JP5156251B2 - Deposition film evaluation method and spectacle lens manufacturing method using the same - Google Patents

Description

  The present invention relates to a vapor deposition film evaluation method suitable for evaluating the surface property of a vapor deposition film located on the outermost surface of an optical member such as a lens. Furthermore, this invention relates to the manufacturing method of the optical member which has a vapor deposition film which uses the said evaluation method.

In order to improve the surface property of an optical member such as a lens, a deposited film is formed by a deposition process. For example, Patent Document 1 proposes imparting water repellency by forming a deposited film on the surface of an optical member such as a lens.
JP-A-5-215905

The deposited film formed on the outermost surface of the optical member such as the water-repellent film described in Patent Document 1 has a practically good slip feeling in addition to imparting a desired surface property (for example, water repellency) to the optical member. It is required to be. In particular, a plastic lens for spectacles needs to frequently wipe off fingerprints, sebum, and other dirt adhering to the lens, and a lens having a good slip feeling is desired. In addition, a favorable feeling of slip means that it can be wiped off smoothly with little resistance when wiped with a cloth or the like.
This slip feeling is usually evaluated by actually wiping with a human hand. However, since this method is a sensory evaluation, there is a possibility that the evaluation result may vary depending on the person to be evaluated, and it is difficult to evaluate a fine difference.
One index that can objectively evaluate surface properties is a coefficient of dynamic friction. However, there may be no clear correlation between the dynamic friction coefficient and the evaluation result of the slip feeling in the sensory evaluation, and the slip feeling may be greatly different even if the dynamic friction coefficient is the same. .

  Accordingly, an object of the present invention is to provide a method for evaluating the surface properties of a deposited film such as a slip feeling with high reliability.

  As a result of intensive studies to achieve the above object, the present inventors have found that there is a good correlation between the phase change measured by the atomic force microscope and the surface property of the deposited film, The present invention has been completed.

（一般式（Ｉ）式中、Ｒｆは、式：−（Ｃ_kＦ_2kＯ）−（ｋは１〜６の範囲の整数である）で表わされる単位を含み、分岐を有しない直鎖状のパーフルオロポリアルキレンエーテル構造を有する二価の基であり、Ｒは炭素原子数１〜８の一価炭化水素基であり、Ｘは加水分解性基またはハロゲン原子であり、ｎおよびｎ'は、それぞれ独立に０〜２の範囲の整数であり、ｍおよびｍ'は、それぞれ独立に１〜５の整数であり、ａおよびｂは、それぞれ独立に２または３である）
成分（Ｂ）：下記一般式（II）で表されるシラン化合物
Ｒ'−Ｓｉ(ＯＲ'')₃および／またはＳｉ(ＯＲ'')₄ ・・・(II)
（一般式（II）式中、Ｒ'は有機基であり、Ｒ''はアルキル基である。）
成分（Ｃ）：下記一般式(III)で表される変性シリコーンオイル

（一般式(III) 式中、ｃは１以上の整数であり、Ｘ₁〜Ｘ₆は、それぞれ独立に有機基であり、Ｘ₁およびＸ₅ならびに／またはＸ₂およびＸ₄はメチル基を有する。）
［６］複数の基材上に蒸着材料を蒸着することにより蒸着膜を有する眼鏡レンズを複数製造する工程と、
製造された複数の眼鏡レンズの少なくとも１つについて、該眼鏡レンズが有する蒸着膜表面の滑り感を、［１］〜［３］のいずれかに記載の方法により評価する工程と、ここで前記蒸着膜は、前記眼鏡レンズの最表面に位置する撥水性膜であり、
評価結果に基づき製品として出荷する眼鏡レンズを決定する工程と、
を含む眼鏡レンズの製造方法。
［７］前記蒸着材料は、フッ素置換アルキル基含有有機ケイ素化合物を含む蒸着材料である［６］に記載の眼鏡レンズの製造方法。
［８］前記蒸着材料は、下記成分（Ａ）〜（Ｃ）を含む蒸着材料である［６］または［７］に記載の眼鏡レンズの製造方法。
成分（Ａ）：一般式(Ｉ)で表されるフッ素置換アルキル基含有有機ケイ素化合物

（一般式（Ｉ）式中、Ｒｆは、式：−（Ｃ_kＦ_2kＯ）−（ｋは１〜６の範囲の整数である）で表わされる単位を含み、分岐を有しない直鎖状のパーフルオロポリアルキレンエーテル構造を有する二価の基であり、Ｒは炭素原子数１〜８の一価炭化水素基であり、Ｘは加水分解性基またはハロゲン原子であり、ｎおよびｎ'は、それぞれ独立に０〜２の範囲の整数であり、ｍおよびｍ'は、それぞれ独立に１〜５の整数であり、ａおよびｂは、それぞれ独立に２または３である）
成分（Ｂ）：下記一般式（II）で表されるシラン化合物
Ｒ'−Ｓｉ(ＯＲ'')₃および／またはＳｉ(ＯＲ'')₄ ・・・(II)
（一般式（II）式中、Ｒ'は有機基であり、Ｒ''はアルキル基である。）
成分（Ｃ）：下記一般式(III)で表される変性シリコーンオイル

