JP4501462B2 - Object with composite hard coat layer and method for forming composite hard coat layer - Google Patents

Description

  The present invention relates to novel fluorine-containing acetophenone derivatives useful as photoinitiators. The present invention relates to a surface layer material containing the fluorine-containing acetophenone derivative as a photoinitiator.

  The present invention provides an object with a composite hard coat layer using a surface layer material containing the fluorine-containing acetophenone derivative as a photoinitiator, and a composite hard using a surface layer material containing the fluorine-containing acetophenone derivative as a photoinitiator. The present invention relates to a method for forming a coat layer. In the present invention, the composite hard coat layer is a hard coat layer provided on the surface of the object responsible for scratch resistance and wear resistance, and an antifouling surface provided on the surface of the hard coat layer for antifouling properties and lubricity. Including layers. More specifically, in the field of various objects that require antifouling and lubricating properties, scratch resistance and wear resistance, the present invention is provided with a composite hard coat layer having these various performances on the surface. The present invention relates to an object and a method for forming a composite hard coat layer.

  In particular, the present invention provides an optical recording medium, a magneto-optical recording medium, an optical lens, an optical filter, an antireflection film, and a surface of various display elements such as a liquid crystal display, a CRT display, a plasma display, and an EL display. The present invention relates to a method for forming a composite hard coat having antifouling and lubricating properties, scratch resistance and wear resistance without impairing performance and recording characteristics, and a product on which the hard coat is formed.

  Furthermore, the present invention also relates to an object provided with a fluorine-containing surface layer using a surface layer material containing the fluorine-containing acetophenone derivative as a photoinitiator. The fluorine-containing surface layer imparts antifouling properties and lubricity to the object surface.

  Various objects that require scratch resistance and wear resistance, such as optical recording media such as CD (Compact Disk) and DVD (Digital Versatile Disk), magneto-optical recording media, optical lenses, optical filters, and antireflection films In addition, a protective layer (hard coat layer) is usually provided on the surface of various display elements such as a liquid crystal display, a CRT display, a plasma display, and an EL display.

  In these various objects, dirt such as fingerprints, sebum, sweat, cosmetics and the like often adheres to the surface of the various objects depending on the use of the user. Such stains are not easy to remove once attached, and particularly in optical recording media and optical lenses used for recording and reproduction, the attached stains cause significant trouble in recording and reproducing information signals. Therefore, it becomes a big problem.

  In the magneto-optical recording medium, since the magnetic field head runs on the organic protective layer provided on the recording layer, it is required to increase the wear resistance of the protective layer and reduce the friction coefficient.

  As means for solving the former problem, various methods have been proposed for forming a layer having a property that dirt is difficult to adhere and can be easily wiped off, that is, an antifouling property, on the surface of an optical lens or the like. Specifically, a method of providing a layer made of a fluorine-based or silicone-based compound on the surface, imparting water repellency or oil repellency to the surface, and improving antifouling properties is often employed.

  On the other hand, many countermeasures have been proposed for the latter problem, that is, a method for reducing the coefficient of friction on the surface of the protective layer (hard coat layer). Specifically, for example, a method for improving lubricity by providing a film made of a liquid lubricant such as a fluorine-based polymer (for example, perfluoropolyether) or a silicone-based polymer (for example, polydimethylsiloxane) on the surface of the protective layer. Is often used.

  The former antifouling property and the latter lubricity are inherently different properties, but they are common in that they often use a fluorine-based compound or a silicone-based compound as a means to impart their performance. . For this reason, when imparting antifouling property or lubricity to the hard coat surface using a fluorine-based compound or a silicone-based compound, there are many problems that occur in common with both.

Many fluorine-based and silicone-based compounds are soft, and when these compounds are used, it is extremely difficult to obtain sufficient wear resistance. In order to improve such a problem, a method of increasing the wear resistance by adding an inorganic filler such as SiO ₂ fine particles to a fluorine polymer or silicone polymer matrix has been considered. However, with such a method, even if there is some improvement, satisfactory abrasion resistance cannot be obtained as long as a fluorine-based or silicone-based polymer is used as a matrix for dispersing the inorganic filler.

  For this reason, the protective layer has a laminated structure composed of two or more different layers, the lower layer is a layer made of a material having high hardness, and an upper layer made of a fluorine-based or silicone-based compound is provided on the surface thereof, thereby providing antifouling properties and A method of imparting lubricity is considered. In this case, it is preferable to make the upper layer made of a fluorine-based or silicone-based compound as thin as possible so that the upper layer which is the outermost surface of the laminated protective layer reflects the hardness of the lower layer. However, in this method, it is extremely difficult to obtain adhesion between the lower layer and the upper layer made of a fluorine compound or a silicone compound.

For example, the following methods are known as methods for solving the above-mentioned adhesion problem. That is, a lower layer made of an inorganic material such as SiO ₂ is formed by a method such as sputtering or a sol-gel method, and an upper layer made of an alkoxysilane having a fluoroalkyl group is formed on the surface of this lower layer by a method such as vapor deposition or solution coating. Form. Thereafter, by performing a heat treatment in the presence of a small amount of moisture, the hydroxyl group and the silanol group present between the silanol groups generated by hydrolysis of the alkoxysilane and / or the lower layer surface made of SiO ₂ or the like. The dehydration condensation reaction occurs between the upper layer and the upper layer, and the upper layer is fixed to the lower layer surface through chemical bonds and / or hydrogen bonds.

In the above method, it is desirable that the lower layer surface has active groups such as hydroxyl groups at a high density. For this reason, materials that can be used for the lower layer are limited to inorganic compounds, particularly metal oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ , and ZnS, and metal chalcogenides. Moreover, even when the lower layer is made of a metal oxide such as SiO ₂ , the surface of the lower layer is previously formed prior to the formation of the upper layer in order to ensure sufficient adhesion with the alkoxysilane of the upper layer. It is necessary to increase the density of active groups on the surface by subjecting to an activation treatment such as alkali treatment, plasma treatment or corona discharge treatment.

  An attempt has been made to use an organic substance such as polyethylene, polycarbonate or polymethyl methacrylate as a lower layer to make the lower layer surface hydrophilic by a method such as plasma treatment or corona discharge treatment, and to provide an upper layer made of the alkoxysilane on the lower layer surface. ing. However, in this case, compared with the case where the inorganic material is used as the lower layer, the adhesion is greatly inferior, and sufficient durability is not obtained.

Further, when the substrate to be hard-coated is made of resin, it is extremely difficult to obtain wear resistance as a hard coat by the above method using an inorganic material such as SiO ₂ as the lower layer. When a layer made of an inorganic material such as SiO ₂ is provided on the surface of the resin substrate, the film thickness that can be formed is at most about several hundred nm. It is difficult to make the film thickness larger than this, and even if it can be formed, the self-destruction of the inorganic film is easy because the difference in elastic modulus and thermal expansion coefficient from the base material is remarkably large. Arise. However, it is difficult to obtain sufficient wear resistance with an inorganic film having a thickness of several hundred nm. It is also difficult to obtain sufficient adhesion between the resin substrate and the inorganic film. Therefore, the inorganic film is easily peeled off, and it is difficult to obtain sufficient wear resistance from this point.

  For this reason, when the base material to be hard-coated is made of resin, a high elastic modulus primer layer is provided on the resin base material, and a lower layer made of the inorganic film is provided on the primer layer. It is necessary to secure the adhesion between the film and the inorganic film and the strength of the inorganic film, and to activate the surface of the lower layer, and to provide the upper layer made of the fluorine-based alkoxysilane on the lower layer surface. Thus, it is necessary to form the three layers sequentially, and the productivity is extremely poor.

  JP-A-9-137117 discloses a composition containing, on a resin substrate surface, a polymerizable compound having at least two (meth) acryloyloxy groups in the molecule and inorganic compound fine particles such as silica fine particles. It is applied, photopolymerized by irradiation with active energy rays, cured, and the surface of the cured film is subjected to corona treatment or plasma treatment, and then at least one group in the molecule that generates silanol groups by hydrolysis is formed on the treated surface. A method is disclosed in which a silane compound coating is applied to form a silane compound coating with improved adhesion to a cured coating. Also in this case, it is necessary to perform corona treatment or plasma treatment on the surface of the cured coating in order to ensure adhesion between the upper silane compound coating and the lower cured coating.

  On the other hand, in the above-described protective layer of the magneto-optical recording medium, when a lubricant film is formed by applying a liquid lubricant such as perfluoropolyether or polydimethylsiloxane on the surface of the organic protective layer, the lubricant is a viscous liquid. Therefore, the adhesiveness between the organic protective layer and the liquid lubricant film does not need to be considered much. However, in the long term, the lubricant may decrease due to repeated sliding of the magnetic field modulation head, or the lubricant may volatilize little by little during long-term storage. For this reason, also in this method, it is desirable that the lubricant is firmly fixed to the surface of the organic protective layer.

  Incidentally, as described above, in order to obtain antifouling properties, it is necessary to impart water repellency and oil repellency to the surface of the protective layer, but this is not always sufficient. Since the operation of wiping off the attached dirt is generally performed by the user's hand, the friction coefficient on the surface of the protective layer is reduced in order for the user to feel that wiping is easy when wiping off the dirt. It is necessary to plan. The relationship between antifouling properties and coefficient of friction has hardly been pointed out until now, but in fact, when imparting antifouling properties, a low coefficient of friction is an essential characteristic along with water and oil repellency. It can be said.

  In addition, since the surface has a low coefficient of friction, the impact at the time of contact with a hard projection can be slid and released, so that the generation of scratches can be suppressed. Therefore, from the standpoint of further improving the hard coat scratch resistance, a low surface friction coefficient is required.

  JP-A-6-221945 and JP-A-2000-301053 are based on a composition in which a fluoroalkyl acrylate and an acrylic monomer having no compatibility therewith are dissolved in a solvent that dissolves both in a predetermined ratio. It is disclosed that a hard coat layer is formed by coating on a material and irradiating and curing an electron beam immediately after coating. According to these publications, by applying the composition to a thickness of 1 to 15 μm and then immediately irradiating with an electron beam, the solvent is instantly evaporated, and the fluoroalkyl acrylate component and the acrylic monomer component are It is localized and cured in a state where fluoroalkyl acrylate is unevenly distributed on the surface of the coating film.

  However, according to the two publications, since a composition containing incompatible components is used, it is necessary to cure by applying an electron beam and instantly before the localization due to solvent volatilization occurs after the composition is applied. There is. Therefore, the timing of electron beam irradiation from application is also difficult, and the coating method is extremely limited. For example, a coating method with a high solvent evaporation rate such as a spin coating method cannot be used.

  Furthermore, as the biggest problem, the methods described in both publications evaporate the solvent simultaneously with the electron beam irradiation, and therefore there is a high possibility that the solvent in the cured coating cannot be completely removed. The publication does not verify whether the solvent has been completely removed from the cured coating. When a small amount of solvent remains inside, there is a possibility that the film may crack or peel off after long-term use even if there is no problem immediately after the hard coat is formed. Further, the hardness becomes insufficient, and the warp of the base material on which the hard coat is formed tends to gradually increase.

  Further, in the method of evaporating the solvent simultaneously with the electron beam irradiation, the cured film tends to have a porous structure, so that not only the hardness is insufficient but the optical characteristics may be deteriorated. Therefore, even if there is no problem in application to general-purpose products, it is difficult to apply to applications that require extremely high optical characteristics, such as optical lenses and optical recording media.

  That is, there has never been a hard coat that simultaneously realizes antifouling properties, lubricity and wear resistance at a high level.

  Further, when polymerizing and curing a fluorine-containing (meth) acrylate such as fluoroalkyl acrylate, electron beam irradiation or ultraviolet irradiation can be used. However, the electron beam irradiation apparatus is expensive, requires X-ray shielding around the apparatus, and the running cost is high. From this viewpoint, ultraviolet irradiation is preferable to electron beam irradiation.

