfate group-containing organic curable resins, carboxylic acid group-containing organic curable resins, and the like. It is done.
_{S-1: H 2 C =} C (X) COOC 3 H 6 Si (OCH 3) 3,
_{S-2: H 2 C =} C (X) COOC 2 H 4 OTi (OC 2 H 5) 3,
_{S-3: H 2 C =} C (X) COOC 2 H 4 OCOC 5 H 10 OPO (OH) 2,
S-4: (H ₂ C═C (X) COOC ₂ H ₄ OCOC ₅ H ₁₀ O) ₂ POOH,
_{S-5: H 2 C =} C (X) COOC 2 H 4 OSO 3 H,
_{S-6: H 2 C =} C (X) COO (C 5 H 10 COO) 2 H,
_{S-7: H 2 C =} C (X) COOC 5 H 10 COOH,
S-8: 3- (glycidyloxy) propyltrimethoxysilane,
Here, X represents a hydrogen atom or CH ₃ .

The surface modification of these inorganic fine particles is preferably performed in a solution. When inorganic fine particles are mechanically finely dispersed, a surface modifier is present together, or after finely dispersing inorganic fine particles, the surface modifier is added and stirred, or before the fine inorganic particles are finely dispersed. Alternatively, the surface may be modified (if necessary, heated, dried and then heated, or changed in pH), and then finely dispersed.
As the solution for dissolving the surface modifier, an organic solvent having a large polarity is preferable. Specific examples include known solvents such as alcohols, ketones and esters.

The organic fine particles are not particularly limited, but polymer particles composed of monomers having an ethylenically unsaturated group, such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, polyethylene, polypropylene, polystyrene Etc., and polymer particles comprising the general formulas (1) and (3) in the present invention are preferably used. Besides, polysiloxane, melamine resin, benzoguanamine resin, polytetrafluoroethylene, polycarbonate, nylon, polyvinyl alcohol, polytetra Examples thereof include resin particles such as fluoroethylene, polyethylene terephthalate, polyvinyl chloride, acetylcellulose, nitrocellulose, and gelatin. These particles are preferably crosslinked.
As the fine particle disperser, it is preferable to use ultrasonic waves, dispersers, homogenizers, dissolvers, polytrons, paint shakers, sand grinders, kneaders, Eiger mills, dyno mills, coball mills and the like. As the dispersion medium, the above-mentioned solvent for surface modification is preferably used.

  The filling amount of the fine particles is preferably 2 to 40% by volume, more preferably 3 to 25% by volume, and most preferably 5 to 15% by volume with respect to the volume of the hard coat layer after filling.

  The haze of the hard coat layer is preferably 1.5% or less, more preferably 1.2% or less, and most preferably 1.0% or less. The evaluation method of haze is a value automatically measured as haze = (diffuse light / total transmitted light) × 100 (%) measured using a turbidimeter “NDH-1001DP” manufactured by Nippon Denshoku Industries Co., Ltd. Using.

  The hard coat film preferably has a curl value expressed by the following formula B in the range of minus 15 to plus 15, more preferably in the range of minus 12 to plus 12, more preferably minus 10. ~ Plus 10. The measurement direction of the curl in the sample at this time is measured in the film transport direction in the case of application in the web form.

  (Formula B) Curl = 1 / R (R is radius of curvature (m))

This is an important characteristic for preventing cracks and peeling of the film in the manufacture, processing and market handling of hard coat films. It is preferable that the curl value is in the above range and the curl is small. It is possible to reduce the curl to a high surface hardness within the above range by setting the volume shrinkage ratio before and after curing of the curable composition for forming the hard coat layer to 15% or less.
The curl is measured by using the curl measurement template of Method A in “Measurement Method for Curling of Photo Film” of JIS K7619-1988. The measurement conditions are 25, relative humidity 60%, and humidity control time 10 hours.
Here, “curl plus” means a curl in which the hard coat layer coating side of the substrate or the like is inside the curve, and “minus” means a curl in which the coating side is outside the curve.
Further, the hard coat film has an absolute value of the difference between the curl values when only the relative humidity is changed to 80% and 10% based on the curl measurement method described above, preferably 24 to 0, and 15 to 0. More preferably, 8-0 is most preferable. This is a property related to handling, peeling and cracking when films are applied under various humidity conditions.

