JP5332166B2 - Polymer, composition, cured product and optical recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for a stain resistance imparting agent having excellent hardness and scratch resistance, and to provide a cured product and an article using the composition. <P>SOLUTION: The composition contains the following polymer (A) and a radically polymerizable photoinitiator (B). The polymer (A) has a structure produced by allowing a carboxylic acid having 1 to 5 (meth)acryloyl groups in one molecule to react with at least a part of epoxy groups in a radically polymerized product of a monomer mixture that contains: (a1) 1 to 20 pts.wt. of &alpha;,&omega;-dimercapto polysiloxane; (a2) 15 to 60 pts.wt. of (meth)acrylate having an epoxy group; (a3) 0.5 to 5 pts.wt. of monofunctional mercaptan having a molecular weight of 100 to 300; and (a4) 15 to 83.5 pts.wt. of other radically polymerizable monomers, in total 100 pts.wt., with a ratio of mercapto groups of (a1)/mercapto groups of (a3) ranging from 0.2 to 20 (mol/mol). <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a polymer and a composition useful as a stain resistance imparting agent having excellent hardness and scratch resistance, and an article such as a cured product and an optical recording medium using the composition. In particular, the present invention relates to a composition that provides a cured film having sufficient performance even in a thin film.

  The present invention relates to an optical article, in particular, an optical recording medium such as a read-only optical disc, an optical recording disc, a magneto-optical recording disc, or a transparent article for an optical display such as a touch panel or a liquid crystal television. The present invention also relates to a polymer capable of providing an article excellent in stain resistance (antifouling property) on a reproduction beam incident surface (optical recording medium) or a surface (touch panel or the like) directly touched by a finger, and a composition thereof.

  Plastic products such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile butadiene styrene copolymer (ABS), methyl methacrylate-styrene copolymer (MS resin), acrylonitrile styrene copolymer (AS resin), etc. Resin materials such as styrene resin, vinyl chloride resin, and cellulose acetate such as triacetyl cellulose are particularly excellent in lightness, ease of processing, impact resistance, etc. It is used for various applications such as outer plates, window materials, roof materials, packaging materials, various housing materials, optical disk substrates, plastic lenses, liquid crystal displays, plasma displays, base materials for display devices such as projection TVs, and the like.

  However, these plastic products are easily damaged due to their low surface hardness, and transparent resins such as polycarbonate and polyethylene terephthalate have the disadvantage that the original transparency or appearance of the resin is significantly impaired. It makes it difficult to use plastic products in the required fields.

  For this reason, a hardened surface film (coating material) is required to increase the surface hardness of these plastic products and to provide wear resistance.

  On the other hand, in the application of the next-generation optical disk that is written and erased with the blue laser developed recently, touch panel display of car navigation system, PDA and mobile phone, large screen flat panel TV display such as liquid crystal TV and plasma TV, etc. Not only hardness and durability but also high level of contamination resistance is required.

In addition, in optical products such as next-generation optical information media and touch panels, in recent years, fingerprint contamination has a problem not only in appearance but also in performance and safety. Optical information media have come to be regarded as serious problems that directly affect performance, such as an increase in recording / reproducing errors. Depending on the usage environment as well as fingerprint smudges, contamination with other contaminants such as dust and dust may occur, which also cause serious errors such as recording failure and reproduction failure.
In particular, as a high-density optical information medium, the aperture diameter (N / A) of the objective lens is increased and / or the recording / reproducing wavelength is shortened to 400 nm, thereby reducing the beam condensing spot diameter. A medium having a recording density per density higher than the conventional (DVD) has been proposed. For example, a new optical information medium such as Blu-Ray Disc or HD DVD has appeared.
When the recording density is increased in this way, the diameter of the condensing spot of the recording / reproducing beam on the recording / reproducing beam incident side surface of the medium becomes smaller, so that it becomes particularly sensitive to dirt such as fingerprints, dust and dust. Especially for dirt containing organic substances such as fingerprints, if the dirt adheres to the surface on the laser beam incident side of the medium, it will cause serious effects such as recording / playback errors and it will be difficult to remove them. Necessary.

  Under such circumstances, recently, a hard coat film from a specific hard coat agent composition containing an active energy ray-curable group-containing silicone-based compound and fluorine-based compound is used as a next-generation optical disk (high-density optical recording information medium). It is described that it is formed on the surface and exhibits excellent fingerprint resistance (for example, Patent Document 1 and Patent Document 2). Such a film exhibits excellent water and oil repellency to reduce the fingerprint adhesion diameter, but it cannot be said that the fingerprint wiping property and its durability are sufficient. This is because, although the hard coat layer is as thin as about 2 μm, the active energy ray curable group is not a group having sufficient thin film curability, or the skeleton of the stain resistance imparting agent itself is still relatively hard. Because of the low structure.

  On the other hand, the present inventors have already demonstrated that a specific copolymer containing a specific polysiloxane group and an epoxy group, or a (meth) acrylic acid reaction product thereof, is extremely effective as a stain resistance imparting agent. Has already been found (Patent Document 3, Patent Document 4).

Patent Document 5 describes a method for producing a copolymer of such mercaptosiloxanes and a general free radical polymerizable monomer, and a release coating and a coated material using the same. Does not describe a free radical polymerizable monomer having a functional group that easily reacts with a mercapto group (for example, an epoxy group, an isocyanate group, an alkoxysilyl group, etc.).
JP 2004-152418 A JP-A-2005-112900 JP 2006-160802 A WO2006 / 059702 Publication Japanese Patent Laid-Open No. 3-88815

As described above, in Patent Documents 3 and 4, a specific copolymer containing a specific polysiloxane group and an epoxy group, or a (meth) acrylic acid reaction product thereof is extremely effective as a stain resistance imparting agent. However, in the stain resistance imparting agent described in Patent Documents 3 and 4, in order to suppress cross-linking / insolubilization / gelation due to side reaction between the mercapto group and the epoxy group, the mercapto in the polysiloxane group is suppressed. It is necessary to control the molar ratio of groups to epoxy groups within a certain range. For this reason, applications that require a particularly high polysiloxane group content (oil-based magic repellency, oil-based magic wiping, surface slipperiness, etc. are required) There has been a problem that there is a limit in application to (use).
As one of the methods for solving such problems, the present inventors have conceived that monofunctional mercaptan is used in combination. However, Patent Document 3, Patent Document 4, and Patent Document 5 both use such a monofunctional mercaptan. , There is no description that the cross-linking due to the reaction between the mercapto group and the epoxy group of the polysiloxane, the thickening due to branching, the decrease in solubility, etc. can be substantially prevented, and there is no description that suggests this. It was a completely unknown problem what kind of monofunctional mercaptan could be controlled under what conditions.

The present invention solves the above-mentioned problems, and can impart high anti-staining property and high anti-staining property even with a thin film, and can provide excellent anti-staining properties and anti-staining properties. It is an object to provide a polymer capable of realizing an agent and the like and a composition thereof.
The present invention also provides a polymer capable of providing a stain resistance imparting agent capable of imparting weather resistance while maintaining these performances, or imparting more excellent thin film and surface curability, if necessary. And its composition.
Furthermore, the present invention is a cured product of such a composition, and an article having a cured film on its surface, particularly an article for optical applications such as an optical recording medium and a touch panel display, and has high hardness and abrasion resistance on the surface. It is another object of the present invention to provide an article that has excellent anti-staining properties and anti-staining properties.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that a specific molecular weight of the dimercaptopolysiloxane has a specific molecular weight in order to suppress crosslinking / insolubilization / gelation caused by a side reaction in which a mercapto group and an epoxy group of dimercaptopolysiloxane react. By adding monofunctional mercaptan and using a predetermined amount of monofunctional mercaptan with respect to the mercapto group of dimercaptopolysiloxane, it is difficult to reduce the content of dimercaptopolysiloxane in the past. The inventors found that a polymer can be obtained without causing cross-linking / insolubilization / gelation even if the amount is increased to a certain range, and the present invention has been completed.
That is, the gist of the present invention is as follows.

[1] (a1) α, ω-dimercaptopolysiloxane: 1 to 20 parts by weight,
(A2) (meth) acrylate having an epoxy group: 15 to 60 parts by weight,
(A3) Monofunctional mercaptan having a molecular weight of 100 to 300: 0.5 to 5 parts by weight
And (a4) Other radical polymerizable monomer: 15 to 83.5 parts by weight in total, and 100 parts by weight of (a1) mercapto group / (a3) mercapto group is 0.2 to 20 (mol / (Mole) having a structure corresponding to a structure obtained by reacting 1 to 5 (meth) acryloyl group-containing carboxylic acid with at least part of the epoxy group of the radical polymer of the monomer mixture. (A).

[2] The polymer (A) according to [1], wherein the (a1) α, ω-dimercaptopolysiloxane is α, ω-dimercaptopropylpolydimethylsiloxane.

[3] The monomer mixture contains 1 to 60 parts by weight of (a4-1) a radical polymerizable monomer having a perfluoroalkyl group and / or a perfluoroalkylene group as the other radical polymerizable monomer (a4) [ The polymer (A) according to [1] or [2].

[4] A composition in which 100 parts by weight of the polymer (A) is mixed with 3 parts by weight of 1-hydroxycyclohexyl phenyl ketone (however, this composition contains only the polymer (A) and 1-hydroxycyclohexyl phenyl ketone as solids. Is applied onto a 100 μm-thick easy-adhesive PET substrate, and the obtained coating film is irradiated with UV light having a wavelength of 254 nm using a high-pressure mercury lamp with an output density of 120 W / cm, and an integrated light quantity of 500 mJ / cm ² . The pencil hardness of a cured film having a film thickness of 5 μm formed by irradiation so as to be B or more, the contact angle of water of the cured film with water being 90 degrees or more, and the contact angle with hexadecane of 30 degrees or more The polymer (A) according to any one of [1] to [3].

[5] A composition comprising the polymer (A) according to any one of [1] to [4] and a radical polymerizable photoinitiator (B).

[6] Furthermore, polyfunctional (meth) acrylate (C1) containing 3 or more (meth) acryloyl groups in one molecule and / or inorganic oxide fine particles containing colloidal silica as a main component is added to —O—Si. An organic-inorganic composite (C2) having a (meth) acryloyl group bonded via a —R— bond (R represents a linear or branched alkylene group having 2 to 10 carbon atoms) [5] A composition according to 1.

[7] Further, a polymer having a radical polymerizable group other than the radical polymerizable organic (meth) acrylate compound and / or the radical polymerizable organic (meth) acrylamide compound (D) and the polymer (A) (E The composition according to [5] or [6], which contains at least one selected from the group consisting of:

[8] The composition is applied onto a 100 μm-thick easy-adhesion PET substrate, and the obtained coating film is integrated with 500 mJ / cm ² of ultraviolet light having a wavelength of 254 nm using a high-pressure mercury lamp with an output density of 120 W / cm. The content of the stain resistance-imparting group at the position of 3 nm thickness from the surface of the 5 μm-thick cured film formed by irradiating with a light amount is the amount of the contamination-resistance imparting group of the entire cured film. The composition according to any one of [5] to [7], which is at least 3 times the average content.

[9] A cured product obtained by irradiating the composition according to any one of [5] to [8] with active energy rays.

[10] An article having on its surface a cured film obtained by irradiating the composition according to any one of [5] to [8] with active energy rays.

[11] The article according to [10], which is an article used for optics.

[12] The article according to [10], which is an optical recording medium or a laminate for an optical display.

[13] An optical recording medium having a multilayer film including at least a recording layer or a reflective layer on a substrate, wherein the outermost surface on the light incident side of the medium is any one of [5] to [8] An optical recording medium comprising a cured film made of the composition described above.

[14] The optical recording medium according to [13], wherein the cured film is provided on the outermost surface of the recording layer or the reflective layer opposite to the substrate.

[15] The optical recording medium according to [13] or [14], wherein a light transmission layer is provided between the multilayer film and the cured film.

[ 16 ] A laminate comprising a transparent resin substrate, and having a cured film formed by irradiating the composition according to any one of [5] to [8] with active energy rays on at least one outermost surface. An optical display laminate.

[ 17 ] (a1) α, ω-dimercaptopolysiloxane: 1 to 20 parts by weight,
(A2) (meth) acrylate having an epoxy group: 15 to 60 parts by weight,
(A3) Monofunctional mercaptan having a molecular weight of 100 to 300: 0.5 to 5 parts by weight
And (a4) Other radical polymerizable monomer: 15 to 83.5 parts by weight in total, and 100 parts by weight of (a1) mercapto group / (a3) mercapto group is 0.2 to 20 (mol / Mol) monomer mixture is subjected to radical polymerization, and then at least part of the epoxy group of the obtained radical polymer is reacted with carboxylic acid having 1 to 5 (meth) acryloyl groups in one molecule. The manufacturing method of the polymer (A) characterized by these.

[ 18 ] The method for producing the polymer (A) according to [ 17 ], wherein the (a1) α, ω-dimercaptopolysiloxane is α, ω-dimercaptopropylpolydimethylsiloxane.

[ 19 ] The monomer mixture includes 1 to 60 parts by weight of (a4-1) a radical polymerizable monomer having a perfluoroalkyl group and / or a perfluoroalkylene group as the other radical polymerizable monomer (a4) [ 17 ] or the manufacturing method of the polymer (A) as described in [ 18 ].

If it is a composition containing the polymer (A) of the present invention, even if it is a thin film obtained by thinly applying it to the surface of an article or the like and curing it, the article or the like has excellent curability, scratch resistance, and transparency. It has the property and the stain resistance, and the durability of those performances is very excellent.
Therefore, the present invention is suitable for a wide range of applications such as protection of optical recording medium surfaces, optical displays such as touch panels and flat displays, mobile phone casings, automobile transparent parts protection, and protection of transparent parts such as farmhouses (houses). Can be applied.

Hereinafter, embodiments of the present invention will be described in detail.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
Further, “polymerization” in the present invention is a broad sense polymerization including so-called “copolymerization” unless otherwise specified. Therefore, in the present invention, “polymer” includes “copolymer”.
In addition, the “room temperature” in the present invention refers to the temperature of the place where the experiment or the like is being performed, for example, a temperature of 15 to 30 ° C., more preferably 20 to 25 ° C.
The “normal oxygen concentration” means 18 to 22%, more preferably 19 to 21%.
Further, “(meth) acrylate” means “acrylate and / or methacrylate”, and the same applies to “(meth) acryloyl” and “(meth) acryl”.

[Polymer (A)]
The polymer (A) of the present invention is
(A1) α, ω-dimercaptopolysiloxane: 1 to 20 parts by weight,
(A2) (meth) acrylate having an epoxy group: 15 to 60 parts by weight,
(A3) Monofunctional mercaptan having a molecular weight of 100 to 300: 0.5 to 5 parts by weight
And (a4) Other radical polymerizable monomer: 15 to 83.5 parts by weight in total, and 100 parts by weight of (a1) mercapto group / (a3) mercapto group is 0.2 to 20 (mol / Mole) having a structure corresponding to a structure in which at least a part of the epoxy group of the radical polymer of the monomer mixture is reacted with a carboxylic acid having 1 to 5 (meth) acryloyl groups in one molecule. is there.

The preferable manufacturing method of a polymer (A) is described below.
In the following, the amount (part by weight) of each component in 100 parts by weight of the monomer mixture as a raw material for producing the polymer (A) of the present invention may be referred to as “use amount”.

