JP2009251008A - Optical product and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical product in which an antifouling layer has excellent antifouling properties and scratch resistance, and to provide a method for producing the same. <P>SOLUTION: The optical product 10 is provided with a plastic substrate 11 and a hard coat layer 12, an antireflection layer 13 and the antifouling layer 14 which are formed on both surfaces of the plastic substrate 11. The antifouling layer 14 contains a reactive compound having a reactive group which is reacts with the plastic substrate and a non-reactive compound which does not react with the plastic substrate. The reactive compound and the non-reactive compound are preferably fluorine-containing organic silicon compounds. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an optical article having an antifouling layer as a surface layer and a method for producing the same.

Various films and layers are formed on the surface of an optical article such as a spectacle lens in order to increase the added value. For example, an antireflection layer for reducing reflection on the surface is formed, and an antifouling layer is provided on the surface as a surface layer having water and oil repellency. This antifouling layer is provided in order to prevent adhesion of dirt such as dirt, sweat or cosmetics attached when using an optical article, and even if such dirt adheres, it is provided.
For the formation of the antifouling layer, organic compounds containing fluorine are mainly used as antifouling molecules (
For example, see Patent Document 1).
Such an organic compound has a reactive group, and this reactive group reacts with the substrate surface or a film formed on the substrate surface, thereby bonding to the substrate surface.

Japanese Patent Laid-Open No. 9-258003

However, in the configuration described in Patent Document 1, since all the reactive groups of the organic compound are bonded to the substrate surface, the bonding is strong. Therefore, when a sliding force acts on the substrate surface, for example,
When the surface of the spectacle lens is wiped off with a cloth or the like, the sliding force is directly applied to the bonded portion, so that there is a problem that the antifouling agent molecules fall off and the substrate surface is easily damaged.

Accordingly, an object of the present invention is to provide an optical article excellent in antifouling property and scratch resistance of an antifouling layer and a method for producing the same.

The optical article of the present invention is an optical article having an antifouling layer on a plastic substrate, and the antifouling layer does not react with the reactive compound having a reactive group that reacts with the plastic substrate and the plastic substrate. It is formed from a non-reactive compound.

Here, the plastic substrate includes those in which at least one of a hard coat layer and an antireflection layer is laminated. For example, there are a plastic substrate only, a plastic substrate in which only a hard coat layer is laminated, and a plastic substrate in which a hard coat layer and an antireflection layer are laminated. In addition, it is more preferable that an antireflection layer is formed on the uppermost layer from the viewpoint of good reactivity with the antifouling layer.
The antifouling layer reacts with the plastic substrate. For example, both the antifouling layer and the plastic substrate contain a compound having a reactive group capable of bonding (condensing) to each other such as an alkoxysilyl group or an aminosilyl group. Say to bind through these.

According to this invention, a reactive compound and a non-reactive compound are mixed in the antifouling layer. The reactive compound reacts with the plastic substrate (antireflection layer) and bonds strongly with the reactive compound,
Since the non-reactive compound does not react with the plastic substrate (antireflection layer), the molecules of the non-reactive compound are present in the antifouling layer with a degree of freedom.
Therefore, when a sliding force is applied to the surface of the optical article (for example, when the surface of the optical article such as an eyeglass lens is wiped with a cloth or the like), the molecules of the non-reactive compound freely move, The applied sliding force can be absorbed in the antifouling layer. Thereby, since the force applied to the bonding portion between the reactive compound and the plastic substrate (antireflection layer) can be reduced, the antifouling layer is less likely to fall off, and the scratch resistance can be improved.

In the optical article of the present invention, the reactive compound and the non-reactive compound are preferably fluorine-containing organosilicon compounds.
According to this invention, since the fluorine-containing organic silicon compound is excellent in water and oil repellency, it can exhibit excellent antifouling properties.

In the optical article of the present invention, the non-reactive compound is preferably one in which the reactive group of the reactive compound is deactivated.
In this invention, the reactive compound is used as a non-reactive compound by end-capping by self-condensation or the like. Thus, by using the same compound, an optical article excellent in scratch resistance can be provided while maintaining the original water and oil repellency.

In the optical article of the present invention, the antifouling layer is formed from a composition obtained by blending the reactive compound and the non-reactive compound in a mass ratio of 8: 2 to 2: 8. It is preferable.

Here, when the ratio of the reactive compound is less than 2 in terms of solid content, the plastic substrate (
The amount of antifouling molecules bound to the antireflective layer is reduced, and the antifouling layer is easily peeled off. In addition, when the ratio of the reactive compound is more than 8 in terms of the solid mass ratio, the number of molecules having a degree of freedom is reduced, so that a sliding force is applied to the bonding portion between the few reactive compounds and the plastic substrate (antireflection layer). , And the reactive compound falls off and the antifouling layer is easily peeled off.
In addition, as for the compounding ratio of a reactive compound and a non-reactive compound, it is more preferable that it is the range of 6: 4-4: 6 by solid content mass ratio.

In the optical article of the present invention, the reactive compound is preferably a compound represented by the following formula (1).

Wherein Rf ¹ is a perfluoroalkyl group, X ¹ is hydrogen, bromine, or iodine, Y is hydrogen or a lower alkyl group, Z is a fluorine or trifluoromethyl group, R ¹ is a hydroxyl group or a hydrolyzable group, R ² represents hydrogen or a monovalent hydrocarbon. A, b, c, d and e are 0 or an integer of 1 or more, a + b + c + d + e is at least 1 or more, a, b, c,
The order of presence of each repeating unit divided by d and e is not limited in the general formula (1).
f represents 0, 1 or 2. g represents 1, 2 or 3. h represents an integer of 1 or more.