  The crack resistance of the hard coat film is preferably 50 mm or less, more preferably 40 mm or less, and most preferably 30 mm or less, when the hard coat layer is rolled with the coated side of the hard coat layer outside. preferable. About the crack of an edge part, it is preferable that there is no crack or the length of a crack is less than 1 mm on average. This crack resistance is an important characteristic for preventing crack defects during handling such as coating, processing, cutting, and sticking of a hard coat film.

  The active energy ray curable coating liquid (curing composition coating liquid) is prepared by dissolving the polyfunctional monomer and the polymerization initiator mainly in an organic solvent such as ketone, alcohol, or ester. Furthermore, it can be prepared by adding a surface-modified hard inorganic fine particle dispersion and a soft fine particle dispersion.

The hard coat layer is prepared by dipping the active energy ray curable coating solution on the film, spinner method, spray method, roll coater method, gravure method, wire bar method, slot extrusion coater method (single layer, multi-layer), slide It can be prepared by coating by a known thin film forming method such as a coater method, drying, irradiating with active energy rays and curing.
Drying is preferably performed under conditions where the organic solvent concentration in the applied liquid film is 5% by mass or less after drying, more preferably 2% by mass or less, and even more preferably 1% by mass or less. The drying conditions are affected by the thermal strength of the substrate and the like, the conveyance speed, and the length of the drying process. However, it is preferable that the content of the organic solvent is as low as possible in order to increase the polymerization rate.

Furthermore, for the purpose of improving the adhesion between the substrate or the like and the hard coat layer, one or both surfaces of the substrate or the like can be subjected to a surface treatment by an oxidation method, an unevenness method, or the like as desired. Examples of the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like.
Furthermore, one or more undercoat layers can be provided. Examples of the material for the undercoat layer include copolymers such as vinyl chloride, vinylidene chloride, butadiene, (meth) acrylic acid ester, and vinyl ester, or water-soluble polymers such as latex, low molecular weight polyester, and gelatin. Further, the undercoat layer may contain tin oxide, a metal oxide such as tin oxide / antimony oxide composite oxide, tin oxide / indium oxide composite oxide, or an antistatic agent such as a quaternary ammonium salt.

  The hard coat layer may have a multi-layer structure, and may be formed by appropriately stacking in the order of hardness.

  The type of the optical information recording medium of the present invention may be any of a read-only type, a write-once type, a rewritable type, etc., but is preferably a write-once type. The recording format is not particularly limited, such as a phase change type, a magneto-optical type, and a dye type, but is preferably a dye type.

  As an optical information recording medium of the present invention, the details and the light of the present invention will be described by taking as an example a structure having a reflective layer, a recording layer, an adhesive layer (or adhesive layer), a light transmission layer, and a hard coat layer in this order on a substrate. A method for manufacturing the information recording medium will be described below.

(substrate)
Specific examples of substrate materials include glass; acrylic resins such as polycarbonate and polymethyl methacrylate; vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers; epoxy resins; amorphous polyolefins; polyesters; metals such as aluminum; These may be used together if desired.
Among the above materials, polycarbonate and amorphous polyolefin are preferable, and polycarbonate is particularly preferable from the viewpoints of moisture resistance, dimensional stability, and low cost. Further, the thickness of the substrate (the average thickness of the region where the recording layer is formed) is preferably in the range of 1.1 ± 0.3 mm.

  The substrate is provided with projections and depressions (referred to as on-groove and in-groove. Here, “on-groove” may also be referred to as “groove”) representing information such as a guide groove for tracking or an address signal. In order to achieve a higher recording density, it is preferable to use a substrate on which grooves having a narrower track pitch are formed as compared with CD-R and DVD-R.

The track pitch of the groove is preferably in the range of 300 to 360 nm. More preferably, the range is 310 to 340 nm.
Moreover, it is preferable to make the depth (groove depth) of a groove into the range of 20-50 nm. By setting it as such a range, it becomes possible to prevent the molding from becoming difficult while preventing the tracking error signal from becoming small and making tracking difficult. More preferably, it is 25-40 nm.

  The groove width (on-groove half-value width) is preferably in the range of 50 to 140 nm. By setting this range, it is possible to reduce jitter while preventing a tracking error from being lowered. More preferably, it is set as the range of 70-130 nm, More preferably, it is set as 90-120 nm.