（一般式(III) 式中、ｃは１以上の整数であり、Ｘ₁〜Ｘ₆は、それぞれ独立に有機基であり、Ｘ₁およびＸ₅ならびに／またはＸ₂およびＸ₄はメチル基を有する。） That is, the above object has been achieved by the following means.
[1] A phase change is measured by scanning while vibrating a probe of an atomic force microscope on the surface of the vapor deposition film of a spectacle lens having a vapor deposition film on a substrate, and the phase change is measured based on the measured phase change. A vapor deposition film evaluation method for evaluating the slipperiness of the vapor deposition film surface,
The vapor deposition film evaluation method, wherein the vapor deposition film is a water-repellent film located on the outermost surface of the spectacle lens .
[2] The deposited film evaluation method according to [1], wherein the scanning is performed by intermittently bringing a probe into contact with the surface of the deposited film.
[3] The deposited film evaluation method according to [1], wherein the scanning is performed with the surface of the deposited film and the probe in a non-contact state.
[4] The vapor deposition film to be evaluated is any one of [1] to [3], which is a vapor deposition film formed by vapor-depositing a vapor deposition material containing a fluorine-substituted alkyl group-containing organosilicon compound on a substrate. Evaluation method of deposited film.
[5] The deposited film to be evaluated is any one of [1] to [4], which is a deposited film formed by depositing a deposition material containing the following components (A) to (C) on a substrate. The vapor deposition film evaluation method of description.
Component (A): a fluorine-substituted alkyl group-containing organosilicon compound represented by the general formula (I)

(In the general formula (I), Rf includes a unit represented by the formula: — (C _k F _2k O) — (k is an integer in the range of 1 to 6), and is a straight chain having no branch. R is a monovalent hydrocarbon group having 1 to 8 carbon atoms, X is a hydrolyzable group or a halogen atom, and n and n ′ are each a divalent group having a perfluoropolyalkylene ether structure. Each independently represents an integer ranging from 0 to 2, m and m ′ each independently represent an integer from 1 to 5, and a and b each independently represent 2 or 3.
Component (B): Silane compound R′—Si (OR ″) ₃ and / or Si (OR ″) ₄ represented by the following general formula (II) (II)
(In the general formula (II), R ′ is an organic group and R ″ is an alkyl group.)
Component (C): Modified silicone oil represented by the following general formula (III)

(In the general formula (III), c is an integer of 1 or more, X _{1 to} X ₆ are each independently an organic group, and X ₁ and X ₅ and / or X ₂ and X ₄ are each a methyl group. Have)
[6] A step of producing a plurality of spectacle lenses having a deposited film by depositing a deposition material on a plurality of base materials;
For at least one of the plurality of spectacle lenses produced, the Smoothness of the deposited film surface to which the spectacle lens has a step of evaluating by the method according to any one of [1] to [3], the deposition here The film is a water-repellent film located on the outermost surface of the spectacle lens ,
Determining a spectacle lens to be shipped as a product based on the evaluation results;
Of eyeglass lenses including
[7] The method for manufacturing a spectacle lens according to [6], wherein the vapor deposition material is a vapor deposition material containing a fluorine-substituted alkyl group-containing organosilicon compound.
[8] The method for manufacturing a spectacle lens according to [6] or [7], wherein the vapor deposition material is a vapor deposition material including the following components (A) to (C).
Component (A): a fluorine-substituted alkyl group-containing organosilicon compound represented by the general formula (I)

(In the general formula (I), Rf includes a unit represented by the formula: — (C _k F _2k O) — (k is an integer in the range of 1 to 6), and is a straight chain having no branch. R is a monovalent hydrocarbon group having 1 to 8 carbon atoms, X is a hydrolyzable group or a halogen atom, and n and n ′ are each a divalent group having a perfluoropolyalkylene ether structure. Each independently represents an integer ranging from 0 to 2, m and m ′ each independently represent an integer from 1 to 5, and a and b each independently represent 2 or 3.
Component (B): Silane compound R′—Si (OR ″) ₃ and / or Si (OR ″) ₄ represented by the following general formula (II) (II)
(In the general formula (II), R ′ is an organic group and R ″ is an alkyl group.)
Component (C): Modified silicone oil represented by the following general formula (III)

(In the general formula (III), c is an integer of 1 or more, X _{1 to} X ₆ are each independently an organic group, and X ₁ and X ₅ and / or X ₂ and X ₄ are each a methyl group. Have)

  According to the present invention, it is possible to evaluate the slipperiness of the deposited film on the outermost surface of the optical member with high reliability. Further, by determining a product to be shipped based on the evaluation result, a high quality product can be provided. This is particularly effective in an optical member that requires a good feeling of slip such as a plastic lens for eyeglasses.

The present invention measures the phase change on the surface of the vapor deposition film of the optical member having the vapor deposition film on the substrate while oscillating the probe of the atomic force microscope, and based on the measured phase change. The present invention relates to a deposited film evaluation method for evaluating the deposited film.
Hereinafter, the deposited film evaluation method of the present invention will be described in detail.

  In the deposited film evaluation method of the present invention, the evaluation is performed using an atomic force microscope (AFM). The atomic force microscope is not limited as long as it can oscillate the probe and measure the phase change (the mode for performing this measurement is generally called “phase mode”), and a commonly used atomic force microscope can be used. .

