JP2000308846A - Method for formation of antifouling layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form an antifouling layer excellent in antifouling property, resis tance to scuffing and wear and solvent resistance in a short time by pretreating a base material to be treated before the antifouling layer is formed and forming the antifouling layer on the pretreated surface in the case of forming the antifouling layer using an antifouling agent on the base material to be treated. SOLUTION: When the antifouling layer 2 is formed by using the antifouling agent at least on one side surface of the base material 1 to be treated, at least one side surface 3 of the base material 1 to be treated is pretreated before the antifouling layer 2 is formed and the antifouling layer 2 is film formed on the pretreated surface 3. As the pretreatment, a high-frequency discharge plasma method, an electron beam method, an ion beam method, or the like is applied. As the base material to be treated, an optical member is applicable. As the optical member, a beam splitter, a mirror, a window glass, or the like, in addition to an optical lens, a spectacle lens and a lens for optical device is applied. As the antifouling agent, an organic silane compound containing a perfluoro polyether group, or the like, is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an antifouling layer on the surface of various kinds of substrates requiring antifouling properties. More specifically, it is a method of quickly fixing an antifouling layer on various kinds of substrates to be treated.

[0002]

2. Description of the Related Art Conventionally, optical lenses, spectacle lenses, and lenses such as cameras and binoculars are usually provided with an antireflection treatment on the surface thereof in order to reduce the reflection of light and increase the transmittance of light. . When these optical members are used by humans, stains such as fingerprints, sebum, sweat, and cosmetics often adhere.

In general, since the surface energy of the antireflection film is as large as about 60 J / m ² , it is not easy to adhere such dirt and to remove it due to the presence of fine irregularities. In addition, there is a problem that high reflection occurs only in a portion where such dirt adheres, and the dirt is conspicuous.

[0004] Therefore, as means for solving these problems of dirt, there has been devised a method of providing an antifouling layer having a property that dirt hardly adheres and that can easily be wiped off even if it adheres.

[0005] For example, Japanese Patent Application Laid-Open No. 64-86101 discloses an anti-reflection film formed by providing an antireflection film mainly composed of silicon dioxide on the surface of a substrate and further treating the surface with a compound containing an organic silicon substituent. There have been proposed scratch-resistant antireflective coating articles.

Japanese Unexamined Patent Publication (Kokai) No. 4-338901 proposes a stain-resistant and scratch-resistant CRT filter in which a surface of a substrate is coated with a silanol-organic polysiloxane.

Further, Japanese Patent Publication No. 6-29332 discloses that
A low-reflection and antifouling plastic having an antireflection film on a plastic surface comprising a mono- or di-silane compound containing a polyfluoroalkyl group and a halogen, alkyl or alkoxy silane compound has been proposed.

Further, Japanese Patent Application Laid-Open No. 7-16940 discloses that
Optical articles have been proposed in which a copolymer of a perfluoroalkyl (meth) acrylate and a monomer having an alkoxysilane group is formed on an optical thin film mainly composed of silicon dioxide.

[0009]

However, in the conventional technology for forming an antifouling layer, after forming the antifouling layer, several steps are taken until the antifouling resistance, abrasion resistance, solvent resistance and the like are maximized. It takes a long time, sometimes several days, in some cases, during which time dirt and scratches are likely to occur, and when it comes into contact with other articles, part of the antifouling layer is transferred and the antifouling layer peels off There was a problem.

An object of the present invention is to solve the problems of the prior art as described above, and an object of the present invention is to perform a pre-treatment on the surface of a substrate to be processed such as various optical members, thereby to improve the durability. An object of the present invention is to provide a method for forming an antifouling layer which can form an antifouling layer excellent in antifouling properties, scratch resistance, solvent resistance and the like in a short time.

[0011]

In order to solve the above-mentioned problems, the invention according to claim 1 has at least one surface on a substrate to be processed,
A method for forming an antifouling layer by using an antifouling agent, wherein before forming the antifouling layer, at least one surface of the substrate to be treated is pretreated, and an antifouling layer is formed on the pretreated surface. Is a method for forming an antifouling layer.

The invention of claim 2 includes a high-frequency discharge plasma method, an electron beam method, an ion beam method, a vapor deposition method, a sputtering method, an alkali treatment method, an acid treatment method, a corona treatment method,
2. The method for forming an antifouling layer according to claim 1, wherein the method is any one of an atmospheric pressure glow discharge plasma method.

[0013] The invention of claim 3 is the method of forming an antifouling layer according to claim 1 or 2, wherein the substrate to be treated is an optical member.