In the present invention, the fluorine-containing organosilicon compound represented by the formula (1) has a high fluorine atom content, a molecular weight of several thousand and a long chain length of a perfluoroalkyl group, and thus has a low critical surface tension. Therefore, the surface of the antifouling layer containing this has lower energy and antifouling properties are improved.

In the optical article of the present invention, the reactive compound is preferably a compound represented by the following formula (2).

In the formula, Rf ² includes a unit represented by — (C _k F _2k ) O— (k is an integer of 1 to 6),
It represents a divalent group having a linear perfluoropolyalkylene ether structure having no branch. R ³ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, and X ² represents a hydrolyzable group or a halogen atom. p represents 0, 1 or 2. n represents an integer of 1 to 5. m and r are
2 or 3 is represented.

In the present invention, the fluorine-containing organosilicon compound represented by the formula (2) has a high fluorine atom content, a molecular weight of several thousand and a long chain length of a perfluoroalkyl group, and therefore has a low critical surface tension. Therefore, the surface of the antifouling layer containing this has lower energy and antifouling properties are improved.

In the optical article of the present invention, the reactive compound is preferably a compound represented by the following formula (3).
F ₁₇ C ₈ —C ₂ H ₄ —Si (NH) _3/2 (3)

According to this invention, since the fluorine-containing organosilicon compound represented by the formula (3) exhibits antifouling properties, it is possible to impart antifouling properties to the surface of the optical article.

In the optical article of the present invention, the reactive compound is preferably a compound represented by the following formula (4).
F ₃ C— (CF ₂ ) _n — (CH ₂ ) _m —Si (O—R) ₃ (4)
In the formula, n is an integer of 1 to 11, m is an integer of 1 to 4, and R is an alkyl group having 1 or more carbon atoms.

According to this invention, since the fluorine-containing organosilicon compound represented by the formula (4) exhibits antifouling properties, it is possible to impart antifouling properties to the surface of optical articles.

In the optical article of the present invention, the non-reactive compound includes the reactive compound and the following formula (5):
It is preferable that it is a composition obtained by making it react with the compound represented by this.
F ₁₇ C ₈ —C ₂ H ₄ —Si (NH) _3/2 (5)

According to this invention, (NH) _3/2 becomes a reactive group and reacts with a reactive compound that is an antifouling agent. Thereby, the terminal of a reactive compound can be sealed and it can be set as a non-reactive compound.
And the reactive compound, the non-reactive compound reacted with the compound represented by the above formula (5),
When a sliding force acts on the surface of an optical article (for example, when wiping the surface of an optical article such as a spectacle lens with a cloth), the molecules of the non-reactive compound move freely. The applied sliding force can be absorbed in the antifouling layer. Therefore, the scratch resistance can be improved.

In the optical article of the present invention, the non-reactive compound includes the reactive compound and the following formula (6):
It is preferable that it is a composition obtained by making it react with the compound represented by this.
F ₃ C— (CF ₂ ) _n — (CH ₂ ) _m —Si (O—R) ₃ (6)
In the formula, n is an integer of 1 to 11, m is an integer of 1 to 4, and R is an alkyl group having 1 or more carbon atoms.

Specific examples of the formula (6) include CF ₃ (CF ₂ ) ₄ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ).
₄ CH ₂ CH ₂ SiCH ₃ (OC ₂ H ₅ ) ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ C
F ₂ CH ₂ CH ₂ Si (OC ₃ H ₇ ) ₃ , CF ₃ (CF ₂ ) ₂ CH ₂ CH ₂ Si (OC ₃ H ₇ ) ₃ , CF ₃ (CF
_{2) 4 CH 2 CH 2 SiCH} 3 (OC 3 H 7) 2, CF 3 (CF 2) 5 CH 2 CH 2 SiCH 3 (OC 3 H 7) 2,
And perfluoroalkylalkylene alkoxysilane compounds such as CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCH ₃ (OC ₃ H ₇ ) ₂ .

In the compound represented by the above formula (6), R becomes a reactive group and reacts with a reactive group of a reactive compound that is an antifouling agent. That is, the end of the reactive compound is sealed with the compound represented by the above formula (6) to make a non-reactive compound. In addition, since reactive compounds and non-reactive compounds are mixed, non-reactive properties occur when a sliding force acts on the surface of an optical article (for example, when the surface of an optical article such as a spectacle lens is wiped off with a cloth). As the compound molecules move freely, the applied sliding force can be absorbed in the antifouling layer. Therefore, the scratch resistance can be improved.

In the optical article of the present invention, the antifouling layer is preferably formed on the antireflection layer.
The antireflection layer is formed of a multilayer in which low refractive index layers and high refractive index layers are alternately stacked. These layers are, for example, SiO ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ , Ti ₂ O ₅ ,
Al ₂ O ₃ , TaO ₂ , Ta ₂ O ₅ , NbO, Nb ₂ O ₃ , NbO ₂ , Nb ₂ O ₅ , CeO ₂ ,
It is formed of MgO, Y ₂ O ₃ , SnO ₂ , MgF ₂ , WO ₃ or the like, but the layer forming the uppermost layer preferably contains SiO ₂ .
In this invention, since the component of the antireflection layer and the reactive group of the component constituting the antifouling layer easily react, the antireflection layer and the antifouling layer are firmly bonded. Accordingly, since the antifouling layer is difficult to peel off, an optical article excellent in antifouling durability can be provided.

The optical article of the present invention is preferably a spectacle lens.
According to the present invention, a spectacle lens capable of achieving the above-described effects can be provided. In the spectacle lens, since the dirt is particularly conspicuous, the above-described effect is further increased.