In addition, it is preferable to form an undercoat layer on the surface of the substrate on the side where a reflective layer, which will be described later, is provided, for the purpose of improving planarity and adhesion.
Examples of the material for the undercoat layer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleic anhydride copolymer, polyvinyl alcohol, N-methylol acrylamide, styrene / vinyl toluene copolymer, and chloro. Polymer materials such as sulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, polyethylene, polypropylene, polycarbonate, etc .; silane coupling Surface modifiers such as agents;
The undercoat layer is formed by dissolving or dispersing the above materials in an appropriate solvent to prepare a coating solution, and then applying this coating solution to the substrate surface by a coating method such as spin coating, dip coating, or extrusion coating. can do. The thickness of the undercoat layer is generally in the range of 0.005 to 20 μm, and preferably in the range of 0.01 to 10 μm.

(Reflective layer)
For the reflective layer, a light reflective material having a high reflectance with respect to the laser beam is used. The reflectance is preferably 70% or more.
As a light reflecting material having high reflectance, Mg, Se, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Ru, Rh, Pd , Ir, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Si, Ge, Te, Pb, Po, Sn, Bi, and other metals and semi-metals or stainless steel. These light reflecting materials may be used alone, or may be used in combination of two or more kinds or as an alloy. Among these, Cr, Ni, Pt, Cu, Ag, Au, Al, and stainless steel are preferable. Particularly preferred is Au, Ag, Al or an alloy thereof, and most preferred is Ag or an alloy containing Ag as a main component (Ag: 50% by mass or more).

  The reflective layer can be formed on the substrate, for example, by vapor deposition, sputtering or ion plating of the light reflective material. The thickness of the reflective layer is generally in the range of 10 to 300 nm and preferably in the range of 50 to 200 nm.

(Recording layer)
The recording layer is a layer formed on the interface layer and capable of recording information with a laser beam having a wavelength of 500 nm or less, and is preferably a dye type containing an organic dye.
Specific examples of the organic dye include a cyanine dye, an oxonol dye, a metal complex dye, an azo dye, and a phthalocyanine dye.

Examples of organic dyes include JP-A-4-74690, JP-A-8-127174, JP-A-11-53758, JP-A-11-334204, JP-A-11-334205, and JP-A-11-334206. 11-334207, JP-A 2000-43423, 2000-108513, 2000-158818, and the like are preferably used.
Further, separately from or together with the organic dye, triazole compound, triazine compound, cyanine compound, merocyanine compound, aminobutadiene compound, phthalocyanine compound, cinnamic acid compound, viologen compound, azo compound, oxonol benzoxazole compound, Organic compounds such as benzotriazole compounds are also preferably used. Among these compounds, cyanine compounds, aminobutadiene compounds, benzotriazole compounds, and phthalocyanine compounds are particularly preferable.

  The recording layer is prepared by dissolving a recording substance such as an organic dye in a suitable solvent together with a binder and the like, and then coating the coating liquid on the reflective layer formed on the substrate surface. After forming, it is formed by drying. The concentration of the recording substance in the coating solution is generally in the range of 0.01 to 15% by mass, preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 5% by mass, and most preferably. Is in the range of 0.5-3 mass%.

Examples of the solvent of the coating solution include esters such as butyl acetate, ethyl lactate and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane and chloroform; dimethylformamide and the like Amides; Hydrocarbons such as methylcyclohexane; Ethers such as tetrahydrofuran, ethyl ether, dioxane; Alcohols such as ethanol, n-propanol, isopropanol, n-butanol diacetone alcohol; 2,2,3,3-tetrafluoropropanol, etc. Fluorinated solvents; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether; That.
The above solvents can be used alone or in combination of two or more in consideration of the solubility of the recording material used. Various additives such as an antioxidant, a UV absorber, a plasticizer, and a lubricant may be further added to the coating solution depending on the purpose.