  In order to polymerize and cure the fluorine-containing (meth) acrylate by ultraviolet irradiation, it is necessary to add a photoradical initiator to obtain sufficient reactivity. Fluorine-containing (meth) acrylates dissolve well in fluorine-based solvents such as perfluorocarbon, but ordinary photopolymerization initiators do not dissolve in fluorine-based solvents.

  JP-A-8-508733 discloses a fluorinated photoinitiator. However, the fluorinated photoinitiator disclosed in this publication generates benzyl radicals by cleavage, and yellowing occurs in the resulting cured coating. This is considered to be due to recombination of the generated radicals. Yellowing is a significant disadvantage for applications that require very high optical properties, such as optical lenses and optical recording media, and it is difficult to apply photoinitiators that cause yellowing to these applications. .

Japanese Patent Laid-Open No. 9-137117 JP-A-6-221945 JP 2000-301053 A Japanese translation of PCT publication No. 8-508733

  Thus, the object of the present invention is to solve the above-mentioned problems of the prior art, and to initiate photo radicals that are soluble in fluorine-based solvents such as perfluorocarbon and have good compatibility with fluorine-containing (meth) acrylate compounds. It is to provide an agent. An object of the present invention is to provide a surface layer material that does not cause yellowing.

  Another object of the present invention is to provide an object provided with a hard coat excellent in antifouling property and lubricity, scratch resistance and abrasion resistance at low cost. Another object of the present invention is to provide a method for easily and inexpensively forming a hard coat excellent in antifouling property and lubricity, scratch resistance and abrasion resistance.

  Furthermore, the objective of this invention is providing the object provided with the fluorine-containing surface layer excellent in antifouling property and lubricity at low cost.

  As a result of intensive studies, the present inventors have found a novel fluorine-containing acetophenone derivative useful as a photo radical initiator. Furthermore, the present inventors use a surface layer material containing a fluorine-containing (meth) acrylate compound for the fluorine-containing surface layer and the fluorine-containing acetophenone derivative as a photoinitiator, to provide scratch resistance and wear resistance. By providing the hard coat layer to be applied on the surface of the target object and the fluorine-containing surface layer having antifouling properties and lubricity on the hard coat layer surface by simultaneously curing with ultraviolet irradiation, these fluorine-containing surface layer and hard The inventors have found that a transparent composite hard coat layer in which the coat layer is firmly adhered is formed, and the present invention has been achieved.

［一般式（Ｉ）において、Ｒ ₁ 、Ｒ ₂ 及びＲ ₃ は、それぞれ独立して、水素原子、ハロゲン原子、ヒドロキシル基、炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、炭素原子数２〜７のアルキルカルボニルオキシ基、フッ化炭素原子数の合計が５以上５０以下のパーフルオロアルキルカルボニルオキシ基、フェニルカルボニルオキシ基、又はアミノ基を表す。ただし、Ｒ ₁ 、Ｒ ₂ 及びＲ ₃ の全てが同時に水素原子となることはない。また、Ｒ ₁ 、Ｒ ₂ 及びＲ ₃ のいずれか２つが互いに連結されて環を形成してもよい。
Ｒ ₄ は、フッ素含有有機基を表し、前記フッ素含有有機基は、
(a) -[C(X)F]k - 、
(b) -[C(X)F-O]l - 、
(c) -[C(X)F-C(Y)F-O]m - 、及び
(d) -[C(X)F-C(Y)F-C(Z)F-O]n -
（ここで、Ｘ、Ｙ及びＺは、それぞれ独立して、Ｆ原子又はＣＦ ₃ 基を表し、ｋ、ｌ、ｍ及びｎは、各フッ素含有単位の数を表す。）
からなる群から選ばれる少なくとも１つのフッ素含有単位を、選ばれたフッ素含有単位中に含まれるフッ化炭素原子数の合計が５以上５０以下となるように有するものである。］で示されるフッ素含有アセトフェノン誘導体とを含む表面層用材料の硬化物からなる、複合ハードコート層が付与された物体である。前記含フッ素表面層は前記ハードコート層に固着されている。ここで、固着とは、例えば実施例で示されるように、複合ハードコート層の撥水性として、ハードコート表面の水の接触角が初期及びウェスでの摺動後のいずれにおいても８５度以上であることを意味する。固着していなければ、特に摺動後において、８５度以上の接触角は達成できない。
前記フッ素含有アセトフェノン誘導体は、例えば、前記一般式（Ｉ）において、Ｒ ₄ が表すフッ素含有有機基が、前記フッ素含有単位(a) -[C(X)F]k - （５≦ｋ≦５０）を含むパーフルオロアルキル基Ｒfaを有するＲfa−Ｌ−基［ここで、Ｌは、
(f) -COO- 、
(g) -COO-(CH ₂ )j-O-、
(h) -CH ₂ CH(OH)CH ₂ O- 、
(i) -CH ₂ CH(OH)CH ₂ O-(CH ₂ )j-O-、
(j) -CH ₂ O-、
(k) -CH ₂ O-(CH ₂ )j-O- 、
(l) -(CH ₂ )j-、又は
(m) -NHCOO-(CH ₂ )j-O-
（ここで、ｊは、２〜６の整数を表す。）で示される２価の連結基を表す。］であるものである。
また、前記フッ素含有アセトフェノン誘導体は、例えば、前記一般式（Ｉ）において、Ｒ ₄ が表すフッ素含有有機基が、前記フッ素含有単位(a) -[C(X)F]k - （５≦ｋ≦５０）を含むパーフルオロアルキル基Ｒfaを有するＲfa-COO-(CH ₂ )j-O-基（ここで、ｊは、２〜６の整数を表す。）又はＲfa-NHCOO-(CH ₂ )j-O-基（ここで、ｊは、２〜６の整数を表す。）であるものである。
また、前記フッ素含有アセトフェノン誘導体は、例えば、前記一般式（Ｉ）において、Ｒ ₄ が表すフッ素含有有機基が、前記フッ素含有単位(b) -[C(X)F-O]l - 、(c) -[C(X)F-C(Y)F-O]m - 、及び(d) -[C(X)F-C(Y)F-C(Z)F-O]n - からなる群から選ばれる少なくとも１つを含むパーフルオロエーテル含有基Ｒfeを有するＲfe−Ｌ−基［ここで、Ｌは、
(f) -COO- 、
(g) -COO-(CH ₂ )j-O-、
(h) -CH ₂ CH(OH)CH ₂ O- 、
(i) -CH ₂ CH(OH)CH ₂ O-(CH ₂ )j-O-、
(j) -CH ₂ O-、
(k) -CH ₂ O-(CH ₂ )j-O- 、
(l) -(CH ₂ )j-、又は
(m) -NHCOO-(CH ₂ )j-O-
（ここで、ｊは、２〜６の整数を表す。）で示される２価の連結基を表す。］であるものである。
また、前記フッ素含有アセトフェノン誘導体は、例えば、前記一般式（Ｉ）において、Ｒ ₄ が表すフッ素含有有機基が、前記フッ素含有単位(b) -[C(X)F-O]l - 、(c) -[C(X)F-C(Y)F-O]m - 、及び(d) -[C(X)F-C(Y)F-C(Z)F-O]n - からなる群から選ばれる少なくとも１つを含むパーフルオロエーテル含有基Ｒfeを有するＲfe-COO-(CH ₂ )j-O-基（ここで、ｊは、２〜６の整数を表す。）又はＲfe-NHCOO-(CH ₂ )j-O-基（ここで、ｊは、２〜６の整数を表す。）であるものである。 The present invention is an object provided with a composite hard coat layer including a hard coat layer provided on the object surface and a fluorine-containing surface layer provided on the hard coat layer surface,
The hard coat layer consists of a cured product of a hard coat agent composition containing an active energy ray-curable compound,
The fluorine-containing surface layer includes a fluorine-containing (meth) acrylate compound,
As a photoinitiator, the following general formula (I):

[In General Formula (I), R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy having 1 to 6 carbon atoms. A group, a C 2-7 alkylcarbonyloxy group, a perfluoroalkylcarbonyloxy group having a total number of fluorocarbon atoms of 5 to 50, a phenylcarbonyloxy group, or an amino group. However, all of R ₁ , R ₂ and R ₃ do not become hydrogen atoms at the same time. Further, any _{two of} R ₁ , R ₂ and R ₃ may be connected to each other to form a ring.
R ₄ represents a fluorine-containing organic group, and the fluorine-containing organic group is
(a)-[C (X) F] k-,
(b)-[C (X) FO] l-,
(c)-[C (X) FC (Y) FO] m-, and
(d)-[C (X) FC (Y) FC (Z) FO] n-
(Here, X, Y, and Z each independently represent an F atom or a CF ₃ group, and k, l, m, and n represent the number of each fluorine-containing unit.)
And at least one fluorine-containing unit selected from the group consisting of such that the total number of fluorocarbon atoms contained in the selected fluorine-containing unit is 5 or more and 50 or less. ] The object to which the composite hard-coat layer which consists of hardened | cured material of the material for surface layers containing the fluorine-containing acetophenone derivative shown by this was provided. The fluorine-containing surface layer is fixed to the hard coat layer. Here, for example, as shown in the examples, the adhesion means that the water contact angle of the hard coat surface is 85 degrees or more both in the initial stage and after sliding on the waste as the water repellency of the composite hard coat layer. It means that there is. If not fixed, a contact angle of 85 degrees or more cannot be achieved especially after sliding.
In the fluorine-containing acetophenone derivative, for example, in the general formula (I), the fluorine-containing organic group represented by R ₄ is the fluorine-containing unit (a)-[C (X) F] k-(5 ≦ k ≦ 50 Rfa-L-group having a perfluoroalkyl group Rfa [where L is
(f) -COO-,
(g) -COO- (CH ₂ ) jO-,
(h) -CH ₂ CH (OH) CH ₂ O-,
(i) -CH ₂ CH (OH) CH ₂ O- (CH ₂ ) jO-,
(j) -CH ₂ O-,
(k) -CH ₂ O- (CH ₂ ) jO-,
(l)-(CH ₂ ) j-, or
(m) -NHCOO- (CH ₂ ) jO-
(Where j represents an integer of 2 to 6), and represents a divalent linking group. ].
The fluorine-containing acetophenone derivative is, for example, the fluorine-containing organic group represented by R ₄ in the general formula (I) , wherein the fluorine-containing unit (a)-[C (X) F] k-(5 ≦ k Rfa—COO— (CH ₂ ) jO— group having a perfluoroalkyl group Rfa containing ≦ 50) (where j represents an integer of 2 to 6) or Rfa—NHCOO— (CH ₂ ) jO— A group (where j represents an integer of 2 to 6).
The fluorine-containing acetophenone derivative is, for example, the fluorine-containing organic group represented by R ₄ in the general formula (I) , wherein the fluorine-containing unit (b)-[C (X) FO] l-, (c) -[C (X) FC (Y) FO] m-and (d)-[C (X) FC (Y) FC (Z) FO] n-perfluoro containing at least one selected from the group consisting of Rfe-L-group having an ether-containing group Rfe [where L is
(f) -COO-,
(g) -COO- (CH ₂ ) jO-,
(h) -CH ₂ CH (OH) CH ₂ O-,
(i) -CH ₂ CH (OH) CH ₂ O- (CH ₂ ) jO-,
(j) -CH ₂ O-,
(k) -CH ₂ O- (CH ₂ ) jO-,
(l)-(CH ₂ ) j-, or
(m) -NHCOO- (CH ₂ ) jO-
(Where j represents an integer of 2 to 6), and represents a divalent linking group. ].
The fluorine-containing acetophenone derivative is, for example, the fluorine-containing organic group represented by R ₄ in the general formula (I) , wherein the fluorine-containing unit (b)-[C (X) FO] l-, (c) -[C (X) FC (Y) FO] m-and (d)-[C (X) FC (Y) FC (Z) FO] n-perfluoro containing at least one selected from the group consisting of (where, j represents an integer of 2 to _{6.) Rfe-COO- (CH 2} ) jO- group having an ether-containing group RFE or Rfe-NHCOO- (CH ₂₎ jO- group (here, j Represents an integer of 2 to 6).