<(A1) α, ω-Dimercaptopolysiloxane>
In the present invention, (a1) α, ω-dimercaptopolysiloxane has a polysiloxane structure in which two or more of the following repeating structural units are linked.
-(SiR ¹ R ² -O)-
In the formula, each of R ¹ and R ² independently represents an optionally substituted alkyl group or an optionally substituted phenyl group, preferably substituted with a hydroxyl group or an alkoxy group. An alkyl group that may be substituted (more preferably, the alkoxy group and the alkyl group have 1 to 3 carbon atoms), more preferably an alkyl group having 1 to 3 carbon atoms that has no substituent, and most preferably Is a methyl group.

  Examples of such compounds include α, ω-dimercaptopolydimethylsiloxane, α, ω-dimercaptopolydiethylsiloxane, α, ω-dimercaptopolymethylethylsiloxane, α, ω-dimercaptopolydihydroxymethylsiloxane. , Α, ω-dimercaptopolydimethoxymethylsiloxane, and the like, among which α, ω-dimercaptopolydimethylsiloxane is preferred, and this mercapto group may be directly linked to the polysiloxane group, or alkylene. It may be linked to a polysiloxane group via a group. More preferred is a polysiloxane (α, ω-dimercaptopropylpolydimethylsiloxane) in which a mercapto group is linked to a polysiloxane group via a propylene group. However, it is not limited to these.

  (A1) The α, ω-dimercaptopolysiloxane preferably has a number average molecular weight of about 1000 to 5000 in order to achieve a good balance between stain resistance and hardness.

  Such (a1) α, ω-dimercaptopolysiloxane may be used alone or in combination of two or more.

  In the present invention, the amount of (a1) α, ω-dimercaptopolysiloxane used is 1 to 20 parts by weight, preferably 3 to 15 parts by weight. (A1) If the amount of α, ω-dimercaptopolysiloxane used is less than 1 part by weight, the stain resistance is insufficient, and if it exceeds 20 parts by weight, it is compatible with other components (of the system during the polymerization reaction). Uniform compatibility and compatibility between the polymer (A) and other components when used as a composition) are decreased, and the hardness of the cured film is decreased.

<(A2) (Meth) acrylate having epoxy group>
(A2) Some typical specific examples of the (meth) acrylate having an epoxy group include (meth) acrylate having a glycidyl group such as glycidyl acrylate and glycidyl methacrylate; 3,4-epoxycyclohexyl acrylate, 3, Examples include (meth) acrylates in which an epoxy group is directly bonded to an alicyclic structure such as 4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate. Is not to be done.
Among these, glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate are easily available and easily modified with (meth) acrylic acid. 3,4-epoxycyclohexylmethyl methacrylate and the like are particularly preferable.

  Such (a2) (meth) acrylates having an epoxy group may be used alone or in admixture of two or more.

  (A2) The usage-amount of the (meth) acrylate which has an epoxy group is 15-60 weight part, Preferably it is 25-55 weight part. (A2) If the amount of the (meth) acrylate having an epoxy group is less than 15 parts by weight, the effect of increasing the curability and the hardness by photoradical polymerization by modifying the carboxylic acid having a (meth) acryloyl group, the effect of improving the surface curability In the range exceeding 60 parts by weight, the viscosity of the polymer solution and the decrease in the liquid stability may be observed, and further high curability and hardness are not observed, both of which are preferable. Absent.

<(A3) Monofunctional mercaptan having a molecular weight of 100 to 300>
Examples of monofunctional mercaptans having a molecular weight of 100 to 300 include alkyl mercaptans such as hexyl mercaptan, decyl mercaptan, dodecyl mercaptan, hexadecyl mercaptan, stearyl mercaptan; cycloalkyl mercaptans such as cyclohexyl mercaptan; thiophenol, chlorothiophenol, mercapto Examples include aromatic mercaptans such as naphthalene, but are not limited thereto. Of these, alkyl mercaptans having 9 to 15 carbon atoms such as decyl mercaptan and dodecyl mercaptan are most preferable in consideration of reactivity, reaction selectivity, odor and the like.

  When the molecular weight of the monofunctional mercaptan used in the present invention is less than 100, the volatility is high, and it escapes from the reaction system during the polymerization reaction, and the effect may not be exhibited, which is not preferable. On the other hand, if the molecular weight of the monofunctional mercaptan exceeds 300, compatibility with other monomers is lowered and phase separation may occur, which is also not preferable. The preferred molecular weight of the monofunctional mercaptan is 150-250.

  Such (a3) monofunctional mercaptans may be used alone or in combination of two or more.

  (A3) Monofunctional mercaptan having a molecular weight of 100 to 300 is used in an amount of 0.5 to 5 parts by weight, particularly 0.8 to 2.5 parts by weight, and (a1) a mercapto of α, ω-dimercaptopolysiloxane Molar ratio M (a1) / M of a group (hereinafter referred to as “M (a1)”) and (a3) a mercapto group of monofunctional mercaptan having a molecular weight of 100 to 300 (hereinafter referred to as “M (a3)”). The amount (a3) is 0.2 to 20, preferably 0.5 to 10, more preferably 1 to 5. When M (a1) / M (a3) is less than 0.2, (a1) a mercapto group of α, ω-dimercaptopolysiloxane and (a2) an epoxy group of (meth) acrylate having an epoxy group In some cases, it cannot be controlled so that cross-linking by reaction, thickening due to branching, lowering of solubility, etc. do not occur substantially. If it exceeds 20, the molecular weight of the resulting polymer (A) is remarkably lowered, or unreacted monomers Is likely to remain, which may be undesirable. Moreover, even if M (a1) / M (a3) is in the range of 0.2 to 20, when (a3) the amount of monofunctional mercaptan used is less than 0.5 parts by weight, (a3) monofunctional mercaptan The concentration of is too low, the reactivity is insufficient, and (a1) α, ω-dimercaptopolysiloxane and (a2) the (meth) acrylate having an epoxy group may not be controlled so as not to cause a side reaction. On the other hand, when the amount of (a3) monofunctional mercaptan used exceeds 5 parts by weight, the molecular weight of the resulting polymer (A) is remarkably lowered, or unreacted monomers are likely to remain, which may not be preferable.

<(A4) Other radical polymerizable monomer>
The (a4) other radical polymerizable monomer is not particularly limited as long as it is a radical polymerizable monomer capable of radical polymerization with the above-described (a1) component, (a2) component, and (a3) component. What has low reactivity with the group and does not decrease the stability of the polymer produced, or has a rigid skeleton and does not lower the hardness, and can further improve the stain resistance, are required.

  Some specific examples of such (a4) radical polymerizable monomer include styrene, its lower (1 to 4 carbon) alkyl group, alkenyl group-substituted derivatives, and 1 to 20 alkyl (meta) Radical polymerization such as) acrylate, alkyl (meth) acrylamide, cycloalkyl (meth) acrylate having a (poly) cycloalkyl side chain having 5 to 20 carbon atoms, (meth) acrylamides, (meth) acrylate containing a fluorine atom, etc. A monomer etc. can be illustrated.

  In the present invention, (a4) part or all of the other radical polymerizable monomers are preferably (a4-1) a radical polymerizable monomer having a perfluoroalkyl group and / or a perfluoroalkylene group, Particularly preferable examples of such radical polymerizable monomers include (meth) acrylates having a perfluoroalkyl group and / or a perfluoroalkylene group.

  Specific examples of (a4-1) (meth) acrylates having a perfluoroalkyl group and / or a perfluoroalkylene group include perfluorooctylethyl methacrylate, perfluorodecylethyl methacrylate, perfluorohexylethyl (meth) acrylate. 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 3-perfluorooctyl-1,2-epoxypropane acrylic acid adduct, 3- Examples include acrylic acid adducts of perfluorohexyl-1,2-epoxypropane, pentafluoroethyl methacrylate, methoxyethyl perfluoroethylene ethyl acrylate, and terminal acrylates of perfluoropolyether. That is, the present invention is not of course limited to these. Particularly preferably, perfluorooctylethyl methacrylate, perfluorohexylethyl (meth) acrylate, acrylic acid adduct of 3-perfluorooctyl-1,2-epoxypropane, acrylic acid of perfluorohexyl-1,2-epoxypropane And adducts.

  (A4-1) A radical polymerizable monomer having a perfluoroalkyl group and / or a perfluoroalkylene group is included. (A4) Other radical polymerizable monomers may be used alone or in combination of two or more. May be used.

  (A4) The amount of other radical polymerizable monomer used is 15 to 83.5 parts by weight, preferably 20 to 80 parts by weight. (A4) When the amount of other radical polymerizable monomer used is less than 15 parts by weight, the stain resistance is not sufficiently imparted, and when it exceeds 83.5 parts by weight, the scratch resistance and pencil hardness of the surface are lowered.

  When (a4) a radically polymerizable monomer having a perfluoroalkyl group and / or a perfluoroalkylene group is used as the other radically polymerizable monomer (a4), the amount used is 1 to 60 parts by weight, particularly It is preferable that it is 5-55 weight part. (A4-1) If the amount of the radical polymerizable monomer having a perfluoroalkyl group and / or a perfluoroalkylene group is 1 part by weight or more, (a4-1) a perfluoroalkyl group and / or a perfluoroalkylene group The effects of improving the oil resistance and stain resistance derived from the oil repellency of the radically polymerizable monomer having the above are expressed, and if it is 60 parts by weight or less, the resulting polymer (A) has a high hardness and the surface resistance This is preferable because scratchability and pencil hardness are improved.

<Solvent>
In radical polymerization of the monomer mixture containing the components (a1) to (a4) described above, a solvent may be added in order to improve uniformity.
Examples of such solvents include ketone solvents such as acetone and methyl ethyl ketone (MEK); alcohol solvents such as ethanol, methanol, isopropyl alcohol (IPA), and isobutanol; ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether. Preferred examples include ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, and 2-ethoxyethyl acetate; aromatic hydrocarbon solvents such as toluene; and water.
These solvents may be used alone or in combination of two or more.

<Radical polymerization initiator>
A radical polymerization initiator is preferably used for radical polymerization of the monomer mixture containing the components (a1) to (a4) described above.
As the radical polymerization initiator, known initiators generally used for radical polymerization can be used. Organic peroxides such as benzoyl peroxide and di-t-butyl peroxide; 2,2′-azobisbutyl Preferred examples include azo compounds such as rhonitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile).
One of these radical polymerization initiators may be used alone, or two or more thereof may be mixed and used.

<Radical polymerization method and conditions>
In particular, the method for mixing and dissolving the monomer component and the solvent when performing radical polymerization using the solvent and the radical polymerization initiator as necessary further on the monomer mixture containing the components (a1) to (a4) described above Although there is no limitation, for example, it is preferable to start the polymerization by adding a radical polymerization initiator within a certain time, preferably within 3 hours after mixing the monomer component and the solvent.
The total concentration of the monomer components in the reaction solution subjected to radical polymerization is preferably 10 to 60% by weight, and the radical polymerization initiator is preferably 0.1 to 10% by weight, more preferably based on the total of the monomer components. Is used in an amount of 0.2 to 2% by weight.
Moreover, although preferable polymerization conditions change with radical polymerization initiators to be used, the polymerization temperature is usually 20 to 150 ° C., and the polymerization time is usually 1 to 72 hours.

<Carboxylic acid having 1 to 5 (meth) acryloyl groups in one molecule>
In the present invention, a carboxylic acid having 1 to 5 (meth) acryloyl groups in one molecule is added to at least a part of the epoxy group of the radical polymer obtained as described above.

  Examples of the carboxylic acid having 1 to 5 (meth) acryloyl groups in one molecule used here include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxy. Ethylhexahydrophthalic acid, pentaerythritol tri (meth) acrylate and acid anhydride adducts such as succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, dipentaerythritol penta (meth) acrylate and succinic anhydride, phthalic anhydride Examples include acids and adducts of acid anhydrides such as hexahydrophthalic anhydride. One of these may be used alone, or two or more thereof may be mixed and used.

<Addition reaction method and conditions>
In this addition reaction, the epoxy group of the radical polymer reacts with the carboxyl group of the carboxylic acid having a (meth) acryloyl group.
The radical polymer and the carboxylic acid having a (meth) acryloyl group are the ratio of the epoxy group of the radical polymer to the carboxyl group of the carboxylic acid having a (meth) acryloyl group (hereinafter simply referred to as “epoxy group / carboxyl group”). In some cases) is preferably used at a ratio of 1 or more, particularly preferably at a ratio of epoxy group / carboxyl group = 1-10. More preferably, the epoxy group / carboxyl group is 1.01 to 5, more preferably 1.02 to 2.
When the epoxy group / carboxyl group is 1 or more, a decrease in stability due to a carboxylic acid having a (meth) acryloyl group remaining unreacted can be prevented, and when it is 10 or less, the stability due to the remaining epoxy group can be prevented. Since it can prevent a fall, it is preferable.
Moreover, it is preferable that 50 to 99% reacts with the carboxyl group of the carboxylic acid having a (meth) acryloyl group among the epoxy groups of the radical polymer.

  This addition reaction is preferably carried out at 50 to 110 ° C. for 3 to 50 hours.

  In this reaction, in order to accelerate the reaction, for example, one or more known catalysts such as triethylamine, tributylamine, triethylenediamine, N, N-dimethylbenzylamine, benzyltrimethylammonium chloride and triphenylphosphine are used. Can be used. The amount used is preferably 0.01 to 2% by weight, ie 0.05 to 1% by weight, based on the reaction mixture (that is, the total of the radical polymer and the carboxylic acid having a (meth) acryloyl group). It is more preferable that

Further, in this reaction, in order to prevent radical polymerization of a carboxylic acid having a (meth) acryloyl group due to the (meth) acryloyl group, for example, hydroquinone, hydroquinone monomethyl ether, catechol, pt-butylcatechol, phenothiazine, etc. It is preferable to use one or more polymerization inhibitors. The amount of the polymerization inhibitor used is preferably 0.01 to 1% by weight, more preferably 0.05 to 5% by weight, based on the reaction mixture.
Thus, the polymer (A) of the present invention can be obtained.
In addition, the polymer (A) should just have the structure corresponded to the polymer obtained by the said method, and is not limited to what was obtained by the said manufacturing method.

<Physical properties>
The polymer (A) of the present invention is a cured film that is polymerized by irradiation with active energy rays, even if only the polymer (A) is used without using any polymerizable monomer other than the polymer (A). In addition, the cured film is characterized by a certain degree of hardness and excellent water repellency and oil repellency. In particular, 1-hydroxy is added to 100 parts by weight of the polymer (A) of the present invention. A composition in which 3 parts by weight of cyclohexyl phenyl ketone is mixed (however, this composition contains only the polymer (A) and 1-hydroxycyclohexyl phenyl ketone as a solid content) on a 100 μm-thick highly adhesive PET substrate. coated, the resulting coating film, using a high-pressure mercury lamp with an output density of 120 W / cm, was formed by irradiation of ultraviolet light of wavelength 254nm so that the integrated light quantity of 500 mJ / cm ^2, membrane Cured film of 5μm preferably has the following physical properties. In addition, this ultraviolet irradiation is normally performed in an oxygen concentration atmosphere.
The preferred physical properties of the cured film are the same as the preferred physical properties of the cured product of the present invention described later.
(1) Pencil hardness is B or higher
(2) Contact angle with water is 90 degrees or more
(3) The contact angle with respect to hexadecane is 30 degrees or more. The composition that gives the cured film with high pencil hardness even if the polymer (A) has the physical properties of the above (1) without containing many polymerizable monomers having high curing shrinkage. This is preferable because the amount of warpage can be reduced when a cured film is formed on a thin substrate or when a thick cured film is formed.