  When a binder is used, examples of the binder include natural organic polymer materials such as gelatin, cellulose derivatives, dextran, rosin and rubber; hydrocarbon resins such as polyethylene, polypropylene, polystyrene and polyisobutylene; Vinyl resins such as vinyl, polyvinylidene chloride, polyvinyl chloride / polyvinyl acetate copolymers, acrylic resins such as polymethyl acrylate and polymethyl methacrylate, polyvinyl alcohol, chlorinated polyethylene, epoxy resins, butyral resins, rubber And synthetic organic polymers such as derivatives and initial condensates of thermosetting resins such as phenol / formaldehyde resins. When a binder is used in combination as a material for the recording layer, the amount of binder used is generally in the range of 0.01 times to 50 times (mass ratio), preferably 0.1 times the recording substance. The amount is in the range of 5 to 5 times (mass ratio). The concentration of the recording substance in the coating solution thus prepared is generally in the range of 0.01 to 10% by mass, preferably in the range of 0.1 to 5% by mass.

  Examples of the coating method include a spray method, a spin coating method, a dip method, a roll coating method, a blade coating method, a doctor roll method, and a screen printing method. The recording layer may be a single layer or a multilayer. The recording layer generally has a thickness in the range of 20 to 500 nm, preferably in the range of 30 to 300 nm, and more preferably in the range of 50 to 100 nm.

The recording layer can contain various anti-fading agents in order to improve the light resistance of the recording layer.
As the antifading agent, a singlet oxygen quencher is generally used. As the singlet oxygen quencher, those described in publications such as known patent specifications can be used.
Specific examples thereof include JP-A Nos. 58-175893, 59-81194, 60-18387, 60-19586, 60-19587, and 60-35054. 60-36190, 60-36191, 60-44554, 60-44555, 60-44389, 60-44390, 60-54892, JP-A-60-47069, JP-A-63-209995, JP-A-4-25492, JP-B-1-38680, JP-A-6-26028, etc., German Patent 350399, and Japan Examples include those described in Chemical Society Journal, October 1992, page 1141.

  The amount of the antifading agent such as the singlet oxygen quencher used is usually in the range of 0.1 to 50% by mass, preferably in the range of 0.5 to 45% by mass, based on the amount of the dye. Preferably, it is the range of 3-40 mass%, Most preferably, it is the range of 5-25 mass%.

A barrier layer may be formed between the recording layer and a light transmission layer described later. By forming such a layer, it is possible to prevent moisture and organic components from diffusing into the recording layer.
The material constituting the barrier layer as long as the material transmits the laser beam is not particularly limited, is preferably a dielectric, and more _{specifically, ZnS, TiO 2, SiO 2} , ZnS-SiO ₂ , GeO ₂ , Si ₃ N ₄ , Ge ₃ N ₄ , MgF ₂ , and other inorganic oxides, nitrides, and sulfides. ZnS—SiO ₂ or SiO ₂ is preferable. The barrier layer can be formed by sputtering, ion plating, or the like, and the thickness is preferably 1 to 100 nm.

(Light transmission layer)
Examples of the light transmission layer include a layer made of a transparent sheet, an ultraviolet curable resin, or the like, and is formed to prevent the inside of the optical information recording medium from being impacted. The light transmission layer is not particularly limited as long as it is a transparent material, but is preferably polycarbonate, cellulose triacetate, or the like, more preferably a material having a moisture absorption rate of 5% or less at 23 ° C. and 50% RH. .
Note that “transparent” means that the recording light and the reproduction light are so transparent that the light is transmitted (transmittance: 90% or more).

The transparent sheet can be provided as follows, for example. After preparing a coating solution by dissolving the photocurable resin in an appropriate solvent, this coating solution is applied onto the recording layer (if a barrier layer or the like is formed) at a predetermined temperature to form a coating film. For example, a cellulose triacetate film (TAC film) obtained by, for example, plastic extrusion is laminated on the coating film, and the coating film is cured by irradiating light from the laminated TAC film. Is done. The TAC film preferably contains an ultraviolet absorber. The thickness of the transparent sheet is in the range of 0.01 to 0.2 mm, preferably in the range of 0.03 to 0.1 mm, and more preferably in the range of 0.05 to 0.095 mm.
In addition, a polycarbonate sheet etc. can also be used as a transparent sheet. When the adhesive is given to the bonding surface of a transparent sheet, the said adhesive agent is unnecessary.
Moreover, you may form the light transmissive layer which consists of ultraviolet curable resin etc. instead of a transparent sheet as already stated.