According to a fourth aspect of the present invention, the optical member is an optical lens, a spectacle lens, a lens of a camera or a binocular, or another optical device, a beam splitter, a prism, a mirror, a window glass, an antireflection film, an optical filter. 4. The method for forming an antifouling layer according to claim 3, wherein the method is any one of them.

According to a fifth aspect of the present invention, the antifouling agent for forming the antifouling layer is an organic silane compound containing a perfluoropolyether group. It is a method of forming the antifouling layer described above.

The invention according to claim 6 is that the antifouling agent has a general formula
It is characterized by comprising an organosilane compound represented by (1).
The method for forming an antifouling layer according to claim 1.
You. R_f-(OC_Three F₆ )_n-O- (CF_Two )_m― (CH_Two )_l-O- (CH_Two ) _s -Si (R)_Three ... (1) (However, R_fIs a linear or branched chain having 1 to 16 carbon atoms.
-Fluoroalkyl group, n is an integer of 1 to 50, m is 0 to
An integer of 3, 1 is an integer of 0 to 3, s is an integer of 0 to 6,
And 6 ≧ m + 1> 0, R represents a hydrolyzable group. )

The invention according to claim 7 is characterized in that the antifouling agent is heated and evaporated in a vacuum to form a film on the substrate to be treated. This is a method for forming a layer.

The invention according to claim 8 is characterized in that the heating method for evaporating the antifouling agent is a resistance heating method, an electron beam heating method, a light heating method, an ion beam heating method, or a high frequency heating method. The method for forming an antifouling layer according to claim 1.

A ninth aspect of the present invention is a method for manufacturing an optical member having an antifouling layer, wherein the antifouling layer is formed by the method according to any one of the third to eighth aspects.

According to a tenth aspect of the present invention, there is provided an optical member with an antifouling layer, wherein at least one surface of the optical member is a pretreated surface.

In the eleventh aspect, the optical member may be an optical lens, a spectacle lens, a lens of a camera or binoculars, or another optical device, a beam splitter, a prism, a mirror, a window glass, an antireflection film, or an optical filter. The optical member with an antifouling layer according to claim 10, which is any one of the optical members.

According to a twelfth aspect of the present invention, there is provided the optical member with an antifouling layer according to any one of claims 10 to 11, wherein the antifouling agent is an organic silane compound containing a perfluoropolyether group. is there.

According to a thirteenth aspect of the present invention, the antifouling agent has a general formula
It is characterized by comprising an organosilane compound represented by (1).
The optical part with an antifouling layer according to claim 10.
Material. R_f-(OC_Three F₆ )_n-O- (CF_Two )_m― (CH_Two )_l-O- (CH_Two ) _s -Si (R)_Three ... (1) (However, R_fIs a linear or branched chain having 1 to 16 carbon atoms.
-Fluoroalkyl group, n is an integer of 1 to 50, m is 0 to
An integer of 3, 1 is an integer of 0 to 3, s is an integer of 0 to 6,
And 6 ≧ m + 1> 0, R represents a hydrolyzable group. )

[0024]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail.

When forming an antifouling layer on a substrate to be treated, an antifouling agent comprising an organic silane compound containing a perfluoropolyether group is used. The organic silane compound is preferably a compound represented by the following general formula (1) or a polymer thereof. _{R f - (OC 3 F 6} ) n -O- (CF 2) m - (CH 2) l -O- (CH 2) s -Si (R) 3 ... (1)

In the general formula (1), R _f has 1 to 1 carbon atoms.
It is a 16 linear or branched perfluoroalkyl group, particularly preferably CF ₃ —, C ₂ F ₅ —, or C ₃ F ₇ —. R is a hydrolyzable group, -Cl, -Br, -I,-
OR ¹ , -OOCR ¹ , -OC (R ¹ ) C = C (R ² )
₂ , -ON = C (R ¹ ) ₂ , -ON = CR ³ , -N (R
² ) ₂ , —R ² NOCR ^{1 and the} like are preferable.

However, R ¹ is a group having 1 to 1 carbon atoms such as an alkyl group.
An aliphatic hydrocarbon group having 0 or a carbon number of 6 such as a phenyl group;
To 20 aromatic hydrocarbon groups, R ² is a C 1-5 aliphatic hydrocarbon group such as a hydrogen atom or an alkyl group, and R ³ is a C 3-6 divalent aliphatic hydrocarbon such as an alkylidene group. It is a hydrogen group.

