JP4370846B2 - Antifouling hard coat, method for producing the same, and antifouling substrate - Google Patents

Description

  The present invention relates to an antifouling hard coat in which antifouling properties are imparted to the hard coat surface and a method for producing the same.

  Conventionally, acrylic hard coats have been widely applied in various fields because they have excellent strength characteristics and transparency. For example, an acrylic hard coat is used as a transparent organic base material that substitutes for glass, particularly an optical base material. The acrylic hard coat may be laminated on the metal layer by vapor deposition or sputtering in order to form a laminate composed of an acrylic hard coat layer and a metal layer. Furthermore, the acrylic hard coat is also widely used as a surface protective material for optical disks, touch panels and the like.

However, the conventional acrylic hard coat has a problem that the antifouling property of the surface against fingerprints and oil-based pens is poor and the optical characteristics are deteriorated. Therefore, it has been proposed to improve the antifouling property of the acrylic hard coat by using a fluorine-containing resin, which is a coating resin that is excellent in durability, water repellency, and stain resistance and is soluble in an organic solvent. Specifically, the following means are disclosed in order to improve the antifouling property of the acrylic hard coat.
(1) An antifouling hard coat agent obtained by mixing an acrylic monomer with an antifouling substance (for example, a non-crosslinked fluorosurfactant) (for example, see Patent Document 1)
(2) Antifouling composition for coating comprising a copolymer of an ultraviolet curable acrylic monomer, a fluorinated (meth) acrylate and a polysiloxane group-containing (meth) acrylate, and a fluorinated olefin polymer ( For example, see Patent Document 2)

JP-A-10-110118 JP-A-7-228820

  However, in the above-described prior art, if an already hardened acrylic hard coat surface is provided with antifouling properties, there arises a problem that optical characteristics deteriorate due to a decrease in transmittance due to film thickness. Moreover, in the above-mentioned conventional technology, since a sufficient number of fluorine groups do not exist on the surface of the hard coat, good antifouling properties cannot be obtained.

Accordingly, an object of the present invention is to provide an antifouling hard coat capable of realizing excellent antifouling properties and optical properties, a method for producing the same , and an antifouling substrate .

In order to solve the above-mentioned problem, the first invention
An acrylic hard coat layer;
A coupling agent layer formed directly on the acrylic hard coat layer;
A fluorine-based antifouling layer directly formed on the coupling agent layer,
The coupling agent layer contains a compound having two types of functional groups with different reactivity in one molecule,
The fluorine-based antifouling layer is an antifouling hard coat containing an alkoxysilane compound having a perfluoropolyether group.
The second invention is
An acrylic hard coat layer;
A coupling agent layer formed directly on the acrylic hard coat layer;
A fluorine-based antifouling layer directly formed on the coupling agent layer,
The coupling agent layer contains a compound having two types of functional groups with different reactivity in one molecule,
The fluorine-based antifouling layer is an antifouling hard coat containing an alkoxysilane compound having a fluoroalkyl group.

The third invention is
Forming a coupling agent layer directly on the acrylic hard coat layer;
Forming a fluorine-based antifouling layer directly on the coupling agent layer,
The coupling agent layer contains a compound having two types of functional groups with different reactivity in one molecule,
The fluorine-based antifouling layer is a method for producing an antifouling hard coat containing an alkoxysilane compound having a perfluoropolyether group.
The fourth invention is:
Forming a coupling agent layer directly on the acrylic hard coat layer;
Forming a fluorine-based antifouling layer directly on the coupling agent layer,
The coupling agent layer contains a compound having two types of functional groups with different reactivity in one molecule,
The fluorine-based antifouling layer is a method for producing an antifouling hard coat containing an alkoxysilane compound having a fluoroalkyl group.

  The antifouling hard coat of this invention comprises an acrylic hard coat layer, a coupling agent layer formed on the acrylic hard coat layer, and a fluorine antifouling layer formed on the coupling agent layer. Therefore, the coupling agent layer mediates the bond between the acrylic hard coat layer and the fluorine antifouling layer, and the affinity between the acrylic hard coat and the fluorine antifouling layer can be increased.

  According to the present invention, the affinity between the acrylic hard coat layer and the fluorine-based antifouling layer can be increased, whereby the antifouling hard coat having excellent antifouling properties, durability and optical properties. Can be provided.