(Hard coat layer)
The material of the hard coat layer is as described above. The hard coat layer can be formed on the substrate by forming a reflective layer, a recording layer, etc., forming a light transmission layer thereon, and then applying the light transmission layer on the light transmission layer. Further, when the light transmission layer is a transparent sheet, before the transparent sheet is bonded onto the recording layer, a hard coat layer is formed on the transparent sheet so that the hard coat layer is the outermost surface, The optical information recording medium of the present invention may be produced by laminating on the recording layer.

  In the optical information recording medium of the present invention, the structure before the hard coat layer is formed includes a structure having a recording layer, a light reflecting layer and a protective layer in this order on the substrate on which the pregroove is formed, or on the substrate. In addition, a structure having a light reflecting layer, a recording layer, and a protective layer in this order may be used. Alternatively, a structure in which two laminated bodies in which a recording layer and a light reflection layer are provided on a transparent substrate on which a pre-groove is formed is joined so that each recording layer is on the inner side.

Next, a description will be given of a method for recording information and a method for reproducing recorded information when the optical information recording medium of the present invention is applied to an optical information recording medium that records and reproduces information with a short-wavelength laser beam.
Information is recorded on the optical information recording medium, for example, as follows.
First, while rotating the optical information recording medium at a constant linear velocity, for example, a laser beam of 350 to 500 nm (preferably 400 to 440 nm) for recording is applied from the transparent sheet side (substrate side in the case of a bonded type). Irradiate. By this laser light irradiation, the recording layer absorbs the light and the temperature rises locally, causing a physical or chemical change (for example, generation of pits) and changing its optical characteristics. Information is recorded by this change in optical characteristics.

Examples of the laser light source having an oscillation wavelength of 350 to 500 nm include a blue-violet semiconductor laser having an oscillation wavelength in the range of 390 to 415 nm, a blue-violet SHG laser having a central oscillation wavelength of about 430 nm, and the like.
In order to increase the recording density, the numerical aperture (NA) of the objective lens used for the pickup is preferably 0.7 or more, and more preferably 0.80 or more.

  On the other hand, the recorded information is reproduced by rotating the optical information recording medium at the same constant linear velocity as described above, and transmitting laser light having the same wavelength as or less than that of the laser used for information recording on the transparent sheet side ( In the case of a bonding type, irradiation can be performed by irradiating from the substrate side) and detecting the reflected light.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[Example 1]
(Production of optical information recording medium)
On the surface having the groove of an injection-molded polycarbonate resin (polycarbonate product name Panlite AD5503 manufactured by Teijin Chemicals Ltd.) having a spiral groove (depth 100 nm, width 120 nm, track pitch 320 nm) having a thickness of 1.1 mm and a diameter of 120 mm Then, Ag was sputtered to form a reflective layer having a thickness of 100 nm. Thereafter, a phthalocyanine dye (Orazol Blue GN: manufactured by ciba Specialty Chemicals) was mixed with 2,2,3,3-tetrafluoropropanol and dissolved by ultrasonication for 2 hours to prepare a dye coating solution. This dye coating solution was applied onto the reflective layer by a spin coating method under the conditions of 23 ° C. and 50% RH while changing the rotation speed from 300 rpm to 4000 rpm.

Then, after storing at 23 ° C. and 50% RH for 1 hour, ZnS · SiO ₂ was formed as a barrier layer to a thickness of 5 nm by sputtering. Thereafter, the hard coat layer and the cover film with pressure-sensitive adhesive prepared by the following method are bonded together using a pressing means such as a roller, and the reflective layer, the recording layer, the barrier layer, the pressure-sensitive adhesive layer, the light transmitting layer ( An optical recording medium having a cover film) and a hard coat layer in this order was produced.

(Preparation of hard coat layer and cover film with adhesive)
(1) Preparation of additive-containing hard coat layer coating solution:
Glycidyl methacrylate was dissolved in methyl ethyl ketone (MEK) and reacted at 80 ° C. for 2 hours while dropwise adding a thermal polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd.). The obtained reaction solution was dropped into hexane, and a solution was prepared by dissolving polyglycidyl methacrylate (polystyrene equivalent molecular weight: 12000) obtained by drying the precipitate under reduced pressure in methyl ethyl ketone so as to have a concentration of 50% by mass. 100 parts by mass of the solution, 150 parts by mass of trimethylolpropane triacrylate (Biscoat # 295, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 6 parts by mass of a radical photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy) and photocationic polymerization 30 parts by weight of methyl isobutyl ketone containing 6 parts by weight of an initiator (Lordsil 2074, Rhodia) and 10 parts by weight of an antifouling agent F-531A (manufactured by DIC Corporation, F content: 48%). The dissolved one was mixed with stirring to prepare an antifouling agent-containing hard coat layer coating solution (h-1). The general structural formula of the antifouling agent F-531A and the antifouling agent F-531A used in Example 1 are shown below.