The method for producing an optical article of the present invention includes an antifouling treatment liquid preparation step for preparing an antifouling treatment liquid by mixing the reactive compound and the nonreactive compound, and the antifouling treatment liquid is used as the plastic substrate. And an antifouling layer forming step to be applied to the surface.

According to this invention, after the antifouling liquid is adjusted, the antifouling liquid is applied to the plastic substrate to form the antifouling layer. The antifouling liquid contains a mixture of reactive compounds and non-reactive compounds, providing excellent adhesion between the reactive compounds and the plastic substrate (antireflection layer) and free movement of the non-reactive compounds. Thus, an optical article having excellent scratch resistance can be provided.
As the reactive compound and the non-reactive compound, it is preferable to use a fluorine-containing organosilicon compound as described above. Moreover, what deactivated the reactive group of the reactive compound may be used for a non-reactive compound.

In the method for producing an optical article of the present invention, the antifouling layer forming step is preferably carried out by a dry method.
Examples of the dry method include a vacuum deposition method and a sputtering method.
According to this invention, since no solvent is used, the environmental load is low. Moreover, since it is easy to change the conditions in the antifouling layer forming step, the film thickness control of the antifouling layer is also simple. Further, since a fibrous or porous medium is used, the heating efficiency of the fluorine-containing organosilicon compound is high. Note that a material having high thermal conductivity is preferable as the medium, and a conductive material such as metal is preferable.

In the method for producing an optical article of the present invention, the antifouling layer forming step is preferably performed by a wet method.
Examples of the wet method include a dipping method.
By performing the wet method, large equipment such as a vacuum apparatus is not necessary, and the manufacturing cost can be reduced.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 shows a schematic cross-sectional view of an optical article 10 of the present embodiment. This optical article 10
Is, for example, a spectacle lens.
[Configuration of optical article]
The optical article 10 includes a plastic substrate 11, and a hard coat layer 12, an antireflection layer 13, and an antifouling layer 14 are provided on both surfaces of the plastic substrate 11.
The plastic substrate 11 is not particularly limited, but includes (meth) acrylic resin, styrene resin, polycarbonate resin, allyl resin, allyl carbonate resin such as diethylene glycol bisallyl carbonate resin (CR-39), vinyl resin, polyester resin, Polyether resins, urethane resins obtained by reacting isocyanate compounds with hydroxy compounds such as diethylene glycol, thiourethane resins obtained by reacting isocyanate compounds with polythiol compounds, and having one or more disulfide bonds in the molecule (thio) The transparent resin etc. which are obtained by hardening | curing polymeric composition containing an epoxy compound can be illustrated.

The hard coat layer 12 only needs to improve the scratch resistance, which is the original function. For example, the hard coat layer 12 may be a hard coat layer using a melamine resin, a silicone resin, a urethane resin, an acrylic resin, or the like, and a hard coat using a silicone resin is most preferable. For example, a hard coat layer is provided by applying and curing a coating composition comprising metal oxide fine particles and a silane compound. This coating composition may contain components such as colloidal silica and a polyfunctional epoxy compound.
Specific examples of the metal oxide fine particles include SiO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Ta ₂ O _5.
, CeO ₂ , La ₂ O ₃ , Fe ₂ O ₃ , ZnO, WO ₃ , ZrO ₂ , In ₂ O ₃ , TiO _2, etc. Examples thereof include those obtained by dispersing fine particles in a colloidal form in a dispersion medium such as water, alcohols or other organic solvents. In the present embodiment, the antireflection layer 13 can be provided directly on the plastic substrate 11 without providing the hard coat layer 12.
As a method for forming such a hard coat layer 12, after applying the composition of the hard coat layer 12 by dipping method, spinner method, spray method, flow method, 40-2
The method of heat-drying for several hours at the temperature of 00 degreeC can be illustrated.

The antireflection layer 13 is formed by sequentially laminating a low refractive index layer and a high refractive index layer. The antireflection layer 13 includes a first layer 131, a second layer 132, a third layer 133, a fourth layer 134, and a fifth layer 135, which are sequentially arranged from the plastic substrate 11 side toward the outside. The first layer 131, the third layer 133, and the fifth layer 135 are low refractive layers, and the second layer 132 and the fourth layer 134 are high refractive layers.
Examples of inorganic materials used for the layers 131 to 135 of the antireflection layer 13 include SiO ₂ , S
_{iO, ZrO 2, TiO 2,} TiO, Ti 2 O 3, Ti 2 O 5, Al 2 O 3, TaO 2, Ta 2 O 5
_{, NbO, Nb 2 O 3,} NbO 2, Nb 2 O 5, CeO 2, MgO, Y 2 O 3, SnO 2, M
Examples thereof include gF ₂ and WO ₃ . These inorganic substances are used alone or in a mixture of two or more.
For example, the first layer 131, the third layer 133, and the fifth layer 135 are SiO ₂ layers, and the second layer 1
32 and the fourth layer 134 may be ZrO ₂ layers.

The antifouling layer 14 is a layer having water and oil repellency. The antifouling layer 14 contains a reactive compound that reacts with the antireflection layer 13 and a nonreactive compound that does not react with the antireflection layer 13.
As the reactive compound and the non-reactive compound, a fluorine-containing organosilicon compound is preferably used. For example, the compounds represented by the following formulas (1) to (4) can be used.

Wherein Rf ¹ is a perfluoroalkyl group, X ¹ is hydrogen, bromine, or iodine, Y is hydrogen or a lower alkyl group, Z is a fluorine or trifluoromethyl group, R ¹ is a hydroxyl group or a hydrolyzable group, R ² represents hydrogen or a monovalent hydrocarbon. A, b, c, d and e are 0 or an integer of 1 or more, a + b + c + d + e is at least 1 or more, a, b, c,
The order of presence of each repeating unit divided by d and e is not limited in the general formula (1).
f represents 0, 1 or 2. g represents 1, 2 or 3. h represents an integer of 1 or more.