The hydrolyzable groups in the above-mentioned organosilane compounds can be used not only as one kind but also as a mixture of two or more kinds. In particular, —OCH ₃ , —OC ₂ H
₅ , —OOCCH ₃ and —NH ₂ are preferred. Further, n is an integer of 1 to 50, m is an integer of 0 to 3, l is an integer of 0 to 3, s is an integer of 0 to 6, provided that 6 ≧ m + 1> 0.

From the viewpoint of the working environment and the control of the film thickness, it is preferable to use the PVD method without using a diluting solvent when forming the antifouling layer, and it is particularly preferable to use the vacuum evaporation method. In the method, the antifouling agent is heated at a pressure of 1 Pa or less,
Evaporate and form on the substrate to be treated.

As a heating method, a method such as a resistance heating method, an electron beam heating method, a light heating method, an ion beam heating method or a high frequency heating method is effective. According to the PVD method, the thickness of the antifouling layer, which has conventionally been difficult, can be accurately controlled on the order of angstroms.

It is considered that the antifouling agent containing the organic silane compound reacts with the OH group on the surface of the substrate to be treated and the hydrolyzable group of the organic silane compound to cause hydrolysis to form a chemical bond. I have. However, in general, the hydrolysis reaction between the antifouling layer and the surface of the substrate to be treated is slow, the antifouling layer is completely fixed, and the maximum antifouling resistance, abrasion resistance, solvent resistance, etc. It takes hours to tens of days to occur.

On the other hand, the high-frequency discharge plasma method, the electron beam method, the ion beam method, the vapor deposition method, the sputtering method, the alkali treatment method, the acid treatment method, the corona treatment method, and the atmospheric pressure glow discharge plasma method which are the pretreatment methods of the present invention. In addition to cleaning the surface of the substrate to be treated, it is possible to cut off the bonding between molecules on the surface and create an active surface, so that an antifouling layer made of an antifouling agent containing an organic silane compound can be easily formed. The surface of the substrate to be treated, which easily adheres to the surface, can be created.

The substrate to be treated is an optical lens, a spectacle lens,
Lenses, beam splitters, prisms, mirrors, windowpanes, anti-reflective coatings for cameras and binoculars or other optical devices,
This is particularly effective for optical members such as optical filters.

[0034]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Embodiment 1> The anti-reflection film is made of a parallel plate type high circumference.
Installed in a wave discharge device, and the inside of the device is 1.0 × 10 ^-3Pa
Exhausted. Hydrogen gas at 10 sccm /
min. At a flow rate of 1.0 × 10^-1To Pa
Adjusted. High frequency (frequency = 13.56 MH)
z) was applied, and the reflected 100 W plasma was generated.
By exposing the anti-reflection film for 1 minute,
Pretreatment was performed.

Next, the organosilane compound represented by the general formula (2) was put on a molybdenum boat, and an antifouling layer was formed on the antireflection film by a vacuum deposition method (resistance heating method).
After evacuating the inside of the vacuum evaporation machine to 1.0 × 10 ⁻³ Pa or less,
The boat was heated to 400 ° C. to evaporate the organosilane compound. _{CF 3 - (OC 3 F 6} ) 24 -O- (CF 2) 2 - (CH 2) 2 -O-CH 2 - Si (OCH 3) 3 ... (2)

<Example 2> The surface of the antireflection film was heated at 50 W / m ² · min. A pretreatment was performed by exposing to a corona discharge. Next, an antifouling layer was formed on the antireflection film in the same manner as in Example 1.

<Comparative Example 1> An antifouling layer was formed on an antireflection film which had not been subjected to pretreatment in the same manner as in Example 1 using the above-mentioned organosilane compound. In the above Examples 1 and 2 and Comparative Example, various physical property evaluation methods and results (Table 1) are shown below.

(A) Contact angle measurement: Using a contact angle meter [CA-X: manufactured by Kyowa Interface Science Co., Ltd.], a diameter of 1.0 mm in a dry state (20 ° C.-65% RH).
Was formed at the tip of a needle, and this was brought into contact with the surface of a substrate (solid) to form a droplet. The contact angle is the angle between the solid surface and the tangent to the liquid surface at the point where the solid liquid touches,
Defined by the angle containing the liquid. Distilled water was used as the liquid.

(B) Abrasion resistance: The substrate surface is made of a cellulose nonwoven fabric [Bencott M-3: manufactured by Asahi Kasei Corporation] and the load is 5
After rubbing 100 times at 00 gf / m ² , the physical properties were evaluated.