  In the present invention, the fluorine-containing surface layer is an object provided with the composite hard coat layer having a thickness of 1 nm to 100 nm.

  In the present invention, the active energy ray-curable compound contained in the hard coat agent composition has at least one reactive group selected from the group consisting of a (meth) acryloyl group, a vinyl group, and a mercapto group. An object provided with the composite hard coat layer.

  The present invention is an object provided with the composite hard coat layer, wherein the hard coat agent composition contains a photoinitiator and, if necessary, an inorganic filler.

  In the present invention, examples of the object include an optical recording medium, a magneto-optical recording medium, an optical lens, an optical filter, an antireflection film, and various display elements. Examples of the display element include a liquid crystal display, a CRT display, a plasma display, an EL display, and the like.

［一般式（Ｉ）において、Ｒ ₁ 、Ｒ ₂ 及びＲ ₃ は、それぞれ独立して、水素原子、ハロゲン原子、ヒドロキシル基、炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、炭素原子数２〜７のアルキルカルボニルオキシ基、フッ化炭素原子数の合計が５以上５０以下のパーフルオロアルキルカルボニルオキシ基、フェニルカルボニルオキシ基、又はアミノ基を表す。ただし、Ｒ ₁ 、Ｒ ₂ 及びＲ ₃ の全てが同時に水素原子となることはない。また、Ｒ ₁ 、Ｒ ₂ 及びＲ ₃ のいずれか２つが互いに連結されて環を形成してもよい。
Ｒ ₄ は、フッ素含有有機基を表し、前記フッ素含有有機基は、
(a) -[C(X)F]k - 、
(b) -[C(X)F-O]l - 、
(c) -[C(X)F-C(Y)F-O]m - 、及び
(d) -[C(X)F-C(Y)F-C(Z)F-O]n -
（ここで、Ｘ、Ｙ及びＺは、それぞれ独立して、Ｆ原子又はＣＦ ₃ 基を表し、ｋ、ｌ、ｍ及びｎは、各フッ素含有単位の数を表す。）
からなる群から選ばれる少なくとも１つのフッ素含有単位を、選ばれたフッ素含有単位中に含まれるフッ化炭素原子数の合計が５以上５０以下となるように有するものである。］で示されるフッ素含有アセトフェノン誘導体とを含む表面層用材料を塗布して表面材料層を形成し、
形成されたハードコート剤組成物層及び表面材料層に紫外線を照射して、前記両層を同時に硬化させ、対象物体表面に接するハードコート層とハードコート層表面に接する含フッ素表面層とを形成することを含む、対象物体表面にハードコート層と含フッ素表面層とを含む複合ハードコート層を形成する方法である。 Furthermore, the present invention applies a hard coating agent composition containing an active energy ray-curable compound to the surface of an object to be hard coated to form a hard coating agent composition layer,
On the surface of the hard coat agent composition layer, a fluorine-containing (meth) acrylate compound and the following general formula (I) as a photoinitiator :

[In General Formula (I), R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy having 1 to 6 carbon atoms. A group, a C 2-7 alkylcarbonyloxy group, a perfluoroalkylcarbonyloxy group having a total number of fluorocarbon atoms of 5 to 50, a phenylcarbonyloxy group, or an amino group. However, all of R ₁ , R ₂ and R ₃ do not become hydrogen atoms at the same time. Further, any _{two of} R ₁ , R ₂ and R ₃ may be connected to each other to form a ring.
R ₄ represents a fluorine-containing organic group, and the fluorine-containing organic group is
(a)-[C (X) F] k-,
(b)-[C (X) FO] l-,
(c)-[C (X) FC (Y) FO] m-, and
(d)-[C (X) FC (Y) FC (Z) FO] n-
(Here, X, Y, and Z each independently represent an F atom or a CF ₃ group, and k, l, m, and n represent the number of each fluorine-containing unit.)
And at least one fluorine-containing unit selected from the group consisting of such that the total number of fluorocarbon atoms contained in the selected fluorine-containing unit is 5 or more and 50 or less. A surface layer material comprising a fluorine-containing acetophenone derivative represented by the following formula:
The hard coat agent composition layer and the surface material layer thus formed are irradiated with ultraviolet rays, and both the layers are cured simultaneously to form a hard coat layer in contact with the target object surface and a fluorine-containing surface layer in contact with the hard coat layer surface. And forming a composite hard coat layer including a hard coat layer and a fluorine-containing surface layer on the surface of the target object.

  The present invention is the method for forming a composite hard coat layer, wherein the fluorine-containing surface layer is formed to a thickness of 1 nm to 100 nm.

  In the present invention, after the hard coat agent composition was applied to the surface of the target object to form the hard coat agent composition layer, the hard coat agent composition layer was dried and contained in the hard coat agent composition. In the method for forming a composite hard coat layer, the solvent is removed from the hard coat agent composition layer, and then a surface layer material is formed on the surface of the hard coat agent composition layer to form a surface material layer.

  The present invention uses the above-mentioned composite hard coat, which uses a solvent that does not substantially dissolve the active energy ray-curable compound in the hard coat agent composition layer that has already been formed as the solvent when applying the surface layer material. This is a method of forming a layer.

  The present invention is the above-described method for forming a composite hard coat layer, in which ultraviolet irradiation is performed in an atmosphere having an oxygen concentration of 500 ppm by volume or less.

  In the present invention, after the hard coat agent composition is applied to the surface of the target object to form a hard coat agent composition layer, the hard coat agent composition layer is dried as necessary and irradiated with active energy rays. In the method for forming a composite hard coat layer, the hard coat agent composition layer is set in a semi-cured state, and then a surface material layer is formed on the surface of the hard coat agent composition layer.

The present invention forms a hard coat agent composition layer by applying a hard coat agent composition containing an active energy ray-curable compound to the surface of an object to be hard-coated,
On the surface of the hard coat agent composition layer, a surface material layer is formed by applying a surface layer material containing a fluorine-containing (meth) acrylate compound and any one of the fluorine-containing acetophenone derivatives as a photoinitiator,
The hard coat agent composition layer and the surface material layer thus formed are irradiated with ultraviolet rays, and both the layers are cured simultaneously to form a hard coat layer in contact with the target object surface and a fluorine-containing surface layer in contact with the hard coat layer surface. This is an object obtained by applying a composite hard coat layer including a hard coat layer and a fluorine-containing surface layer to the target object surface.

  In the present invention, antifouling properties and lubricity are imparted by the fluorine-containing surface layer. In addition, the fluorine-containing surface layer provides antireflection properties as compared with a normal resin layer.

  In this specification, the “hard coat agent composition layer” means an uncured or semi-cured (partially cured) hard coat layer. “Surface material layer” means an uncured fluorine-containing surface layer. An active energy ray-curable compound is a compound that can be cured by irradiation with active energy rays such as ultraviolet rays, electron beams, and visible light.

  Furthermore, in the present invention, a fluorine-containing surface layer comprising a cured product of a material for a surface layer containing a fluorine-containing (meth) acrylate compound and any one of the fluorine-containing acetophenone derivatives as a photoinitiator is provided on the object surface. Object. Also in this case, examples of the object include the same as described above, but only the antifouling property and lubricity are imparted by the fluorine-containing surface layer.

  According to the present invention, a novel fluorine-containing acetophenone derivative is provided, and this compound is soluble in a fluorine-based solvent such as perfluorocarbon and has good compatibility with a fluorine-containing (meth) acrylate compound. It is very useful as a photo radical initiator.

  According to the present invention, there is provided a surface layer material that contains a fluorine-containing (meth) acrylate compound and the fluorine-containing acetophenone derivative as a photoinitiator and does not cause yellowing.

  According to the present invention, the surface layer material is used to provide a hard coat having high scratch resistance and wear resistance, excellent antifouling properties and lubricity, and extremely excellent durability. The provided object is provided inexpensively and easily.

  Furthermore, according to this invention, the fluorine-containing surface layer excellent in antifouling property and lubricity can be formed in the object surface using the said surface layer material.

  First, the fluorine-containing acetophenone derivative represented by the general formula (I) will be described.

In the general formula _{(I), R 1, R} 2 and R ₃ are each independently, i.e., may be the same or different from each other, an organic group other than an aryl group, a hydrogen atom, a halogen atom, or a hydroxyl group To express. However, from the viewpoint of stability of radicals generated by α-cleavage, all of R ₁ , R ₂ and R ₃ do not become hydrogen atoms at the same time. In the molecule, any _{two of} R ₁ , R ₂ and R ₃ may be connected to each other to form a ring. R ₄ represents a fluorine-containing organic group.

Examples of the halogen atom represented by R ₁ , R ₂ and R ₃ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the organic group other than the aryl group represented by R ₁ , R ₂ and R ₃ include an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylcarbonyloxy group, and a substituted group. An arylcarbonyloxy group, an amino group, and the like, which may be present. When any of R ₁ , R ₂ and R ₃ directly becomes an aryl group, when used as a photoinitiator, a benzyl radical is generated by cleavage, and the resulting cured film is strongly yellowed. _1, none of R ₂ and R _3, is not to be directly aryl group.

Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl groups, etc. These alkyl groups may have a halogen atom such as a fluorine atom, and may be substituted with an alkoxy group, an aryl group or the like. It may have a group. Further, any _{two of} R ₁ , R ₂ and R ₃ may be connected to each other to form, for example, a cyclohexyl ring.

  Examples of the alkoxy group include methyloxy, ethyloxy, propyloxy, butyloxy, pentyloxy, hexyloxy groups, and the like. These alkoxy groups may have a halogen atom such as a fluorine atom. It may have a substituent such as a group.

  Examples of the alkylcarbonyloxy group include methylcarbonyloxy, ethylcarbonyloxy, propylcarbonyloxy, butylcarbonyloxy, pentylcarbonyloxy, hexylcarbonyloxy groups, etc., and these alkylcarbonyloxy groups are halogen atoms such as fluorine atoms. And may have a substituent such as an alkoxy group or an aryl group. Preferable examples include perfluoroalkylcarbonyloxy groups having a total number of fluorocarbon atoms of 5 to 50. In this case, from the viewpoint of obtaining good solubility in a fluorine-based solvent such as perfluorocarbon, the total number of fluorocarbon atoms is preferably 5 or more and 50 or less. Even if the number of fluorocarbon atoms exceeds 50, not only improvement in solubility is not expected, but acquisition of raw materials and synthesis and purification of the target compound may become difficult.

  Examples of the arylcarbonyloxy group include a phenylcarbonyloxy group, and the phenyl group may have various substituents. Examples of amino groups include morpholino groups.

A preferred combination of R ₁ , R ₂ and R ₃ is not particularly limited,
R ₁ = R ₂ = R ₃ = Cl
R ₁ = R ₂ = Cl, R ₃ = H
R ₁ = H, R ₂ = R ₃ = OC ₂ H ₅
R ₁ = OH, R ₂ = R ₃ = CH ₃
R ₁ = OH, R ₂ and R ₃ form a cyclohexyl ring R ₁ = R ₂ = CH ₃ , R ₃ = morpholino group R ₁ = R ₂ = CH ₃ , R ₃ = OCO-perfluoroalkyl group, etc. Is exemplified.

In the general formula (I), R ₄ is a fluorine-containing organic group. When R ₄ contains fluorine, solubility in a fluorine-based solvent such as perfluorocarbon is improved, and compatibility with the fluorine-containing (meth) acrylate compound is improved.

In general formula (I), the fluorine-containing organic group represented by R ₄ is,
(a)-[C (X) F] k-,
(b)-[C (X) FO] l-,
(c)-[C (X) FC (Y) FO] m-, and
(d)-[C (X) FC (Y) FC (Z) FO] n-
(Here, X, Y, and Z each independently represent an F atom or a CF ₃ group, and k, l, m, and n represent the number of each fluorine-containing unit.)
And an organic group having at least one fluorine-containing unit selected from the group consisting of such that the total number of fluorocarbon atoms contained in the selected fluorine-containing unit is 5 or more, preferably 50 or less. By setting the total number of fluorocarbon atoms to 5 or more and 50 or less, good solubility in a fluorine-based solvent such as perfluorocarbon can be obtained. Even if the number of fluorocarbon atoms exceeds 50, not only improvement in solubility is not expected, but acquisition of raw materials and synthesis and purification of the target compound may become difficult.