  Hereinafter, an embodiment of the present invention will be described with reference to the drawings. FIG. 1 shows a cross section of a substrate on which an antifouling hard coat according to an embodiment of the present invention is formed. As shown in FIG. 1, the antifouling hard coat 2 has a configuration in which an acrylic hard coat layer 11, a coupling agent layer 12, and a fluorine antifouling layer 13 are sequentially laminated on a substrate 1.

  The base material 1 is, for example, a film or a substrate. Examples of the material of the substrate 1 include glass and plastic. Examples of the glass include soda glass, lead glass, hard glass, quartz glass, and liquid crystal glass. Plastics include polymethyl methacrylate, methyl methacrylate and other alkyl (meth) acrylates, styrene, etc. from the viewpoints of optical properties such as transparency, refractive index, and dispersion, as well as impact resistance, heat resistance, and durability. (Meth) acrylic resins such as copolymers with vinyl monomers; polycarbonate resins such as polycarbonate and diethylene glycol bisallyl carbonate (CR-39); homopolymers of (brominated) bisphenol A type di (meth) acrylates or Thermosetting (meth) acrylic resins such as copolymers, polymers and copolymers of urethane-modified monomers of (brominated) bisphenol A type mono (meth) acrylate; polyesters, especially polyethylene terephthalate, polyethylene naphthalate and Bad Sum polyester acrylonitrile - styrene copolymers, polyvinyl chloride, polyurethane, and epoxy resin are preferable. In addition, an aramid resin considering heat resistance can be used. In this case, the upper limit of the heating temperature is 200 ° C. or higher, and the temperature range is expected to be widened. When the substrate 1 is made of plastic, for example, the substrate 1 is produced by a method such as stretching the above resin, forming a film after diluting with a solvent, or performing injection molding.

  The acrylic hard coat layer 11 is a transparent organic film. As the material of the acrylic hard coat layer 11, for example, a radical polymerization type ultraviolet curable resin, an ultraviolet curable resin containing colloidal silica coated with an organic substance to increase hardness, and an antistatic property are improved. Examples include ultraviolet curable resins. Examples of the method for forming the acrylic hard coat layer 11 include spin coating, gravure coating, Dip coating, and spray coating.

  Here, the acrylic hard coat layer 11 means an acrylic hard coat layer in a broad sense including a thin film having a thickness of several tens of nm to a sheet-like material having a thickness of several hundreds of μm. The reason for defining the acrylic hard coat layer 11 in a broad sense is that, regardless of the type of the acrylic hard coat, the unreacted acrylic group when cured by photocuring and thermal curing and the coupling agent shown below are selective. It is clear that a uniform coupling agent layer 12 is formed on the surface by bonding or adsorbing to the surface, and OH groups are uniformly formed on the surface of the coupling agent layer 12 by subsequent drying. It is because it originates in.

（但し、式中、Ｘは反応性末端基（ビニル基、エポキシ基、アミノ基、メタクリル基、メルカプト基、イソシアネ−ト基など）を、Ｒ_aはアルキレン基を、Ｒ_bはアルキル基を示す。） The coupling agent layer 12 is made of a compound having two types of functional groups having different reactivity in one molecule represented by the following general formula (1).

(Wherein, X represents a reactive terminal group (vinyl group, epoxy group, amino group, methacryl group, mercapto group, isocyanate group, etc.), R _a represents an alkylene group, and R _b represents an alkyl group. .)

  Specifically, examples of the coupling agent constituting the coupling agent layer 12 include silane-based, titanate-based, aluminum-based, or zircoaluminum-based coupling agents, and these coupling agents are used alone. Alternatively, several types may be mixed and used empirically, but it is particularly preferable to use a silane coupling agent. Especially, it is preferable that the terminal alkoxy group is ethoxy. These include a reactive group (for example, an acrylic group, an amino group, an epoxy group, etc.) having binding properties with the surface component of the acrylic hard coat layer 11 in the molecule, and an antifouling agent that constitutes the fluorine-based antifouling layer 13. It has a reactive group (for example, methoxy group, ethoxy group, etc.) having binding properties with the component, mediates the coupling between the acrylic hard coat layer 11 and the fluorine antifouling layer 13, and both The affinity between them can be increased.

  Specific examples of coupling agents include silane coupling agents, acryl silanes, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, Examples include γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, and γ-acryloxypropylmethyldimethoxysilane.

  In the aminosilane system, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane N- (phenylmethyl) -γ-aminopropyltrimethoxysilane, N-methyl-γ-aminopropyltrimethoxysilane, N, N, N-trimethyl-γ-aminopropyltrimethoxysilane, N, N, N- Tributyl-γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-amino Propyltriethoxysilane, N-ω (amino hex Le) .gamma.-aminopropyltrimethoxysilane, N {N'-β (aminoethyl)} - beta (and an amino ethyl) .gamma.-aminopropyltrimethoxysilane.