[0041]

[Table 1]

[0042]

According to the method of the present invention, various optical members (optical lenses, spectacle lenses, lenses of cameras and binoculars or other optical devices, beam splitters, prisms,
(Mirror, window glass, anti-reflection film, optical filter, etc.) without impairing various optical properties, and it is difficult for dirt such as fingerprints, sebum, sweat, cosmetics, etc. to adhere, and it is easy to wipe off even if it adheres In addition, it is possible to form a durable antifouling layer having high fixing properties and durability.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an optical member of the present invention.

[Explanation of symbols]

 1 transparent substrate 2 antifouling layer 3 treated surface

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 183/00 C09D 183/00 C09K 3/00 112 C09K 3/00 112F 3/18 104 3/18 104 G02B 1/10 G02B 1/10 Z F term (reference) 2K009 BB01 CC42 DD03 DD08 EE05 3B117 AA08 4D075 BB21X BB47X BB49X BB81X BB85X CA34 DA06 DB13 DC24 EA05 EB42 EB52 4H020 BA36 4J038 DF041 GA03 GA08

Claims (13)

[Claims] 1. A method for forming an antifouling layer on at least one surface of a substrate to be treated using an antifouling agent, wherein at least one of the surfaces of the substrate to be processed is formed before the formation of the antifouling layer. A method for forming an antifouling layer, comprising pretreating one surface and forming an antifouling layer on the pretreated surface. 2. The pretreatment includes a high-frequency discharge plasma method, an electron beam method, an ion beam method, a vapor deposition method, a sputtering method,
The method for forming an antifouling layer according to claim 1, wherein the method is any one of an alkali treatment method, an acid treatment method, a corona treatment method, and an atmospheric pressure glow discharge plasma method. 3. The method for forming an antifouling layer according to claim 1, wherein the substrate to be treated is an optical member. 4. An optical member comprising: an optical lens, a spectacle lens, a lens of a camera or binoculars, or a lens of another optical device;
The method for forming an antifouling layer according to claim 3, wherein the antifouling layer is any one of a splitter, a prism, a mirror, a window glass, an antireflection film, and an optical filter. 5. The method for forming an antifouling layer according to claim 1, wherein said antifouling agent is an organic silane compound containing a perfluoropolyether group. 6. An organic compound represented by the general formula (1) wherein said antifouling agent is
6. The method according to claim 1, wherein the material is a silane compound.
A method for forming an antifouling layer according to the above. R_f-(OC_Three F₆ )_n-O- (CF_Two )_m― (CH_Two )_l-O- (CH_Two ) _s -Si (R)_Three ... (1) (However, R_fIs a linear or branched chain having 1 to 16 carbon atoms.
-Fluoroalkyl group, n is an integer of 1 to 50, m is 0 to
An integer of 3, 1 is an integer of 0 to 3, s is an integer of 0 to 6,
And 6 ≧ m + 1> 0, R represents a hydrolyzable group. ) 7. The method according to claim 7, wherein the antifouling agent is applied at a pressure of 1 Pa or less.
The method for forming an antifouling layer according to claim 1, wherein the method is performed by heating, evaporating, and forming a film on the substrate to be treated. 8. A heating method for evaporating the antifouling agent includes a resistance heating method, an electron beam heating method, a light heating method, an ion beam heating method, and a high-frequency heating method. 8. The method for forming an antifouling layer according to any one of claims 7 to 7. 9. A method for producing an optical member having an antifouling layer, comprising forming an antifouling layer by the method according to claim 3. 10. An optical member with an antifouling layer, wherein at least one surface of the optical member is a pretreated surface. 11. An optical member comprising: an optical lens, a spectacle lens,
Lenses, beam splitters, prisms, mirrors, windowpanes, anti-reflective coatings for cameras and binoculars or other optical devices,
The optical member with an antifouling layer according to claim 10, which is any one of optical filters. 12. The optical member with an antifouling layer according to claim 10, wherein the antifouling agent is an organic silane compound containing a perfluoropolyether group. 13. An antifouling agent having the general formula (1):
11. A silane compound,
13. The optical member with an antifouling layer according to any one of 12. R_f-(OC_Three F₆ )_n-O- (CF_Two )_m― (CH_Two )_l-O- (CH_Two ) _s -Si (R)_Three ... (1) (However, R_fIs a linear or branched chain having 1 to 16 carbon atoms.
-Fluoroalkyl group, n is an integer of 1 to 50, m is 0 to
An integer of 3, 1 is an integer of 0 to 3, s is an integer of 0 to 6,
And 6 ≧ m + 1> 0, R represents a hydrolyzable group. )