In the general formula (I), a preferable fluorine-containing organic group represented by R ₄ is a perfluoroalkyl group Rfa containing the fluorine-containing unit (a)-[C (X) F] k-(5≤k). Rfa-L- group (wherein L represents a divalent linking group).

The divalent linking group L may be any one that can link the perfluoroalkyl group Rfa and the benzene ring in the general formula (I), and various linking groups are conceivable. For example,
(f) -COO-
(g) -COO- (CH ₂ ) jO-
(h) -CH ₂ CH (OH) CH ₂ O-
(i) -CH ₂ CH (OH) CH ₂ O- (CH ₂ ) jO-
(j) -CH ₂ O-
(k) -CH ₂ O- (CH ₂ ) jO-
(l)-(CH ₂ ) j-
(m) -NHCOO- (CH ₂ ) jO-
Etc. are exemplified. Among these, (f) -COO-, (g) -COO- (CH ₂ ) jO-, and (m) -NHCOO- (CH ₂ ) jO- are preferable. In the above formulas, — (CH ₂ ) j— is preferably a lower alkylene group, that is, j is preferably an integer of 2 to 6.

In general formula (I), the preferred fluorine-containing organic group represented by R ₄ is, the fluorine-containing units (a) - [C (X ) F] k - include (5 ≦ k), the terminal is a F (where, j represents an integer of 2 to 6.) perfluoro Rfa-COO- (CH ₂₎ having an alkyl group Rfa JO- group, and Rfa-NHCOO- (CH ₂₎ jO- group (wherein , J represents an integer of 2 to 6.). Examples of the perfluoroalkyl group Rfa include an F (CF ₂ ) k- group with 5 ≦ k ≦ 50, and the lower alkylene group represented by — (CH ₂ ) j— , Propylene, butylene, hexylene group and the like.

In the general formula (I), preferred fluorine-containing organic groups represented by R ₄ include the fluorine-containing units (b) 1-[C (X) FO] 1-, (c)-[C (X) FC ( Y) FO] m-, and (d)-[C (X) FC (Y) FC (Z) FO] n-, and optionally the fluorine-containing unit (a)-[C Rx-L- group having a perfluoroether-containing group Rfe containing (X) F] k − (wherein L represents a divalent linking group). The divalent linking group L is the same as described above.

In the general formula (I), preferred fluorine-containing organic groups represented by R ₄ include the fluorine-containing units (b) 1-[C (X) FO] 1-, (c)-[C (X) FC (Y) FO] m −, and (d) 1-[C (X) FC (Y) FC (Z) FO] n −, and optionally the fluorine-containing unit (a)-[C (X ) F] k − Rfe—COO— (CH ₂ ) jO— group having a perfluoroether-containing group Rfe (where j represents an integer of 2 to 6), and Rfe—NHCOO— (CH ₂ ) jO- group (where j represents an integer of 2 to 6). Examples of the lower alkylene group represented by — (CH ₂ ) j— include ethylene, propylene, butylene, and hexylene groups where j = 2 to 6.

Preferred perfluoroether-containing groups Rfe include, for example,
CF ₃ O (CF ₂ O) l-group,
CF ₃ CF ₂ (CF ₂ CF ₂ O) m- group,
CF ₃ CF ₂ CF ₂ O [CF (CF ₃ ) CF ₂ O] m- group,
CF ₃ CF ₂ CF ₂ (CF ₂ CF ₂ CF ₂ O) n-group,
CF ₃ O- [CF (CF ₃ ) CF ₂ O] m-/-(CF ₂ O) l- group,
CF ₃ O- (CF ₂ CF ₂ O) m-/-(CF ₂ O) l- group, etc., where l, m and n are the number of fluorocarbon atoms contained in the perfluoroether-containing group Rfe Is selected so as to be 5 or more, preferably 50 or less.

Specific examples of the fluorine-containing organic group R ₄ include the following.
F (CF ₂ ) ₈ COO-, F (CF ₂ ) ₉ COO-, F (CF ₂ ) ₁₀ COO-, F (CF ₂ ) ₁₁ COO-, F (CF ₂ ) ₁₂ COO-, F (CF ₂ ) ₁₃ COO-, F (CF ₂ ) ₁₄ COO-, F (CF ₂ ) ₁₅ COO-, F (CF ₂ ) ₁₆ COO-, F (CF ₂ ) ₁₇ COO-, H (CF ₂ ) ₈ COO-,
(CF ₃ ) ₂ CF (CF ₂ ) ₂ CH ₂ CH ₂ COO-, (CF ₃ ) ₂ CF (CF ₂ ) ₂ COO-, (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ COO-, (CF ₃ ) ₂ CF (CF ₂ ) ₄ COO-, (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ COO-, (CF ₃ ) ₂ CF (CF ₂ ) ₆ COO-, (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ COO-, (CF ₃ ) ₂ CF (CF ₂ ) ₈ COO-, (CF ₃ ) ₂ CF (CF ₂ ) ₃ CF (CF ₃ ) CF ₂ COO-, CF _{3 CF 2 (CF 2 CF 2} O) 2 CF 2 COO-, CF 3 OCF 2 CF 2 OCF 2 COO -, (CF 3) 3 CCF 2 CF (CF 3) CF 2 COO-,
F (CF ₂ ) ₃ O [CF (CF ₃ ) CF ₂ O] ₂ CF (CF ₃ ) COO-, F (CF ₂ ) ₃ O [CF (CF ₃ ) CF ₂ O] ₃ CF (CF ₃ ) COO -, F [CF (CF ₃ ) CF ₂ O] ₄ CF (CF ₃ ) COO-, CF ₃ O (CF ₂ CF ₂ O) ₂ CF ₂ COO-, CF ₃ CF ₂ (CF ₂ CF ₂ O) ₃ CF ₂ COO-, perfluorocyclohexylcarbonyloxy group (C ₆ F ₁₁ COO-), perfluorodecahydronaphthylcarbonyloxy group (C ₁₀ F ₁₇ COO-),

F (CF ₂ ) ₈ COOCH ₂ CH ₂ O-, F (CF ₂ ) ₉ COOCH ₂ CH ₂ O-, F (CF ₂ ) ₁₀ COOCH ₂ CH ₂ O-, F (CF ₂ ) ₁₁ COOCH ₂ CH ₂ O -, F (CF ₂ ) ₁₂ COOCH ₂ CH ₂ O-, F (CF ₂ ) ₁₃ COOCH ₂ CH ₂ O-, F (CF ₂ ) ₁₄ COOCH ₂ CH ₂ O-, F (CF ₂ ) ₁₅ COOCH ₂ CH _{2 O-, F (CF 2)} 16 COOCH 2 CH 2 O-, F (CF 2) 17 COOCH 2 CH 2 O-, H (CF 2) 8 COOCH 2 CH 2 O-,
(CF ₃ ) ₂ CF (CF ₂ ) ₂ CH ₂ CH ₂ COOCH ₂ CH ₂ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₂ COOCH ₂ CH ₂ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ COOCH ₂ CH ₂ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₄ COOCH ₂ CH ₂ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ COOCH ₂ CH ₂ O -, (CF ₃ ) ₂ CF (CF ₂ ) ₆ COOCH ₂ CH ₂ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ COOCH ₂ CH ₂ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₈ COOCH ₂ CH ₂ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₃ CF (CF ₃ ) CF ₂ COOCH ₂ CH ₂ O-, CF ₃ CF ₂ (CF ₂ CF ₂ O) ₂ CF ₂ COOCH ₂ CH ₂ O-, CF ₃ OCF ₂ CF ₂ OCF ₂ COOCH ₂ CH ₂ O-, (CF ₃ ) ₃ CCF ₂ CF (CF ₃ ) CF ₂ COOCH ₂ CH ₂ O-, F (CF ₂ ) ₃ O [ CF (CF ₃ ) CF ₂ O] ₂ CF (CF ₃ ) COOCH ₂ CH ₂ O-, F (CF ₂ ) ₃ O [CF (CF ₃ ) CF ₂ O] ₃ CF (CF ₃ ) COOCH ₂ CH ₂ O -, F [CF (CF ₃ ) CF ₂ O] ₄ CF (CF ₃ ) COOCH ₂ CH ₂ O-, CF ₃ O (CF ₂ CF ₂ O) ₂ CF ₂ COOCH ₂ CH ₂ O-, CF ₃ CF _{2 (CF 2 CF 2 O) 3} CF 2 COOCH 2 CH 2 O-, 2- ( perfluoro cyclohexyl carbonyloxy) ethyloxy group _{(C 6 F 11 COOCH 2 CH} 2 O -), 2- ( perfluoro decahydronaphthyl Ruboniruokishi) ethyloxy group _{(C 10 F 17 COOCH 2 CH} 2 O-),

CF ₃ (CF ₂ ) ₈ CH ₂ CH (OH) CH ₂ O-, CF ₃ (CF ₂ ) ₉ CH ₂ CH (OH) CH ₂ O-, CF ₃ (CF ₂ ) ₁₀ CH ₂ CH (OH) CH ₂ O-, CF ₃ (CF ₂ ) ₁₁ CH ₂ CH (OH) CH ₂ O-, CF ₃ (CF ₂ ) ₁₂ CH ₂ CH (OH) CH ₂ O-, CF ₃ (CF ₂ ) ₁₃ CH ₂ CH (OH) CH ₂ O-, CF ₃ (CF ₂ ) ₁₄ CH ₂ CH (OH) CH ₂ O-, CF ₃ (CF ₂ ) ₁₅ CH ₂ CH (OH) CH ₂ O-, CF ₃ (CF ₂ ) ₁₆ CH ₂ CH (OH) CH ₂ O-, CF ₃ (CF ₂ ) ₁₇ CH ₂ CH (OH) CH ₂ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₂ CH ₂ CH (OH) CH ₂ O _{-, (CF 3) 2 CF} (CF 2) 4 CH 2 CH (OH) CH 2 O -, (CF 3) 2 CF (CF 2) 6 CH 2 CH (OH) CH 2 O -, (CF 3) ₂ CF (CF ₂ ) ₈ CH ₂ CH (OH) CH ₂ O-, H (CF ₂ ) ₈ CH ₂ OCH ₂ CH (OH) CH ₂ O-,

CF ₃ (CF ₂ ) ₈ CH ₂ CH (OH) CH ₂ OCH ₂ CH ₂ O-, CF ₃ (CF ₂ ) ₉ CH ₂ CH (OH) CH ₂ OCH ₂ CH ₂ O-, CF ₃ (CF ₂ ) ₁₀ CH ₂ CH (OH) CH ₂ OCH ₂ CH ₂ O-, CF ₃ (CF ₂ ) ₁₁ CH ₂ CH (OH) CH ₂ OCH ₂ CH ₂ O-, CF ₃ (CF ₂ ) ₁₂ CH ₂ CH (OH _{) CH 2 OCH 2 CH 2 O-} , CF 3 (CF 2) 13 CH 2 CH (OH) CH 2 OCH 2 CH 2 O-, CF 3 (CF 2) 14 CH 2 CH (OH) CH 2 OCH 2 CH ₂ O-, CF ₃ (CF ₂ ) ₁₅ CH ₂ CH (OH) CH ₂ OCH ₂ CH ₂ O-, CF ₃ (CF ₂ ) ₁₆ CH ₂ CH (OH) CH ₂ OCH ₂ CH ₂ O-, CF ₃ (CF ₂ ) ₁₇ CH ₂ CH (OH) CH ₂ OCH ₂ CH ₂ O-,
(CF ₃ ) ₂ CF (CF ₂ ) ₂ CH ₂ CH (OH) CH ₂ OCH ₂ CH ₂ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH (OH) CH ₂ OCH ₂ CH ₂ O -, (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OH) CH ₂ OCH ₂ CH ₂ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH (OH) CH ₂ OCH ₂ CH ₂ O-, H (CF ₂ ) ₈ CH ₂ OCH ₂ CH (OH) CH ₂ OCH ₂ CH ₂ O-,