In the formula, Rf ² includes a unit represented by — (C _k F _2k ) O— (k is an integer of 1 to 6),
It represents a divalent group having a linear perfluoropolyalkylene ether structure having no branch. R ³ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, and X ² represents a hydrolyzable group or a halogen atom. p represents 0, 1 or 2. n represents an integer of 1 to 5. m and r are
2 or 3 is represented.

F ₁₇ C ₈ —C ₂ H ₄ —Si (NH) _3/2 (3)

F ₃ C— (CF ₂ ) _n — (CH ₂ ) _m —Si (O—R) ₃ (4)
In the formula, n is an integer of 1 to 11, m is an integer of 1 to 4, and R is an alkyl group having 1 or more carbon atoms.

As the reactive compound, any of the compounds represented by the above formulas (1) to (4) can be used, and these may be used alone or in combination.
As the reactive compound, it is preferable to use a compound represented by the above formula (1) or (2). Specific examples of these fluorine-containing organosilicon compounds include KY-130 and KP-801 manufactured by Shin-Etsu Chemical Co., Ltd.

As the non-reactive compound, any of the compounds represented by the above formulas (1) to (4) can be used, and these may be used alone or in combination.
As a non-reactive compound, a compound represented by the above formula (3) or (4) is reacted with a reactive compound represented by the above formula (1) or (2) to form a non-reactive compound Is preferably used. In addition, the compounds represented by the above (1) to (4) may be self-condensed into non-reactive compounds.

The antifouling layer 14 formed of such a compound may be formed by either a dry method or a wet method. Examples of the dry method include a vacuum deposition method and a sputtering method. Examples of the wet method include a dipping method.

[Optical article manufacturing equipment]
Next, a method for manufacturing the optical article 10 will be described with reference to FIG. Here, a film forming method by a vacuum evaporation method will be described.
FIG. 2 shows a schematic diagram of a film forming apparatus that performs coating and surface treatment of an optical article on a plastic substrate.

In the film forming apparatus 100, a plurality of plastic substrates 11 are held by the supporting device 20 in FIG. 2. A hard coat layer 12 is provided on the plastic substrate 11 in advance. The supporting device 20 moves inside the film forming apparatus 100 for each process, and coating and surface treatment are performed on the plastic substrate 11. The support device 20 is rotated by a rotation mechanism (not shown) so that processing on each plastic substrate 11 is uniform.

The film forming apparatus 100 includes three chambers 30, 40 and 50 through which the support device 20 can pass. These chambers are connected, and the supporting device 20 is a plastic substrate 11.
It is possible to pass while holding. The chambers can be sealed with each other by a shutter (not shown) between the chambers, and the internal pressures of the chambers are controlled by the vacuum generators 31, 41, and 51, respectively.

The chamber 30 is an entrance or gate chamber, and after introducing the support device 20 from the outside, the gas adsorbed on the plastic substrate 11 and the support device 20 by heating the inside of the chamber 30 under a constant pressure for a certain time. Is degassed. Chamber 3
The zero vacuum generator 31 includes a rotary pump 32, a roots pump 33, and a cryopump 34.

The chamber 40 is a chamber that performs thin film formation by vacuum deposition or surface treatment by plasma or the like. Similarly to the vacuum generator 31 of the chamber 30, the vacuum generator 41 of the chamber 40 includes a rotary pump 42, a roots pump 43, and a cryopump 44.

In the chamber 40, an evaporation source 61 and an evaporation source 62 are provided in order to efficiently form the antireflection layer 13 by combining vapor deposition materials having different refractive indexes. Then, electron guns 65 and 66 for evaporating vapor deposition materials 63 and 64 disposed in these two evaporation sources 61 and 62 are used.
A pair of openable and closable shutters 67 and 68 for adjusting the deposition amount is provided.
Examples of vapor deposition materials having different refractive indexes include silicon oxide as a low refractive index material, and titanium oxide, niobium oxide, tantalum oxide, and zirconium oxide as high refractive index materials.

The chamber 40 has a high-frequency plasma generator 70 for performing plasma processing.
Is installed. The high frequency plasma generator 70 includes an RF coil 71 installed in the chamber, a matching box 72 connected to the outside of the chamber, and a high frequency transmitter 73.
It consists of and.

Further, the chamber 40 is provided with an ion gun 80 for performing ion-assisted vapor deposition and surface treatment. The ion gun 80 is connected to an RF power source 81 for converting the introduced gas into plasma and generating positive ions, and a DC power source 82 for accelerating the positive ions.
The mass flow controller 7 causes oxygen 74 and argon 75, which are gases used for plasma processing and ion irradiation, to have a predetermined pressure by the auto pressure controller 77.
8 and 83, the flow rate is controlled and introduced.

The chamber 50 is a chamber for forming the antifouling layer 14 by depositing a fluorine-containing organosilicon compound. Inside the chamber, an evaporation source 90 impregnated with a fluorine-containing organosilicon compound, a heater (halogen lamp) 91, and a correction plate 92 are installed. The correction plate 92 is a fixed type, and the deposition amount with respect to the place of the support device 20 can be adjusted by adjusting the opening degree. The chamber 50 includes a rotary pump 52 and a roots pump 5
3 and a vacuum generator 51 equipped with a turbo molecular pump 54.