Atomic force microscopes generally have a cantilever with a tip attached to the tip. When measuring the phase change, in the tapping mode or the non-contact mode, the surface of the evaluation object is scanned while vibrating the cantilever with a constant amplitude to detect the phase change of the cantilever vibration. If there is some physical property difference between a part on the surface and another part, the phase changes depending on the degree of the difference. The present inventors have newly found that this phase change correlates well with the surface property of the deposited film. In particular, a very good correlation was observed between the phase change and the slipperiness of the deposited film. That is, according to the vapor deposition film evaluation method of the present invention, surface properties such as slipperiness of the vapor deposition film based on the phase change measured by scanning the atomic force microscope probe while vibrating the surface of the vapor deposition film. Can be evaluated.

Below, the specific example of the evaluation method by an atomic force microscope is demonstrated based on FIG.
FIG. 1 is an explanatory diagram of a frequency distribution curve created based on a frequency distribution of phase differences obtained by measurement with an atomic force microscope. In FIG. 1, Pm is the mode value, Dm is the relative frequency at the mode value, Pmax is the maximum phase difference value, Pmin is the minimum phase difference value, Wr is the difference between Pmax and Pmin, and Wh is the half width.

  The phase difference frequency distribution curve is created, for example, by analysis software based on the phase difference frequency distribution obtained by scanning the surface while vibrating the probe in the phase mode of the atomic force microscope. The more parts that show a certain phase difference, the greater the relative frequency of that phase difference. The phase difference with the largest relative frequency is the phase difference mode value (Pm in FIG. 1). Therefore, the smaller the difference between the maximum phase difference value (Pmax in FIG. 1) and the minimum phase difference value (Pmin), the smaller the variation in surface physical properties. In the evaluation method of the present invention, for example, the difference between Pmax and Pmin (Pmax−Pmin) can be used as an index for evaluating the deposited film. The smaller the value is, the better the surface property is, and the evaluation can be performed based on the absolute value. However, in order to perform a highly reliable evaluation result, it is possible to set a pass / fail judgment criterion in advance. preferable. For example, a sensory evaluation of slip feeling and measurement of the above (Pmax-Pmin) are performed on some samples in advance, and if the value of the above (Pmax-Pmin) is greater than or equal to that, it is determined that the slip feeling is good. It is preferable to set. And if it evaluates based on the set quality criteria, it will become possible to evaluate a slip feeling without performing sensory evaluation. Further, as an evaluation index, for example, the half-value width (Wh in FIG. 1) of the frequency distribution curve of the phase difference, which is also a value indicating variation, can be used.

  The evaluation can also be performed based on a histogram showing a frequency distribution of phase differences. In this case as well, the difference (Pmax−Pmin) between Pmax and Pmin can be used as an index for evaluating the deposited film. The evaluation index may be based on the phase difference frequency distribution. For example, dispersion, standard deviation, and interquartile range are also used as an index for evaluating a deposited film, preferably as an index for evaluating slip feeling. Can do.

Next, a specific measurement method will be described.
As described above, a general atomic force microscope has a cantilever having a probe at the tip, and the phase change can be measured by scanning the surface of the measurement object by vibrating the cantilever. As the measurement mode, a mode generally called a tapping mode can be used. The measurement mode is divided into a contact mode in which the probe is intermittently brought into contact with the surface of the measurement object and a non-contact mode in which the probe is kept in a non-contact state depending on the presence or absence of contact with the surface. In either case, the phase change can be measured by scanning the surface of the measurement object while gently vibrating the cantilever up and down (tapping). Both are preferable in that they do not damage the evaluated optical member.

（一般式（Ｉ）式中、Ｒｆは、式：−（Ｃ_kＦ_2kＯ）−（ｋは１〜６の範囲の整数である）で表わされる単位を含み、分岐を有しない直鎖状のパーフルオロポリアルキレンエーテル構造を有する二価の基であり、Ｒは炭素原子数１〜８の一価炭化水素基であり、Ｘは加水分解性基またはハロゲン原子であり、ｎおよびｎ'は、それぞれ独立に０〜２の範囲の整数であり、ｍおよびｍ'は、それぞれ独立に１〜５の整数であり、ａおよびｂは、それぞれ独立に２または３である）
成分（Ｂ）：下記一般式（II）で表されるシラン化合物
Ｒ'−Ｓｉ(ＯＲ'')₃および／またはＳｉ(ＯＲ'')₄ ・・・(II)
（一般式（II）式中、Ｒ'は有機基であり、Ｒ''はアルキル基である。）
成分（Ｃ）：下記一般式(III)で表される変性シリコーンオイル

（一般式(III) 式中、ｃは１以上の整数であり、Ｘ₁〜Ｘ₆は、それぞれ独立に有機基であり、Ｘ₁およびＸ₅ならびに／またはＸ₂およびＸ₄はメチル基を有する。）
以下に、成分（Ａ）〜（Ｃ）の詳細を説明する。 Below, the vapor deposition film suitable for application of the evaluation method of the present invention will be described.
The evaluation method of the present invention can be applied to a deposited film formed on a substrate in order to impart properties such as water repellency and antifouling properties to the substrate surface. The vapor deposition film to be evaluated is preferably a thin film having high water repellency generally called a water repellent film. Specifically, the evaluation method of the present invention is preferably applied to a deposited film formed by depositing a deposition material containing a fluorine-substituted alkyl group-containing organosilicon compound on a substrate. As said vapor deposition material, the vapor deposition material containing the following component (A)-(C) is preferable.
Component (A): a fluorine-substituted alkyl group-containing organosilicon compound represented by the general formula (I)

