JP2017215480A - Optical member having modified surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical member having a modified surface, the optical member excelling in antifouling property, durability, chemical resistance, environmental resistance, and UV resistance.SOLUTION: A surface-modified optical member has a buffer layer composed of oxide on a surface thereof, and a surface-modified layer on the buffer layer. In the surface-modified layer, molecules having ether linkages and having no ether linkages are mutually dispersed.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a surface modification technique for improving chemical resistance, environmental resistance and UV resistance of an article surface, and more particularly to an optical member subjected to such surface modification.

  Conventionally known camera devices, optometry devices, surveying devices, personal computers, mobile devices, portable communication devices, and the like may be used outdoors. Therefore, optical elements such as lenses and sensors used in these devices and apparatuses, and optical members such as liquid crystal screens and protective glass plates, depending on the ultraviolet rays contained in sunlight (hereinafter abbreviated as UV) and the usage environment. Under the influence of corrosive components and corrosive chemicals such as sulfides, sulfur oxides and nitrogen oxides contained in exhaust gas and volcanic gases in the atmosphere It was a cause of deterioration of the members.

  In order to solve such a problem, for example, as shown in Patent Documents 1 and 2, a lens or a liquid crystal screen on which an effective UV cut filter is laminated is known.

Japanese Patent No. 4796666 JP 2006-251380 A

  However, although the conventional UV cut filters as shown in Patent Documents 1 and 2 have durability against UV, they are resistant to corrosive components in the atmosphere and are resistant to chemicals that are corrosive. Has not been studied and will deteriorate over time. Moreover, since the UV-resistant layer is laminated via the adhesive composition, there is a problem of affecting the optical characteristics.

  By the way, as a composition for forming a layer having chemical resistance and UV resistance, a fluorine-based water- and oil-repellent coat having no ether bond, such as a fluoroalkylsilane compound, is known. Since this water / oil repellent coat layer does not have an ether bond, the molecules constituting the water / oil repellent coat layer have high stability and high durability against corrosive substances and UV (hereinafter referred to as having an ether group). Fluorine-based water- and oil-repellent coats and raw materials that are not used may be abbreviated as “coat B” and “solvent B”).

  However, the fluorine-based water / oil repellent coat (B) having no ether bond has a low water repellency angle, that is, poor antifouling property. In addition, there is a problem that the durability of the physical film, that is, the adhesion with the substrate is low.

  From the viewpoint of antifouling properties and adhesion to a substrate, for example, monomolecular water / oil repellent coating materials sold by Daikin, Shin-Etsu Chemical, Dow Corning, 3M and the like are known. Since this monomolecular water / oil repellent coating material has an ether bond in the molecule of the active ingredient, the molecules of the long chain structure are oriented in a specific direction to form a monomolecular film on the surface of the article (hereinafter, The water- and oil-repellent coat and the raw material having an ether group may be abbreviated as coat A and solvent A). Since the monomolecular film containing an ether bond has a high water repellency angle, the antifouling property and durability of the water / oil repellent coating layer when applied to an optical element or member are improved.

  However, in the monomolecular water / oil repellent coat (A), the ether bond in the molecule easily reacts with the corrosive substance and UV described above, and this deteriorates the water / oil repellent coat layer. was there.

  Therefore, the inventors have intensively researched, and (A) the solvent that deteriorates because it has the ether bond described above, and (B) the solvent that does not deteriorate because it does not have an ether bond at a desired ratio. When mixed and tested on optical elements and components such as lenses and liquid crystal screens, the surface modification layer has excellent antifouling and durability properties, and has both chemical resistance, environmental resistance, and UV resistance. Was completed.

  An object of the present invention is to provide an optical member having a surface modification layer laminated with a strong adhesion to a lens or a liquid crystal screen, and having excellent antifouling properties, chemical resistance, environmental resistance and UV resistance. To do.