[Method of manufacturing optical article]
Hereinafter, the processing steps for the plastic substrate 11 of the present embodiment will be described with reference to FIG.
Step (A) is a step of forming the hard coat layer 12 on the plastic substrate 11. The hard coat layer 12 is obtained by a method in which a sol-gel having inorganic fine particles is applied to the plastic substrate 11 and then cured. According to this method, the inorganic fine particles can be selected in accordance with the refractive index of the plastic substrate 11, and reflection at the interface between the plastic substrate 11 and the hard coat layer 12 can be suppressed. The hard coat layer 12 is formed on one side and both sides as necessary. In the case of a spectacle lens, it is formed on both sides.

Step (B) is a step of forming the antireflection layer 13. In FIG. 3, the antireflection layer 13 is formed on only one side, but it is formed on both sides after being reversed.
The plastic substrate 11 is introduced into the chamber 30 while being held by the support device 20,
Degassed. Next, the support device 20 is introduced into the chamber 40, and the antireflection layer 13 is formed on the surface of the hard coat layer 12. In this process, a plurality of layers having a high refractive index and a low refractive index are alternately laminated, and a silicon dioxide layer, which is a silicon oxide layer, is formed on the uppermost layer of the antireflection layer 13.

Next, in order to increase the reactivity between the antireflection layer 13 and the fluorine-containing organosilicon compound, plasma treatment for generating silanol groups on the surface of the antireflection layer 13 is performed.
Oxygen 74 or argon 75 is introduced into the chamber 40, and the inside of the chamber 40 is controlled to a constant pressure by the auto pressure controller 77 and the mass flow controller 78. High-frequency plasma can be generated at approximately 10 ⁻³ to 10 ³ Pa, but 1 × 10 ⁻² P
a to 1 × 10 ⁻¹ Pa are suitable. The high frequency was 13.56 MHz. The treatment time is 0.5 to 3 minutes, and silanol groups are generated on the surface of the antireflection layer 13 by this treatment.

In addition, as a treatment for generating a silanol group, the ion gun 80 can be used.
Oxygen 74 or argon 75 is introduced into the ion gun 80 while being controlled at a constant flow rate by the mass flow controller 83. The introduced gas is turned into plasma inside the ion gun 80. The plasma is a high frequency plasma, and the frequency of the RF power source 81 is normally 13.56 MHz.
It is. The generated positive ions are extracted by the acceleration electrode to which a voltage is applied by the DC power source 82 and irradiated on the surface of the antireflection layer 13.
In order to prevent dielectric breakdown from occurring on the plastic substrate 11 and the occurrence of abnormal discharge, electrons are supplied from a built-in neutralizer and neutralized. Processing time is 0.5 ~
In 3 minutes, silanol groups are generated on the surface of the antireflection layer 13 by this treatment.

Step (C) is a step of forming the antifouling layer 14. The support device 20 is guided to the chamber 50. Here, by heating the evaporation source 90 with the heater 91, the antifouling layer 14 made of the aforementioned compound is formed on the surface of the antireflection layer 13 by vapor deposition.
After the antifouling layer 14 is formed, the chamber 50 is gradually returned to atmospheric pressure, and the plastic substrate 11 is taken out together with the support device 20.

The plastic substrate 11 formed on one side up to the antifouling layer 14 is turned upside down and set again on the support device 20, and the same processing as in steps (B) and (C) is performed. Thereby, the antireflection layer 13 and the antifouling layer 14 are formed on both surfaces of the plastic substrate 11.

The plastic substrate 11 formed up to the antifouling layer 14 is removed from the support device 20, and then placed in a constant temperature and humidity chamber (not shown) and annealed in an atmosphere of appropriate humidity and temperature. Alternatively, aging is performed in a room for a predetermined time. Thereafter, if it is necessary to adjust the thickness of the antifouling layer 14, a removal operation such as wiping off the excess with a solvent is performed.

According to the above embodiment, the following effects can be obtained.
(1) In this embodiment, the antifouling layer 14 contains a reactive compound and a non-reactive compound.
For this reason, the reactive group of the reactive compound is firmly bonded to the antireflection layer 13, while the non-reactive compound is present in the antifouling layer 14 as a molecule having a degree of freedom. Therefore, when a sliding force is applied to the surface of the optical article (for example, when the surface of the spectacle lens is wiped with a cloth), the sliding force can be absorbed in the antifouling layer 14. That is, since the sliding force is hardly applied directly to the bonded portion between the reactive compound and the antireflection layer 13, the antifouling agent molecules can be prevented from falling off, and an optical article excellent in scratch resistance can be provided. .

(2) A fluorine-containing organosilicon compound was used as the reactive compound or non-reactive compound of the antifouling layer 14. Since the fluorine-containing organosilicon compound has a large molecular weight, the amount of fluorine contained in the antifouling layer 14 is large, so that the water and oil repellency can be further improved and the wiping property of dirt can be improved.
In particular, the compound represented by the above formula (1) has a high fluorine atom content, a molecular weight of several thousand and a long chain length of a perfluoroalkyl group, and thus has a low critical surface tension. For this reason, the surface of the antifouling layer 14 containing this can have lower energy and improve the antifouling property.

(3) The reactive compound and non-reactive compound of the antifouling layer 14 are blended in a mass ratio of 8: 2 to 2: 8.
By blending in such a range, an optical article excellent in both scratch resistance and durability can be provided.

(4) The antifouling layer 14 is formed on the antireflection layer 13. Moreover, the uppermost layer of the antireflection layer 13 is formed of SiO _2. Therefore, the antifouling agent molecules constituting the antifouling layer 14 and SiO
₂ is firmly bonded. Therefore, the antifouling agent molecules are difficult to fall off and have excellent durability.

(5) The optical article 10 having the above-described effects is used as a spectacle lens. In the spectacle lens, since the dirt is particularly conspicuous, the above-described effect can be further increased.