F (CF ₂ ) ₈ O-, F (CF ₂ ) ₉ O-, F (CF ₂ ) ₁₀ O-, F (CF ₂ ) ₁₁ O-, F (CF ₂ ) ₁₂ O-, F (CF ₂ ) ₁₃ O-, F (CF ₂ ) ₁₄ O-, F (CF ₂ ) ₁₅ O-, F (CF ₂ ) ₁₆ O-, F (CF ₂ ) ₁₇ O-, H (CF ₂ ) ₈ O-,
CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ O-, CF ₃ (CF ₂ ) ₈ CH ₂ CH ₂ O-, CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ O-, CF ₃ (CF ₂ ) ₁₀ CH ₂ CH ₂ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₄ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₆ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₈ O -, CF ₃ CF ₂ (CF ₂ CF ₂ O) ₂ CF ₂ O-, CF ₃ CF ₂ (CF ₂ CF ₂ O) ₃ CF ₂ O-, CF ₃ O (CF ₂ CF ₂ O) ₂ CF ₂ O -,

F (CF ₂ ) ₈ OCH ₂ CH ₂ O-, F (CF ₂ ) ₉ OCH ₂ CH ₂ O-, F (CF ₂ ) ₁₀ OCH ₂ CH ₂ O-, F (CF ₂ ) ₁₁ OCH ₂ CH ₂ O -, F (CF ₂ ) ₁₂ OCH ₂ CH ₂ O-, F (CF ₂ ) ₁₃ OCH ₂ CH ₂ O-, F (CF ₂ ) ₁₄ OCH ₂ CH ₂ O-, F (CF ₂ ) ₁₅ OCH ₂ CH ₂ O-, F (CF ₂ ) ₁₆ OCH ₂ CH ₂ O-, F (CF ₂ ) ₁₇ OCH ₂ CH ₂ O-, H (CF ₂ ) ₈ OCH ₂ CH ₂ O-,
CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCH ₂ CH ₂ O-, CF ₃ (CF ₂ ) ₈ CH ₂ CH ₂ OCH ₂ CH ₂ O-, CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ OCH ₂ CH ₂ O-, CF ₃ (CF ₂ ) ₁₀ CH ₂ CH ₂ OCH ₂ CH ₂ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ OCH ₂ CH ₂ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₄ OCH ₂ CH ₂ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ OCH ₂ CH ₂ O-, (CF ₃ ) ₂ CF (CF ₂ ) ₆ OCH ₂ CH ₂ O _{-, (CF 3) 2 CF} (CF 2) 8 CH 2 CH 2 OCH 2 CH 2 O-, (CF 3) 2 CF (CF 2) 8 OCH 2 CH 2 O-, CF 3 CF 2 (CF 2 CF ₂ O) ₂ CF ₂ OCH ₂ CH ₂ O-, CF ₃ CF ₂ (CF ₂ CF ₂ O) ₃ CF ₂ OCH ₂ CH ₂ O-, CF ₃ O (CF ₂ CF ₂ O) ₂ CF ₂ OCH ₂ CH ₂ O-.

  The fluorine-containing acetophenone derivative represented by the general formula (I) can be synthesized, for example, by the following reaction formula.

  When 1 equivalent of perfluoro fatty acid (i) (for example, 5 ≦ k) is selectively reacted with acetophenone derivative (ii) (commercial product: Irgacure 2959) (route a), one perfluoroalkyl group is introduced. Thus obtained fluorine-containing acetophenone derivative (iii) is obtained. When the perfluoro fatty acid (i) is reacted with 2 equivalents of the acetophenone derivative (ii) (route b), a fluorine-containing acetophenone derivative (iv) into which two perfluoroalkyl groups are introduced is obtained. The esterification at this time is carried out by a conventional method.

  On the other hand, when perfluoroalkyl isocyanate (v) is selectively reacted with one equivalent of acetophenone derivative (ii) (commercial product: Irgacure 2959) (root c), fluorine containing one perfluoroalkyl group introduced An acetophenone derivative (vi) is obtained. When perfluoroalkyl isocyanate (v) is reacted with 2 equivalents of acetophenone derivative (ii) (route d), fluorine-containing acetophenone derivative (vii) into which two perfluoroalkyl groups are introduced is obtained. In this case, urethanization is carried out by a conventional method.

  Even when perfluoroether isocyanate (Rfe-NCO) is used, a fluorine-containing acetophenone derivative having one perfluoroether group introduced or a fluorine-containing acetophenone having two perfluoroether groups introduced by the same reaction. A derivative is selectively obtained.

  In this way, various fluorine-containing acetophenone derivatives can be synthesized.

  Next, with reference to FIG. 1, the object provided with the composite hard coat layer of the present invention and the formation method thereof will be described in detail.

  FIG. 1 is a cross-sectional view schematically showing an example of a layer structure of an object provided with the composite hard coat layer of the present invention. In FIG. 1, a hard coat layer (2) is formed on the surface of an object to be hard coated (1), and a fluorine-containing surface layer (3) is formed in contact with the surface of the hard coat layer (2). Both the hard coat layer (2) and the fluorine-containing surface layer (3) are referred to as a composite hard coat layer for convenience.

  The target object (1) includes various objects that require hard coating. Examples thereof include, but are not limited to, sheets and substrates made of thermoplastic resins such as polyethylene terephthalate (PET), polymethyl methacrylate, polyethylene, polypropylene, and polycarbonate. More specific products include optical recording media, magneto-optical recording media, optical lenses, optical filters, antireflection films, and various display elements such as liquid crystal displays, CRT displays, plasma displays, and EL displays.

  First, on the surface of the target object (1), a hard coat agent composition containing an active energy ray-curable compound is applied to form a hard coat agent composition layer, and then on the hard coat agent composition layer surface, A surface material layer is formed by applying a surface layer material containing a fluorine-containing (meth) acrylate compound and the fluorine-containing acetophenone derivative of the present invention as a photoinitiator. The components of the hard coat agent composition and the surface layer material will be described.

  The active energy ray-curable compound contained in the hard coat agent composition has a particularly limited structure as long as it has at least one active group selected from a (meth) acryloyl group, a vinyl group and a mercapto group. Not. In order to obtain sufficient hardness as a hard coat, the active energy ray-curable compound preferably contains a polyfunctional monomer or oligomer containing two or more, preferably three or more polymerizable groups in one molecule. .

  Among such active energy ray polymerizable compounds, examples of the compound having a (meth) acryloyl group include 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, and ethylene oxide-modified bisphenol. A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples include 3- (meth) acryloyloxyglycerin mono (meth) acrylate, urethane acrylate, epoxy acrylate, and ester acrylate, but are not necessarily limited thereto. Not to.

  Examples of the compound having a vinyl group include ethylene glycol divinyl ether, pentaerythritol divinyl ether, 1,6-hexanediol divinyl ether, trimethylolpropane divinyl ether, ethylene oxide-modified hydroquinone divinyl ether, and ethylene oxide-modified bisphenol A diester. Examples include vinyl ether, pentaerythritol trivinyl ether, dipentaerythritol hexavinyl ether, ditrimethylolpropane polyvinyl ether, and the like, but are not necessarily limited thereto.

  Examples of the compound having a mercapto group include ethylene glycol bis (thioglycolate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (thioglycolate), trimethylolpropane tris (3- Mercaptopropionate), pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (3-mercaptopropionate), and the like, but are not necessarily limited thereto.

  As an active energy ray hardening compound contained in a hard-coat agent composition, only 1 type may be used and 2 or more types may be used together.

  The hard coat agent composition contains a photopolymerization initiator. The photopolymerization initiator is not particularly required when an electron beam is used as the active energy ray, but is required when ultraviolet rays are used. As the photopolymerization initiator, known ones can be used. Among the photopolymerization initiators, examples of the photoradical initiator include Darocur 1173, Irgacure 651, Irgacure 184, and Irgacure 907 (all manufactured by Ciba Specialty Chemicals). ). Content of a photoinitiator is about 0.5 to 5 weight% in a hard-coat agent composition (as solid content), for example.

  In addition, the hard coat agent composition may contain the fluorine-containing acetophenone derivative of the present invention as a photopolymerization initiator instead of the known photopolymerization initiator or together with the known photopolymerization initiator.

  The hard coat agent composition may contain an inorganic filler in order to improve the wear resistance, if necessary. Examples of the inorganic filler include silica, alumina, zirconia, titania and the like. The average particle diameter of the inorganic filler is preferably 100 nm or less, and more preferably 50 nm or less, particularly when transparency is required.

  Furthermore, in order to further increase the strength and wear resistance of the cured coating, the surface of the inorganic filler is preferably modified with a compound having an active energy ray polymerizable group. Examples of inorganic fillers having an average particle diameter of 50 nm or less and surface-modified with a compound having an active energy ray polymerizable group include JP-A-11-60235, JP-A-9-100111, and JP-A-2001. There are reactive silica particles described in JP-A 187812 and can be preferably used in the present invention. The silica particles described in JP-A-11-60235 contain a cation-reactive oxetanyl group as a reactive group, and the silica particles described in JP-A-9-100111 are used as reactive groups. It contains a radically reactive (meth) acryloyl group. The silica particles described in JP-A No. 2001-187812 simultaneously contain a radical-reactive unsaturated double bond such as a (meth) acryloyl group and a cation-reactive group such as an epoxy group. By adding such an inorganic filler to the hard coat agent composition, the wear resistance of the hard coat layer can be further improved. The content of the inorganic filler is, for example, about 5 to 80% by weight in the hard coat agent composition (as a solid content). When the inorganic filler is contained in an amount of more than 80% by weight, the film strength of the hard coat layer tends to be weak.

  In addition, the hard coat agent composition may further comprise a non-polymerizable diluent solvent, a photopolymerization initiation aid, an organic filler, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, and an antifoaming agent, if necessary. , Leveling agents, pigments, silicon compounds and the like may be included. Examples of the non-polymerizable diluent solvent include isopropyl alcohol, n-butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, isopropyl acetate, n-butyl acetate, ethyl cellosolve, toluene and the like.

  The material for the surface layer contains a fluorine-containing (meth) acrylate compound and the fluorine-containing acetophenone derivative of the present invention as a photoinitiator. The cured film of the material for the surface layer has at least one function of antifouling property, lubricity and antireflection property due to the fluorine-containing group, and has no color such as yellow.

  Examples of the fluorine-containing (meth) acrylate compound include 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2, 2-trifluoroethyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluoro Octyl) ethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-9-methyloctyl) ethyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 2- (perfluoro-9-methyldecyl) ethyl (meth) ) Acrylate, IH, IH, 9H-but hexadecafluoro nonyl (meth) fluoride acrylates such as acrylate, not necessarily limited thereto. For example, a polymer compound such as perfluoropolyether having a (meth) acrylate group introduced therein, or a fluorine compound having a vinyl group or a mercapto group instead of the (meth) acrylate group can be preferably used. Specific examples include Fomblin Z DOL (alcohol-modified perfluoropolyether (Audimont)) diacrylate, fluorite ART3, and fluorite ART4 (Kyoeisha Chemical).

  As a fluorine-containing (meth) acrylate compound, only 1 type may be used from the said compound, and 2 or more types may be used together. Moreover, the active energy ray hardening compound used for the hard-coat agent composition mentioned above may be contained as some components in the material for surface layers.

  Moreover, only 1 type may be used from the said compound as a fluorine-containing acetophenone derivative of the said this invention as a photoinitiator, and 2 or more types may be used together.

  As the solvent for the surface layer material, a solvent that can dissolve the fluorine-containing (meth) acrylate compound satisfactorily is used. For example, a fluorine-containing solvent is preferable, and examples thereof include fluorocarbons such as perfluorohexane, perfluoroheptane, and perfluorooctane. Further, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, HFC 43-10mee, 1,1,2,2,3,3,4-heptafluorocyclopentane and the like can be mentioned. The fluorine-containing acetophenone derivative of the present invention dissolves well in these fluorine-containing solvents and is excellent in compatibility with the fluorine-containing (meth) acrylate compound, and is suitable as a photoinitiator.