  The invention according to claim 1, which solves the above problem, is a surface-modified optical member, and the optical member has a buffer layer made of an oxide on the surface and a surface modified layer on the surface of the buffer layer. The surface modified layer is characterized in that molecules having an ether bond and molecules not having an ether bond are dispersed with each other.

  According to the present invention, the solvent (A) obtained by dissolving a solute having an ether bond and the solvent (B) obtained by dissolving a solute having no ether bond are mixed and completely mixed. In the surface modification layer, molecules having an ether bond and molecules not having an ether bond are dispersed with each other, and the antifouling property and durability of the solvent (A) and the solvent (B ) Chemical resistance, environmental resistance, and UV resistance. In addition, since the solvent is laminated after laminating the buffer layer on the surface of the article, the adhesive force between the two is greatly improved by the covalent bond between the OH group of the solvent and the OH group of the buffer layer, antifouling property, durability, Chemical resistance, environmental resistance, and UV resistance can be improved.

It is a schematic diagram of an example of the surface-modified optical member of the present invention, a lens (optical element). It is a schematic diagram which shows the process of surface-modifying an optical member with a surface modifier.

  FIG. 1 is a schematic view showing, for example, a lens as an example of the optical member 4 according to the present invention. An optical member 4 having a surface modified by sequentially laminating a buffer layer (oxide layer) 2 and a surface modification layer 3 on the surface of an optical element such as a lens or a substrate 1 of an optical member such as a glass plate. Form. The material of the lens can be a resin such as glass (silicon dioxide), crystal, or plastic. The present invention is not limited to a lens, but can be applied to any optical element that affects optical characteristics, such as a prism, and to an optical member such as a liquid crystal screen or a protective cover of a sensor. The optical member referred to in the present invention includes an optical element.

  A method of manufacturing the optical member having a modified surface shown in FIG. 1 will be described below. FIG. 2 is a schematic view showing a process of laminating the surface modifier according to the embodiment of the present invention on the optical member. The optical member 4 in FIG. 2 has irregularities on the surface, but the same is true even if it is smooth. The optical member 4 is formed by sequentially laminating the buffer layer 2 and the surface modification layer 3 on the substrate 1 of the optical member.

  As shown to Fig.1 (a), the base material 1 of an optical member is prepared first. The material of the substrate 1 is not limited as long as it is a material that can be used as an optical member, but transparent and translucent glass, crystal, resin, and the like are conceivable.

  Next, the surface of the substrate 1 is modified. This is due to plasma irradiation on the surface of the substrate 1. Further, the surface of the substrate 1 can be activated by irradiating it with excimer laser light. When the excimer laser light is irradiated, the time is about 30 seconds to 1 minute.

Next, as shown in FIG. 1 (b), laminating the silicon dioxide on the substrate 1 of the surface of the optical element is an oxide layer as a buffer layer 2 (SiO _2). The buffer layer 2 is laminated by a wet coating method or a dry coating method. Moreover, it can carry out by any one of an ion assist method, a vacuum evaporation method, a sputtering method, and a chemical vapor deposition method. As the buffer layer 2, any metal oxide such as Al ₂ O ₃ , ZnO, SnO ₂ can be used, but silicon dioxide (SiO ₂ ) is most preferable.

  Next, the water / oil repellent coating material (A) having an ether group is dissolved in a soluble solvent to prepare the solvent (A), and the fluorine-based water / oil repellent coating material having no ether group is prepared. The surface modification of the present invention in which (B) is dissolved in a soluble solvent to prepare a solvent (B), and these solvents are mixed to uniformly mix the water and oil repellent coating raw materials (A) and (B). Prepare a quality material.