(In the general formula (I), Rf includes a unit represented by the formula: — (C _k F _2k O) — (k is an integer in the range of 1 to 6), and is a straight chain having no branch. R is a monovalent hydrocarbon group having 1 to 8 carbon atoms, X is a hydrolyzable group or a halogen atom, and n and n ′ are each a divalent group having a perfluoropolyalkylene ether structure. Each independently represents an integer ranging from 0 to 2, m and m ′ each independently represent an integer from 1 to 5, and a and b each independently represent 2 or 3.
Component (B): Silane compound represented by the following general formula (II) R′—Si (OR ″) ₃ and / or Si (OR ″) ₄ ... (II)
(In the general formula (II), R ′ is an organic group and R ″ is an alkyl group.)
Component (C): Modified silicone oil represented by the following general formula (III)

(In the general formula (III), c is an integer of 1 or more, X _{1 to} X ₆ are each independently an organic group, and X ₁ and X ₅ and / or X ₂ and X ₄ are each a methyl group. Have)
Details of the components (A) to (C) will be described below.

Ingredient (A)
Component (A) is a fluorine-substituted alkyl group-containing organosilicon compound represented by the following general formula (I).

In the general formula (I), Rf is represented by the formula: — (C _k F _2k O) — (wherein k is an integer in the range of 1 to 6, preferably 1 to 4, and (C _k The sequence of F _2k O) is preferably random. It is a divalent group having a linear perfluoropolyalkylene ether structure that includes a unit represented by In addition, when n and n 'in general formula (I) are both 0, it is preferable that the terminal of Rf group couple | bonded with the oxygen atom (O) in general formula (I) is not an oxygen atom. Examples of the Rf group include those represented by the following general formula. However, the present invention is not limited to the following examples.

-CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) _l CF ₂ CF _2-
(In the formula, l is an integer of 1 or more, preferably 1 to 50, more preferably 10 to 40.)
_{-CF 2 (OC 2 F 4)} p - (OCF 2) q -
(Wherein p and q are each an integer of 1 or more, preferably 1 to 50, more preferably 10 to 40, and the sum of p + q is 10 to 100, preferably 20 to 90, (It is preferably an integer in the range of 40 to 80, and the sequence of the repeating units (OC ₂ F ₄ ) and (OCF ₂ ) in the formula is random.)

In general formula (I), X is a hydrolyzable group or a halogen atom. Examples of the hydrolyzable group represented by X include an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; an alkoxyalkoxy group such as a methoxymethoxy group, a methoxyethoxy group, and an ethoxyethoxy group; an allyloxy group, Alkenyloxy groups such as isopropenoxy; acyloxy groups such as acetoxy group, propionyloxy group, butylcarbonyloxy group, benzoyloxy group; dimethyl ketoxime group, methyl ethyl ketoxime group, diethyl ketoxime group, cyclopentanoxime group, cyclohexanoxime A ketoxime group such as a group; N-methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N, N-dimethylamino group, N, N-diethylamino group, N-cyclohexylamino group Amino groups such as N; Chill acetamide group, N- ethyl acetamide group, an amido group such as N- methylbenzamide group; N, N- dimethylamino group, N, can be mentioned an amino group, such as N- diethylamino group.
Moreover, as a halogen atom represented by X, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.
Of these, methoxy, ethoxy, isopropenoxy and chlorine atoms are preferred.

  In the general formula (I), R is a monovalent hydrocarbon group having 1 to 8 carbon atoms, and when a plurality of Rs are present, the Rs may be the same or different. Specific examples of R include, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; Aryl groups such as benzyl group and phenethyl group; alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group and hexenyl group. Among these, a monovalent hydrocarbon group having 1 to 3 carbon atoms is preferable, and a methyl group is particularly preferable.

  In general formula (I), n and n ′ are each independently an integer in the range of 0 to 2, preferably 1. n and n ′ may be the same or different from each other. M and m ′ are each independently an integer of 1 to 5, and is preferably 3. m and m ′ may be the same as or different from each other.

In the general formula (I), a and b are each independently 2 or 3, and preferably 3 from the viewpoints of hydrolysis and condensation reactivity and coating adhesion.

  The molecular weight of the fluorine-substituted alkyl group-containing organosilicon compound (perfluoropolyalkylene ether-modified silane) represented by the general formula (I) is not particularly limited, but in terms of stability, ease of handling, etc., the number average molecular weight 500 to 20,000, preferably 1000 to 10,000 are suitable.

  Specific examples of the perfluoropolyalkylene ether-modified silane represented by the general formula (I) include those represented by the following structural formula. However, the present invention is not limited to the following examples.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ OCH ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₁ CF ₂ CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(CH ₃ O) ₂ CH ₃ SiCH ₂ CH ₂ CH ₂ OCH ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₁ CF ₂ CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ OCH ₂ CF ₂ (OC ₂ F ₄ ) _p (OCF ₂ ) _q OCF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(CH ₃ O) ₂ CH ₃ SiCH ₂ CH ₂ CH ₂ OCH ₂ CF ₂ (OC ₂ F ₄ ) _p (OCF ₂ ) _q OCF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CF ₂ (OC ₂ F ₄ ) _p (OCF ₂ ) _q OCF ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) _{3
(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 OCH 2 CF 2 (OC 2 F 4) p (OCF 2) q OCF 2 CH 2 OCH 2 CH 2 CH 2 Si (OC 2 H 5) 3

  The compound represented by general formula (I) may be used individually by 1 type, and can also be used in combination of 2 or more type. In some cases, the perfluoropolyalkylene ether-modified silane and a partially hydrolyzed condensate of the modified silane can be used in combination.