  In the surface layer material, as in the hard coat agent composition, if necessary, a non-polymerizable diluent solvent, a photopolymerization initiation aid, an organic filler, an inorganic filler, a polymerization inhibitor, an oxidation inhibitor Inhibitors, ultraviolet absorbers, light stabilizers, antifoaming agents, leveling agents, pigments, silicon compounds and the like may be included.

  In the present invention, first, the hard coat agent composition layer is formed by applying the hard coat agent composition to the surface of the target object (1). The coating method is not limited, and various coating methods such as spin coating, dip coating, and gravure coating may be used.

  After applying the hard coat agent composition to the surface of the target object (1), it is preferable to eliminate the fluidity of the hard coat agent composition layer before applying the surface layer material. By eliminating the fluidity of the hard coat agent composition layer, it is possible to prevent fluctuations in the thickness of the hard coat agent composition layer and deterioration of the surface property when a surface layer material is applied thereon. It is easy to uniformly apply and form the surface layer material.

In order to eliminate the fluidity of the hard coat agent composition layer, for example, when the hard coat agent composition contains a diluting solvent, the solvent is dried after coating and contained in the hard coat agent composition. May be removed from the hard coat agent composition layer. Moreover, it is good also as drying after application | coating as needed and irradiating active energy rays, such as an ultraviolet-ray, and making a hard-coat-agent composition layer into a semi-hardened state. Care is taken to irradiate the active energy rays so that the hard coating composition layer is not completely cured. Semi-cured means that a part of the applied hard coat agent composition is unreacted. Therefore, the physical curing degree of the hard coat agent composition layer is not particularly limited, and the surface tackiness (tack) may be lost. The amount of UV irradiation at this time depends on the thickness of the hard coat layer, but is, for example, 1 to 500 mJ / cm ² , preferably 1 to 200 mJ / cm ² . With this amount of ultraviolet irradiation, a semi-cured hard coat agent composition layer is easily obtained.

  The thickness of the hard coat layer obtained by curing the hard coat agent composition layer is not particularly limited, and may be appropriately determined depending on the type and application of the target object. For example, when the target object is an optical recording disk, the target object may be formed to be 1 μm to 10 μm, preferably 1 μm to 5 μm. If it is less than 1 μm, sufficient surface hardness cannot be given to the disk, and if it exceeds 10 μm, cracks tend to occur or the warp of the disk tends to increase.

  Next, the surface material layer is formed by applying the surface layer material onto the surface of the hard coating agent composition layer in an uncured or partially cured (semi-cured) state. The surface material layer may be formed so that the thickness of the fluorine-containing surface layer obtained after curing is 1 nm to 100 nm, preferably 5 nm to 50 nm. If the thickness is less than 1 nm, the effects of antifouling and lubricity are not obtained so much. If the thickness exceeds 100 nm, the hardness of the lower hard coat layer is not reflected so much, and the effects of scratch resistance and wear resistance are reduced. .

  The surface layer material is applied by diluting the above surface layer material with an appropriate solvent, and the coating solution is not limited, and various coating methods such as spin coating, dip coating, gravure coating, spray coating, etc. It is good to apply by a method. It is preferable to perform heat drying after coating. By the heat drying treatment, the solvent evaporates and the surface layer material is leveled by heat, so that a smooth surface is easily obtained.

  As the solvent in this case, it is preferable to select and use a solvent that does not substantially dissolve the active energy ray-curable compound in the uncured or partially cured (semi-cured) hard coat agent composition layer. Whether to substantially dissolve the hard coat agent composition layer depends not only on the type of solvent but also on the coating method. For example, when the spin coating method is used as a coating method for the surface material layer, in most cases, most of the dilution solvent contained in the coating solution is volatilized at the time of spin coating, and therefore, the solvent that dissolves the hard coat agent composition layer to some extent. Even if it is used as a diluting solvent, there is no practical problem. On the other hand, for example, when the dip coating method is used as the coating method for the surface material layer, the contact time between the uncured hard coating agent composition layer surface and the coating material for the surface material layer is long, so the hard coating agent composition It is necessary to use a solvent that does not dissolve the material layer material at all or hardly dissolves it.

  The solvent that can be used in the dip coating method is preferably a fluorine-containing solvent, and examples thereof include fluorocarbons such as perfluorohexane, perfluoroheptane, and perfluorooctane. Moreover, you may use together saturated hydrocarbon solvents, such as n-octane and isooctane, to such an extent that the solubility of a fluorine-containing (meth) acrylate compound is not impaired. Examples of the solvent that can be used in the spin coating method include, in addition to the above-mentioned various solvents, for example, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, HFC 43-10mee, 1,1,2,2,3,3,4-hepta. And fluorocyclopentane. Moreover, you may use together solvents, such as isopropyl alcohol, n-butyl alcohol, dibutyl ether, ethyl cellosolve, and butyl cellosolve, to such an extent that the solubility of a fluorine-containing (meth) acrylate compound is not impaired.

  In this way, an uncured or partially cured (semi-cured) hard coat agent composition layer and an uncured surface material layer are formed on the surface.

Next, the formed hard coat agent composition layer and the surface material layer are irradiated with ultraviolet rays to simultaneously cure the two layers. At this time, an ultraviolet ray having an energy amount sufficient to completely cure both layers is irradiated to complete the curing reaction of both layers. At this time, the irradiation amount of ultraviolet rays, for example 100~5000mJ / cm ^2, may preferably be a 500~3000mJ / cm ^2. By simultaneously curing an uncured or partially cured (semi-cured) hard coat agent composition layer and an uncured surface material layer provided in contact with the surface, these two layers are strengthened at the interface. A fluorine-containing surface layer (3) which is adhered, that is, cured on the cured hard coat layer (2) can be obtained with good adhesion.

  By using such a process of the present invention, a fluorine-containing surface that is thin enough to reflect its hardness on the outermost surface and has good water repellency and lubricity on the high-hardness hard coat layer (2). While providing the layer (3), good adhesion between the hard coat layer (2) and the fluorine-containing surface layer (3) can be obtained.

  Ultraviolet rays are used as means for simultaneously curing the hard coat agent composition layer and the surface material layer. In the present invention, the fluorine-containing surface layer has a thickness of 1 nm or more and 100 nm or less, preferably 5 nm or more and 50 nm or less, and in order to obtain better adhesion to the hard coat layer, the oxygen concentration in the ultraviolet irradiation atmosphere Is preferably 500 ppm by volume or less, preferably 200 ppm by volume or less, more preferably 10 ppm by volume or less, and purge with an inert gas such as nitrogen is preferably performed. This is in order to suppress surface hardening inhibition caused by oxygen radicals generated in the irradiation atmosphere. Alternatively, instead of controlling the oxygen concentration in the irradiation atmosphere, various conventionally known oxygen inhibition inhibitors may be added to the hard coat agent composition and / or the surface layer material. As such an oxygen inhibition inhibitor, for example, oxygen inhibition inhibitors described in JP2000-109828A, JP2000-109828A, and JP2000-144011A can be used. Needless to say, the oxygen inhibition inhibitor and oxygen concentration control in the irradiation atmosphere may be used in combination.

  By using such a material, film formation, and curing method, a composite hard coat layer having excellent wear resistance, water repellency / lubricity, and excellent durability can be formed.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[Example 1: Synthesis of fluorine-containing photoinitiator A]
In a 300 mL round flask equipped with a stirrer, 40 g of perfluorononanoic acid (compound i in the above reaction formula; k = 8) and 2-hydroxy-4 ′-(2-hydroxyethoxy) -2-methylpropiophenone (described above) 6.4 g of compound ii) in the reaction formula was charged and heated to 110 ° C. When the entire raw material was in a molten state, stirring was started slowly and the reaction was continued for 4 hours. After the reaction, the reaction product was once cooled to room temperature, and it was confirmed by gas chromatography analysis that 2-hydroxy-4 ′-(2-hydroxyethoxy) -2-methylpropiophenone was not present. Further, the reaction product was heated to 100 to 160 ° C. under reduced pressure to distill off the remaining perfluorononanoic acid, and then cooled to room temperature again to obtain about 12 g of a white solid.

  The obtained white solid was analyzed by infrared spectroscopic analysis, gel permeation chromatography, gas chromatography, gas chromatography mass spectrometry, etc., and the target fluorine-containing photoinitiator A 2-hydroxy-4 ′-(2 -Perfluorononanoyloxyethoxy) -2-methylpropiophenone (Compound iii in the above reaction formula; k = 8) was confirmed to be obtained as the main product. This white solid was used as fluorine-containing photoinitiator A in the following examples.

Photoinitiator A identification data:
IR (FIG. 2): 3390-3500 cm ⁻¹ O—H stretching;
Around 1770cm ^-1 Ester C = O stretch;
Near 1650 cm ^-1 benzylic C = O stretching;
Around 1600cm ^-1 benzene ring C = C stretching;
Near 1100-1200 cm ^-1 Perfluoroalkyl group CF stretch

When the above white solid was dissolved in perfluorooctane and its ultraviolet absorption spectrum was measured, the absorption derived from the π-π ^* transition of the benzene ring of the target product was observed near the wavelength of 260 nm, and the benzoyl site was observed near the wavelength of 320 nm. Absorption due to the n-π ^* transition of the carbonyl was observed. Furthermore, when a small amount of 2- (perfluorooctyl) ethyl acrylate was added to this solution and irradiated with ultraviolet rays, the absorption near 260 nm was greatly reduced, suggesting the progress of cleavage of the initiator and addition to the acrylate. Therefore, also from this point, the obtained white solid is a target fluorine-containing photoinitiator A 2-hydroxy-4 ′-(2-perfluorononanoyloxyethoxy) -2-methylpropiophenone (the above reaction). It was confirmed that compound iii; k = 8) in the formula was the main product.

[Example 2: Synthesis of fluorine-containing photoinitiator B]
A reaction was carried out in the same manner as in Example 1 except that 48 g of perfluoroundecanoic acid (k = 11) was used instead of 40 g of perfluorononanoic acid (k = 8) to obtain about 20 g of a brown solid substance. This substance was analyzed in the same manner as in Example 1, and the target fluorine-containing photoinitiator B 2-hydroxy-4 ′-(2-perfluoroundecanoyloxyethoxy) -2-methylpropiophenone (the above reaction formula) It was confirmed that compound iii; k = 11) was obtained as the main product. This brown solid material was used as fluorine-containing photoinitiator B in the following examples.

Photoinitiator B identification data:
IR (FIG. 3): 3390-3500 cm ⁻¹ O—H stretching;
Around 1770cm ^-1 Ester C = O stretch;
Near 1650 cm ^-1 benzylic C = O stretching;
Around 1600cm ^-1 benzene ring C = C stretching;
Near 1100-1200 cm ^-1 Perfluoroalkyl group CF stretch

[Example 3: Synthesis of fluorine-containing photoinitiator C]
The same as Example 1 except that 44 g of perfluoro-3,6,9-trioxatridecanoic acid (compound v in the following reaction formula) was used instead of 40 g of perfluorononanoic acid and the reaction temperature was 100 ° C. To obtain about 13 g of a transparent viscous liquid. This liquid was analyzed in the same manner as in Example 1, and the target fluorine-containing photoinitiator C 2-hydroxy-4 ′-[2- (perfluoro-3,6,9-trioxatridecanoyloxy) ethoxy] was analyzed. It was confirmed that 2-methylpropiophenone was obtained as the main product. This liquid was used as fluorine-containing photoinitiator C in the following examples.

[Example 4: Substrate with composite hard coat layer]
An ultraviolet curable hard coating agent (manufactured by JSR, Desolite Z7503) was applied on a polycarbonate substrate (diameter 12 cm) having a thickness of 0.6 mm by spin coating, and then heated in the atmosphere at 60 ° C. for 3 minutes to coat the inside of the coating. The diluted solvent was removed to form an uncured hard coat layer. The hard coat agent was a composition containing a reactive inorganic filler as disclosed in JP-A-9-100111.