  The curing of the coating film containing the polymer (A) is not limited to ultraviolet rays, and active energy rays such as electron beams, α rays, β rays, and γ rays can be used. Preferred examples of “irradiation and polymerization” include photoradical polymerization and photocationic polymerization.

[Composition]
The composition of the present invention comprises the above-described polymer (A) of the present invention and the radical polymerizable photoinitiator (B) as essential components, preferably further,
A polyfunctional (meth) acrylate (C1) containing 3 or more (meth) acryloyl groups in one molecule and / or inorganic oxide fine particles mainly composed of colloidal silica having —O—Si—R— bonds ( R represents a linear or branched alkylene group having 2 to 10 carbon atoms.) An organic-inorganic composite (C2) having a (meth) acryloyl group bonded via
Furthermore,
Polymer (E) having radical polymerizable group other than radical polymerizable organic (meth) acrylate compound and / or radical polymerizable organic (meth) acrylamide compound (D) and / or polymer (A)
including.
Here, the radical polymerizable organic (meth) acrylate compound refers to an organic (meth) acrylate compound having 1 to 2 (meth) acryl groups in one molecule.

<Polymer (A)>
In the composition of the present invention, only one kind of the above-mentioned polymer (A) of the present invention may be contained, or two or more kinds may be contained.

  The content of the polymer (A) of the present invention in the composition of the present invention varies depending on the use of the composition, the type of the polymer (A) used, and the composition of other components, but is preferably 0.00. 5 to 20% by weight, more preferably 1 to 15% by weight. If the content of the polymer (A) is 0.5% by weight or more, the stain resistance is good, and if it is 20% by weight or less, the hardness is high and the coating property is excellent.

<Radically polymerizable photoinitiator (B)>
As the radical polymerizable photoinitiator (B), known ones can be widely used, but preferably an alkylphenone type compound (such as α-hydroxyacetophenone, α-aminoacetophenone, benzyl ketal), acylphosphine oxide. Type compounds, oxime ester compounds, oxyphenyl acetates, benzoin ethers, phenyl formates, ketone / amine compounds and the like. Specifically, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether, diethoxyacetophenone, benzyldimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2, 4,6-trimethylbenzoindiphenylphosphine oxide, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butan-1-one, methylbenzoylformate, Michler's ketone, isoamyl N, N-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone and the like are preferable.
These radical polymerizable photoinitiators (B) may be used alone or in combination of two or more.

  The content of the radical polymerizable photoinitiator (B) in the composition of the present invention can be appropriately determined depending on the type of the radical polymerizable photoinitiator (B) used, but the polymer (A) in the composition In addition, it is preferably 10% by weight or less based on the total of polymerizable components in the composition such as (C1) component and (C2) component, (D) component, and (E) component described later, and 0.5 to 8% by weight. % Is more preferable. If the content of the radical polymerizable photoinitiator (B) is less than this range, curing will be insufficient, and if it is too high, the hardness may decrease and the stain resistance may decrease.

  As the radical polymerizable photoinitiator (B), when one or more of the following components (B1), (B2), and (B3) are used in an amount of 20% by weight or more in the component (B), oxygen Inhibition of polymerization due to water is further reduced, and further improvement in surface curability and thin film curability is observed, which may be particularly preferable.

(B1) α-aminoacetophenone initiators such as 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butan-1-one, etc. (B2) Oxime ester initiators such as Irgacure OXE-01, manufactured by Ciba Specialty Chemicals, Inc. (B3) An α-hydroxyketone initiator and a benzophenone sensitizer Combinations such as 1-hydroxycyclohexyl phenyl ketone and Michler's ketone

<Polyfunctional (meth) acrylate (C1) containing 3 or more (meth) acryloyl groups in one molecule>
As polyfunctional (meth) acrylate (C1) having three or more (meth) acryloyl groups in one molecule, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ditrile Examples include methylolpropane tetraacrylate, polyester acrylates, polyfunctional urethane acrylates, polyepoxy acrylates, and triethoxy acrylate having an isocyanurate ring (for example, manufactured by Toagosei Co., Ltd., Aronix M315, M313, etc.). It is not limited to.
These may be used alone or in combination of two or more.
Suitable content of these (C1) components in a composition is mentioned later.

<Organic-inorganic composite (C2)>
The organic-inorganic composite (C2) that can be used in the composition of the present invention has an —O—Si—R— bond, preferably —O—Si—R—S, to inorganic oxide fine particles mainly composed of colloidal silica. A (meth) acryloyl group is bonded via a bond. Here, R represents a linear or branched alkylene group having 2 to 10 carbon atoms.

  An -O-Si-R- bond (R represents a linear or branched alkylene group having 2 to 10 carbon atoms), preferably an -O-Si-R-S- bond, is formed on the surface of the inorganic oxide fine particles. Thus, in order to bond a group having a (meth) acryloyl group, it is preferable to modify the surface of the inorganic oxide fine particles using a silane coupling agent having a (meth) acryloyl group.

(Inorganic oxide fine particles)
Examples of the inorganic oxide fine particles include silicon, aluminum, zirconium, titanium, zinc, lead, germanium, indium, tin, antimony, cerium, lithium oxide, or a composite oxide thereof, specifically, silicon oxide ( Silica), aluminum oxide (alumina), silicon-aluminum composite oxide, zirconium oxide (zirconia), titanium oxide (titania), zinc oxide, tin oxide, antimony-doped tin oxide, indium-tin composite Examples thereof include oxides (ITO), cerium oxide, and silica-lithium oxide composite oxides. In the present invention, those containing silica (colloidal silica) as a main component are used. In the present invention, “having colloidal silica as the main component” means that 51% by weight or more of the inorganic oxide fine particles is colloidal silica, and includes that it is composed only of colloidal silica.

  The shape of the inorganic oxide fine particles is preferably spherical, hollow, porous, rod-like, fibrous or plate-like, or indefinite, and more preferably spherical. The term “spherical” as used in the present invention is intended to include not only exact spheres but also substantially spherical ones.

  The primary particle diameter of the inorganic oxide fine particles is preferably 1 to 100 nm. By setting the primary particle size to 1 nm or more, the mechanical properties are more effective, and by setting the primary particle size to 100 nm or less, secondary aggregation is more effectively prevented and loss of transparency is more effectively prevented. be able to.

  The inorganic oxide fine particles can be obtained in a dry powder state or dissolved or dispersed in water or an organic solvent. A sol dissolved or dispersed in water or an organic solvent (hereinafter sometimes referred to as an inorganic oxide fine particle sol) is preferable because it exhibits excellent dispersibility. Examples of the organic solvent include methanol, isopropanol (IPA), n-butanol, isobutanol, ethylene glycol, ethyl cellosolve, 1-methoxy-2-propanol (PGM), methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK). , Dimethylacetamide, propylene glycol monomethyl ether acetate (PMA) and xylene, and mixed solvents thereof.

  Specifically, the inorganic oxide fine particle sol is an aqueous silica sol dissolved or dispersed in water; dissolved or dispersed in an organic solvent having an OH group, a polar solvent having an ester group, or a polar solvent having a ketone group It is preferable to use organosilica sol or the like as the main component.

Examples of the aqueous silica sol include basic aqueous silica sol (manufactured by Nissan Chemical Industries, Ltd., ST-20), acidic aqueous silica sol (manufactured by Nissan Chemical Industries, Ltd., ST-O), weakly acidic aqueous silica / alumina sol ( Preferred examples include Nissan Chemical Industries, Ltd. (ST-AK) and basic silica / lithium oxide sol (Nissan Chemical Industries, Ltd., lithium silicate).
As the organosilica sol, IPA-dispersed organosilica sol (manufactured by Nissan Chemical Industries, Ltd., IPA-ST, IPA-ST-ZL), MEK-dispersed organosilica sol (manufactured by Nissan Chemical Industries, Ltd., MEK-ST, MEK-) ST-MS), MIBK-dispersed organosilica sol (manufactured by Nissan Chemical Industries, Ltd., MIBK-ST), PMA-dispersed organosilica sol (manufactured by Nissan Chemical Industries, Ltd., PMA-ST), and other OH A preferred example is a sol (for example, PGM-dispersed organosilica sol) substituted with an organic solvent having a group.

  The solid content in the dispersion is preferably 5 to 50% by weight and more preferably 10 to 40% by weight from the viewpoint of easy handling and availability.

(Silane coupling agent having (meth) acryloyl group)
A preferred example of the silane coupling agent having a (meth) acryloyl group is a silane coupling agent having a molecular weight of 300 or more and containing at least one acryloyl group and / or methacryloyl group as a radical polymerizable functional group.

  The number of acryloyl groups and / or methacryloyl groups in the silane coupling agent is not particularly limited, but preferably has 1 to 5 polymerizable functional groups per molecule. Further, the position is not particularly limited, but is preferably at the end of the molecule. The silane coupling agent is preferably an organic compound having a functional group represented by the following formula (1).

（式（１）中、ＸおよびＹは、それぞれ独立に、酸素原子、イオウ原子、またはイミノ基を表す。）

(In formula (1), X and Y each independently represents an oxygen atom, a sulfur atom, or an imino group.)

  The functional group represented by the formula (1) has an effect of increasing mechanical strength by generating an appropriate cohesive force due to hydrogen bonding between molecules, and improving the adhesion to a base material, heat resistance, etc. It also functions as a spacer between the surface of the inorganic oxide fine particles and the radical polymerizable functional group. Specific examples of such a functional group include —OCONH—, —SCONH—, —SCSNH—, —OCSNH—, —NHCONH—, —NHCSNH— and the like. Of these groups, —OCONH— and —SCONH— are particularly preferred from the viewpoints of thermal stability and ease of synthesis.

  The silane coupling agent having a (meth) acryloyl group may be an organic compound having a thioether group at the same time. The thioether group is also preferable because it acts as a spacer between the surface of the inorganic oxide fine particles and the radical polymerizable functional group or the specific polar functional group, and suppresses excessive aggregation.

  As the functional group of the silane coupling agent that can bind to the inorganic oxide fine particles, an alkoxysilyl group that is a group capable of generating a silanol group is particularly preferable. Examples of the alkoxysilyl group include a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group. Among them, a trialkoxysilyl group of a lower alcohol such as a trimethoxysilyl group or a triethoxysilyl group is reactive. This is particularly preferable. The position of these groups in the molecule is preferably at the molecular end opposite to the polymerizable unsaturated group. Moreover, it is preferable that the number of these groups in 1 molecule is 1-3, and it is more preferable that it is one.

The silanol group or silanol group-generating unit is a generated unit that binds to the inorganic oxide fine particles by a condensation reaction or a condensation reaction that occurs following hydrolysis. Some preferred examples of such compounds include the following 1) to 5), but are not limited thereto.
1) Compound in which OH group of (meth) acrylate compound having OH group and NCO group of trialkoxysilane having NCO group are bonded via —OCONH bond— 2) of trialkoxysilane compound having SH group A compound in which one NCO group of SH group and diisocyanate is bonded via -NHCOS-, and a (meth) acrylate compound having an OH group is allowed to act on the remaining NCO group, and bonded via -NHCOO- 3) NCO group Compound 4) NCO group of (meth) acrylate compound having SH and SH group of trialkoxysilane having SH group are bonded via —NHCOS— The molecule contains two or more (meth) acryloyl groups And a trialkoxysilane having an SH group is a group of the SH group into an unsaturated group ((meth) acryloyl group). Kell addition reaction compound 5 attached via a thioether generated by) alpha, .omega.-hydroxy-terminated poly and alkyl mono (meth) acrylic acid esters of glycol, a compound obtained by reacting a silane coupling agent having an NCO group

  Examples of the (meth) acrylate having an OH group include mono (meth) acrylate (for example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc.), di (meth) acrylate (for example, glycerin di (meth) ) Acrylate, trimethylolpropane di (meth) acrylate, etc.) and tri-poly (meth) acrylate (for example, pentaerythritol triacrylate, dipentaerythritol tri-pentaacrylate, ditrimethylolpropane triacrylate, etc.) are preferred.

  Trialkoxysilane compounds having an NCO group include triethoxysilylpropyl isocyanate (manufactured by Shin-Etsu Chemical, KBE9007, etc.), trimethoxysilylpropyl isocyanate, or trimethoxysilylpropyl mercaptan (manufactured by Shin-Etsu Chemical, KBM803, and Toray Dow Corning Silicon). , SH6062, etc.) and one NCO group of diisocyanate (isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), etc.) are bonded via a thiourethane bond. The compound etc. which were made can be illustrated.

  The —OCONH— bond formed by the reaction between the OH group and the NCO group is generated by blending each compound at a ratio such that NCO group / OH group ≦ 1, and mixing and stirring at 60 to 100 ° C. for 1 to 20 hours. be able to. In this reaction, it is preferable to use a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, catechol, pt-butylcatechol, and phenothiazine in order to prevent polymerization due to the acrylic group during the reaction. The blending amount of the polymerization inhibitor is preferably 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the reaction mixture. In order to accelerate the reaction, a known reaction catalyst such as di-n-butyltin dilaurate or diazabicyclooctane (DABCO) may be added. Further, this reaction is carried out by, for example, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ether solvents such as ethylene glycol diethyl ether and diethylene glycol dimethyl ether, carboxylic acid ester solvents such as ethyl acetate and butyl acetate, aromatics such as xylene and toluene. It can be carried out in a solvent that does not contain a group that can react with an isocyanate group, such as a group hydrocarbon solvent, or at the same time in the presence of a polyfunctional acrylate having three or more (meth) acryloyl groups in the molecule.

  As the (meth) acrylate compound having an NCO group, β-isocyanate ethyl (meth) acrylate (manufactured by Showa Denko, Karenz MOI (methacrylate), Karenz AOI (acrylate)), or (meth) acrylates having an OH group and And a compound in which one NCO group of a diisocyanate (for example, isophorone diisocyanate, hexamethylene diisocyanate, MDI, TDI, etc.) is bonded via a urethane bond, and the like.

  Examples of trialkoxysilane compounds having an SH group include trimethoxysilylpropyl mercaptan (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803, and Toray Dow Corning Silicon Co., Ltd., SH6062).

  The production method of -NHCOS- by the reaction of the NCO group and the SH group can be performed in the same manner as the production of -NHCOO- bond by the reaction of the NCO group and OH group.

  Examples of mono (meth) acrylic acid esters of α, ω-hydroxy-terminated polyalkylene glycol include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, poly (ethylene / Examples thereof include propylene) glycol mono (meth) acrylate and poly (ethylene / tetramethylene) glycol mono (meth) acrylate.

  The reaction of a mono (meth) acrylic acid ester of an α, ω-hydroxy-terminated polyalkylene glycol and a trialkoxysilyl compound having an NCO group is carried out in the same manner as the formation of —NHCOO— bond by the reaction of NCO group and OH group. be able to.