(2) Formation of hard coat layer:
A polycarbonate film wound in a roll (Teijin Pure Ace, thickness: 75 μm, with a single-sided release film) is peeled off, and the antifouling agent-containing hard coat layer coating solution (h-1) is 5 μm thick on the surface. It was applied and dried by an extrusion method. Thereafter, ultraviolet rays were irradiated (700 mJ / cm ² ) to produce a polycarbonate film on which an antifouling agent-containing hard coat layer having a thickness of 80 μm was formed, and wound into a roll.

(3) Preparation of adhesive coating solution:
An acrylic copolymer (solvent: ethyl acetate / toluene = 1: 1) and an isocyanate-based crosslinking agent (solvent: ethyl acetate / toluene = 1: 1) are mixed at a ratio of 100: 1 to give an adhesive coating solution (n-1). Was prepared.

(4) Formation of adhesive layer, drying, winding and punching:
While feeding the polyethylene release film in roll form, the coating solution (n-1) is continuously applied to a dry thickness of 20 μm and dried in a drying zone (100 ° C.). It rolls together in a roll shape so that the polycarbonate surface of the polycarbonate film in which the layer was formed, and the said adhesive surface (adhesion layer) may be bonded together. The roll was wound up and held at 23 ° C. and 50% for 72 hours.
Thereafter, a cover film having a hard coat layer and having an adhesive was punched into the same shape as the disk (substrate).

[Example 2]
An optical information recording medium was produced in the same manner as in Example 1 except that the antifouling agent F-531A (manufactured by DIC Corporation, F content: 43%) was changed to the antifouling agent a (F content 33%). .
The F content was adjusted by changing the ratio of m and n in the compound represented by the above general structural formula of the antifouling agent F-531A used in Example 1 (the following Examples and Comparative Examples). But the same).

That is, in the above general structural formula, m and n are usually integers of 3 to 50, but in this example, m is 4 and n is 4. “M” is the sum of m ₁ , m ₂ , m ₃ and m ₄ .

Example 3
An optical information recording medium was produced in the same manner as in Example 1 except that the antifouling agent F-531A (manufactured by DIC Corporation, F content: 43%) was changed to the antifouling agent b (F content 25%). . In this example, m is 4 and n is 2 in the above general structural formula.

Example 4
An optical information recording medium was produced in the same manner as in Example 1 except that the antifouling agent F-531A (manufactured by DIC Corporation, F content: 43%) was changed to the antifouling agent c (F content 45%). . In this example, m was 3 and n was 9 in the above general structural formula.

Example 5
An optical information recording medium was produced in the same manner as in Example 1 except that the antifouling agent F-531A (manufactured by DIC Corporation, F content: 43%) was changed to the antifouling agent d (F content 55%). . In this example, m is 3 and n is 17 in the above general structural formula.

Example 6
An optical information recording medium was produced in the same manner as in Example 1 except that the thickness of the hard coat layer was 10 μm and the thickness of the adhesive layer was 15 μm.

Example 7
An optical information recording medium was produced in the same manner as in Example 1 except that the thickness of the hard coat layer was 1 μm and the thickness of the adhesive layer was 24 μm.

[Comparative Example 1]
An optical information recording medium was produced in the same manner as in Example 1 except that the antifouling agent F-531A (manufactured by DIC Corporation, F content: 43%) was changed to the antifouling agent e (F content 20%). . In this comparative example, m is 4 and n is 1 in the above general structural formula.

[Comparative Example 2]
An optical information recording medium was produced in the same manner as in Example 1 except that the antifouling agent F-531A (manufactured by DIC Corporation, F content: 43%) was changed to the antifouling agent f (F content 60%). . In this comparative example, m is 3 and n is 24 in the above general structural formula.

[Comparative Example 3]
An optical information recording medium was produced in the same manner as in Example 1 except that the antifouling agent was not added to the hard coat coating solution.