Next, a surface material solution was prepared by adding the following compound to 99.4 parts by weight of fluorinated solvent Fluorinert FC-77 (manufactured by Sumitomo 3M).
Perfluoropolyether diacrylate (Augmont, Fomblin Z DOL modified acrylic, molecular weight: about 2000) 0.33 parts by weight
3-perfluorooctyl-2-hydroxypropyl acrylate (manufactured by Daikin Fine Chemical Laboratory) 0.17 parts by weight Fluorine-containing photoinitiator A 0.1 parts by weight

  This surface material solution was applied onto the uncured hard coat layer by a spin coating method and dried at 60 ° C. for 3 minutes to form an uncured surface layer.

Then, using a high pressure mercury lamp was irradiated with ultraviolet rays of 1000 mJ / cm ² under a nitrogen stream, to cure the hard coat layer and the surface layer simultaneously. The oxygen concentration in the ultraviolet irradiation atmosphere was 80 ppm by volume. The cured hard coat layer had a thickness of 3.4 μm, and the cured surface layer had a thickness of about 30 nm. The film thickness of the hard coat layer was measured with a contact probe type surface shape measuring instrument. The film thickness of the surface layer was measured by fluorescent X-ray analysis (XRF) using perfluoropolyether (Daikin Kogyo Co., Ltd., demnum) as a standard substance. In this way, a substrate with a composite hard coat layer was obtained.

[Example 5: Substrate with composite hard coat layer]
A substrate with a composite hard coat layer was obtained in the same manner as in Example 4 except that the surface material solution having the following composition was used. The cured hard coat layer had a thickness of 3.4 μm, and the cured surface layer had a thickness of about 30 nm.
Fluorinert FC-77 (Sumitomo 3M) 99.4 parts by weight Perfluoropolyether diacrylate (Augmont's Fomblin Z DOL acrylic modified product, molecular weight: about 2000) 0.33 parts by weight
3-perfluorooctyl-2-hydroxypropyl acrylate (manufactured by Daikin Fine Chemical Laboratory) 0.17 parts by weight Fluorine-containing photoinitiator B 0.1 parts by weight

[Example 6: Substrate with composite hard coat layer]
A substrate with a composite hard coat layer was obtained in the same manner as in Example 4 except that the surface material solution having the following composition was used. The cured hard coat layer had a thickness of 3.4 μm, and the cured surface layer had a thickness of about 30 nm.
Fluorinert FC-77 (manufactured by Sumitomo 3M) 99.4 parts by weight Perfluoropolyether diacrylate (Acrymont modified Fomblin Z DOL, molecular weight: about 2000) 0.5 parts by weight Fluorine-containing photoinitiator C 0 .1 part by weight

[Comparative Example 1]
A substrate with a composite hard coat layer was obtained in the same manner as in Example 4 except that the surface material solution having the following composition was used. The cured hard coat layer had a thickness of 3.4 μm, and the cured surface layer had a thickness of about 30 nm.
Fluorinert FC-77 (Sumitomo 3M) 99.5 parts by weight Perfluoropolyether diacrylate (Augmont's Fomblin Z DOL acrylic modified product, molecular weight: about 2000) 0.33 parts by weight
3-perfluorooctyl-2-hydroxypropyl acrylate (manufactured by Daikin Fine Chemical Laboratory) 0.17 parts by weight

[Comparative Example 2]
A substrate with a composite hard coat layer was prepared in the same manner as in Comparative Example 1 except that the hard coat layer and the surface layer were cured by irradiating an electron beam under a nitrogen stream instead of ultraviolet irradiation under a nitrogen stream. Obtained. Curetron (manufactured by Nissin High Voltage Co., Ltd.) was used as the electron beam irradiation apparatus, the electron beam acceleration voltage was 200 kV, and the irradiation dose was 5 Mrad. The oxygen concentration in the irradiation atmosphere was 80 ppm by volume. The cured hard coat layer had a thickness of 3.4 μm, and the cured surface layer had a thickness of about 30 nm.

(Evaluation)
The performance test shown below was done about each sample produced in Examples 4-6 and Comparative Examples 1-2.

(1) Abrasion resistance Using steel wool # 0000, the degree of scratches produced when the hard coat surface of the sample was slid 20 times at a load of 4.9 N / cm ² was visually judged. Judgment criteria are as follows.
○: No scratch occurred △: Slightly scratched ×: Scratch occurred

(2) Water repellency and durability The contact angle of water on the surface of the composite hard coat was measured for the sample after standing at room temperature for 1 week after preparation. The measurement was performed before sliding and after sliding the sample surface with a waste cloth containing a solvent. The sliding conditions were as follows. That is, a nonwoven fabric (Asahi Kasei Kogyo Co., Ltd., Bencott Lint Free CT-8) was impregnated with acetone, and slid 50 times at a load of 4.9 N / cm ² . The contact angle was measured using a contact angle meter CA-D manufactured by Kyowa Interface Science Co., Ltd. in an environment with an air temperature of 20 ° C. and a relative humidity of 60%.

The above measurement results are shown in Table 1.
From Table 1, the board | substrate with a composite hard-coat layer of Examples 4-6 had very high abrasion resistance, was excellent in water repellency, and its durability was also very favorable. The composite hard coat layer was not colored and was excellent in transparency. In addition, as is clear from the comparison with Comparative Example 2, the substrates with the composite hard coat layers of Examples 4 to 6 are wear resistant, contact angle and durability thereof, and any performance of surface smoothness. It was found that the composite hard coat layer obtained by electron beam curing had a performance equivalent to or better than that.

  On the other hand, in Comparative Example 1, since the fluorine-containing photoinitiator was not contained in the surface material solution, the contact angle was remarkably lowered by sliding with an acetone-impregnated waste, and the water repellency durability could not be obtained. . It is considered that the fluorine-containing surface layer was wiped off by sliding with a waste cloth and the contact angle was lowered.

[Example 7: Optical information medium provided with a composite hard coat layer]
This example is a manufacturing example of an optical information medium (hereinafter abbreviated as an optical disk) provided with a composite hard coat layer. In this embodiment, a phase change type optical disc is manufactured. However, the present invention is not limited to this, and can be widely applied regardless of the type of recording layer, such as a read-only optical disc and an optical disc that can be recorded only once. is there.

  FIG. 4 is a schematic cross-sectional view of an example of an optical disc provided with a composite hard coat layer. In FIG. 4, an optical disk (11) has a reflective layer (13) and a second dielectric layer (14) on the surface of the support base (12) on which fine irregularities such as information pits and pregrooves are formed. , A phase change recording material layer (15) and a first dielectric layer (16) in this order, a light transmission layer (18) on the first dielectric layer (16), and a light transmission layer (18 ) Have a hard coat layer (19) and a fluorine-containing surface layer (20). In this example, the reflective layer (13), the second dielectric layer (14), the phase change recording material layer (15), and the first dielectric layer (16) constitute the recording layer (17). Both the hard coat layer (19) and the fluorine-containing surface layer (20) are referred to as a composite hard coat layer for convenience. The optical disk (11) is used so that laser light for recording or reproduction enters through the fluorine-containing surface layer (20), the hard coat layer (19), and the light transmission layer (18).

  An optical recording disk sample having the layer structure shown in FIG. 4 was produced as follows.

On the surface of a disk-shaped support substrate (12) (made of polycarbonate, diameter 120 mm, thickness 1.1 mm) on which grooves are formed for information recording, a thickness of 100 nm made of Al ₉₈ Pd ₁ Cu ₁ (atomic ratio). A reflective layer (13) was formed by sputtering. The depth of the groove was λ / 6 expressed by the optical path length at the wavelength λ = 405 nm. The recording track pitch in the groove recording system was 0.32 μm.

Next, a second dielectric layer (14) having a thickness of 20 nm was formed on the surface of the reflective layer (13) by sputtering using an Al ₂ O ₃ target. A recording material layer (15) having a thickness of 12 nm was formed on the surface of the second dielectric layer (14) by sputtering using an alloy target made of a phase change material. The composition (atomic ratio) of the recording material layer (15) was Sb ₇₄ Te ₁₈ (Ge ₇ In ₁ ). On the surface of the recording material layer (15), a first dielectric layer (16) having a thickness of 130 nm was formed by sputtering using a ZnS (80 mol%)-SiO ₂ (20 mol%) target.

  Next, a radical polymerizable ultraviolet curable resin having the following composition is applied to the surface of the first dielectric layer (16) by a spin coat method, and irradiated with ultraviolet rays so that the thickness after curing becomes 98 μm. A permeable layer (18) was formed.

(Light transmission layer: Composition of UV curable resin)
50 parts by weight of urethane acrylate oligomer (Made by Mitsubishi Rayon Co., Ltd., Diabeam UK6035)
Isocyanuric acid EO-modified triacrylate 10 parts by weight (Aronix M315, manufactured by Toa Gosei Co., Ltd.)
Isocyanuric acid EO-modified diacrylate 5 parts by weight (manufactured by Toa Gosei Co., Ltd., Aronix M215)
Tetrahydrofurfuryl acrylate 25 parts by weight Photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone) 3 parts by weight

  Next, an ultraviolet / electron beam curable hard coating agent having the following composition is applied onto the light transmission layer (18) by a spin coating method, and then the diluted solvent inside the coating is removed by heating at 60 ° C. for 3 minutes in the air. Thus, an uncured hard coat layer (19) was formed.

(Composition of hard coating agent)
Reactive group-modified colloidal silica (dispersion medium: propylene glycol monomethyl ether acetate, nonvolatile content: 40% by weight) 100 parts by weight dipentaerythritol hexaacrylate 48 parts by weight tetrahydrofurfuryl acrylate 12 parts by weight propylene glycol monomethyl ether acetate 40 parts by weight ( Non-reactive diluent solvent)
Irgacure 184 (polymerization initiator) 5 parts by weight

Next, a surface material solution was prepared by adding the following compound to 99.7 parts by weight of fluorinated solvent Fluorinert FC-77 (manufactured by Sumitomo 3M).
Perfluoropolyether diacrylate (Augmont's Fomblin Z DOL acrylic modified product, molecular weight: about 2000) 0.06 parts by weight
3-perfluorooctyl-2-hydroxypropyl acrylate (Daikin Fine Chemical Laboratory Co., Ltd.) 0.19 parts by weight Fluorine-containing photoinitiator C 0.05 parts by weight

  This surface material solution was applied onto the uncured hard coat layer (19) by a spin coating method and dried at 60 ° C. for 3 minutes to form an uncured surface layer (20).

Next, the hard coat layer (19) and the surface layer (20) were simultaneously cured by irradiating with 1000 mJ / cm ² of ultraviolet light under a nitrogen stream using a high pressure mercury lamp. The oxygen concentration in the ultraviolet irradiation atmosphere was 80 ppm by volume. The cured hard coat layer (19) had a thickness of 2.5 μm, and the cured surface layer (20) had a thickness of about 28 nm. In this way, the optical recording disk sample No. 1 provided with the composite hard coat layer was used. 1 was obtained.

(Evaluation)
The produced optical recording disk sample No. For No. 1, recording / reproduction characteristics were evaluated under the following conditions using an optical disk evaluation apparatus (DDU-1000, manufactured by Pulstec).
Laser wavelength: 405 nm
Objective lens numerical aperture NA: 0.85
Linear velocity: 6.5 m / s
Recording signal: 1-7 modulation signal (shortest signal length 2T)
Recording area: groove recording

(1) Abrasion resistance A random signal was recorded in the vicinity of a radius of 40 mm of the optical recording disk sample, and an initial jitter value was measured. Next, the composite hard coat surface of the disk was rubbed 20 reciprocating times with a load of ^2.5 N / cm ² using steel wool # 0000, and then the jitter value was measured again (jitter value after test). The sliding direction with steel wool was the radial direction of the disk, and steel wool having a size of 1.0 cm × 1.0 cm was used.