  In the epoxy silane system, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane , Γ-glycidoxypropylmethyldimethoxysilane and the like.

  Titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecyl benzene sulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetraisopropyl bis (dioctyl phosphite) titanate Tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, Isopropyldimethacrylisostearoyl titanate, isopropylisostearoyl diacryl titanate Isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, dicumiphenyloxyacetate titanate, diisostearoyl ethylene titanate and the like.

  The coupling agent may be dissolved in a solvent and used as a solution, or may be used as a stock solution. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, isopropanol, 2-methoxypropanol, butyl cellosolve, or a mixed solvent such as Solmix, acetone, MEK, 2-pentanone, 3-pentanone, and the like. Examples thereof include ketone solvents and aromatic hydrocarbon solvents such as toluene and xylene. These may be used alone, or may be used by mixing several kinds thereof, or may be used by mixing with water. In particular, butyl cellosolve is preferable.

  The film thickness of the coupling agent solution is preferably in the range of 0.1 nm to 100 μm, more preferably 0.1 nm to 1 μm. On the other hand, if the film thickness is larger than 100 μm, cracks tend to occur. On the other hand, when the thickness is less than 0.1 nm, it becomes impossible to mediate the acrylic hard coat layer and the fluorine antifouling layer and increase the affinity between them.

Before applying the coupling agent to the acrylic hard coat layer 11, it is preferable to subject the surface of the acrylic hard coat layer 11 to surface treatment such as corona discharge treatment, oxygen plasma, and UV treatment. The power density of the corona discharge is preferably selected in consideration of the type and thickness of the acrylic hard coat, and is preferably set in the range of 100 to 700 W · min / m ² , for example. Further, the power density of the oxygen plasma treatment is preferably set in the range of 100 to 200 W · min / m ² , the oxygen flow rate is 30 to 100 mm ³ , and the material of the electrode is not particularly limited. It is selected appropriately.

  Moreover, as a method of attaching the coupling agent solution on the acrylic hard coat layer 11, for example, a method of applying a coupling agent solution on the surface of the acrylic hard coat layer 11, the surface of the acrylic hard coat layer 11 is applied. Examples include a method of rubbing with a coupling agent solution, a method of spraying a coupling agent solution on the surface of the acrylic hard coat layer 11, and a method of immersing the acrylic hard coat layer 11 in the coupling agent solution. Examples of the method of rubbing with a coupling agent solution include a method of applying a physical mechanical force to the surface of the acrylic hard coat layer 11 in the presence of the coupling agent solution. A method of rubbing (or wiping) the surface of the acrylic hard coat with a cloth impregnated with the agent solution, a method of rubbing the surface of the acrylic hard coat layer 11 in the coupling agent solution, or an acrylic with the coupling agent solution attached thereto And a method of rubbing the surface of the hard coat layer 11.

  Specifically, the fluorine-based antifouling layer 13 is made of a fluorine-based resin. This fluororesin is an alkoxysilane compound having a perfluoropolyether group or a fluoroalkyl group.

  Since the alkoxysilane compound having a perfluoropolyether group or a fluoroalkyl group has a low surface energy, it exhibits an excellent antifouling and water repellent effect, and exhibits a lubricating effect by including a perfluoropolyether group.

  The fluorine-based antifouling layer 13 is an alkoxysilane compound having a perfluoropolyether group represented by the following general formula (2) or (3), or a fluoroalkyl group represented by the following general formula (4) or (5) An alkoxysilane compound having

但し、式中、Ｒfはパーフルオロポリエーテル基を、Ｒ¹は２価の原子又は基（例えば、Ｏ、ＮＨ、Ｓのいずれか）を、Ｒ²は炭化水素基（例えば、アルキレン基）を、Ｒ³はアルキル基を示す。

In the formula, Rf represents a perfluoropolyether group, R ¹ represents a divalent atom or group (for example, any of O, NH, and S), and R ² represents a hydrocarbon group (for example, an alkylene group). , R ³ represents an alkyl group.

但し、式中、Ｒfはパーフルオロポリエーテル基を、Ｒ¹はＯ、ＮＨ、Ｓのいずれかを、Ｒ²はアルキレン基を、Ｒ³はアルキル基を示す。

In the formula, Rf represents a perfluoropolyether group, R ¹ represents any ^one of O, NH and S, R ² represents an alkylene group, and R ³ represents an alkyl group.