(Specific manufacturing method (1))
The bond between the inorganic oxide fine particles and the silane coupling agent having a (meth) acryloyl group can be achieved by various methods generally used in producing this type of compound. Basically, a method is generally used in which the alkoxysilyl group of the inorganic oxide fine particles is hydrolyzed to form a silanol group, and a condensation reaction is performed with the alkoxy group and the hydroxy group on the surface of the inorganic oxide.

In this case, the water used is used within a range that does not impair the performance of the cured film described below and the stability of the coating solution. The amount of water added may be an amount that is at least the amount that the inorganic oxide fine particles can be hydrolyzed by 100% as a theoretical amount, preferably 100 to 300% equivalent, more preferably 100 to 200% equivalent.
Examples of the water used include distilled water, ion exchange water, industrial water and soft water.

  Furthermore, in order to accelerate this hydrolysis condensation reaction, it is also possible to add an acid or an alkali, or another suitable compound as a catalyst. Also for these, various materials can be used as long as the performance of the cured film described below is not impaired and the performance of the coating solution is not impaired. Examples of the acid catalyst include inorganic acids such as hydrogen chloride solution, phosphoric acid solution and boric acid, and organic acids such as citric acid, maleic acid, acetic acid, and paratoluenesulfonic acid. Alkaline catalysts include alcoholic hydroxylation. Examples include potassium, ammonia, trialkylamines, and heterocyclic-containing amines such as dimethylaminopyridine. In addition, metal acetylacetone complexes such as aluminum triacetylacetonate are also effective. The amount of these catalysts used is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the silane coupling agent having a (meth) acryloyl group.

The reaction is preferably performed at 20 to 100 ° C. for 1 hour to 100 hours, more preferably at 20 ° C. to 25 ° C. for 4 hours or more, and then heated at 40 to 70 ° C. for 1 to 10 hours to advance the reaction. Is done.
At this time, the reaction system may be diluted with a solvent in order to suppress side reactions. In this case, the solvent used is preferably a solvent that is compatible with the water or catalyst used, for example, alcohols such as methanol, ethanol, isopropanol and isobutanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, tetrahydrofuran and Examples include ethers such as dioxane, and hydroxyl group-containing ethers such as propylene glycol monomethyl ether.

  The weight ratio (inorganic oxide fine particles / silane coupling agent) of the inorganic oxide fine particles (solid content) to be subjected to the reaction and the silane coupling agent having a (meth) acryloyl group is preferably 100 / 0.1 to 100/10. More preferably, it is 100/1 to 100/5. By setting it within such a range, an appropriate amount of mercapto groups can be introduced into the inorganic oxide fine particles, which is preferable.

Apart from the above, among the components capable of synthesizing the inorganic oxide fine particles, the bonding group represented by the formula (1), preferably -OCONH-, -SCONH-, -SCSNH-, -OCSNH-, -NHCONH- Then, after reacting the alkoxysilyl compound having a functional group capable of generating —NHCSNH— with the inorganic oxide fine particle sol, the other compound is reacted, whereby the polymerizable unsaturated group and the formula (1) A method of introducing a linking group represented, preferably —OCONH—, —SCONH—, —SCSNH—, —OCSNH—, —NHCONH—, —NHCSNH— can also be employed.
For example, among the bonding groups represented by the formula (1), as a compound having an alkoxysilyl group, a trialkoxysilane compound having an SH group is reacted in advance with inorganic oxide fine particles, and then the SH group is converted into a diisocyanate compound. The same structure as in the previous method, in which one NCO group is used to connect with an NHCOS bond, and the remaining NCO group is reacted with a (meth) acrylate compound having an OH group and then connected with an NHCOO bond. Can be obtained.

  In addition, a trialkoxysilane having an SH group is reacted with inorganic oxide fine particles, and then reacted with a (meth) acrylate compound and / or a (meth) acrylamide compound having an NCO group, whereby the same structure as the previous method is obtained. Can be obtained.

  In this case, the weight ratio (trialkoxysilane / inorganic oxide fine particles) of trialkoxysilane having an SH group to be subjected to the reaction to inorganic oxide fine particles is usually 0.1 / 99.9 to 95/5, preferably 2 / 98-90 / 10. By setting it in such a range, the surface of the inorganic oxide fine particles can be more sufficiently protected, and further, the dispersion state due to polymerization and crosslinking of the alkoxysilane itself can be further stabilized, and an increase in viscosity can be prevented. More preferable. Further, the molecular weight of the trialkoxysilane having an SH group is desirably 150 or more. Use of a material having a molecular weight of 150 or more is preferable because the effect of generating a protective colloid is further increased, and aggregation and gelation due to condensation and crosslinking of the trialkoxysilane itself having an SH group can be more effectively suppressed.

This reaction is preferably performed by heating at room temperature to 100 ° C. for 1 hour to 100 hours, more preferably at room temperature for 4 hours or more, followed by heating at room temperature to 70 ° C. for 1 to 10 hours. .
At this time, the reaction system may be diluted with a solvent in order to suppress side reactions. In this case, the solvent used is preferably a hydrolyzate silane alkoxide, water or a catalyst compatible with the catalyst, for example, alcohols such as methanol, ethanol, isopropanol, isobutanol, acetone, methyl ethyl ketone, methyl Examples thereof include ketones such as isobutyl ketone, ethers such as tetrahydrofuran (THF) and dioxane, and OH-containing ethers such as propylene glycol monomethyl ether.

  Further, a part of the silane coupling agent having a (meth) acryloyl group (less than 50% by weight) may be replaced with another silane coupling agent. Examples of other silane coupling agents include various known commercially available silane coupling agents, silane coupling agents having a polyalkylene glycol structure having no radical polymerizable functional group, COOH or COOR ′ group (R ′ is a substituted group). Silane coupling agent having an alicyclic structure, and a silane coupling agent obtained by reaction of a bulky alcohol having a branched structure with an alkoxysilyl group having an NCO group. can do.

(Specific manufacturing method (2))
Of the organic-inorganic composite (C2) used in the present invention, —O—Si—R—S—P (R represents a linear or branched alkylene group having 2 to 10 carbon atoms, and P is at least one. In addition to the above-described method, the organic-inorganic composite having a (meth) acryloyl group can be produced by the following method, and this method has a product purity and the like. It has the feature of being high.

  That is, the inorganic oxide fine particles are hydrolyzed and condensed in the presence of mercaptosilane (first step), and at least one monomer having at least one epoxy group and one radical polymerizable group is converted into a radical. This is a method in which polymerization is performed (second step), and a compound having a carboxyl group and a (meth) acryloyl group is added thereto (third step).

<First step>
Regarding the reaction and bonding of mercaptosilane and inorganic oxide fine particle sol in the first step of hydrolyzing and condensing inorganic oxide fine particles in the presence of mercaptosilane, various methods generally used in the production of this type of compound are used. Is achievable. Basically, a method is generally employed in which alkoxysilyl of mercaptosilane is hydrolyzed to form a silanol group, and then subjected to a hydrolysis condensation reaction with an alkoxy group and / or a hydroxy group on the surface of the inorganic oxide fine particles to bond them.

At this time, the water used is used in a range that does not impair the performance of the cured film described later and the stability of the coating solution. The amount of water added may be an amount equal to or more than the amount capable of hydrolyzing 100% as a theoretical amount of mercaptosilane, preferably 100-300% equivalent, more preferably 100-200% equivalent.
Examples of the water used include distilled water, ion exchange water, industrial water and soft water.

  In order to promote this hydrolysis condensation, it is also possible to add an acid or alkali, or other suitable compound as a catalyst. Also for these, various materials can be used as long as the performance of the cured film described below is not impaired and the performance of the coating solution is not impaired. Examples of the acid catalyst include inorganic acids such as hydrogen chloride solution, phosphoric acid solution and boric acid, and organic acids such as citric acid, maleic acid, acetic acid and p-toluenesulfonic acid. Alkaline catalysts include alcoholic water. Mention may be made of heterocyclic oxides such as potassium oxide, ammonia, trialkylamines and dimethylaminopyridine. In addition, metal acetylacetone complexes such as aluminum triacetylacetonate are also effective. The amount of these catalysts used is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of mercaptosilane.

The reaction is preferably performed at 20 to 100 ° C. for 1 hour to 100 hours, more preferably at 20 to 25 ° C. for 4 hours or more, and then heated at 40 to 70 ° C. for 1 to 10 hours to advance the reaction. Is done.
At this time, the reaction system may be diluted with a solvent in order to suppress side reactions. In this case, the solvent used is preferably one that is compatible with the water or catalyst to be used, for example, alcohols such as methanol, ethanol, isopropanol and isobutanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, tetrahydrofuran and dioxane. And ethers containing hydroxyl groups such as propylene glycol monomethyl ether.

  The weight ratio (mercaptosilane / inorganic oxide fine particles) of mercaptosilane and inorganic oxide fine particles (solid content) in this reaction system is preferably 0.1 / 99.9 to 95/5, more preferably 2/98. ~ 90/10. By making it within this range, an appropriate amount of mercapto groups can be introduced into the inorganic oxide fine particles, which is preferable.

<Second process>
In the second step, at least one monomer having at least one epoxy group and one radical polymerizable group is radically polymerized in the presence of the compound obtained in the first step.

  By performing radical polymerization of the above monomer in the presence of the mercapto group-containing inorganic oxide fine particles obtained in the first step, the monomer radical of the growth reaction was bonded to the inorganic oxide fine particles in the polymerization process. A chain transfer reaction with a mercapto group occurs, and the polymer and the inorganic oxide fine particles are bonded through a sulfide bond. At this time, the epoxy group in the monomer is maintained as it is.

As the monomer having at least one epoxy group and one radical polymerizable group used in the second step (hereinafter sometimes referred to as “monomer having an epoxy group”), glycidyl (meth) acrylate, 3, Preferred examples include 4-epoxycyclohexyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate.
If necessary, the monomer having the epoxy group can be radical copolymerized with other monomers. Other monomers are not particularly limited as long as they do not react with epoxy groups.

  The monomer (the monomer having an epoxy group and other monomer used in combination as required) and the inorganic oxide fine particle (solid content) having a mercapto group obtained in the first step are in a weight ratio (monomer / inorganic oxide fine particle). ) The polymerization reaction is preferably carried out at a ratio of 30/70 to 95/5, more preferably 50/50 to 90/10. By setting the weight ratio of the inorganic oxide fine particles to 70 or less, the inorganic oxide fine particles become more stable, and by setting the weight ratio to 5 or more, higher wear resistance can be obtained.

This radical polymerization reaction is carried out in a solvent using a normal radical polymerization initiator.
Solvents include alcohols (ethanol, isopropanol, isobutanol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohols having an alkoxy group (methoxyethanol, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, etc.) ), Ethers (ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc.), ether esters (propylene glycol monomethyl ether acetate, 2-ethoxyethyl acetate, etc.), aromatic hydrocarbons (toluene, xylene, etc.), esters (ethyl acetate, (Propyl acetate etc.) etc. are mentioned as a preferred example, and these may be used alone or in combination of two or more.

Examples of the radical polymerization initiator used in the polymerization reaction include peroxides such as benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, 2,2′-azoisobutyronitrile, 2,2′- Azo compounds such as azobis- (2,4-dimethylvaleronitrile) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) are preferably used.
The concentration of the monomer in the reaction system is preferably 10 to 60% by weight, and the amount of the polymerization initiator used is preferably 0.1 to 10% by weight based on the total weight of the monomers.

<Third process>
In the third step, a compound having a carboxyl group and a (meth) acryloyl group is added to the polymer synthesized in the second step.

  Examples of the compound having a carboxyl group and a (meth) acryloyl group used in the third step include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydro. Adducts of phthalic acid, pentaerythritol tri (meth) acrylate and acid anhydrides such as succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, dipentaerythritol penta (meth) acrylate and succinic anhydride, phthalic anhydride, hexahydro Examples include adducts of acid anhydrides such as phthalic anhydride.

  In this third step, the epoxy group of the polymer reacts with the carboxyl group of the compound having a carboxyl group and a (meth) acryloyl group. The polymer, the carboxyl group, and the compound having a (meth) acryloyl group are preferably mixed at a ratio of epoxy group / carboxyl group of 1 or more, more preferably 1-10.

  The reaction is preferably carried out at 50 to 110 ° C. for 3 to 50 hours. In this reaction, known catalysts such as triethylamine, tributylamine, triethylenediamine, N, N-dimethylbenzylamine, benzyltrimethylammonium chloride, and triphenylphosphine can be used to accelerate the reaction. The amount used is preferably 0.01 to 2% by weight, more preferably 0.05 to 1% by weight, based on the reaction mixture.

  In this reaction, it is preferable to use a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, catechol, pt-butylcatechol, or phenothiazine in order to prevent radical polymerization due to the (meth) acryloyl group. The amount of the polymerization inhibitor used is preferably 0.01 to 1% by weight, more preferably 0.05 to 5% by weight, based on the reaction mixture.

(Specific manufacturing method (3))
As a method for producing the organic-inorganic composite (C2), the following method may be preferable because the purity of the product is further improved.
That is, in the presence of mercaptosilane, at least one monomer having at least one epoxy group and one radical polymerizable group is radical polymerized to obtain a polymer having an alkoxysilyl group at one end, In this method, a compound having a carboxyl group and a (meth) acryloyl group is added, and the inorganic oxide fine particles are hydrolyzed and condensed in the presence of this addition reaction product.
Various conditions in this method (detailed conditions for polymerization, addition and hydrolysis condensation) are the same as those in the specific production method (2) described above.

<Content of (C1) component and / or (C2) component>
In the composition of the present invention, the component (C1) (polyfunctional (meth) acrylate containing 3 or more (meth) acryloyl groups in one molecule) and / or the component (C2) (inorganic based on colloidal silica) Organic-inorganic composite having (meth) acryloyl group bonded to fine oxide particles through —O—Si—R— bond (R represents a linear or branched alkylene group having 2 to 10 carbon atoms) )), The total content is not particularly defined unless it departs from the spirit of the present invention. However, when used as a composition requiring particularly high hardness, ((C1) component and // (C2 component)) / Polymer (A) weight ratio is preferably 99.5 / 0.5 to 80/20, more preferably 99/1 to 85/15. By setting the polymer (A) to be equal to or lower than the above upper limit, it is possible to maintain a higher hardness, and by setting the polymer (A) to be equal to or higher than the lower limit, good stain resistance can be exhibited.

<Radically polymerizable organic (meth) acrylate compound and / or (meth) acrylamide compound (D)>
As radically polymerizable organic (meth) acrylate compound and / or radically polymerizable (meth) acrylamide compound (D), organic (meth) acrylate having 1 to 2 (meth) acryl groups in one molecule Compounds and organic (meth) acrylamide compounds are preferably used for adjusting the viscosity and other physical properties of the composition.

  Examples of (meth) acrylate compounds having one (meth) acryl group in one molecule include alkyl (meth) acrylates such as butyl methacrylate and stearyl acrylate; alicyclic (meth) such as cyclohexyl acrylate and isobornyl methacrylate Examples include acrylates; heteroatom-containing cyclic structure-containing acrylates such as tetrahydrofurfuryl acrylate, etc. Other (meth) acrylates having aromatic rings, (meth) acrylates having hydroxy groups, polyalkylene glycol chains (meta) ) Acrylate and the like can be preferably used in some cases. Of course, nothing other than these is not excluded.