  The perfluoropolyalkylene ether-modified silane represented by the general formula (I) is preferably diluted with a solvent. Examples of the solvent that can be used include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-di (trifluoromethyl) benzene, trifluoro Fluorine-modified ether solvents (methyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbons Examples thereof include petroleum solvents (petroleum benzine, mineral spirits, toluene, xylene, etc.) and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). These may be used alone or in combination of two or more. Among these, a fluorine-modified solvent is preferable from the viewpoint of the solubility and wettability of the modified silane, and in particular, 1,3-di (trifluoromethyl) benzene, perfluoro (2-butyltetrahydrofuran), and Perfluorotributylamine is preferred.

Ingredient (B)
Component (B) is a silane compound represented by the following general formula (II).

In the general formula (II), R ′ is an organic group having 1 to 50 carbon atoms (preferably 1 to 10).
Alkyl groups (methyl group, ethyl group, propyl group, etc.), epoxyethyl group, glycidyl group, amino group and the like. These may be substituted.

  In the general formula (II), R ″ is an alkyl group, preferably an alkyl group having 1 to 48 carbon atoms (methyl group, ethyl group, propyl group, etc.), more preferably a methyl group or an ethyl group.

  Specific examples of the silane compound represented by the general formula (II) include the following compounds. However, the present invention is not limited to the following specific examples.

(C ₂ H ₅ O) ₃ SiC ₃ H ₆ NH ₂ , (CH ₃ O) ₃ SiC ₃ H ₆ NH ₂ , (C ₂ H ₅ O) ₄ Si, (C ₂ H ₅ O) ₃ Si—O— Si (OC ₂ H ₅ ) ₃ .

The silane compound represented by the general formula (II) may be used alone or in combination of two or more.
In the compound of the general formula (II), R′—Si (OR ″) ₃ is preferably used alone or more than Si (OR ″) ₄ . In this case, the reaction product with the component (C) has a more complicated three-dimensional structure, and durability and wear resistance can be improved.

Ingredient (C)
Component (C) is a modified silicone oil represented by the following general formula (III).

  In general formula (III), c is an integer greater than or equal to 1, It is preferable that it is 1-60, More preferably, it is 1-10.

In the general formula (III), X _{1 to} X ₆ are each independently an organic group, and specific examples thereof include an alkyl group having 1 to 20 carbon atoms (methyl group, ethyl group, propyl group, etc.), epoxyethyl, etc. Group, glycidyl group, amino group, carboxyl group and the like. These may be substituted. In the general formula (III), X ₁ and X ₅ and / or X ₂ and X ₄ have a methyl group.

The compound represented by general formula (III) may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of the modified silicone oil represented by the general formula (III) include, for example, those represented by the following structural formula. However, the present invention is not limited to the following examples.

[（ａ）および（ｂ）の有機基におけるＲ₁は、アルキレン基（メチレン基、エチレン基、プロピレン基等）等であり、ｒは１〜２０、ｓは１〜２０、ｔは１〜４０の整数である。]

[R ₁ in the organic groups of (a) and (b) is an alkylene group (methylene group, ethylene group, propylene group, etc.), r is 1 to 20, s is 1 to 20, and t is 1 to 40 Is an integer. ]

When component (A) is mixed with component (B) and component (C) to form a vapor deposition material, the durability and wear resistance of the deposited thin film are improved. This is because a compound having a complicated steric structure can be formed by bonding the modified silicone oil of the general formula (III) with the silane compound of the general formula (II) which is a silane coupling agent. The fluorine-substituted alkyl group-containing organosilicon compound of the general formula (I) is considered to be protected by the reaction product of the silane compound of the general formula (II) and the modified silicone oil of the general formula (III). . More preferably, the silane compound of the general formula (II) and the modified silicone oil of the general formula (III) are mixed and reacted in advance, and the fluorine-substituted alkyl group-containing organosilicon compound of the general formula (I) is mixed with the reaction product. . In this case, the fluorine-substituted alkyl group-containing organosilicon compound of the general formula (I) is more preferable because it does not hinder the reaction between the silane compound of the general formula (II) and the modified silicone oil of the general formula (III). . More specifically, the vapor deposition material of the present invention in this case is prepared by mixing the silane compound of the general formula (II) and the modified silicone oil of the general formula (III), for example, mixing and stirring for 1 to 168 hours. And react to form a skeletal material. Thereafter, it is obtained by dispersing the organosilicon compound of the general formula (I).
Examples of the structure of the skeleton substance reacted with the silane compound of the general formula (II) and the modified silicone oil of the general formula (III) include a mixture of a secondary amine body and a tertiary amine body. Such a structure is mentioned.

  The ratio of the secondary amine body and the tertiary amine body is substantially the same, the left end -Si- is, for example, an ethoxy group, and the right end is, for example, a dimethylsiloxane structure.

  The vapor deposition film to be evaluated in the evaluation method of the present invention is, for example, a vapor deposition film formed by heating and solidifying the vapor deposition material and then depositing the solidified vapor deposition material on a substrate by heating with a heating means. Can be. In addition, the vapor deposition material containing the above-mentioned components (A), (B), and (C) tends to increase in viscosity because the component (B) and the component (C) react to increase the molecular weight. For this reason, when a porous material is impregnated with a vapor deposition material, the vapor deposition material may not easily soak into the porous material. In addition to impregnating the porous material with the vapor deposition material, in order to obtain a uniform vapor deposition film, the liquid vapor deposition material is solidified (so that it does not sag from the porous substance or the container and does not adhere to the surface even if touched. It is preferable that the vapor deposition material is hardened even when heated. This is considered to be due to the fact that the solvent used for diluting the component (A) is less likely to volatilize even when heated.