(6) The optical article 10 described above was manufactured by a dry method.
The dry method has a low environmental impact because no solvent is used. Moreover, since it is easy to change the conditions in the antifouling layer forming step, the film thickness control of the antifouling layer is also simple.
Moreover, according to the dry method, the optical article 10 that can achieve the above-described effects can be manufactured.

[Modification of the present invention]
The present invention is not limited to the above-described embodiments, and various improvements and modifications can be made within a range in which the object of the present invention can be achieved.

For example, in the embodiment, the antifouling layer 14 is formed by a dry method, but the antifouling layer 1 is formed by a wet method.
4 may be formed. In the case of the wet method, it is possible to employ a method in which any of the fluorine-containing organosilicon compounds described above is dissolved in an organic solvent, adjusted to have a predetermined concentration, and applied to the surface of the plastic substrate 11. The organic solvent is preferably an organic compound having a perfluoro group excellent in solubility of the fluorine-containing organosilicon compound and having 4 or more carbon atoms, such as perfluorohexane, perfluorocyclobutane, perfluorooctane, perfluorodecane. Perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, perfluoro-4-methoxybutane, perfluoro-4-ethoxybutane,
Mention may be made of metaxylene hexafluoride. Perfluoroether oil,
Chlorotrifluoroethylene oligomer oil can be used. In addition, Freon 2
25 (mixture of CF ₃ CF ₂ CHCl ₂ and CClF ₂ CF ₂ CHClF). One of these organic solvents can be used alone or in admixture of two or more.

The concentration when diluted with an organic solvent is preferably in the range of 0.03% by mass to 1% by mass. If it is lower than 0.03% by mass, it is difficult to form the antifouling layer 14 having a sufficient thickness, and sufficient water and oil repellency effects and sufficient slipperiness may not be obtained. On the other hand, if the concentration is higher than 1% by mass, the antifouling layer 14 may become too thick, and the burden of rinsing work for eliminating coating unevenness after application may increase.

Moreover, in the said embodiment, although the reactive compound represented by Formula (1) and the compound represented by Formula (3) were made to react, the non-reactive compound was produced | generated, but the reactive group of a reactive compound was deactivated. You may use what was made to react as a non-reactive compound. In this case, the reactive compound is added to the reactive compound by adding a catalyst (for example, a transesterification catalyst (CH ₃ (CH ₂ ) ₃ —Sn— (OCCH ₃ )) in a solid content ratio of 0.1%). Can be condensed.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples at all.

In this embodiment, a spectacle lens as an optical article is manufactured.
[Example 1]
The following A1 liquid and B liquid are mixed so that the solid content mass ratio is 8: 2, and an organic solvent “HFE-7200” (trade name, manufactured by Sumitomo 3M Limited) is added to obtain a solid content concentration of 0.1.
% To prepare a dipping treatment solution.
Moreover, the following A1 liquid and B liquid were mixed so that it might become 8: 2 by solid content mass ratio, and after dripping impregnation to a porous pellet, it dried and prepared so that solid content mass might be 30 mg. This was used as a pellet for vapor deposition.

(A1 liquid) The compound represented by the above-mentioned general formula (1) ("OPTOOL DSX" (trade name), compound x, manufactured by Daikin Industries, Ltd.)
(Liquid B) The compound (compound x) used in the liquid A1 and the compound represented by the general formula (4) described above (“TSL8257”, compound y) manufactured by Toshiba Silicone Co., Ltd.) have a solid content mass ratio of 1 :
The mixture was mixed to be 12. This ratio is a mixing ratio that is approximately 1: 1 in molar ratio. Here, both compound x and compound y have a structure in which a reactive group exists at one end of the molecular chain.
Then, 0.1% CH ₃ (CH ₂ ) ₃ —Sn— (OCCH ₃ ) as a transesterification catalyst was added to the liquid in a solid content ratio. Then, it stirred at normal temperature for 24 hours. Thereby, antifouling agent molecules condense. In addition, the combination of condensation can consider three patterns of the compound x and the compound y, the compounds x, and the compounds y.

[Example 2]
A1 liquid and the following A2 liquid are mixed so that it may become 8: 2 by solid content mass ratio, and organic solvent "HFE-7200" (brand name, Sumitomo 3M Co., Ltd. product) is added, and solid content concentration is set to 0.
A dipping treatment solution was prepared to 1%.
Moreover, A1 liquid and the following A2 liquid were mixed so that it might become 8: 2 by solid content mass ratio, and after dripping impregnation to a porous pellet, it dried and prepared so that solid content mass might be 30 mg. This was used as a pellet for vapor deposition.

(Liquid A2) CH ₃ (CH ₂ ) ₃ —Sn— (OCCH ₃ ) as a transesterification catalyst was added to Compound x at a solid content ratio of 0.1%. Then, it stirred at normal temperature for 24 hours. Thereby, antifouling agent molecules condense.

[Example 3]
In Example 2, the mixed solid mass ratio of the A1 liquid and the A2 liquid was 7: 3.

[Example 4]
In Example 2, the mixed solid mass ratio of the A1 liquid and the A2 liquid was 6: 4.

[Example 5]
In Example 2, the mixed solid mass ratio of the A1 liquid and the A2 liquid was 5: 5.

[Example 6]
In Example 2, the mixed solid mass ratio of the A1 liquid and the A2 liquid was 4: 6.

[Example 7]
In Example 2, the mixed solid mass ratio of the A1 liquid and the A2 liquid was 3: 7.

[Example 8]
In Example 2, the mixed solid mass ratio of the A1 liquid and the A2 liquid was 2: 8.