但し、式中、Ｒｆ`はフルオロアルキル基を、Ｒ¹は二価の原子又は原子団を、Ｒ²はアルキレン基を、Ｒ³はアルキル基を示す。

In the formula, Rf ′ represents a fluoroalkyl group, R ¹ represents a divalent atom or atomic group, R ² represents an alkylene group, and R ³ represents an alkyl group.

但し、式中、Ｒｆ`はフルオロアルキル基を、Ｒ¹は炭素数７未満のアルキル基を、Ｒ²はアルキル基を示す。

In the formula, Rf ′ represents a fluoroalkyl group, R ¹ represents an alkyl group having less than 7 carbon atoms, and R ² represents an alkyl group.

  Further, the molecular structure of the perfluoropolyether group as Rf represented by the general formula (2) is not particularly limited, and includes a perfluoropolyether group having various chain lengths. Are preferred.

  In the perfluoropolyether group represented by the general formula (6), p and q are preferably in the range of 1-50.

  The molecular weight of the alkoxysilane compound having a perfluoropolyether group represented by the general formula (6) is not particularly limited, but from the viewpoint of stability, ease of handling, etc., the number average molecular weight is 400 to 10,000. The thing of 500-4000 is more preferable.

In the alkoxysilane compound having a perfluoropolyether group represented by the general formula (6), R ¹ represents a divalent atom or group, and is a bonding group between R ² and the perfluoropolyether group. However, in terms of synthesis, atoms or atomic groups other than carbon, such as O, NH, and S, are preferable. R ² is a hydrocarbon group, and the carbon number is preferably in the range of 2 to 10. Examples of R ² include an alkylene group such as a methylene group, an ethylene group, and a propylene group, and a phenylene group.

In the alkoxysilane compound having a perfluoropolyether group represented by the general formula (6), R ³ is an alkyl group constituting an alkoxy group, and usually has 3 or less carbon atoms, that is, an isopropyl group, a propyl group, an ethyl group. A methyl group can be exemplified, but the carbon number may be more than this.

  The fluorine-based antifouling layer 13 is not particularly limited as the molecular structure of the perfluoropolyether group as Rf represented by the following general formula (3). A group having a molecular structure shown below is preferable.

  Rf is a group in which a hydrogen atom of an alkyl group is substituted with a fluorine atom, and examples thereof include those represented by the following chemical formulas (7) to (9). However, it is not necessary that the hydrogen atoms of all alkyl groups are substituted with fluorine atoms, and hydrogen may be partially contained.

但し、ｎは、１以上の整数である。

但し、ｌ、ｍは、１以上の整数である。

但し、ｋは、１以上の整数である。

However, n is an integer of 1 or more.

However, l and m are integers of 1 or more.

However, k is an integer of 1 or more.

  In the compound (8), m / l is preferably in the range of 0.5 to 2.0.

  The molecular weight of the alkoxysilane compound having a perfluoropolyether group is not particularly limited, but from the viewpoint of stability, ease of handling, etc., the number average molecular weight is preferably 400 to 10,000, preferably 500 to 4000. Those are more preferably used.

  The molecular structure of the fluoroalkyl group as Rf` is not particularly limited, and examples thereof include those in which a hydrogen atom of the alkyl group is substituted with a fluorine atom. Fluoroalkyl groups having various chain lengths and various degrees of fluorine substitution can be used. Although included, those having the molecular structure shown below are preferred.

この式中、ｓは６〜１２の整数、ｔは２０以下の整数を示す。

In this formula, s represents an integer of 6 to 12, and t represents an integer of 20 or less.

  The film thickness of the fluorine-based antifouling layer 13 made of a compound is not particularly limited, but is preferably 0.5 to 100 nm in view of the balance between water repellency, stain resistance, applicability, and surface hardness.

  In addition, as the antifouling agent containing a perfluoropolyether group, materials known to those skilled in the art can be employed. As the material, for example, a perfluoropolyether having a polar group at a terminal (see JP-A-9-127307), and an antifouling film formation containing an alkoxysilane compound having a perfluoropolyether group having a specific structure. Surface modifiers obtained by combining a composition (see JP-A-9-255919) and an alkoxysilane compound having a perfluoropolyether group with various materials (JP-A-9-326240, JP-A-10-26701) Gazette, JP-A-10-120442, JP-A-10-148701) and the like.