The vapor deposition material is preferably diluted with a fluorine-based solvent that has a low kinematic viscosity and high volatility and does not substantially react with other components. By doing so, the viscosity of the reaction product of the component (B) and the component (C) can be lowered, so that the injection property into the porous material can be improved, and the vapor deposition material can be easily solidified. It is thought that the fluorine-based solvent may also serve to reduce the solvent added to the component (A) when it volatilizes. As the fluorinated solvent, a hydrofluoroether represented by the following general formula (IV) is preferably blended.
Formula (IV)
CF _3- (CF ₂ ) _d -OR '''
In the general formula (IV), d is an integer in the range of 1 to 50, and R ′ ″ is a methyl group or an ethyl group. d is preferably an integer in the range of 1 to 20, more preferably 1 to 10.
Specific examples of the hydrofluoroether represented by the general formula (IV) include, for example, C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , C ₆ F ₁₃ OCH ₃ , C ₆ F ₁₃ OC ₂ H ₅ etc. are mentioned. However, the present invention is not limited to these examples.
The compound represented by general formula (IV) may be used individually by 1 type, and can also be used in combination of 2 or more type.
In addition to the hydrofluoroether represented by the general formula (IV), other solvents, silicon-free perfluoropolyether, and the like may be added to the vapor deposition material.
In particular, the hydrofluoroether of the general formula (IV) is preferable because it does not react with other components and has high volatility, so that it evaporates by heating and the components (A) to (C) are solidified.

  The compounding ratio of each component in the vapor deposition material is, for example, a component (A) having a concentration of 20% by mass of 30 to 95% by mass (preferably 50 to 85% by mass) and a component (B) of 1 to 50% by mass (preferably 10%). To 40% by mass), component (C) 1 to 50% by mass (preferably 10 to 40% by mass), hydrofluoroether represented by formula (IV) 0 to 50% by mass (preferably 5 to 40% by mass) ). If it is the above range, a sufficient effect will be acquired.

The vapor deposition material is mixed with a fluorine-based solvent added in a solution or as necessary, for example, a hydrofluoroether represented by the general formula (IV), another solvent or a silicon-free perfluoropolyether. It can be used in the form of a solution and deposited on a substrate. These solutions may be put in a container and heated as they are, but it is more preferable to impregnate a porous material from the viewpoint that many uniform vapor deposition films can be obtained. As the porous material, it is preferable to use a sintered filter obtained by sintering a metal powder having high thermal conductivity such as copper or stainless steel. The porous material has a mesh of 40 to 200 microns, preferably 80 to 120 microns, from the viewpoint of obtaining an appropriate deposition rate.
In addition, it is preferable to use in the form which heated and solidified, after adding a fluorine-type solvent, even when it is the case where a solution is put into a container or a porous material is impregnated. What is necessary is just to set the temperature at the time of solidifying within the temperature which a vapor deposition material does not decompose | disassemble, Preferably it is 50-100 degreeC, More preferably, it is 70-90 degreeC. The heating time is preferably 60 minutes or more, more preferably 60 to 180 minutes. As the heating means, a dry oven or the like can be used.

The vapor deposition film to be evaluated is a vapor deposition film formed by vapor deposition of a vapor deposition material on a substrate under reduced pressure by heat vapor deposition (using a halogen heater, resistance heating, an electron gun, etc.). it can. When heated and evaporated using an electron gun, a thin film with high accuracy can be formed. The degree of vacuum in the vacuum vapor deposition apparatus in that case is not particularly limited, but is preferably 1.33 × 10 ⁻¹ Pa to 1.33 × 10 ⁻⁶ Pa from the viewpoint of obtaining a homogeneous vapor deposition film. (10 ⁻³ to 10 ⁻⁸ Torr), particularly preferably 6.66 × 10 ⁻¹ Pa to 8.00 × 10 ⁻⁴ Pa (5.0 × 10 ^{−3 to} 6.0 × 10 ⁻⁶ Torr) It is.
As the substrate, a plastic lens or a plastic lens having an antireflection film can be used. Details thereof will be described later.

  Although the specific temperature at the time of heating vapor deposition material changes with the kind of vapor deposition material and the vacuum conditions to vapor-deposit, it is preferable to carry out in the range which does not exceed decomposition temperature from the vapor deposition start temperature of vapor deposition material in desired vacuum degree. Here, the vapor deposition start temperature refers to the temperature when the vapor pressure of the solution containing the vapor deposition material becomes equal to the degree of vacuum, and the decomposition temperature of the vapor deposition material refers to 50 mass of the vapor deposition material during one minute. % Is the temperature at which the compound decomposes (in the presence of no substance reactive with the compound under a nitrogen atmosphere).