[Example 9]
The following C liquid and D liquid are mixed so that the solid content mass ratio is 8: 2, and the organic solvent “
HFE-7200 "(trade name, manufactured by Sumitomo 3M Co., Ltd.) and solid content concentration 0.1%
To prepare a dipping treatment solution.
Moreover, the following C liquid and D liquid were mixed so that it might become 8: 2 by solid content mass ratio, and after dripping impregnation to a porous pellet, it dried and prepared so that solid content mass might be 30 mg. This was used as a pellet for vapor deposition.

(Liquid C) Compound represented by the above general formula (2), anti-fouling agent “KY-” manufactured by Shin-Etsu Chemical Co., Ltd.
130 "(compound z)
(Liquid D) Compound z and the compound represented by the above general formula (3) (“Shin-Etsu Chemical Co., Ltd.“
KP-801M "and compound v) were mixed so that the solid content mass ratio was 3: 1. This ratio is a mixing ratio of approximately 1: 2 in terms of molar ratio. Here, the compound z has a structure in which a reactive group exists at both ends of the molecular chain, and the compound v has a structure in which a reactive group exists at one end.
Then, 0.1% CH ₃ (CH ₂ ) ₃ —Sn— (OCCH ₃ ) as a transesterification catalyst was added to the liquid in a solid content ratio. Then, it stirred at normal temperature for 24 hours. Thereby, antifouling agent molecules condense. In addition, the combination of condensation can consider three patterns of the compound z, the compound v, the compounds z, and the compounds v.
In addition, since the compound z has reactive groups at both ends, the case where both are sealed and the case where only one is sealed are assumed.

[Comparative Example 1]
Only the A1 liquid used in Example 1 was used.

[Comparative Example 2]
Only the liquid C used in Example 9 was used.

[Formation of antifouling layer]
Next, an antifouling layer was formed by a dry method using the deposition pellets prepared in Examples 1 to 9 and Comparative Examples 1 and 2.
As a substrate 10, a plastic lens for spectacles (“Seiko Epson Corporation“ Seiko Super Sovereign ”) having a hard coat layer 12 formed on a plastic substrate 11 is set on the support device 20 and degassed in the chamber 30. In the chamber 40, SiO ₂
And ZrO ₂ layers were alternately deposited to form an antireflection layer 13 composed of these layers. The uppermost layer of the antireflection layer 13 is a SiO ₂ layer.
Subsequently, 100% oxygen gas was introduced into the chamber 40, and plasma was generated by a high-frequency plasma generator while controlling the pressure to 4.0 × 10 ⁻² Pa. Plasma generation condition is 1
The treatment was performed at 3.56 MHz and 0.4 kW for 1 minute.

Thereafter, the support device 20 was moved to the chamber 50 to form the antifouling layer 14. As the evaporation source 90, the pellets for vapor deposition produced in Examples 1 to 9 and Comparative Examples 1 and 2 were used.
During film formation, a halogen lamp is used as the heater 91, and the pellets of the evaporation source 90 are 6
By heating to 00 ° C., the fluorine-containing organosilicon compound was evaporated. The deposition time is 3 minutes.
After the antifouling layer is formed, the support device 20 is removed from the chamber 50, the lens is inverted and set on the support device 20 again, and the same processing as described above is performed again, whereby the antifouling layer 1 is formed on both surfaces of the lens.
4 was formed. Thereafter, the optical article 10 was taken out, put into a high-temperature and high-humidity tank set at 60 ° C. and 60% RH, and held for 2 hours, so that the reaction between the antifouling agent and the lens surface was advanced.

In this embodiment, the antifouling layer is formed by a dry method, but the antifouling layer can also be formed by a wet method using the dipping treatment liquid described above. Specifically, it is carried out as follows.
As a processing substrate, a plastic lens for spectacles (“Seiko Super Sovereign” manufactured by Seiko Epson Corporation) having a hard coat layer and an antireflection layer (the outermost layer is an SiO ₂ film) is prepared, and plasma is used to clean the substrate surface. Processing (processing pressure: 0.1 Torr, introduced gas: dry air, distance between electrodes: 24 cm, power output: DC 1 KV, processing time: 15 seconds) is performed. Then, the plasma-treated lens is immersed in a dipping treatment solution containing the above-described reactive compound and non-reactive compound and held for 1 minute, and then pulled up at 150 mm / min to apply an antifouling treatment solution. Thereafter, as an annealing process, the antifouling layer can be formed by putting it in a constant temperature and humidity chamber set at 60 ° C. and 60% RH and holding it for 2 hours.

[Evaluation]
About the spectacle lens produced as described above, the performance of the antifouling layer was evaluated by the scratch resistance by steel wool, the contact angle in the alkali immersion test and the ink wiping property.
(1) Scratch resistance The surface of the spectacle lens is made of steel wool (Nihon Steel Wool Co., Ltd. Bonster # 000).
The load of 1 kg was applied to 0), and the distance of about 30 mm was rubbed back and forth 10 times, and then the state of scratches entering the lens surface was visually evaluated according to the following criteria A to D.
A: There is no scratch at all.
B: One or two scratches are confirmed.
C: 3 to 5 scratches are confirmed.
D: Six or more scratches are confirmed.

(2) Alkaline immersion test The test piece is immersed in an aqueous sodium hydroxide solution adjusted to 0.1 N for 3 hours, and the test piece after immersion is thoroughly washed with water. The antifouling performance before and after the alkali immersion test was evaluated by the contact angle and the wipeability of the oil-based ink.
(2-1) Contact angle measurement Using a contact angle meter ("CA-D type" manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of pure water was measured by the droplet method.
(2-2) Wipe of oil-based ink A straight line of about 4 cm is drawn on the convex surface of the lens with a black oil-based marker ("Himacy Care" manufactured by Zebra Co., Ltd.) and left for 5 minutes. The product was wiped off by Crescia: Kei Dry, and the ease of wiping was determined according to the following criteria.
○: Can be completely removed by wiping 10 times or less. △: Can be completely removed by wiping 11 to 20 times. X: A portion that is not removed remains after wiping 20 times. The above evaluation results are shown in Table 1 below. .