  Examples of (meth) acrylate compounds having two (meth) acrylic groups in one molecule include poly (alkylenes) such as di (meth) acrylates of aliphatic or alicyclic diols such as hexanediol diacrylate, and polyethylene glycol diacrylate. Glycol di (meth) acrylate and the like are preferable. Of course, nothing other than these is not excluded.

  Examples of (meth) acrylamide compounds having 1 to 2 (meth) acrylic groups in one molecule include alkyl (meth) acrylamides such as ethyl acrylamide and aminoalkyl-containing (meth) such as N, N-dimethylaminopropyl acrylamide. Acrylamide and the like are preferable. Of course, nothing other than these is not excluded.

  These (D) components (radically polymerizable organic (meth) acrylate compounds and / or radical polymerizable organic (meth) acrylamide compounds) may be used alone or in combination of two or more. It may be used.

When the composition of the present invention contains the component (D) (radically polymerizable organic (meth) acrylate compound and / or radical polymerizable organic (meth) acrylamide compound), the content is appropriately determined depending on the type. However, it is preferably 90% by weight or less, more preferably 10 to 80% by weight based on the total of the polymerizable components of the polymer (A) and the component (C1) and / or the component (C2).
By using the component (D), physical properties such as viscosity can be adjusted as described above. However, when the content is 90% by weight or less, particularly 80% by weight or less, the hardness is reduced or cured. It is preferable that the lowering of the coating property can be suppressed to an allowable range, and the viscosity of 10% by weight or more can be adjusted to a viscosity in a range substantially excellent in coating property.

<Polymer (E) other than polymer (A) having radical polymerizable group>
The polymer (E) other than the polymer (A) having a radically polymerizable group is preferably a (meta) other than the polymer (A) having a radically polymerizable group such as an acryloyl group or a methacryloyl group in the side chain. ) Acrylate polymers and copolymers of such polymers with other radical polymerizable monomers such as styrene.

  Specifically, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate were polymerized as main components. A polymer obtained by adding (meth) acrylic acid to a polymer and having a (meth) acryloyl group in the side chain is preferred. Of course, nothing other than these is not excluded. These may be used alone or in combination of two or more.

  When the composition of the present invention contains a component (E) (a polymer other than the polymer (A) having a radical polymerizable group), the content can be appropriately determined depending on the type, but the polymer (A ) And (C1) component and / or 60% by weight or less, more preferably 0 to 40% by weight, based on the total of the polymerizable components of component (C2).

  By using the component (E), other performances can be imparted or contamination resistance can be controlled. However, if the amount is too large, the hardness decreases, the applicability deteriorates, and the contamination resistance decreases. In addition, if the amount is too small, a sufficient addition effect cannot be obtained.

<Other ingredients>
In addition to the components described above, other components can be added to the composition of the present invention for the purpose of imparting various functionalities.
For example, when an ultraviolet absorber (F) and a hindered amine light stabilizer (G) are blended, the weather resistance is significantly improved, which may be preferable.

Preferred examples of the ultraviolet absorber (F) include benzotriazole, benzophenone, salicylic acid, cyanoacrylate, and triazine ultraviolet absorbers.
The hindered amine light stabilizer (G) is preferably an N-methyl compound such as Sanol LS765 (N-methyl compound of bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate). A normal NH form such as 770 (bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate) may be used.
In the case of using the ultraviolet absorber (F) and the hindered amine light stabilizer (G), the preferred blending amounts thereof vary depending on the desired weather resistance level, but in many cases, the polymers (A) and (C1) 0.5-30 weight part is preferable with respect to 100 weight part of the sum total of a component and / or (C2) component, (D) component, and (E) component, and 1-10 weight part is more preferable.

  The composition of the present invention also has an antioxidant (for example, hindered phenol-based, sulfur-based, phosphorus-based antioxidant, etc.), anti-blocking agent, slip agent, leveling agent, etc. for the purpose of improving the physical properties of the coating film. Various additives to be blended with this kind of stain resistance imparting agent may be blended. As a compounding quantity of these additives, it is preferable to set it as 0.01 to 2 weight% with respect to other solid content, respectively.

Moreover, in the composition of this invention, you may mix | blend the inorganic oxide fine particle used for the above-mentioned organic inorganic composite (C2) with an untreated for the purpose of improving hardness, blocking resistance, etc. further.
In this case, it is preferable that the compounding quantity of inorganic oxide microparticles | fine-particles shall be 0.01-20 weight% with respect to other solid content as solid content. By blending inorganic oxide fine particles, it is possible to improve the hardness and blocking resistance as described above, but if it is 20% by weight or less, an increase in viscosity can be avoided, and 0.01% by weight or more. When it is, sufficient addition effect can be acquired.

<Solvent>
The composition of the present invention may contain a solvent for viscosity adjustment for the purpose of improving handleability and coating properties. In this case, the solvent includes the above-described polymer (A) of the present invention. It may be the same as the solvent used in the production of, or may be various reaction solvents used in the production process of the organic-inorganic composite (C2), for example, used in the first process. It may be a dispersion medium of inorganic oxide fine particles to be used, or a solvent used in the reaction of the second step. Furthermore, after manufacturing the said inorganic oxide microparticles | fine-particles, the solvent used for viscosity adjustment may be sufficient. These solvents may be desirably added particularly when the composition of the present invention contains the organic-inorganic composite (C2).

  The composition of the present invention is prepared to have a solid content concentration of 10 to 80% by weight, particularly 20 to 60% by weight, particularly when used in coating applications as described later, by including such a solvent. It is preferable.

<Physical properties>
The composition of the present invention was applied to a 100 μm-thick easy-adhesion PET substrate, and an ultraviolet ray having a wavelength of 254 nm was applied to the obtained coating film with a high-pressure mercury lamp having an output density of 120 W / cm at 500 mJ / cm ^2. The content of the stain resistance-imparting group at a position of 3 nm thickness from the surface of the cured film having a thickness of 5 μm formed by irradiating with the accumulated light amount of The average content of the group is preferably 3 times or more. In addition, this ultraviolet irradiation is normally performed in an oxygen concentration atmosphere.
The preferable content of the stain resistance-imparting group will be described in detail in the section of the cured product of the present invention.

<Application>
The composition of the present invention is preferably used as a stain resistance imparting agent by applying it on a plastic substrate or a transparent substrate.
For example, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polymethyl methacrylate (PMMA), or methyl methacrylate (MMA) copolymer (for example, methyl methacrylate-styrene copolymer resin (MS resin)), polycarbonate , Special polycarbonate (for example, Teijin's Pure Ace), triacetyl cellulose, acrylonitrile butadiene styrene copolymer resin (ABS resin), modified polyolefin resin, hydrogenated polystyrene resin, cycloolefin-based transparent resin (for example, ASR made by JSR) Zeonor made by Nippon Zeon Co., Ltd.).
In addition, other transparent substrates such as thermosetting and photocurable transparent resins (for example, transparent epoxy resins, transparent urethane resins, thermosetting acrylic resins, photocurable acrylic resins, thermosetting resins) Of various organic / inorganic hybrid resins and cured products such as various photo-curable organic / inorganic hybrid resins).

  Among these, when used in optical article applications, that is, when a transparent film for optics, an optical sheet, and an optical plate are used as the transparent substrate, the substrate is coated, melt-extruded, solvent cast method It is desirable that it is a transparent resin molding formed of any of the above. Moreover, when such a base material contains a functional group that can be cured by light or heat, it may be more preferable to cure by irradiation with active energy rays or heating. These base materials may be in the form of molded articles (articles), or other layers may be interposed between the base material and the coated surface.

  Preferred examples of the method for applying the composition of the present invention include spin coating, dip coating, flow coating, spray coating, bar coating, gravure coating, roll coating, blade coating, and air knife coating.

  After applying the composition of the present invention to the base material by the above coating method, forming a coating film by solvent drying, and then irradiating an active energy ray to polymerize the polymerizable component in the composition and cure. A membrane can be obtained. The thickness of the film obtained by coating, drying, polymerization, and curing is not particularly defined, and may be, for example, 5 μm or more, or 2 μm or less. That is, the composition of the present invention is extremely significant in that both thinning and thickening are possible. The thickness of the cured film is particularly preferably 0.01 to 50 μm, particularly preferably 2 to 20 μm when the hardness is important, and particularly preferably 0.04 to 2 μm when the hardness is not relatively important. .

As the active energy ray irradiation, an ultraviolet ray emitted from a light source such as a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a carbon arc lamp, or a tungsten lamp, or an electron beam usually extracted from a particle accelerator of 20 to 2000 kV , Α-rays, β-rays, γ-rays and other active energy rays can be used, and these active energy rays are irradiated onto the coating film and cured to form a cured film.
A cured film formed by irradiation with such active energy rays is particularly preferable because of its excellent balance between productivity and physical properties.

[Cured product]
The cured product of the present invention is obtained by irradiating the above-described composition of the present invention with active energy rays to polymerize a polymerizable component in the composition, and it is particularly preferable to satisfy the following suitable physical properties. . In the following, ultraviolet irradiation is usually performed in an oxygen concentration atmosphere.

1) Pencil hardness The composition of the present invention was applied on a 100 μm thick easy-adhesive PET substrate, and the obtained coating film was irradiated with ultraviolet light having a wavelength of 254 nm of 500 mJ / cm using a high-pressure mercury lamp with an output density of 120 W / cm. It is preferable that the pencil hardness of a cured film having a film thickness of 5 μm formed by irradiating with an integrated light quantity of ² is B or more, particularly HB or more.
The pencil hardness is 6B, 5B,..., B, HB, F, H, 2H, 3H,.
In particular, when the composition of the present invention contains (C2) an organic-inorganic composite, it is applied onto a 100 μm-thick easy-adhesion PET substrate, and a high-pressure mercury lamp with an output density of 120 W / cm is used for the obtained coating film. The pencil hardness of a 10 μm-thick cured film formed by irradiating ultraviolet light having a wavelength of 254 nm so as to have an integrated light quantity of 500 mJ / cm ² is preferably 3H or more.
However, the composition used for the evaluation of the pencil hardness uses only 1-hydroxycyclohexyl phenyl ketone as the radical polymerizable photoinitiator (B) and 100 parts by weight of solid content other than 1-hydroxycyclohexyl phenyl ketone. 2 parts by weight of 1-hydroxycyclohexyl phenyl ketone.
Further, this pencil hardness depends on the radical polymerizable photoinitiator (B) for the polymerizable component in the composition in the present composition, and the base material is not PET (for example, from polycarbonate (PC)) Even if the thickness of the cured film is 2 μm or more and not 5 μm (for example, 2 μm), the suitable pencil hardness is about the same. In addition, in the cured film formed with a film thickness of 2 μm on the PC substrate as in Examples 12 and 13 to be described later, the preferable pencil hardness is HB or more.

2) Warpage amount The composition of the present invention was applied on a 100 μm-thick easy-adhesive PET substrate, and the obtained coating film was irradiated with ultraviolet light having a wavelength of 254 nm of 500 mJ / cm using a high-pressure mercury lamp with an output density of 120 W / cm. ^The amount of warpage of a cured film having a thickness of 10 μm formed by irradiating with an integrated light quantity of ² is preferably 10 mm or less, particularly preferably 2 mm or less. A method for measuring the amount of warpage will be described in the section of Examples described later.

3) Curability The composition of the present invention was applied on a 100 μm-thick easy-adhesive PET substrate, and the resulting coating film was set to an illuminance of 1000 mW / cm ² using a high-pressure mercury lamp with an output density of 120 W / cm. When a cured film having a film thickness of 0.5 μm is formed by irradiating with an ultraviolet ray having a wavelength of 254 nm, it is preferable that the curing proceeds until it becomes completely tack-free with an ultraviolet ray irradiation amount of 300 mJ / cm ² . In particular, when a cured film having a film thickness of 2 μm is formed by the same method, it is preferable that the curing proceeds until the film is completely tack-free with an ultraviolet irradiation amount of 150 mJ / cm ² . The method for evaluating the curability is described in the section of Examples below.

4) Contact angle The composition of the present invention was applied on a 100 μm-thick easy-adhesion PET substrate, and the obtained coating film was irradiated with ultraviolet light having a wavelength of 254 nm of 500 mJ / cm using a high-pressure mercury lamp with an output density of 120 W / cm. ^The contact angle of water on the surface of a cured film having a thickness of 5 μm formed by irradiating with an integrated light quantity of ² is 90 degrees or more and 120 degrees or less, particularly 95 degrees or more and 115 degrees or less. The contact angle is preferably 30 ° or more and 90 ° or less, particularly 33 ° or more and 75 ° or less. In addition, the measuring method of this contact angle is described in the item of the below-mentioned Example.

5) ESCA (XPS)
The composition of the present invention was applied on a 100 μm thick easy-adhesive PET substrate, and the obtained coating film was irradiated with UV light having a wavelength of 254 nm using a high-pressure mercury lamp with an output density of 120 W / cm, and an integrated light quantity of 500 mJ / cm ² . The content of the stain resistance-imparting group at a position of 3 nm thickness from the film surface of the 5 μm-thick cured film formed by irradiation so that The content is preferably 3 times or more, and more preferably 3.2 to 100 times. That is, according to the composition of the present invention, it is preferable that the stain resistance-imparting group is present at a high concentration specifically on the surface of the film. Such a configuration is one of the characteristics of the composition of the present invention. As a result, even if the content of the stain resistance-imparting group in the composition is low, the contamination resistance-imparting group on the surface of the coating film can be obtained. The amount increases, and the contamination resistance as a film becomes excellent.
In the present invention, the stain resistance-imparting group refers to a group that can impart stain resistance, such as a perfluoroalkyl group, a polysiloxane group, and a long-chain alkyl group having 12 or more carbon atoms.
The content of the stain resistance-imparting group can be determined, for example, by measurement with an X-ray photoelectron spectrometer (hereinafter referred to as ESCA or XPS). That is, using ESCA (XPS), the atomic ratio in the range of 3 nm from the surface can be determined and compared with the average composition ratio of the composition. Here, for example, when a fluorine-based stain resistance imparting group is used, the F / C ratio can be compared by obtaining an Si / C ratio when a silicone stain resistance imparting group is used. .

6) Abrasion resistance The composition of the present invention was applied on a 100 μm thick easy-adhesion PET substrate, and the obtained coating film was irradiated with UV light having a wavelength of 254 nm at 500 mJ / cm using a high-pressure mercury lamp with an output density of 120 W / cm. The cured film having a film thickness of 5 μm formed by irradiating so as to have an integrated light quantity of cm ² preferably has an abrasion resistance of 25.0 or less. In addition, this abrasion resistance measuring method is described in the item of the below-mentioned Example.

7) Fingerprint resistance On the surface of the cured product or cured film of the composition of the present invention, fingerprint or artificial fingerprint liquid (artificial fingerprint liquid is a mixture of triolein / 11 powders for testing, Kanto loam / methoxypropanol, Is a liquid used for the fingerprint resistance evaluation of generation optical discs), and when wiping with tissue paper at a load of 200 g, the fingerprint is completely removed by wiping within 3 reciprocations, more preferably within 2 reciprocations. It is preferable that it has a very high fingerprint resistance so that can be removed.