  Although the deposition rate varies depending on the heating method, in the case of using an electron gun, it is preferable that the time from the start of heating the organosilicon compound to the completion of deposition is within 120 seconds, on condition that the temperature range is maintained, Furthermore, it is preferable to set it within 50 seconds, within 40 seconds, and within 30 seconds. Providing an optical member having a vapor deposition film excellent in durability by completing vapor deposition in the above heating temperature range in a short time, that is, giving high energy to the organosilicon compound in a short time. it can. Further, even when two-component water repellents having slightly different deposition start temperatures are used, by selecting the deposition temperature within the range from the evaporation start temperature of the raw material having a high evaporation start temperature to the decomposition temperature of the raw material having a low decomposition temperature, Vapor deposition can be performed simultaneously, and a uniform film can be obtained.

As a method for achieving the vapor deposition rate, a method of irradiating the organosilicon compound with an electron beam is preferably used, and a method of generating an electron beam uses an electron gun conventionally used in a vapor deposition apparatus. Can be used. If an electron gun is used, the entire organosilicon compound can be irradiated with uniform energy, and a uniform water repellent film can be easily applied. The power of the electron gun varies depending on the substance used, the vapor deposition apparatus, the degree of vacuum, and the irradiation area, but preferable conditions are an acceleration voltage of about 6 kV and an applied current of about 5 to 40 mA.
The vapor deposition film has a refractive index of 1.30 to 1.47 (preferably 1.40 to 1.45) and a film thickness of 1 to 20 nm (preferably 3 to 15 nm), for example. If the film thickness is 3 nm or more, sufficient durability and wear resistance can be obtained, and if it is 15 nm or less, there is no possibility that the transmittance is lowered due to cloudiness or the like.

Furthermore, the present invention provides
A step of producing a plurality of optical members having a deposited film by depositing a deposition material on a plurality of substrates (hereinafter referred to as “step I”);
For at least one of the produced optical members, a step of evaluating the vapor deposition film of the optical member by the vapor deposition film evaluation method of the present invention (hereinafter referred to as “step II”),
A process of determining an optical member to be shipped as a product based on the evaluation result (hereinafter referred to as “process III”);
The manufacturing method of the optical member containing this.

In the present invention, the optical member is a spectacle lens . As the substrate, a plastic substrate, specifically, a methyl methacrylate homopolymer, a copolymer having methyl methacrylate and one or more other monomers as monomer components, diethylene glycol bisallyl carbonate homopolymer, Copolymer comprising diethylene glycol bisallyl carbonate and one or more other monomers as monomer components, sulfur-containing copolymer, halogen-containing copolymer, polycarbonate, polystyrene, polyvinyl chloride, unsaturated polyester, polyethylene terephthalate, polyurethane And plastic optical substrates. Alternatively, an inorganic glass optical substrate may be used. The substrate may have an antireflection film or a hard coat layer on the substrate. Examples of the hard coat layer include a cured film containing an organosilicon compound, an acrylic compound, and the like.

The antireflection film is, for example, ZrO ₂ , SiO ₂ , TiO ₂ , Ta ₂ O ₅ , Y ₂ O ₃ , MgF ₂ , Al ₂ O provided to reduce reflection on the surface of an optical substrate such as a lens. A single layer or multilayer film formed from ₃ or the like (however, the outermost layer preferably has a SiO ₂ film) or a colored film such as CrO ₂ (however, the outermost layer preferably has a SiO ₂ film) be able to. These films can be vapor deposited films formed by vapor deposition, preferably by vacuum vapor deposition. As the antireflection film, a film having a layer mainly composed of silicon dioxide as the outermost layer is preferable. Here, silicon dioxide as a main component means a layer substantially composed of silicon dioxide or a hybrid layer composed of silicon dioxide, aluminum oxide and an organic compound.

  Details of the vapor deposition material, vapor deposition treatment, etc. used in step I are as described above. In the vapor deposition apparatus, for example, the vapor deposition process can be simultaneously performed on about 100 substrates. In the present invention, at least one of a plurality of optical members in the same lot, such as a plurality of optical members that have been subjected to vapor deposition in the same apparatus, is subjected to Step II. The number of optical members applied to the step II may be at least one, and in order to provide a high-quality product with high reliability, it is preferable to add two or more optical members to the step II.

  In Step II, the optical member selected as the evaluation sample in Step I is evaluated by the evaluation method of the present invention. The details are as described above.

In step III, an optical member to be shipped as a product is determined based on the evaluation result obtained in step II. Determination of the optical member to ship can be performed with the following method, for example.
(1) If the evaluation result of the sample evaluated in step II satisfies the pass / fail judgment criteria, the optical member in the same lot as the sample is judged to satisfy the pass / fail judgment criteria, and the optical in the same lot is determined. The parts are shipped as products. In this case, when the evaluation is performed in the non-contact mode, the evaluation has almost no influence on the surface property of the sample, and thus the evaluated sample can be shipped as a product. Even in the contact mode, the contact between the sample and the probe is negligible, and the influence on the sample surface property due to the evaluation is negligibly small. Therefore, in this case, the evaluated sample may be shipped as a product.
(2) Each manufactured optical member is subjected to Step II, and if the evaluation result in Step II satisfies the pass / fail criteria, the optical member is shipped as a product. By evaluating all the products before shipment, it becomes possible to provide high-quality products with higher reliability.

  In addition, for the optical member determined to be defective by the evaluation method of the present invention, the deposited film formed on the optical member is removed to form a new deposited film, or the deposited film is further formed on the deposited film. Can also be given. As a result, the number of optical members discarded as defective products can be reduced, which is preferable in terms of cost and environmental considerations.

  Below, the present invention will be further explained based on examples. However, this invention is not limited to the aspect shown in the Example.