  When the surface modifier can be applied, the surface of the buffer layer 2 is modified by plasma or DUV (far ultraviolet, wavelength of about 200 nm or less). Thereby, as shown in FIG.1 (c), the oxygen atom of the buffer layer 2 is excited as a (buffer layer Si) -OH group. Then, the prepared surface modifier is applied to the surface of the buffer layer 2 to form a surface modified layer 3 exhibiting water and oil repellency. At this time, when a fluoroalkylsilane having an alkoxyl group described later is used as the fluorine-based water / oil repellent coating raw material (B) having no ether group in the surface modifier, the alkoxyl group is hydrolyzed (surface modification). Layer Si) —OH groups, and Si—O—Si (siloxane) bonds are formed with the OH groups of the buffer layer 2 as shown in the schematic diagram of FIG. The buffer layer 2 is firmly adhered, and the state shown in FIG.

  The surface-modified layer 3 can be formed by any one of an immersion method, a vacuum vapor deposition method, a sputtering method, and a chemical vapor deposition method. Thereby, the buffer layer 2 and the surface modification layer 3 are formed on the surface of the substrate 1 of the optical member, and the optical member 4 is prepared.

  In the surface-modified optical member according to the present embodiment, the water- and oil-repellent coat (A) containing an ether bond gives the element antifouling property and durability (adhesion between the element and the surface modified layer), and Chemical resistance, environmental resistance, and UV resistance can be made extremely high by the water / oil repellent coat (B) containing no ether bond. Further, the buffer layer and the environment-resistant layer are firmly bonded to each other by a chemical bond, that is, an OH group-derived siloxane bond, whereby the adhesion can be further enhanced.

  The surface modification layer 3 of the present invention is a chemical substance having a composition having an ether bond such as fluoroalkylsilane and a slight amount of an ether bond. The fluorine compound which does not have can exhibit the effect of chemical resistance, environmental resistance, and UV resistance similarly as shown below.

As the solute used for the fluorine-based water / oil repellent coating material (B) having no ether group, it is preferable to use an organosilane containing a fluoroalkyl group. Known fluorine-based silane coupling agents can be widely used, and specific examples thereof include one or two or more hydrolyzed condensates or cohydrolyzed condensates of fluoroalkylsilanes shown below.
_{CF 3 (CF 2) 3 CH} 2 CH 2 Si (OCH 3) 3;
_{CF 3 (CF 2) 5 CH} 2 CH 2 Si (OCH 3) 3;
_{CF 3 (CF 2) 7 CH} 2 CH 2 Si (OCH 3) 3;
_{CF 3 (CF 2) 9 CH} 2 CH 2 Si (OCH 3) 3;
(CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ;
(CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ;
(CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ;
_{CF 3 (C 6 H 4)} C 2 H 4 Si (OCH 3) 3;
_{CF 3 (CF 2) 3 (} C 6 H 4) C 2 H 4 Si (OCH 3) 3;
_{CF 3 (CF 2) 5 (} C 6 H 4) C 2 H 4 Si (OCH 3) 3;
_{CF 3 (CF 2) 7 (} C 6 H 4) C 2 H 4 Si (OCH 3) 3;
_{CF 3 (CF 2) 3 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 5 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 7 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 9 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
(CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ;
(CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ;
_{(CF 3) 2 CF (CF} 2) 8 CH 2 CH 2 SiCH 3 (OCH 3) 2;
_{CF 3 (C 6 H 4)} C 2 H 4 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 3 (} C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 5 (} C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 7 (} C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 3 CH} 2 CH 2 Si (OCH 2 CH 3) 3;
_{CF 3 (CF 2) 5 CH} 2 CH 2 Si (OCH 2 CH 3) 3;
CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ ; and CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃

  As a solute used for the water / oil repellent coating material (A) having an ether group, a compound having an ether group can be selected from known water / oil repellent coating materials, and is not particularly limited. As disclosed in Japanese Patent No. -527777, Japanese Patent Application Laid-Open No. 2004-225209, Japanese Patent No. 3275402, Japanese Patent No. 3343024 and the like, various aliphatic ethers, aromatic ethers and other compounds are known and functional Those in which the group is fluorine-substituted are preferred.