  Conventionally, many antifouling agents that have been developed as antifingerprinting agents for DVDs and next-generation optical disks and antifingerprinting agents for optical displays can be wiped off even if the attached amount or attached diameter is small. Sometimes, the slipperiness (slip property) is too high or the hardness is insufficient, so that it is easy to spread on the surface, and many wipes have more than 3 reciprocations, but the composition of the present invention has a hardness after curing. Since it is devised so as not to have excessive sliding properties, it has a feature that it can be wiped off with a small number of wiping.

In addition, even if fingerprints or artificial fingerprint liquids are attached, wiped 3 times with tissue paper at a load of 200 g, and wiping operations repeated 20 times, the fingerprint removal property does not deteriorate.
Even if using a stain resistance imparting agent that wipes off with a small number of wiping cycles, the conventional one is insufficient in hardness or not fixed to the film surface, so if you repeat the adhesion and wiping operation several times ~ In a few dozen times, fine scratches entered the surface, and fingerprints (or artificial fingerprint liquid) entered the gaps, or the stain resistance imparting agent itself was lost from the surface, resulting in poor fingerprint removal durability. However, since the composition of the present invention has high hardness after curing and is fixed to the film surface, the fingerprint (or artificial fingerprint liquid) can be wiped off even if the operation is repeated 20 times or more, preferably 40 times or more. It has the characteristic that it has extremely high wiping performance durability that the performance does not deteriorate.

[Article having a cured film of the composition of the present invention]
As described above, a cured product obtained by irradiating the composition of the present invention with active energy rays to polymerize a polymerizable component in the composition is excellent in characteristics such as stain resistance and hardness.
Accordingly, an article having on its surface a cured film obtained by irradiating the composition of the present invention with active energy rays is excellent in properties such as stain resistance and hardness.
The cured film may be formed by applying the composition of the present invention to the surface of the article main body and then irradiating and polymerizing with active energy rays, or may be formed by irradiating and polymerizing active energy rays. May be separately formed and then laminated on the article.
Hereinafter, an article provided with the cured film of the present invention is explained.

  The cured film of the present invention can be applied to various articles. For example, an optical recording medium, an optical display, a transparent film for agricultural greenhouses (because it is necessary to take in sunlight effectively, a contamination resistance function is necessary), Surface protection transparent film for solar cells (contamination-resistant function is necessary to prevent battery efficiency degradation), transparent film for retroreflective sign surface protection (to make the sign characters easier to see even in relatively dark lights such as headlamp lights and outside light) Therefore, it can be applied to optical lenses, optical prisms, prism sheets, automobile window materials, building window materials, spectacle lenses, and the like. In particular, it is preferably applied to an optical article that requires high transparency.

  The composition of the present invention is suitably used for forming a hard coat layer by coating, drying and curing on various substrates. In this case, the type of the substrate is not particularly limited, but a substrate made of a resin is preferable because of its high adhesiveness. The resin base material may be any of a plate shape, a sheet shape, and a film shape, and may be a molded product having an arbitrary shape. Moreover, a base material may be a part of laminated body, and another layer may be interposed between a base material and a cured film.

  The resin substrate may be a thermoplastic resin or a cured resin cured by heat or active energy rays.

  Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polymethyl methacrylate (PMMA), and methyl methacrylate (MMA) -containing copolymers (methyl methacrylate-styrene copolymer resin (MS Resin)), polycarbonate (PC), triacetyl cellulose, acrylonitrile-butadiene-styrene copolymer (ABS resin), modified polyolefin resin, fluororesin (for example, vinylidene fluoride resin (PVDF), vinyl fluoride resin (PVF)) Etc.), hydrogenated polystyrene resins, cycloolefin resins (for example, Arton manufactured by JSR, ZEONEX manufactured by ZEON, ZEONOR, and APPEL manufactured by Mitsui Chemicals, Inc.).

  Examples of the curable resin include an epoxy resin, a urethane resin, a cured product of a thermosetting or photocurable acrylic resin, a cured product such as a thermosetting or photocurable organic-inorganic hybrid resin, and the like.

  These base materials may be, for example, films formed by coating themselves, or may be molded products by various molding methods.

  Since the cured film of the present invention is excellent in transparency, stain resistance, and hardness, it is highly effective when applied to optical articles that require high transparency. At this time, when the base material needs to be transparent, the base material is preferably formed by any one of a coating method, a melt extrusion method, and a solvent cast method. Moreover, when a base material contains the functional group which can be hardened | cured with an active energy ray or a heat | fever, it may be more preferable when it hardens | cures by active energy ray irradiation or a heating. Further, in order to increase the hardness of the base material or reduce the curing shrinkage, it is preferable to contain inorganic oxide fine particles and / or urethane acrylate. The term “transparent” generally means that the transmittance of light having a target wavelength is 80% or more.

  The cured film of the present invention can also be suitably used as a stain-resistant hard coat layer for optical recording media. A typical optical recording medium is an optical disk, but the type may be any of a phase change type, a dye type, a magneto-optical type, a read-only type, and the like. Among these, high-density recording optical disks such as DVDs, HD DVDs, and Blu-Ray Discs. In order to increase the recording density, the recording mark and the beam diameter of the recording / reproducing laser beam are reduced, so that it is sensitive to dirt and scratches, and jitter is likely to increase, and recording / reproducing errors are likely to increase. Is required.

  A preferred configuration is an optical recording medium having a multilayer film having at least a recording layer or a reflective layer on a substrate, and having the cured film of the present invention on at least the outermost surface on the light incident side of the optical recording medium. is there. If there is dirt or scratches on the outermost surface on the light incident side, the recording / reproducing beam is blocked and an error occurs. Therefore, it is preferable to provide the cured film of the present invention on the outermost surface on the light incident side as a stain-resistant hard coat layer. For example, (1) the light-incident surface is opposite to the substrate side with respect to the recording layer or reflective layer, such as Blu-Ray Disc, and (2) the substrate side is opposite to the recording layer or reflective layer, such as DVD. Some are light incident surfaces. In this case, the hard coat layer needs to be light transmissive. The light transmissive property generally refers to a state where the transmittance is 80% or more with respect to light having a wavelength of recording / reproducing light. The cured film of the present invention may be provided on the outermost surface opposite to the light incident side.

  A preferred layer structure of the optical recording medium will be described below.

(1) Optical recording medium in which the multilayer film side surface is the recording / reproducing beam incident side surface The preferred layer structure of such an optical recording medium is a (reflection layer) recording layer, hard coat layer (cured film) on a substrate. ) In this order. More preferably, a light transmission layer is provided between the recording layer and the hard coat layer. Providing the light transmission layer is preferable because the distance between the light incident side outermost surface of the optical recording medium and the recording layer (reflection layer) is widened, and the recording / reproducing beam is less susceptible to contamination and scratches on the surface of the medium. The thickness of the light transmission layer is preferably 30 μm or more, and more preferably 70 μm or more. Further, the thickness of the light transmission layer is preferably 200 μm or less, and more preferably 150 μm or less.

  Arbitrary layers may be provided between the respective layers according to the purpose. For example, an inorganic protective layer made of a dielectric or the like may be provided above and below the recording layer. Alternatively, in order to increase the recording capacity, a plurality of recording layers and reflection layers may be provided via a light transmission spacer layer. The light transmissive spacer layer is provided to prevent signals from being mixed between a plurality of recording layers, and the film thickness is preferably the same as that of the light transmissive layer.

  Examples of particularly preferable layer configurations include a substrate / reflection layer / inorganic protective layer / recording layer / inorganic protective layer / light transmission layer / hard coat layer, substrate / reflection layer / light transmission layer / hard coat layer, and substrate / Reflective layer / inorganic protective layer / recording layer / inorganic protective layer / light transmissive spacer layer / reflective layer / inorganic protective layer / recording layer / inorganic protective layer / light transmissive layer / hard coat layer, substrate / inorganic protective layer / recording layer Preferred examples include / inorganic protective layer / light transmission layer / hard coat layer, but are not limited thereto.

  The materials for the substrate, the recording layer, the reflective layer, and the inorganic protective layer are not particularly limited, and any known material for optical recording media can be used.

  As the substrate, resins such as polycarbonate, polyacrylate, and polyolefin, or glass can be used. When recording / reproducing light is incident from the substrate side, the substrate needs to be transparent to the recording / reproducing light. The thickness of the substrate is usually 0.3 to 1.2 μm. In many cases, grooves (pits) or pits are formed on the substrate.

  The recording layer includes a phase change type, a dye type, and a magneto-optical type. The read-only type may not have a recording layer. For the phase change recording layer, a chalcogen-based alloy is often used, and examples thereof include a GeSbTe-based alloy, an InSbTe-based alloy, a GeSnTe-based alloy, and an AgInSbTe-based alloy. The thickness of the phase change recording layer is usually 3 nm to 50 nm. For the dye-type recording layer, azo dyes, cyanine dyes, phthalocyanine dyes, porphyrin dyes, and the like can be used, but are not limited thereto. The thickness of the dye-type recording layer is usually 50 nm to 10 μm.

  The material of the inorganic protective layer is determined in consideration of the refractive index, thermal conductivity, chemical stability, mechanical strength, adhesion, and the like, and usually a dielectric is used. As the material for the inorganic protective layer, generally, a transparent or high melting point metal, semiconductor oxide, sulfide, oxysulfide, nitride, or fluoride such as Ca, Mg, or Li is used. The thickness of the inorganic protective layer is usually about 5 to 200 nm.

  The reflective layer is preferably made of a material having high reflectance and thermal conductivity. Examples of the reflective layer material having a high reflectance and thermal conductivity include metals mainly composed of Ag, Au, Al, Cu and the like. Among them, Ag has a higher reflectance and thermal conductivity than Au, Al, and Cu. These include Cr, Mo, Mg, Zr, V, Ag, In, Ga, Zn, Sn, Si, Cu, Au, Al, Pd, Pt, Pb, Ta, Ni, Co, O, Se, V, Nb , Ti, O, N, etc. may be included up to about 5 atomic%. The thickness of the reflective layer is usually 30 to 200 nm. The reflective layer may be a so-called semi-reflective layer.

  The light-transmitting layer and the light-transmitting spacer layer need only be light-transmitting and have a predetermined thickness, and the material and formation method are not particularly limited, but a resin composition is usually used, and the following two methods are typically used. Formed with. The first method is a method in which a curable resin composition is applied by spin coating or the like and then cured by light or heat to form a film. When urethane acrylate is contained at this time, the hardness and scratch resistance of the surface can be increased while suppressing warpage due to curing shrinkage, which is preferable. In addition, it is also preferable to contain inorganic oxide fine particles such as colloidal silica within the range not impairing the light transmittance, in order to increase the surface hardness and scratch resistance. The second method is a method in which a film produced by solvent casting or melt extrusion molding is attached directly or via an adhesive. At this time, in order to further increase the hardness and scratch resistance of the surface, it is preferable to contain inorganic oxide fine particles such as colloidal silica as long as the light transmittance is not impaired. In some cases, grooves (pits) or pits are formed in the light transmitting spacer layer.

  The formation method of the hard-coat layer which consists of a cured film of the composition of this invention is demonstrated. A general method is to form a cured film by applying an active energy ray after coating on the above-described layer by spin coating or the like. Alternatively, after coating on a peelable film and polymerizing and curing by irradiation with active energy rays to form a film, the film side is attached to the optical recording medium directly or via an adhesive, and the film is peeled off to form a hard coat layer A method is also preferred. Furthermore, after applying the composition of the present invention to a film produced by solvent casting or melt extrusion molding, it is polymerized by irradiation with active energy rays to form a cured film, directly or via an adhesive. A method of forming the light transmission layer and the hard coat layer at the same time is also preferable.

Examples of the optical recording medium having such a layer structure include a Blu-Ray Disc.
In either method, in order to further increase the hardness and scratch resistance of the surface, it may be preferable to mix the inorganic oxide fine particles within a range that does not impair other properties such as transparency.
In particular, when the composition is formed by spin coating, cured, and formed into a film, the use of a composition that increases the hardness of the film usually tends to cause warping due to curing shrinkage. In order to avoid this, it may be particularly preferable to include inorganic oxide fine particles and / or urethane acrylate.

(2) Optical recording medium whose surface on the substrate side is the surface on the recording / reproducing beam incident side A preferable layer structure of such an optical recording medium has a recording layer (reflection layer) on the substrate in this order, and the other side of the substrate A hard coat layer is provided on the surface. Recording / reproducing light is incident on the recording layer and the reflecting layer through the hard coat layer and the substrate. A light transmission layer may be provided between the substrate and the hard coat layer.

  Arbitrary layers may be provided between the respective layers according to the purpose. For example, an inorganic protective layer made of a dielectric or the like may be provided above and below the recording layer. In order to increase the recording capacity, a plurality of recording layers and reflection layers may be provided via a light transmission spacer layer.

  Examples of particularly preferred layer structures include hard coat layer / substrate / inorganic protective layer / recording layer / inorganic protective layer / reflective layer, hard coat layer / substrate / reflective layer, and hard coat layer / substrate / inorganic protective layer. / Recording layer / Inorganic protective layer / Reflective layer / Light transmissive spacer layer / Inorganic protective layer / Recording layer / Inorganic protective layer / Reflective layer, Hard coat layer / Light transmissive layer / Substrate / Inorganic protective layer / Recording layer / Inorganic protective layer / Reflective layers and the like are preferred, but are not limited thereto.

  The material and thickness of each layer are preferably the same as (1).

  Examples of the optical recording medium having such a layer structure include various DVDs (including a DVD having a plurality of recording layers) such as DVD ± R, DVD ± RW, and DVD-RAM, and HD DVD.

  The formation method of the hard coat layer in this configuration is generally a method in which the composition of the present invention is applied on a substrate or the like by spin coating or the like, and then polymerized and cured by irradiation with active energy rays to form a film.

  The composition of the present invention can also be suitably used for optical display applications. In particular, it is preferable as an agent for imparting stain resistance to the display panel surface of flat display (liquid crystal display, plasma display, rear projection display, front projector screen, inorganic EL display, organic EL display, etc.). It can be preferably used as a hard coat layer on the surface of a mobile information terminal (PDA, etc.), a display having a touch panel input function in a PC monitor or the like, or a flat TV (particularly a liquid crystal television) widely used at home.

  When the composition of the present invention is applied to a laminate used for such a display, a transparent resin substrate is used, and at least one outermost surface of the laminate is irradiated with active energy rays on the composition of the present invention. It is preferable to form a cured film formed by polymerization.

A cured product obtained by polymerizing the composition of the present invention by irradiation with active energy rays is excellent in properties such as stain resistance and hardness.
An article having on its surface a film obtained by polymerizing the composition of the present invention by irradiating active energy rays is excellent in properties such as stain resistance and hardness. After the composition is applied to the surface of the article, the composition may be polymerized by irradiation with active energy rays, or a film polymerized by irradiation with active energy rays may be laminated on the article.

The present invention will be described more specifically with reference to the following examples. The materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
In the examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.

  The evaluation method of the general physical properties of the coating film in Examples etc. is shown below.

(1) Transparency: The haze value was evaluated based on the conditions of JIS K-7105.

(2) Pencil hardness: Using a JIS-compliant pencil hardness meter (manufactured by Dazai Equipment Co., Ltd.), measurement was performed based on the conditions of JIS K-5400, and the hardness was indicated by the hardest pencil number without scratches.