(2) Antifouling property A random signal was recorded in the vicinity of a radius of 40 mm of the optical recording disk sample, and an initial jitter value was measured. Next, a fingerprint was adhered to the surface of the hard coat side surface of the disk by pressing the middle finger for 10 seconds with a pressure of 9.8 N for about 10 seconds. After that, the attached fingerprint was slowly wiped from the inner periphery to the outer periphery of the disc using eight sets of commercially available tissue paper (manufactured by Crecia Co., Ltd.). The pressure at the time of wiping was 4.9 N / cm ² and the number of times of wiping was one. Thereafter, the jitter value was measured again (jitter value after the test).

The above measurement results are shown in Table 2.
From Table 2, the optical recording disk sample No. No. 1 was excellent in initial and post-test jitter values in both the abrasion resistance and antifouling tests. The composite hard coat layer was not colored and was excellent in transparency.

[Example 8: Lens provided with fluorine-containing surface layer] (Reference Example)
In this example, a fluorine-containing surface layer was applied to the surface of a spherical lens with a diameter of 80 mm produced by injection molding of polycarbonate.

Both surfaces of the spherical lens were subjected to hydrophilization treatment by irradiating energy of 400 W · min / m ² using a corona treatment machine (3005DW-SLR, manufactured by Sophthal Japan Co., Ltd.). Next, a 0.3 wt% isopropyl alcohol solution of 3-acryloxypropyltrimethoxysilane (silane coupling agent, KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) was applied to both surfaces of the lens by an immersion method. The lens was allowed to stand in the dark at room temperature overnight, and then a surface material solution having the following composition was applied to both surfaces of the lens by a dipping method and dried at 60 ° C. for 3 minutes to form an uncured surface layer. The treatment with the silane coupling agent was performed to improve the adhesion between the lens surface and the surface layer.

(Surface material solution composition)
Fluorine solvent Fluorinert FC-77 (manufactured by Sumitomo 3M) 99.4 parts by weight Perfluoropolyether diacrylate (Acrymont modified Fomblin Z DOL, molecular weight: about 2000) 0.33 parts by weight
3-perfluorooctyl-2-hydroxypropyl acrylate (Daikin Fine Chemical Laboratory Co., Ltd.) 0.17 parts by weight Fluorine-containing photoinitiator C 0.10 parts by weight

Next, using a high pressure mercury lamp, the surface layer was cured by irradiating with 1000 mJ / cm ² of ultraviolet rays under a nitrogen stream. The oxygen concentration in the ultraviolet irradiation atmosphere was 80 ppm by volume. Then, in order to fix a silane coupling agent, it heated at 60 degreeC for 24 hours. The film thickness of the cured surface layer was about 30 nm. In this way, a lens provided with a fluorine-containing surface layer on both sides was obtained.

(Evaluation: Water repellency and its durability)
About the lens sample after standing at room temperature for 1 week after production, the water repellency of the lens surface and its durability were measured by the same method as the evaluation in Examples 4-6. The contact angle of water on the lens surface before sliding was 103.3 degrees, and the contact angle of water on the lens surface after sliding with a nonwoven fabric impregnated with acetone was 102.4 degrees. The lens surface was not colored and was excellent in transparency. It has been shown that a fluorine-containing surface layer excellent in antifouling property and durability can be formed using the surface layer material of the present invention depending on the use and material of the object.

  Examples 4 to 6 show application of a composite hard coat layer on a polycarbonate substrate, and Example 7 shows application of a composite hard coat layer to a phase change optical disk. However, the present invention is applied not only to a phase change type optical disc but also to a read-only optical disc and a write once optical disc. Furthermore, the present invention is applied not only to an optical information medium but also to an optical lens, an optical filter, an antireflection film, and various display elements. For this reason, the above-described embodiment is merely an example in all respects and should not be interpreted in a limited manner. Further, all modifications belonging to the equivalent scope of the claims are within the scope of the present invention.

It is sectional drawing which shows typically the example of a layer structure of the object to which the composite hard-coat layer of this invention was provided. It is IR chart (wave number cm ^<-1 > VS. transmission%) of fluorine-containing photoinitiator A. It is IR chart (wave number cm ^<-1 > VS. transmission%) of fluorine-containing photoinitiator B. It is a schematic sectional drawing of an example of the optical disk to which the composite hard-coat layer of this invention was provided.

Explanation of symbols

(1): Target object
(2): Hard coat layer
(3): Fluorine-containing surface layer
(11): Optical disc
(12): Support base
(13): Reflective layer
(14): Second dielectric layer
(15): Phase change recording material layer
(16): First dielectric layer
(18): Light transmission layer
(19): Hard coat layer
(20): Fluorine-containing surface layer

Claims (12)

An object provided with a composite hard coat layer including a hard coat layer provided on the object surface and a fluorine-containing surface layer provided on the hard coat layer surface,
The hard coat layer consists of a cured product of a hard coat agent composition containing an active energy ray-curable compound,
The fluorine-containing surface layer includes a fluorine-containing (meth) acrylate compound,
As a photoinitiator, the following general formula (I):

[In General Formula (I), R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy having 1 to 6 carbon atoms. A group, a C 2-7 alkylcarbonyloxy group, a perfluoroalkylcarbonyloxy group having a total number of fluorocarbon atoms of 5 to 50, a phenylcarbonyloxy group, or an amino group. However, all of R ₁ , R ₂ and R ₃ do not become hydrogen atoms at the same time. Further, any _{two of} R ₁ , R ₂ and R ₃ may be connected to each other to form a ring.
R ₄ represents a fluorine-containing organic group, and the fluorine-containing organic group is
(a)-[C (X) F] k-,
(b)-[C (X) FO] l-,
(c)-[C (X) FC (Y) FO] m-, and
(d)-[C (X) FC (Y) FC (Z) FO] n-
(Here, X, Y, and Z each independently represent an F atom or a CF ₃ group, and k, l, m, and n represent the number of each fluorine-containing unit.)
And at least one fluorine-containing unit selected from the group consisting of such that the total number of fluorocarbon atoms contained in the selected fluorine-containing unit is 5 or more and 50 or less. ] The object to which the composite hard-coat layer was provided which consists of hardened | cured material of the material for surface layers containing the fluorine-containing acetophenone derivative shown by these . The fluorine-containing acetophenone derivative is represented by R in the general formula (I). _Four Wherein the fluorine-containing organic group is an Rfa-L- group having a perfluoroalkyl group Rfa containing the fluorine-containing unit (a)-[C (X) F] k-(5≤k≤50) [wherein L is
(f) -COO-,
(g) -COO- (CH ₂ ) j-O-,
(h) -CH ₂ CH (OH) CH ₂ O-,
(i) -CH ₂ CH (OH) CH ₂ O- (CH ₂ ) j-O-,
(j) -CH ₂ O-,
(k) -CH ₂ O- (CH ₂ ) j-O-,
(l)-(CH ₂ j-or
(m) -NHCOO- (CH ₂ ) j-O-
(Where j represents an integer of 2 to 6), and represents a divalent linking group. The object to which the composite hard coat layer according to claim 1 is applied. The fluorine-containing acetophenone derivative is represented by R in the general formula (I). _Four Rfa-COO- (CH having a perfluoroalkyl group Rfa containing the fluorine-containing unit (a)-[C (X) F] k-(5≤k≤50). ₂ ) j-O- group (where j represents an integer of 2 to 6) or Rfa-NHCOO- (CH ₂ The object provided with the composite hard coat layer according to claim 1, wherein the object is a j—O— group (where j represents an integer of 2 to 6). The fluorine-containing acetophenone derivative is represented by R in the general formula (I). _Four Is represented by the fluorine-containing unit (b)-[C (X) FO] l-, (c)-[C (X) FC (Y) FO] m-, and (d)-[ An Rfe-L- group having a perfluoroether-containing group Rfe containing at least one selected from the group consisting of C (X) FC (Y) FC (Z) FO] n −, wherein L is
(f) -COO-,
(g) -COO- (CH ₂ ) j-O-,
(h) -CH ₂ CH (OH) CH ₂ O-,
(i) -CH ₂ CH (OH) CH ₂ O- (CH ₂ ) j-O-,
(j) -CH ₂ O-,
(k) -CH ₂ O- (CH ₂ ) j-O-,
(l)-(CH ₂ j-or
(m) -NHCOO- (CH ₂ ) j-O-
(Where j represents an integer of 2 to 6), and represents a divalent linking group. The object to which the composite hard coat layer according to claim 1 is applied. The fluorine-containing acetophenone derivative is represented by R in the general formula (I). _Four Is represented by the fluorine-containing unit (b)-[C (X) FO] l-, (c)-[C (X) FC (Y) FO] m-, and (d)-[ Rfe-COO- (CH having a perfluoroether-containing group Rfe containing at least one selected from the group consisting of C (X) FC (Y) FC (Z) FO] n − ₂ ) j-O- group (where j represents an integer of 2 to 6) or Rfe-NHCOO- (CH ₂ The object provided with the composite hard coat layer according to claim 1, wherein the object is a j—O— group (where j represents an integer of 2 to 6). The object to which the composite hard coat layer according to any one of claims 1 to 5 is provided, wherein the fluorine-containing surface layer has a thickness of 1 nm to 100 nm. The active energy ray-curable compounds contained in the hard coat agent composition has at least one reactive group selected from the group consisting of (meth) acryloyl group, vinyl group and mercapto group, claim 1 An object provided with the composite hard coat layer according to any one of -6. The object provided with the composite hard coat layer according to any one of claims 1 to 7 , wherein the hard coat agent composition contains a photoinitiator and, if necessary, an inorganic filler. . The composite hard coat layer according to any one of claims 1 to 8 , wherein the object is an optical recording medium, a magneto-optical recording medium, an optical lens, an optical filter, an antireflection film, or various display elements. Granted object. A hard coat agent composition layer containing an active energy ray-curable compound is applied to the surface of an object to be hard-coated to form a hard coat agent composition layer,
On the surface of the hard coat agent composition layer, a fluorine-containing (meth) acrylate compound and the following general formula (I) as a photoinitiator :

[In General Formula (I), R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy having 1 to 6 carbon atoms. A group, a C 2-7 alkylcarbonyloxy group, a perfluoroalkylcarbonyloxy group having a total number of fluorocarbon atoms of 5 to 50, a phenylcarbonyloxy group, or an amino group. However, all of R ₁ , R ₂ and R ₃ do not become hydrogen atoms at the same time. Further, any _{two of} R ₁ , R ₂ and R ₃ may be connected to each other to form a ring.
R ₄ represents a fluorine-containing organic group, and the fluorine-containing organic group is
(a)-[C (X) F] k-,
(b)-[C (X) FO] l-,
(c)-[C (X) FC (Y) FO] m-, and
(d)-[C (X) FC (Y) FC (Z) FO] n-
(Here, X, Y, and Z each independently represent an F atom or a CF ₃ group, and k, l, m, and n represent the number of each fluorine-containing unit.)
And at least one fluorine-containing unit selected from the group consisting of such that the total number of fluorocarbon atoms contained in the selected fluorine-containing unit is 5 or more and 50 or less. A surface layer material comprising a fluorine-containing acetophenone derivative represented by the following formula:
The hard coat agent composition layer and the surface material layer thus formed are irradiated with ultraviolet rays, and both the layers are cured simultaneously to form a hard coat layer in contact with the target object surface and a fluorine-containing surface layer in contact with the hard coat layer surface. A method of forming a composite hard coat layer including a hard coat layer and a fluorine-containing surface layer on a target object surface. After the hard coat agent composition is applied to the surface of the target object to form a hard coat agent composition layer, the hard coat agent composition layer is dried to hard coat the solvent contained in the hard coat agent composition. The formation method of the composite hard-coat layer of Claim 10 which removes from an agent composition layer and then apply | coats the material for surface layers on the hard-coat-agent composition layer surface, and forms a surface material layer. The method of forming a composite hard coat layer according to claim 10 or 11 , wherein the irradiation with ultraviolet rays is performed in an atmosphere having an oxygen concentration of 500 ppm by volume or less.

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