  Methods for forming the fluorine-based antifouling layer 13 include a method in which an organic fluorine compound is dissolved in a solvent and applied by a gravure coater, a method of applying by dipping or spraying, a spin coating method, and a method of applying by rubbing. In addition, the method of forming by a vacuum method etc. are mentioned.

  In general, the surface energy of the substrate 1 can be reduced by applying an organic fluorine compound to the surface of the substrate 1. However, sufficient effects cannot be obtained by simply applying an organic fluorine compound. In other words, an organic compound having a balance between a polar group and a hydrophobic group that aligns molecules is required. The affinity with the substrate 1 cannot be easily inferred.

  The antifouling agent solution is usually an alkoxysilane compound having a perfluoropolyether group represented by formula (1) or (2) or an alkoxysilane compound having a fluoroalkyl group represented by formula (3) or (4) Is diluted in a solvent and used. The solvent is not particularly limited, but is determined in consideration of the stability of the composition, the wettability of the coated surface with respect to the outermost layer, volatility, and the like. For example, a fluorinated hydrocarbon solvent is used. The fluorinated hydrocarbon solvent is a compound in which part or all of the hydrogen atoms of a hydrocarbon solvent such as an aliphatic hydrocarbon, a cyclic hydrocarbon, and an ether are substituted with a fluorine atom. For example, trade names ZEORORA-HXE (boiling point 78 ° C.), perfluoroheptane (boiling point 80 ° C.), perfluorooctane (boiling point 102 ° C.) manufactured by Nippon Zeon Co., Ltd., trade names H-GALDEN-ZV75 (boiling point 75 ° C.) manufactured by Outdmont Co., Ltd. ), H-GALDEN-ZV85 (boiling point 85 ° C.), H-GALDEN-ZV100 (boiling point 95 ° C.), H-GALDEN-C (boiling point 130 ° C.), H-GALDEN-D (boiling point 178 ° C.), etc. Examples include ethers, perfluoropolyethers such as SV-110 (boiling point 110 ° C.) and SV-135 (boiling point 135 ° C.), and perfluoroalkanes such as FC series manufactured by Sumitomo 3M. Among these fluorinated hydrocarbon solvents, as a solvent for dissolving the fluorine compound of the general formula (1), (2) or (3), in order to obtain an organic film having a uniform film thickness without unevenness, Select one having a boiling point in the range of 70 to 240 ° C., further select hydrofluoropolyether (HFPE) or hydrofluorocarbon (HFC), and use one of these alone or in combination of two or more. Is preferred. If the boiling point is too low, for example, coating unevenness tends to occur. On the other hand, if the boiling point is too high, drying tends to fail and the coating form tends not to improve. Moreover, HFPE or HFC is excellent in the solubility with respect to the compound represented by General formula (1), (2) or (3), and can obtain the outstanding coating surface.

According to one embodiment of the present invention, the following effects can be obtained.
Since the acrylic hard coat layer 11, the coupling agent layer 12, and the fluorine antifouling layer 13 are sequentially laminated on one main surface of the substrate 1, the following effects can be obtained.
(1) It is difficult to get smudges due to fingerprints, hand dirt, etc., and it is difficult to stand out, and furthermore, these effects can be maintained permanently.
(2) Even if scales adhere and are dried, they can be easily removed.
(3) The surface slipperiness can be improved.
(4) Dirt such as dust can be hardly adhered, and usability can be improved.
(5) The durability against wear can be improved.

  The material for forming the coupling agent layer 12 includes reactive groups (for example, an acrylic group, an amino group, an epoxy group, etc.) having a binding property with the material for forming the acrylic hard coat layer 11 in the molecule, fluorine The coupling agent layer 12 is composed of the acrylic hard coat layer 11 and the fluorine-based layer because it has a reactive group (for example, methoxy group, ethoxy group, etc.) having binding properties with the material forming the antifouling layer 13. The bond with the antifouling layer 13 is mediated (coupled), and the affinity between them can be increased. Thereby, the advantageous effect that the outstanding antifouling property and abrasion resistance are realizable can be acquired.

  Further, by forming a fluorine-based antifouling layer 13 of a compound on the coupling agent layer 12 by chemical bonding, it has excellent antifouling water resistance, water repellency and surface slipperiness, and contamination when fingerprints or dust adhere to the surface. In addition, problems such as scratches can be solved.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples. Table 1 shows the chemical formula of the coupling agent constituting the coupling agent layer 12 in each example. Table 2 shows chemical formulas of the antifouling agent constituting the fluorine-based antifouling layer 13 in each example and each comparative example.