[Comparative Example 4]
An optical information recording medium was produced in the same manner as in Example 1 except that no hard coat was formed.

[Evaluation]
About the produced optical information recording medium, (1) Strength ratio of C and F, (2) Pencil hardness test, (3) Friction resistance, (4) Antifouling property, (5) Evaluation of measurement of recording characteristics went. The results are shown in Table 4 below. Moreover, the specific method of each said evaluation is as follows.

(1) Strength ratio between C and F on the hard coat layer surface (measurement of (F / C) _Ar and (F / C) _surface ):
For the measurement, ESCA-3400 manufactured by Shimadzu Corporation was used. Measurement is performed at an interval of 10 seconds from 0 to 450 seconds, and the intensity ratio between F and C at 0 seconds (depth 0 nm: surface) and the intensity ratio between F and C at 45 seconds (depth 10 nm). _Were measured as (F / C) _surface and (F / C) _Ar , respectively.
The measurement conditions were as follows.
1) Irradiation X-ray: Monochrome Al / Kα, 12 kV, 10 mA
2) Measurement spectrum: 1s peak of C, 1s peak of F 3) Vacuum degree in sample chamber: 1 × 10 ⁻⁸ Torr
4) Output of Ar ⁺ ion beam when performing sputter etching: 12 keV

(2) Pencil hardness test:
The prepared optical information recording medium is conditioned at a temperature of 25 ° C. and a relative humidity of 60% for 2 hours, and then a pencil hardness specified by JIS-K-5400 is used using a pencil specified by JIS-S-6006. According to the evaluation method, the hardness of a pencil with no scratches observed at a load of 9.8 N was determined. In Table 4, ◎ indicates a case where no scratch is observed with a 3H pencil, ◯ indicates a case where a scratch is slightly observed, and x indicates a case where a scratch is observed.

(3) Friction resistance:
It was evaluated by using # 0000 (ultra-fine) steel wool on the surface whether or not scratches could be visually observed when rubbed while applying a load of 1.96 N / cm ² .
In Table 4, ◎ indicates a state where no scratches are visible even after rubbing 300 times, ○ indicates a state where few scratches are visible even after rubbing 300 times, and x indicates a scratch that can be visually observed after less than 100 times Indicates the state that will occur.

(4) Antifouling property:
The state of the quick-drying oil-based ink (Zebra, “Mackey (R)”) written on the surface was wiped by rubbing several times using “Toraysee (R)” manufactured by Toray Industries, Inc.
In Table 4, “◎” indicates a state in which written marks are completely wiped off, “◯” indicates a state in which the written mark is almost wiped off, but a slight amount remains, and “×” indicates a state in which most of the mark remains.

(5) Measurement of recording characteristics:
After performing the friction resistance test with steel wool of (3) above, a recording / reproducing apparatus DDU- having a blue-violet laser emitting at a wavelength of 405 nm and a pickup composed of an objective lens having a numerical aperture (NA) of 0.85 An optical information recording medium produced at 1000 (manufactured by Pulstec Industrial Co., Ltd.) was mounted, and a 17 pp modulated signal with the shortest pit length set to 0.16 μm was recorded and reproduced to measure signal reproduction jitter.

  From Table 4 above, in the optical information recording media of Comparative Examples 1 to 4, any of the pencil hardness test, abrasion resistance, antifouling property, and recording characteristics was evaluated as low. On the other hand, in the optical information recording media of Examples 1 to 7, all the above evaluations were high.

Claims (3)

An optical information recording medium in which a recording layer, a light transmission layer, and a hard coat layer are provided on a substrate,
A ratio of F peak intensity to C peak intensity when the hard coat layer surface is measured by X-ray photoelectron spectroscopy (F / C) _surface is 0.01 to 1.0. Optical information recording medium. After measuring the (F / C) _surface by the X-ray photoelectron spectroscopy, the peak intensity of F on the hard coat layer surface after performing sputter etching (12 keV) with Ar ⁺ ion beam for 5 to 500 seconds, 2. The optical information recording medium according to claim 1, wherein the ratio of C to the peak intensity (F / C) _Ar is 1/20 or more of the (F / C) _surface .   The optical information recording medium according to claim 1, wherein an F content in the additive contained in the hard coat layer is 30 to 60% by mass.