  The fluorine-based water / oil repellent coating material (B) having no ether group is prepared by dissolving the selected compound in a soluble solvent. Examples of such a solvent include alcohol, and isopropyl alcohol (IPA), methanol, ethanol and the like are preferable, and IPA is particularly preferable.

  The water / oil repellent coating material (A) having an ether group is prepared by dissolving the selected compound in a soluble solvent. Examples of such a solvent include fluorine-based solvents, and HFEs, HFCs, and HFOs are preferable, and HFEs are particularly preferable.

  When the water / oil repellent coating solvent (A) and the water / oil repellent coating solvent (B) are thus prepared, the two solvents are completely mixed at a predetermined ratio. At this time, even if both solvents are added at once, they are separated and become cloudy. In the present invention, the solvent used in a relatively small amount of both solvents is added and stirred in a small amount to the solvent used in a relatively large amount, and after confirming that the solvent does not separate, the addition and stirring are repeated. A surface modifier is used. Whether the adjusted surface modifier is completely mixed can be determined by the fact that the solvent is transparent without being clouded. Specifically, the scattering of the solvent may be measured.

  The mixing ratio of the water / oil repellent coating solvent (A) and the water / oil repellent coating solvent (B) in the surface modifying agent of the present invention is such that the water / oil repellent coating (A) in the surface modified layer after drying. The water / oil repellent coat (B) has a weight ratio of preferably 1: 2 to 2: 1, and more preferably 1: 1.

  The surface modifier used in the present invention can be applied to any article that requires chemical resistance, environmental resistance, and UV resistance, and is not limited to the optical member described in the present embodiment. It can also be applied to other metal products, glass, resin and the like. In addition, when forming a surface modification layer on glass, formation of a buffer layer can be abbreviate | omitted.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
(1) Examination of mixing ratio of water / oil repellent coating solvent A having an ether group and water / oil repellent coating solvent B having no ether group [Example 1]
Product name: DSX (manufactured by Daikin Industries) was dissolved in hydrofluoroether (HFE) to give 0.1% solvent A. In addition, trade name: XC98-C4626 (manufactured by Momentive) was dissolved in isopropyl alcohol (IPA) to obtain 0.1% solvent B. These were mixed so that the solutes of A and B were 1.0: 0.5 by weight to prepare the surface modifier of Example 1. Hereinafter, in all examples, in order to prevent separation of both solvents in mixing, a small amount of solvent is added little by little to a large amount of solvents A and B, and added after confirming that they do not separate. And stirring was repeated until the final blending ratio was reached.

[Example 2]
The surface modifier of Example 2 was prepared in the same manner as in Example 1 except that the solutes A and B were mixed so that the weight ratio was 1.0: 1.0.

[Example 3]
The surface modifier of Example 3 was prepared in the same manner as in Example 1 except that the solutes of A and B were mixed so that the weight ratio was 1.0: 2.0.

[Comparative Example 1]
Only the solvent A was used as the surface modifier of Comparative Example 1.

[Comparative Example 2]
A surface modifier of Comparative Example 2 was prepared in the same manner as in Example 1 except that the solutes of A and B were mixed so that the weight ratio was 1.0: 0.1.

[Comparative Example 3]
A surface modifier of Comparative Example 3 was prepared in the same manner as in Example 1 except that the solutes of A and B were mixed so that the weight ratio was 1.0: 10.0. In this case, the liquid became cloudy.

[Comparative Example 4]
Only the solvent B was used as the surface modifier of Comparative Example 4.

  A silicon dioxide buffer layer was formed on the surface of the base white glass (BK7) by vapor deposition. Subsequently, the surface of the buffer layer was activated by DUV irradiation using an excimer barrier lamp, and the surface modifiers of Examples 1 to 3 and Comparative Examples 1 to 4 were applied to the surface using a dip, spin, or slit coater. A surface modified layer was formed.