(3) Abrasion resistance: A wear wheel (manufactured by Calibrase: CS-10F) was used to perform a 100-rotor Taber abrasion test at a load of 500 g, and the difference ΔH (% between the haze value after the Taber abrasion test and the haze value before the test ).

(4) Contact angle The contact angle with water was measured by using a contact angle meter (DropMaster 500, manufactured by Kyowa Interface Science Co., Ltd.) after 1 minute of dropping 0.002 ml of pure water on the cured film. ).
The contact angle with respect to hexadecane was measured using a contact angle meter (DropMaster 500, manufactured by Kyowa Interface Science Co., Ltd.) 1 minute after dropping 0.002 ml of hexadecane on the cured film.

(5) Adhesiveness: Tested by a grid pattern method described in JIS K5400. The cured film was filled with 100 grids at 1 mm intervals and tested with cellophane tape (manufactured by Nichiban Co., Ltd.). For the evaluation method, the same operation was repeated five times (a new cellophane tape was always used), no scratch or peeling occurred at all, △ 10% or less scratching or peeling occurred, and the others x , And changed the method to be evaluated.

(6) Fingerprint wiping property (1-1): The nasal oil was used as a substitute for sebum, the nasal oil was applied to the thumb, and the thumb was pressed against the cured film for 3 seconds, thereby attaching the fingerprint to the cured film. The surface of the fingerprint was lightly wiped with tissue paper (manufacturer: Crecia), and the number of reciprocations until it became visually invisible with a distance of 15 cm was defined as fingerprint wiping property (1-1).

(7) Fingerprint wiping property (1-50): The above-described fingerprint wiping property (1-1) operation was repeated on the same cured film, and the number of repetitions was repeated up to the 50th. In the 50th operation, the surface of the fingerprint was lightly wiped with tissue paper (manufacturer: Crecia), and the number of reciprocations until it was visually invisible in a state 15 cm away was defined as fingerprint wiping property (1-50).
If the fingerprint wiping property (1-1) and the fingerprint wiping property (1-50) are the same number of reciprocations, the fingerprint wiping repeatability is excellent.

(8) Fingerprint wiping property (2): The surface of the cured film was rubbed 100 times with an eraser and evaluated in the same manner as the fingerprint wiping property (1-1).

(9) Durability of fingerprint wiping: The nasal oil was used as a substitute for sebum, the nasal oil was placed on the thumb, the thumb was pressed against the cured film for 3 seconds, and the cured film was fingerprinted. An operation of wiping the fingerprint with a tissue paper (manufacturer: Crecia) wound around a weight of 200 g was performed three times. This operation was repeated up to the 20th time. After the 20th operation, it was marked as ◯ if it was not visible visually at a distance of 15 cm, and x if visible.
Compared with the evaluations in (6) and (7), this is a durability test under a high load.

(10) Artificial fingerprint liquid adhesion: Artificial fingerprint liquid (artificial fingerprint liquid is a mixture of triolein / 11 powders for testing, Kanto loam / methoxypropanol = 1 / 0.4 / 10 (weight ratio), next generation. A liquid used in the fingerprint resistance evaluation of optical discs) was spin-coated on a polycarbonate resin substrate at 3000 rpm and dried at 60 ° C. for 3 minutes to prepare an artificial fingerprint liquid master.
On this master, no. 1. Prepare a transfer material with the smaller end face of silicone rubber uniformly roughened with # 240 abrasive paper, press the roughened end face with a constant load of 4.9 N for 10 seconds, and then evaluate the curing The end face is pressed against the film surface with a constant load of 4.9 N (operation L1).
Further, the operation of pressing the roughened end face on the master disk with a constant load of 4.9 N for 10 seconds was repeated n times continuously to increase the adhesion amount of the artificial fingerprint liquid, and then to the cured film surface to be evaluated. The end face is pressed with a constant load of 4.9 N (operation Ln).
By visually observing the adhesion diameter of the artificial fingerprint liquid by this operation with a microscope with a scale of 100 times, the operation Ln in which n is maximum within the range where the maximum adhesion diameter is kept to 20 μm or less is defined as the artificial fingerprint liquid adhesion. did.
L3 or L4 is preferable, and L4 is more preferable.

(11) Artificial fingerprint liquid wiping property: L4 of the artificial fingerprint liquid adhesion operation described in the evaluation in (10) was performed, and the surface of the artificial fingerprint liquid adhered was lightly wiped with tissue paper (manufacturer: Crecia), 15 cm away In such a state, the number of reciprocations until visual invisibility was lost was defined as the artificial fingerprint liquid wiping property.

(12) Durability of wiping artificial fingerprint liquid: Tissue paper (manufacturer: Crecia) in which L4 of the artificial fingerprint liquid adhesion operation described in the evaluation of (10) was performed and the adhered artificial fingerprint liquid was wrapped around a 200 g weight The wiping operation was performed three times. This operation was repeated up to the 20th time. After the 20th operation, it was marked as ◯ if it was not visible visually at a distance of 15 cm, and x if visible.

(13) Sensation of wiping: The above-mentioned fingerprint wiping property (2) is large or small on the surface, and the wiping sensation is either ◯: large slipping, Δ: small slipping, ×: no slipping. Evaluated.

(14) Anti-magic adhesion: Draw a line on the cured film with an oil-based magic marker (Zebra's Mackie Care extra-fine (black) thin), and after 30 seconds, if the line is repelled, ○, otherwise it is × did.

(15) Magic wipeability: Draw a line on the cured film with an oil-based magic marker (Zebra's Mackey Care extra fine (black) fine), and after 30 seconds, wipe the surface with tissue paper (manufacturer: Crecia) within 3 reciprocations If it was wiped off, it was rated as ○, and if it was not wiped out, it was marked as x.

Reference Example 1: Synthesis of polymer (A-01) within the scope of the present invention 40 g of perfluorooctylethyl methacrylate, 20 g of methyl methacrylate, 10 g of α, ω-dimercaptopropylpolydimethylsiloxane (number average molecular weight 1600), glycidyl methacrylate 30 g, 2 g of dodecyl mercaptan (M (a1) / M (a3) = 1.78, SH group / epoxy group = 0.106), 200 g of 1-methoxy-2-propanol (PGM) are added, and the internal temperature is a nitrogen stream The temperature was raised to about 60 ° C. below. Thereafter, 2,2-azobis (2,4-dimethylvaleronitrile) (V65) was divided into two portions, a total of 1.5 g was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C., V65 was completely deactivated, and then returned to room temperature. The solid concentration was about 34%.
Next, after heating to 90 ° C. in an air atmosphere, 0.1 g of p-methoxyphenol and 0.5 g of triphenylphosphine were added. After 5 minutes, 15.3 g of acrylic acid was dissolved in 50 g of PGM and added dropwise over 30 minutes. During this time, the liquid temperature was kept at 90 to 105 ° C. Thereafter, the liquid temperature was raised to 110 ° C., maintained at this temperature for 8 hours, and then returned to room temperature. The solid content was 33% (A-01).

Reference Example 2: Synthesis of polymer (A-02) within the scope of the present invention Perfluorooctylethyl methacrylate 50 g, lauryl methacrylate 10 g, α, ω-dimercaptopropylpolydimethylsiloxane (number average molecular weight 1600) 10 g, glycidyl methacrylate 30 g, 2 g of dodecyl mercaptan (M (a1) / M (a3) = 1.78, SH group / epoxy group = 0.106) and 200 g of PGM were added, and the internal temperature was raised to about 60 ° C. in a nitrogen stream. Thereafter, V65 was divided into two portions, 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C., V65 was completely deactivated, and then returned to room temperature. The number average molecular weight was 15000 and the solid content concentration was about 34%.
Next, after heating to 90 ° C. in an air atmosphere, 0.1 g of p-methoxyphenol and 0.5 g of triphenylphosphine were added. After 5 minutes, 15.3 g of acrylic acid was dissolved in 50 g of PGM and added dropwise over 30 minutes. During this time, the liquid temperature was kept at 90-105 ° C. Thereafter, the liquid temperature was raised to 110 ° C., maintained at this temperature for 8 hours, and then returned to room temperature. The solid content was 33% (A-02).

Reference Example 3: Synthesis of polymer (A-03) within the scope of the present invention 50 g of perfluorooctylethyl methacrylate, 10 g of lauryl methacrylate, 10 g of α, ω-dimercaptopropylpolydimethylsiloxane (number average molecular weight 1600), glycidyl methacrylate 30 g, 2 g of dodecyl mercaptan (M (a1) / M (a3) = 1.78, SH group / epoxy group = 0.106) and 200 g of PGM were added, and the internal temperature was raised to about 60 ° C. in a nitrogen stream. Thereafter, V65 was divided into two portions, 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C., V65 was completely deactivated, and then returned to room temperature. The solid concentration was about 34%.
Next, after heating to 90 ° C. in an air atmosphere, 0.1 g of p-methoxyphenol and 0.5 g of triphenylphosphine were added. After 5 minutes, 125.7 g of TO-756 (Nippon Kayaku; pentaerythritol triacrylate modified with succinic anhydride) was dissolved in 150 g of PGM and added dropwise over 30 minutes. During this time, the liquid temperature was kept at 90-105 ° C. Thereafter, the liquid temperature was raised to 110 ° C., maintained at this temperature for 8 hours, and then returned to room temperature. The solid content was 39% (A-03).

Reference Example 4: Synthesis of polymer (A-04) within the scope of the present invention 35 g of methyl methacrylate, 15 g of α, ω-dimercaptopropylpolydimethylsiloxane (number average molecular weight 1600), 50 g of glycidyl methacrylate, 2 g of dodecyl mercaptan (M (A1) / M (a3) = 0.52, SH group / epoxy group = 0.081) and 200 g of PGM were added, and the internal temperature was raised to about 60 ° C. under a nitrogen stream. Thereafter, V65 was divided into two portions, 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C., V65 was completely deactivated, and then returned to room temperature. The solid concentration was about 34%.
Next, after heating to 90 ° C. in an air atmosphere, 0.1 g of p-methoxyphenol and 0.5 g of triphenylphosphine were added. After 5 minutes, 25.5 g of acrylic acid was dissolved in 50 g of PGM and added dropwise over 30 minutes. During this time, the liquid temperature was kept at 90-105 ° C. Thereafter, the liquid temperature was raised to 110 ° C., maintained at this temperature for 8 hours, and then returned to room temperature. The solid content was 35% (A-04).

Reference Example 5: Synthesis of polymer (X-01) outside the scope of the present invention 40 g of perfluorooctylethyl methacrylate, 20 g of methyl methacrylate, 10 g of α, ω-dimercaptopropylpolydimethylsiloxane (number average molecular weight 1600), glycidyl methacrylate 30 g, 0.1 g of dodecyl mercaptan (M (a1) / M (a3) = 0.039, SH group / epoxy group = 0.061) and 200 g of PGM were added, and the internal temperature was raised to about 60 ° C. in a nitrogen stream. . Thereafter, V65 was divided into two portions, 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C., V65 was completely deactivated, and then returned to room temperature. The solid concentration was about 34%, but the liquid was partially turbid and insoluble was present.
Next, after heating to 90 ° C. in an air atmosphere, 0.1 g of p-methoxyphenol and 0.5 g of triphenylphosphine were added. After 5 minutes, 15.3 g of acrylic acid was dissolved in 50 g of PGM and added dropwise over 30 minutes. During this time, the liquid temperature was kept at 90-105 ° C. Thereafter, the liquid temperature was raised to 110 ° C., maintained at this temperature for 8 hours, and then returned to room temperature. Although the solid content was 33%, insoluble matter and agglomerates were considerably generated, which was not preferable for subsequent use (X-01).

Reference Example 6: Synthesis of polymer (X-02) outside the composition range of the present invention 45 g of methyl methacrylate, 15 g of α, ω-dimercaptopropylpolydimethylsiloxane (number average molecular weight 1600), 40 g of glycidyl methacrylate, 0 of dodecyl mercaptan 0 0.1 g (M (a1) / M (a3) = 0.026, SH group / epoxy group = 0.069) and PGM 200 g were added, and the internal temperature was raised to about 60 ° C. under a nitrogen stream. Thereafter, V65 was divided into two portions, 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C., V65 was completely deactivated, and then returned to room temperature. The solid concentration was about 34%, but the liquid was partially turbid and a slight gel content was generated.
Next, after heating to 90 ° C. in an air atmosphere, 0.1 g of p-methoxyphenol and 0.5 g of triphenylphosphine were added. After 5 minutes, 25.5 g of acrylic acid was dissolved in 50 g of PGM and added dropwise over 30 minutes. During this time, the liquid temperature was kept at 90-105 ° C. Thereafter, the liquid temperature was raised to 110 ° C., maintained at this temperature for 8 hours, and then returned to room temperature. Although the solid content was 35%, a considerable amount of insoluble matter and gel content was generated, which was not preferable for subsequent use (X-02).

Reference Example 7: Synthesis of silane coupling agent having polyfunctional acrylic group by reaction of OH-containing polyfunctional acrylate and NCO-containing silane coupling agent Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku) , Kaylad DPHA) 1 kg, γ-triethoxysilylpropyl isocyanate (Shin-Etsu Silicone, KBE9007) 50 g, dibutyltin dilaurate 0.2 g, hydroquinone monomethyl ether 0.5 g were stirred and mixed, and then heated to 90 ° C. in an air stream. The temperature was maintained for 1 hour. It was confirmed by IR that the absorption corresponding to the NCO group had completely disappeared, and then returned to room temperature, and the product was taken out (silane coupling agent 1, hereinafter referred to as SC1). This reaction was quantitative.

Reference Example 8: A (meth) acryloyl group is bonded to the surface of an inorganic oxide fine particle through a -O-Si-R- bond by a reaction between colloidal silica and a silane coupling agent having a polyfunctional acrylic group. Synthesis of Organic-Inorganic Composite (C2-01) 400 g of MEK-dispersed organosilica sol (manufactured by Nissan Chemical Industries, MEK-ST, 30% MEK dispersion, primary particle size 10-20 nm), 400 g of SC1 above, hydroquinone monomethyl ether 4 g and 4 g of acetylacetone aluminum are thoroughly stirred and mixed, 8 g of pure water is added, and stirring is continued for 3 hours or more at room temperature. Thereafter, the temperature is raised to 50 to 70 ° C. in an air atmosphere, and stirring is continued at that temperature for 2 hours or more. A silane coupling agent is reacted with the surface of the silica sol to form a protective colloid, and the target organic-inorganic composite (C2 −01) was obtained.

Reference Example 9: A (meth) acryloyl group is bonded to the surface of an inorganic oxide fine particle through a -O-Si-R- bond by a reaction between colloidal silica, a silane-terminated polymer having an acrylic group, and colloidal silica. After mixing 95 g of glycidyl methacrylate, 3 g of mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803), 200 g of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMAc), The temperature was raised to about 60 ° C. in a nitrogen stream. Thereafter, V65 was divided into two portions, 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 100 ° C., and V65 was completely deactivated. Then, 200 g of PGMAc and 1.5 g of triphenylphosphine were added, and stirring was continued in an air atmosphere until uniform. Thereafter, a mixture of 49 g of acrylic acid / 10 g of PGMAc was added over about 20 minutes, and then the internal temperature was raised to 110 ° C. and maintained and stirred for 8 hours or more to complete the reaction between acrylic acid and epoxy groups. After returning the content mixture to room temperature, 163 g of MEKST and 0.04 g of aluminum acetylacetonate were added. After stirring until uniform, 0.99 g of pure water was added, and at room temperature for 3 hours, about 4 hours at 50 to 70 ° C. Time reaction was performed. Thereafter, the internal temperature was returned to room temperature. The solid content concentration was about 30%, and the target organic-inorganic composite (C2-02) was obtained.