(Example A-1)
(1) Production of acrylic hard coat layer 11 An acrylic ultraviolet curable resin was uniformly applied by a gravure coater on a polycarbonate sheet 1 having a sheet thickness of 79 μm produced by an extrusion molding method. Then, the applied ultraviolet curable resin was irradiated with ultraviolet rays and cured to form an acrylic hard coat layer 11 having a thickness of 2.7 μm on the polycarbonate sheet 1.

(2) Preparation of coupling agent layer forming composition 10 parts by weight of another coupling agent (1) shown in Table 1 was dissolved in 2-methoxypropanol to obtain a coupling agent layer forming composition.

(3) Preparation of composition for forming antifouling layer 0.1 part of antifouling agent A shown in Table 2 was added to 100 parts of a hydrofluoropolyether having a boiling point of 178 ° C. (trade name H-GALDEN, manufactured by Augmont). The composition for antifouling film formation was obtained.

(4) Formation of coupling agent layer 12 The acrylic hard coat layer 11 formed in (1) is subjected to a corona treatment for 2 seconds under the condition of 700 W · min / m ² , and then obtained in (2). The composition for forming a coupling agent layer was dip coated on the acrylic hard coat layer 11 at a pulling rate of 1 cm / sec, and then dried in an environment of 40 degrees Celsius for 1 hour to form a coupling agent layer 12.

(5) Formation of fluorine-based antifouling layer 13 After dip coating the antifouling layer type composition prepared in (3) on the coupling agent layer 12 formed in (4) at a lifting speed of 1 cm / sec. The fluorine-based antifouling layer 13 was formed on the coupling agent layer 12 by drying for 1 hour in an environment of 40 degrees Celsius and 90% humidity. Thereby, the polycarbonate sheet 1 in which the antifouling hard coat 2 was formed on one main surface was obtained.

(6) Performance evaluation The performance of the obtained antifouling hard coat 2 was evaluated by conducting a test according to the following method. Tables 3 and 4 show the evaluation results of each example and each comparative example.

(A) Contact angle The contact angle of pure water was measured. Kyowa Interface Chemical Co., Ltd. CA-XE type was used for the measurement. And in order to see solvent resistance, after performing ethanol washing | cleaning, the contact angle was measured again. Here, if the measured value of the contact angle of pure water is 90 degrees or more, it can be evaluated that the antifouling hard coat 2 has good contamination resistance. In Table 3, the items “front” and “rear” indicate the contact angle before ethanol cleaning and the contact angle after ethanol cleaning, respectively.

(B) Antifouling durability The polycarbonate sheet 1 on which the antifouling hard coat 2 was formed was subjected to a load of 2 kg on a cloth soaked with ethanol, wiped 20 times and wiped, and then the contact angle of pure water was measured. Similarly, Kyowa Interface Chemical Co., Ltd. CA-XE type was used for the measurement. And antifouling durability was determined based on the measured contact angle. “◯” and “×” in Table 3 indicate the following determination results.
○: Contact angle value is 90 degrees or more ×: Contact angle value is less than 90 degrees In addition, it was produced if the contact angle value of pure water measured after the above test was maintained at 90 degrees or more. It can be evaluated that the antifouling hard coat 2 has good antifouling durability.

(C) Fingerprint adhesion (1) Ease of fingerprint attachment The finger was touched on the antifouling hard coat 2 to visually determine whether or not the fingerprint adhered. “◯”, “×”, and “Δ” in Table 3 indicate the following determination results.
○: There is little adhesion of the fingerprint, and the attached fingerprint is not conspicuous.
X: Fingerprints adhere to the same extent as untreated glass plates.
Δ: Both are difficult to determine.
(2) Ease of wiping off fingerprints Fingerprints were attached and wiped back and forth with a Kimwipe (manufactured by Jujo Kimberley), and the ease of fingerprint removal was visually determined. “◯”, “×”, and “Δ” in Table 3 indicate the following determination results.
○: Fingerprints can be completely wiped off.
Δ: A fingerprint trace remains.
X: The trace of wiping off the fingerprint spreads and is difficult to remove.

(D) Adhesion of oil-based pen A letter was written on the antifouling hard coat 2 with an oil-based pen, and the adhesion of the oil-based pen was visually determined. “◯” and “×” in Table 3 indicate the following determination results.
○: Characters cannot be written with an oil pen.
X: Characters can be clearly written with an oil pen.