  In order to confirm the effect of corrosive and oxidizing gas damage in the actual usage environment of the surface-modified article, create an environment that attacks the bond considered to be damaged, and change the performance confirmed. Specifically, water droplets were attached to the sample surfaces of the examples and comparative examples, and the contact angle indicating wettability was measured. Thereafter, each sample was placed in a gas atmosphere (sulfur, chlorine, nitrate, peroxide, etc.) and held at 190 ° C. for 48 hours for a gas resistance test. After the gas resistance test, water droplets were attached to the sample surface and the contact angle was measured again. Table 1 shows solvent mixing ratios and gas resistance test results in Examples and Comparative Examples.

  As shown in Table 1, in the surface modifiers of the examples, the initial contact angle slightly decreases, but the decrease in the contact angle after the gas resistance test is suppressed, that is, the gas resistance is low. It has improved. In Comparative Examples 1 and 2, the contact angle is greatly reduced, which means that the surface modified layer is deteriorated by the corrosive gas. In Comparative Examples 3 and 4, the contact angle hardly decreased before and after the test, which is due to the presence of the solvent B having no ether group. In the examples, although the solvent B was halved, the same performance was exhibited.

(2) Gas resistance and UV resistance test The sample of Example 2 and Comparative Example 1, which had the highest performance in examining the solvent blend ratio, were placed in a gas atmosphere and held at 190 ° C for 48 hours and 120 hours. The gas resistance test was performed. Moreover, sunlight was irradiated for 100 hours and 300 hours, and it was set as the sunshine weather test. The contact angle before and after the test was measured as in (1). The test results are shown in Table 2.

  As shown in Table 2, in the surface modifier of Example 2, the decrease in contact angle after 120 hours was suppressed, whereas in Comparative Example 1, the contact angle was reduced to less than half. Thus, the high gas resistance of the present invention was shown.

  In the sunshine weather test, although the contact angle of Example 2 slightly decreased after 100 hours from the time before the test, the numerical value did not change after 300 hours. The 300 hour test was stopped because the horns were significantly reduced. Thus, the high UV resistance of the present invention was shown.

(3) Abrasion resistance test For the surface modified layer of Example 2 and Comparative Example 1 that had the highest performance in the investigation of the solvent compounding ratio, an eraser was used, the moving distance was 30 mm, the load was 500 g, and the contact area was 10 mm. Then, a rubbing test was performed by reciprocating a predetermined number of times. Similar to (1), the contact angles before and after the test were measured. The test results are shown in Table 3.

  As shown in Table 3, since the comparative example mainly contains the water / oil repellent coating solvent A having an ether group and has high durability, the contact angle was hardly reduced. On the other hand, in the examples, although the content of the water- and oil-repellent coating solvent A having an ether group was halved, the decrease in the contact angle was slight and the performance equivalent to that of the current product was exhibited.

  Thus, the surface modifier of the present invention is mixed with the solvent A having an ether group and the solvent B having no ether group, and compared with a solvent substantially consisting of the solute A and a solvent consisting essentially of the solute B. In spite of the fact that each component is halved, the performance of both components does not decrease with the decrease in the content, and an unexpected effect of achieving both performances is achieved.

1: Optical member base material 2: Buffer layer 3: Surface modification layer 4: Optical member, member

Claims (3)

A surface-modified optical member,
The optical member has a buffer layer made of an oxide on the surface thereof, and a surface modification layer on the surface of the buffer layer,
In the optical member, the surface modification layer includes molecules having an ether bond and molecules not having an ether bond dispersed in each other.   The compounding ratio of the molecule having the ether bond and the molecule not having the ether bond in the surface modified layer is 1: 2 to 2: 1 by weight. Optical member. The optical member according to claim 2, wherein the buffer layer is silicon dioxide, and a siloxane bond exists between the buffer layer and the surface modification layer.

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