Reference Example 10: A (meth) acryloyl group is bonded to the surface of an inorganic oxide fine particle through a -O-Si-R- bond by a reaction between colloidal silica, a silane-terminated polymer having an acrylic group, and colloidal silica. After mixing 95 g of glycidyl methacrylate, 2 g of mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803), 200 g of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMAc), The temperature was raised to about 60 ° C. in a nitrogen stream. Thereafter, V65 was divided into two portions, 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 100 ° C., and V65 was completely deactivated. Then, 200 g of PGMAc and 1.5 g of triphenylphosphine were added, and stirring was continued in an air atmosphere until uniform. Thereafter, a mixture of 39 g of acrylic acid / 10 g of PGMAc was added over about 20 minutes, and then the internal temperature was raised to 110 ° C. and maintained and stirred for 8 hours or more to complete the reaction between acrylic acid and epoxy groups. After returning the content mixture to room temperature, 163 g of MEKST and 0.04 g of aluminum acetylacetonate were added. After stirring until uniform, 0.99 g of pure water was added, and at room temperature for 3 hours, about 4 hours at 50 to 70 ° C. Time reaction was performed. Thereafter, the internal temperature was returned to room temperature. The solid content concentration was about 28%, and the target organic-inorganic composite (C2-03) was obtained.

Reference Example 11: Synthesis of polymer (X-03) outside the scope of the present invention 70 g of methyl methacrylate, 30 g of cyclomer M100 (manufactured by Daicel) and 200 g of MEK were added, and the internal temperature was raised to about 60 ° C. under a nitrogen stream. Thereafter, V65 was divided into two portions, 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C., V65 was completely deactivated, and then returned to room temperature. The solid concentration was about 34% (X-03).
Since this product is a polymer having no stain-resistant group, the contact angle of the coating film does not exceed 90 degrees.

Examples 1-13, Comparative Examples 1-3
The composition (weight ratio) shown in Table 1 was applied to the substrate shown in Table 1 so that a cured film having the thickness shown in Table 1 was formed, and then dried at 80 ° C. to remove the solvent. Thus, a dry film was formed. Using a high-pressure mercury lamp with an output density of 120 W / cm, this was cured by irradiating ultraviolet rays with a wavelength of 254 nm in an ordinary oxygen concentration atmosphere so as to have an integrated light quantity of 500 mJ / cm ² , and the cured film had transparency (haze), Pencil hardness, abrasion resistance, contact angle and adhesion were evaluated.
The evaluation results are shown in Table 2.
Examples 12 and 13 in which a cured film having a thickness of 2 μm was formed on a PC film correspond to DVD applications.

As is clear from the above results, the cured film obtained from the polymer (A) of the present invention, as shown in Examples 1 to 13, is a single cured film (Examples 1 to 4) or pencil hardness. It was clear that the hardness was higher (both HB and higher), and the hardness was superior to the polymer outside the present invention such as Comparative Example 1. In addition, it was excellent in wear resistance and adhesion, and water and oil repellency was clearly superior to the case of using a polymer outside the present invention as in Comparative Examples 1 and 2.
Comparative Example 3 is excellent in abrasion resistance, water repellency / oil repellency, but since a polymer outside the scope of the present invention was used, an agglomerate was formed, and the coating film appearance, transparency, adhesion, etc. were poor. Clearly it is not preferred.

Further, the cured films of Examples 1 to 13 and Comparative Examples 1 to 3 were evaluated for durability of stain resistance (fingerprint resistance). Specifically, fingerprint wiping property (1-1), fingerprint wiping property (1-50), fingerprint wiping property (2), fingerprint wiping durability, and wiping feeling were evaluated.
The results are shown in Table 3.

From the above results, the following is clear.
It was confirmed that the cured films of Examples 1 to 13 were able to substantially wipe off the attached fingerprint by reciprocating the tissue paper 1 to 2 and had excellent fingerprint wiping properties. In addition, even after fingerprinting and wiping operations after 100 reciprocations with an eraser, the original feeling of wiping (slippery when wiping off, can be wiped off with a slight rub) is not impaired and is durable. It was excellent in nature.
On the other hand, the cured films of Comparative Examples 1 to 3 require two or more reciprocations to wipe off the attached fingerprint (fingerprint wiping properties (1-1) and (1-50)), or are inferior in repeated wiping durability ( The fingerprint wiping property (1-50) is larger than the fingerprint wiping property (1-1)), and the performance is clearly inferior to that of the present invention.

In addition, about the cured film of Example 3, when F / C ratio was measured in ESCA (Shimadzu Corporation ESCA1000), while the average composition of the whole cured film was F / C = 0.066, cured film The composition at a position 3 nm thick from the surface was F / C = 0.226, and it was confirmed that fluorine atoms were concentrated 3.4 times on the surface.
As a result, even if the amount of the stain resistance imparting group in the composition is, for example, 1% by weight, the stain resistance imparting group is efficiently concentrated on the surface of the cured film, thereby realizing high stain resistance. It was recognized that it was possible.

Moreover, the composition of Examples 1 and 5 was made into PET film (Mitsubishi Chemical Polyester Film T600EU07 thickness 100 μm (Haze = 1.1%)) and the cured thickness to 0.5, 2, 5, and 10 μm, respectively. The total irradiation dose required to cure by changing the dose at an illuminance of 1000 mW / cm ² using a high-pressure mercury lamp with an output density of 120 W / cm for the coating film formed with varying thickness. The curability was evaluated by measuring. The amount of warpage of the obtained cured film is obtained by cutting the film having the cured film obtained above into 10 cm squares, measuring the amount of warpage of the four corners with a gap gauge, and taking the average value thereof. It was measured by. The results are shown in Table 4.

  From Table 4, it can be seen that the composition of the present invention is excellent in curability and has a small amount of warpage.

Reference Example 12
A reflective layer, a second dielectric layer, a recording layer, a first layer are formed on the surface on which a groove of a disk-shaped support substrate (made of polycarbonate, thickness 1.1 mm, diameter 120 mm) on which grooves are formed for information recording is formed. An optical recording medium for Blu-ray disc (intermediate product) on which one dielectric layer was formed was prepared.
After applying a radical polymerizable active energy ray curable material having the following composition to the surface of the first dielectric layer by a spin coating method, an integrated light quantity of 1000 mJ / cm ² is obtained using a high-pressure mercury lamp with an output density of 60 W / cm. UV light irradiation was performed to form a light-transmitting protective layer having a thickness of 98 μm after curing. The pencil hardness of this surface was 4B.

(Composition of radically polymerizable active energy ray-curable material for light transmission protective layer)
60 parts by weight of urethane acrylate oligomer (urethane acrylate produced by reacting an isocyanate-terminated oligomer obtained by adding isophorone diisocyanate to polytetramethylene glycol having an average molecular weight of 800 to hydroxyethyl acrylate)
Isocyanuric acid ethylene oxide modified triacrylate (Toagosei Co., Ltd., Aronix M313) 20 parts by weight Tetrahydrofurfuryl acrylate 20 parts by weight Irgacure 184 3 parts by weight

Examples 14-18, Comparative Examples 4-6
A composition for spin coating was prepared with a composition (weight ratio) as shown in Table 5.
This composition was applied onto the transparent protective layer formed in Reference Example 12 by a spin coating method to form a film. In this step, the solvent was substantially removed and a dry coating film could be obtained. A high pressure mercury lamp with an output density of 60 W / cm was used to irradiate the coating film with ultraviolet rays in an atmosphere of a normal oxygen concentration at an integrated light quantity of 1000 mJ / cm ² to form a hard coat layer having a thickness of 2 μm after curing. About the surface physical properties of the hard coat layer, appearance (visual evaluation), pencil hardness, adhesion, contact angle (water, hexadecane), stain resistance (artificial fingerprint liquid adhesion, artificial fingerprint liquid wiping property, artificial fingerprint liquid wiping) Durability, anti-magic adhesion, and magic wiping properties were evaluated. The results are shown in Table 7 for contamination resistance and Table 6 for other physical properties.

As is clear from the above results, the hard coat layers prepared from the compositions within the scope of the present invention (Examples 14 to 18) have a high contact angle, and thus have excellent adhesion resistance out of the contamination resistance. As a result, it is preferable because it is excellent in wiping property and wiping durability, but it is a composition outside the scope of the present invention (Comparative Examples 4 to 6; all of them have been proposed as a stain resistance imparting agent for hard coating agents for optical discs. The contact angle to hexadecane is low among the contact angles, and it is inferior to the anti-fouling property of the stain resistance, or the fingerprint stains are likely to spread during wiping, resulting in wiping properties and wiping. It was inferior in durability and inferior to a hard coat layer prepared from the composition of the present invention.
In addition, Examples 14-18 which formed the cured film with a film thickness of 2 micrometers on the PC base material through the light transmission protective layer respond | correspond to Blu-ray Disk use.

For reference, we evaluated the pencil hardness, contact angle, and stain resistance of optical discs (next generation optical discs (Blu-ray Discs)) that have a hard coat film coated and cured with a commercially available anti-contamination hard coat agent. did.
The results are shown in Table 8.
Except for TDK data, the adhesion of the artificial fingerprint liquid was at the L3 level, the wiping property exceeded 3 reciprocations, and was clearly inferior to the hard coat film coated and cured with the composition of the present invention.
For TDK data, it is excellent in pencil hardness, artificial fingerprint liquid adhesion, wiping, and anti-magic adhesion, but it has a multi-layer hard coat layer structure consisting of an antifouling layer and a hard coat layer. Further, it is clearly disadvantageous as compared with the disks of Examples 14 to 18 using the composition of the present invention.

Claims (19)

(A1) α, ω-dimercaptopolysiloxane: 1 to 20 parts by weight,
(A2) (meth) acrylate having an epoxy group: 15 to 60 parts by weight,
(A3) Monofunctional mercaptan having a molecular weight of 100 to 300: 0.5 to 5 parts by weight
And (a4) Other radical polymerizable monomer: 15 to 83.5 parts by weight in total, and 100 parts by weight of (a1) mercapto group / (a3) mercapto group is 0.2 to 20 (mol / (Mole) having a structure corresponding to a structure obtained by reacting 1 to 5 (meth) acryloyl group-containing carboxylic acid with at least part of the epoxy group of the radical polymer of the monomer mixture. (A).   The polymer (A) according to claim 1, wherein the (a1) α, ω-dimercaptopolysiloxane is α, ω-dimercaptopropylpolydimethylsiloxane.   The monomer mixture contains 1 to 60 parts by weight of (a4-1) a radically polymerizable monomer having a perfluoroalkyl group and / or a perfluoroalkylene group as the (a4) other radically polymerizable monomer. 2. The polymer (A) according to 2. A composition in which 100 parts by weight of the polymer (A) is mixed with 3 parts by weight of 1-hydroxycyclohexyl phenyl ketone (however, this composition contains only the polymer (A) and 1-hydroxycyclohexyl phenyl ketone as a solid content) Is applied to a 100 μm-thick easy-adhesive PET substrate, and a high-pressure mercury lamp with an output density of 120 W / cm is used for the obtained coating film so that ultraviolet light with a wavelength of 254 nm has an integrated light quantity of 500 mJ / cm ^2. The pencil hardness of a cured film having a thickness of 5 μm formed by irradiating the film is B or more, the contact angle with water of the cured film is 90 degrees or more, and the contact angle with hexadecane is 30 degrees or more. Item 4. The polymer (A) according to any one of Items 1 to 3.   A composition comprising the polymer (A) according to any one of claims 1 to 4 and a radical polymerizable photoinitiator (B).   Furthermore, a polyfunctional (meth) acrylate (C1) containing 3 or more (meth) acryloyl groups in one molecule and / or inorganic oxide fine particles containing colloidal silica as a main component is added to —O—Si—R—. The organic-inorganic composite (C2) having a (meth) acryloyl group bonded via a bond (R represents a linear or branched alkylene group having 2 to 10 carbon atoms). Composition.   Furthermore, from a radically polymerizable organic (meth) acrylate compound and / or a radically polymerizable organic (meth) acrylamide compound (D) and a polymer (E) having a radically polymerizable group other than the polymer (A). The composition according to claim 5 or 6, comprising at least one selected from the group consisting of: The composition is applied onto a 100 μm-thick easy-adhesive PET substrate, and an ultraviolet ray having a wavelength of 254 nm is applied to the obtained coating film with an output density of 120 W / cm to obtain an integrated light quantity of 500 mJ / cm ^2. The content of the stain resistance imparting group at a position of 3 nm thickness from the surface of the cured film having a film thickness of 5 μm formed by irradiation as described above is the average content of the stain resistance imparting group in the entire cured film. The composition according to any one of claims 5 to 7, which is 3 times or more of the above.   Hardened | cured material formed by irradiating an active energy ray to the composition in any one of Claims 5 thru | or 8.   An article having on its surface a cured film formed by irradiating the composition according to any one of claims 5 to 8 with active energy rays.   The article according to claim 10, which is an article used for optics.   The article according to claim 10, which is an optical recording medium or a laminate for an optical display.   An optical recording medium having a multilayer film including at least a recording layer or a reflective layer on a substrate, wherein the composition according to any one of claims 5 to 8 is formed on the outermost surface of the light incident side of the medium. An optical recording medium having a cured film.   The optical recording medium according to claim 13, wherein the cured film is provided on the outermost surface of the recording layer or the reflective layer opposite to the substrate.   15. The optical recording medium according to claim 13, further comprising a light transmission layer between the multilayer film and the cured film.   An optical system comprising a laminate comprising a transparent resin substrate, the cured film formed by irradiating the composition according to any one of claims 5 to 8 with active energy rays on at least one outermost surface in the lamination direction. Laminate for display. (A1) α, ω-dimercaptopolysiloxane: 1 to 20 parts by weight,
(A2) (meth) acrylate having an epoxy group: 15 to 60 parts by weight,
(A3) Monofunctional mercaptan having a molecular weight of 100 to 300: 0.5 to 5 parts by weight
And (a4) Other radical polymerizable monomer: 15 to 83.5 parts by weight in total, and 100 parts by weight of (a1) mercapto group / (a3) mercapto group is 0.2 to 20 (mol / Mol) monomer mixture is subjected to radical polymerization, and then at least part of the epoxy group of the obtained radical polymer is reacted with carboxylic acid having 1 to 5 (meth) acryloyl groups in one molecule. The manufacturing method of the polymer (A) characterized by these. The method for producing a polymer (A) according to claim 17 , wherein the (a1) α, ω-dimercaptopolysiloxane is α, ω-dimercaptopropylpolydimethylsiloxane. The monomer mixture as the (a4) other radical polymerizable monomer, (a4-1) according to claim 17 comprising 1 to 60 parts by weight of radical polymerizable monomer having a perfluoroalkyl group and / or a perfluoroalkylene group or The manufacturing method of the polymer (A) of 18 .