As shown in Table 1, since Example 1 is mixed with B liquid which is a terminal blocking component, Comparative Example 1
Compared to, it has excellent scratch resistance.
Moreover, since Example 9 mixes D liquid which is an end-capping component, it has better scratch resistance than Comparative Example 2.
And as shown in Example 2 to Example 8, when the mixing ratio of the A2 liquid as the end-capping component is increased, the scratch resistance is improved, while the alkali resistance tends to be reduced. There was no problem.
As described above, when the optimum mixing ratio is set by various mixing systems, it becomes possible to perform surface treatment of a substrate having both chemical resistance typified by scratch resistance and alkali resistance.

The present invention can be used not only for plastic eyeglass lenses but also for plastic liquid crystal display panels, lenses for optical devices, and the like.

The schematic diagram which shows the cross section of the optical article concerning embodiment of this invention. Schematic which shows the film-forming apparatus concerning embodiment of this invention. The figure which shows the process process concerning embodiment of this invention.

Explanation of symbols

10 ... Optical article, 11 ... Plastic substrate, 12 ... Hard coat layer, 13.
..Antireflection layer, 14 ... Anti-fouling layer, 100 ... Film forming apparatus

Claims (15)

An optical article having an antifouling layer on a plastic substrate,
The antifouling layer is formed of a reactive compound having a reactive group that reacts with the plastic substrate and a non-reactive compound that does not react with the plastic substrate. The optical article according to claim 1.
The optical article, wherein the reactive compound and the non-reactive compound are fluorine-containing organosilicon compounds. The optical article according to claim 1 or 2,
The optical article, wherein the non-reactive compound deactivates the reactive group of the reactive compound. The optical article according to any one of claims 1 to 3,
The antifouling layer comprises the reactive compound and the non-reactive compound in a solid content mass ratio of 8: 2 to 2.
An optical article characterized in that it is formed from a composition blended at a ratio of 2: 8. The optical article according to any one of claims 1 to 4,
The said reactive compound is a compound represented by the following formula | equation (1), The optical article characterized by the above-mentioned.

Wherein Rf ¹ is a perfluoroalkyl group, X ¹ is hydrogen, bromine, or iodine, Y is hydrogen or a lower alkyl group, Z is a fluorine or trifluoromethyl group, R ¹ is a hydroxyl group or a hydrolyzable group, R ² represents hydrogen or a monovalent hydrocarbon, and a, b, c, d, e
Is an integer of 0 or 1 or more, a + b + c + d + e is at least 1 or more, a, b, c
The order of presence of each repeating unit delimited by, d and e is not limited in the general formula (1). f represents 0, 1 or 2. g represents 1, 2 or 3. h represents an integer of 1 or more. ) The optical article according to any one of claims 1 to 4,
The optical article, wherein the reactive compound is a compound represented by the following formula (2):

(In the formula, Rf ² includes a unit represented by — (C _k F _2k ) O— (k is an integer of 1 to 6) and has a linear perfluoropolyalkylene ether structure having no branch. R ³ represents a divalent group, R ³ represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, X ² represents a hydrolyzable group or a halogen atom, and p represents 0, 1 or 2. n Represents an integer of 1 to 5. m and r represent 2 or 3.) The optical article according to any one of claims 1 to 4,
The said reactive compound is a compound represented by the following formula | equation (3), The optical article characterized by the above-mentioned.
F ₁₇ C ₈ —C ₂ H ₄ —Si (NH) _3/2 (3) The optical article according to any one of claims 1 to 4,
The said reactive compound is a compound represented by the following formula | equation (4), The optical article characterized by the above-mentioned.
F ₃ C— (CF ₂ ) _n — (CH ₂ ) _m —Si (O—R) ₃ (4)
(In the formula, n is an integer of 1 to 11, m is an integer of 1 to 4, and R is an alkyl group having 1 or more carbon atoms.) The optical article according to any one of claims 1 to 8,
The optical article, wherein the non-reactive compound is a composition obtained by reacting the reactive compound with a compound represented by the following formula (5).
F ₁₇ C ₈ —C ₂ H ₄ —Si (NH) _3/2 (5) The optical article according to any one of claims 1 to 8,
The optical article, wherein the non-reactive compound is a composition obtained by reacting the reactive compound with a compound represented by the following formula (6).
F ₃ C— (CF ₂ ) _n — (CH ₂ ) _m —Si (O—R) ₃ (6)
(In the formula, n is an integer of 1 to 11, m is an integer of 1 to 4, and R is an alkyl group having 1 or more carbon atoms.) The optical article according to any one of claims 1 to 10,
The optical article, wherein the antifouling layer is formed on the antireflection layer. The optical article according to any one of claims 1 to 11, wherein the optical article is a spectacle lens. A method for producing an optical article according to any one of claims 1 to 12,
An antifouling treatment liquid preparation step of preparing the antifouling treatment liquid by mixing the reactive compound and the non-reactive compound;
An antifouling layer forming step of applying the antifouling treatment liquid to the surface of the plastic substrate, and a method for producing an optical article. In the manufacturing method of the optical article according to claim 13,
The method for producing an optical article, wherein the antifouling layer forming step is carried out by a dry method. In the manufacturing method of the optical article according to claim 13,
The method for producing an optical article, wherein the antifouling layer forming step is performed by a wet method.

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