(E) Steel Wool Abrasion Resistance Test A polycarbonate sheet 1 on which a # 0000 steel wool is mounted on a circular pad surface having a diameter of 25 mm and an antifouling hard coat 2 is formed is placed on a table of a reciprocating abrasion tester. The hard coat 2 side surface is fixed, the antifouling hard coat 2 is brought into contact with the above circular pad surface, and the polycarbonate sheet 1 is worn back and forth 1000 times with a load of 200 g / cm ^2. A sex test was performed. And after completion | finish of this abrasion test, the polycarbonate sheet 1 was observed 50 times with the optical microscope, and abrasion resistance was determined. “◯”, “×”, and “Δ” in Table 3 indicate the following determination results.
○: There is no scratch.
Δ: There are fine scratches.
X: Scratch is remarkable.

(Examples A-2 to A-10)
Antifouling on the polycarbonate sheet 1 in the same manner as in Example A-1, except that compounds 2 to 10 shown in Table 1 were used instead of compound 1 in the composition for forming a coupling agent layer of Example A-1. Hard coat 2 was produced. And the performance evaluation of this antifouling hard coat 2 was performed like Example A-1. The results of performance evaluation are also shown in Table 3.

(Example B-1)
An antifouling hard coat was applied on the polycarbonate sheet 1 in the same manner as in Example A-1, except that compound B shown in Table 2 was used instead of compound A in the antifouling layer forming composition of Example A-1. 2 was produced. Then, in the same manner as in Example 1, performance evaluation of this antifouling hard coat 2 was performed. Table 4 shows the results of the performance evaluation.

(Examples B-2 to B-10)
Antifouling on the polycarbonate sheet 1 in the same manner as in Example B-1 except that compounds 2 to 10 shown in Table 1 were used instead of compound 1 in the composition for forming a coupling agent layer of Example B-1. Hard coat 2 was produced. Then, in the same manner as in Example 1, performance evaluation of this antifouling hard coat 2 was performed. The results of performance evaluation are also shown in Table 4.

(Comparative Example 1)
An acrylic hard coat layer 11 was formed on the polycarbonate sheet 1 in the same manner as in Example A-1. And performance evaluation was performed like Example A-1 without forming the coupling agent layer 12 and the fluorine-type antifouling layer 13 on this acrylic type hard-coat layer 11. FIG. The results of performance evaluation are also shown in Table 3.

(Comparative Example A)
Except for omitting the formation of the coupling agent layer 12, the same procedure as in Example A-1 was performed to obtain a polycarbonate sheet 1 in which an acrylic hard coat layer 11 and a fluorine antifouling layer 13 were sequentially formed on one main surface. . And performance evaluation was performed like Example A-1. The results of performance evaluation are also shown in Table 3.

(Comparative Example B)
Except for omitting the formation of the coupling agent layer 12, the same procedure as in Example B-1 was performed to obtain a polycarbonate sheet 1 in which the acrylic hard coat layer 11 and the fluorine antifouling layer 2 were sequentially formed on one main surface. . And performance evaluation was performed like Example A-1. The results of performance evaluation are also shown in Table 3.

  From Tables 3 and 4, in Examples A-1 to A-7, A-10 and Examples B-1 to B-7, B-10, good antifouling properties, durability and wear resistance were obtained. You can see that Moreover, it turns out that the antifouling property excellent also with respect to hand dirt, an oil-based pen, etc. is acquired. On the other hand, it can be seen that in Comparative Example 1, the characteristics of all the evaluation items are clearly inferior to those of Examples, and in Comparative Examples A and B, the contact angle is clearly inferior to that of Examples. Further, in Comparative Examples A and B, it can be seen that the contact angle is greatly deteriorated by ethanol cleaning.

  The embodiment of the present invention has been specifically described above, but the present invention is not limited to the above-described embodiment, and various modifications based on the technical idea of the present invention are possible.

  For example, the numerical values given in the above-described embodiment are merely examples, and different numerical values may be used as necessary.

The cross section of the base material in which the antifouling hard coat by one Embodiment of this invention was formed is shown.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Base material, 2 ... Preventive hard coat, 11 ... Hard coat layer, 12 ... Coupling agent layer, 13 ... Fluorine-type antifouling layer

Claims (11)

An acrylic hard coat layer;
A coupling agent layer formed directly on the acrylic hard coat layer;
A fluorine-based antifouling layer directly formed on the coupling agent layer,
The coupling agent layer contains a compound having two types of functional groups with different reactivity in one molecule represented by the following general formula (1),
The fluorine-based antifouling layer is an antifouling hard coat containing an alkoxysilane compound having a perfluoropolyether group represented by the following general formula (2) or (3).

(Wherein, X represents a reactive end group, R _a represents an alkylene group, and R _b represents an alkyl group.)

(In the formula, Rf represents a perfluoropolyether group, R ¹ represents any ^one of O, NH and S, R ² represents an alkylene chain, and R ³ represents an alkyl chain.)

(In the formula, Rf represents a perfluoropolyether group, R ¹ represents any ^one of O, NH, and S, R ² represents an alkylene group, and R ³ represents an alkyl group.) An acrylic hard coat layer;
A coupling agent layer formed directly on the acrylic hard coat layer;
A fluorine-based antifouling layer directly formed on the coupling agent layer,
The coupling agent layer contains a compound having two types of functional groups with different reactivity in one molecule represented by the following general formula (1),
The fluorine-based antifouling layer is an antifouling hard coat containing an alkoxysilane compound having a fluoroalkyl group represented by the following general formula (4) or (5).

(Wherein, X represents a reactive end group, R _a represents an alkylene group, and R _b represents an alkyl group.)

(In the formula, Rf ′ represents a fluoroalkyl group, R ¹ represents a divalent atom or atomic group, R ² represents an alkylene group, and R ³ represents an alkyl group.)

(In the formula, Rf ′ represents a fluoroalkyl group, R ¹ represents an alkyl group having less than 7 carbon atoms, and R ² represents an alkyl group.) The coupling agent contained in the coupling agent layer is
A reactive group having affinity with the material constituting the acrylic hard coat layer;
The antifouling hard coat according to claim 1 or 2, comprising a material constituting the antifouling layer and a reactive group having binding properties.   The antifouling hard coat according to claim 1 or 2, wherein the acrylic hard coat layer is a transparent organic film formed by photocuring or heat curing.   The antifouling hard coat according to claim 1 or 2, wherein the reactive terminal group is a vinyl group, an epoxy group, an amino group, a methacryl group, a mercapto group, or an isocyanate group.   An antifouling substrate having the antifouling hard coat according to any one of claims 1 to 5. Forming a coupling agent layer directly on the acrylic hard coat layer;
Forming a fluorine-based antifouling layer directly on the coupling agent layer,
The coupling agent layer contains a compound having two types of functional groups with different reactivity in one molecule represented by the following general formula (1),
The fluorine-based antifouling layer is a method for producing an antifouling hard coat containing an alkoxysilane compound having a perfluoropolyether group represented by the following general formula (2) or (3).

(Wherein, X represents a reactive end group, Ra represents an alkylene group, and Rb represents an alkyl group.)

(In the formula, Rf represents a perfluoropolyether group, R ¹ represents any ^one of O, NH and S, R ² represents an alkylene chain, and R ³ represents an alkyl chain.)

(In the formula, Rf represents a perfluoropolyether group, R ¹ represents any ^one of O, NH, and S, R ² represents an alkylene group, and R ³ represents an alkyl group.) Forming a coupling agent layer directly on the acrylic hard coat layer;
Forming a fluorine-based antifouling layer directly on the coupling agent layer,
The coupling agent layer contains a compound having two types of functional groups with different reactivity in one molecule represented by the following general formula (1),
The fluorine-based antifouling layer is a method for producing an antifouling hard coat containing an alkoxysilane compound having a fluoroalkyl group represented by the following general formula (4) or (5).

(Wherein, X represents a reactive end group, Ra represents an alkylene group, and Rb represents an alkyl group.)

(In the formula, Rf ′ represents a fluoroalkyl group, R ¹ represents a divalent atom or atomic group, R ² represents an alkylene group, and R ³ represents an alkyl group.)

(In the formula, Rf ′ represents a fluoroalkyl group, R ¹ represents an alkyl group having less than 7 carbon atoms, and R ² represents an alkyl group.) The coupling agent contained in the coupling agent layer is
A reactive group having affinity with the material constituting the acrylic hard coat layer;
The method for producing an antifouling hard coat according to claim 7 or 8, comprising a material constituting the antifouling layer and a reactive group having binding properties.   The method for producing an antifouling hard coat according to claim 7 or 8, wherein the acrylic hard coat layer is a transparent organic film formed by photocuring or heat curing.   The method for producing an antifouling hard coat according to claim 7 or 8, wherein the reactive end group is a vinyl group, an epoxy group, an amino group, a methacryl group, a mercapto group, or an isocyanate group.

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