1. Preparation of vapor deposition material (water repellent treatment agent) A vapor deposition material (water repellent treatment agent) was prepared by the following method. The container used was a 30 cc glass screw bottle from ASONE, and the stirring speed of the stirrer was set to 500 rpm.

(Step 1) Production of reaction solution of silane compound and silicone oil As a silane compound of general formula (II), KBE903 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd.,
(C ₂ H ₅ O) ₃ SiC ₃ H ₆ NH ₂ , molecular weight 221.4, refractive index (25 ° C.) 1.420) 10 g and the structure of the above oil (a) as a silicone oil of the general formula (III) KF105 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd., kinematic viscosity 15 mm ² / s (25 ° C.), refractive index (25 ° C.)
1042 of 1.442, functional group equivalent 490 g / mol) was mixed and stirred for 24 hours.
The silane compound has an amino group, and the silicone oil has an epoxyethyl group. Thereby, the amino group and the glycidyl group reacted to produce a dimethylsiloxane-containing mixture having secondary and tertiary amines. This reaction requires about 24 hours, and H, C, and NMR analyzes confirmed the formation of a compound having a molecular weight of about 200 to 1000.
(Step 2) Mixing of a fluorine-substituted alkyl group-containing organosilicon compound (water repellent) and a reaction solution of a silane compound and a silicone oil compound Next, as the fluorine-substituted alkyl group-containing organosilicon compound of the general formula (I), The following structure: (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ OCH ₂ CF ₂ (OC ₂ F ₄ ) _p (OCF ₂ ) _q OCF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (formula In the middle, p = 22, q = 22, and the repeating unit (OC ₂ F ₄ ) and the arrangement of (OCF ₂ ) are random. And stirred for 24 hours.
(Step 3) Mixing process of hydrofluoroether for improving injectability and drying property To 18.5 g of the mixed solution prepared in step 2, HFE7200 as a hydrofluoroether of general formula (IV) (trade name: Sumitomo 3M ( Co., Ltd., C ₄ F ₉ OC ₂ H ₅ , viscosity 5.7 × 10 ⁻⁴ Pa · s, kinematic viscosity 0.40 mm ² / s, refractive index (25 ° C. 1.28) 3 g is charged, 24 hours Stirring was performed.
The vapor-deposited film obtained from the obtained vapor-deposited material (water repellent treatment agent) comprises a cured product having a three-dimensional structure generated by hydrolysis and condensation reaction of X in general formula (I), and general formulas (II) and (III). It is comprised from the hardened | cured material of the three-dimensional structure produced by hydrolysis and condensation reaction of the mixture of these compounds.

2. Formation of water repellent film
Sample 1
A stainless sintered filter (pore diameter: 80-100 μm, diameter: 18 mmΦ, thickness: 3 mm) impregnated with 0.35 ml of the above water repellent treatment agent is heated in a dry oven at 80 ° C. for 2 hours, and then placed in a vacuum deposition apparatus. I set it. The entire sintered filter was heated using an electron gun (EB) under the following conditions to form a water repellent film on the plastic lens with the antireflection film. The surface morphology of the plastic lens deposited with the water-repellent film was observed with an atomic force microscope. The luminous reflectance of this lens was 0.4%.
(1) Degree of vacuum: 3.1 × 10 ⁻⁴ to 8.0 × 10 ⁻⁴ Pa (2.3 × 10 ^{−6 to} 6.0 × 10 ⁻⁶ Torr)
(2) Electron gun condition accelerating voltage: 6 kV, applied voltage: 11 mA, irradiation area: 3.5 × 3.5 cm ² , irradiation time: 120 seconds

Samples 2 and 3
A water repellent film was formed on a plastic lens with an antireflection film by the same method as Sample 1 except that the amount of the water repellent agent was changed as shown in Table 2. The surface morphology of the plastic lens deposited with the water-repellent film was observed with an atomic force microscope. The luminous reflectance of this lens was 0.4%.

3. Evaluation Method The following evaluation was performed for samples 1 to 3 and the plastic lens with an antireflection film (sample 4) before forming the water-repellent film.
(1) Static contact angle for water Using a contact angle meter (product of Kyowa Interface Science Co., Ltd., CA-D type), a water drop with a diameter of 2 mm is made on the needle tip at 25 ° C., and this is the top of the convex surface of the lens To make a droplet. The angle between the droplet and the surface generated at this time was measured to obtain a static contact angle. The static contact angle θ can be obtained by the following equation, where r is the radius of the water droplet (the radius of the portion where the water droplet is in contact with the lens surface) and h is the height of the water droplet.
θ = 2 × tan ⁻¹ (h / r)
The measurement of the static contact angle was performed within 10 seconds after the water droplet touched the lens in order to minimize the measurement error due to water evaporation.
(2) Sensory evaluation of slipperiness The sensation of rubbing the vapor deposition surface of the plastic cleans on which the water repellent film was deposited with Sylbon paper was evaluated in the following four stages.
◎: Better than ○
○: Better than △
Δ: better than ×
X: No slipperiness (3) Evaluation based on frequency distribution of phase difference by atomic force microscope An atomic force microscope (D3000, manufactured by DI) was used, and the phase difference was measured under the following conditions.
Measurement conditions Pretreatment: None Cantilever: Si single crystal Measurement mode: Tapping mode Observation area: 10 μm ²
Number of data: 256 x 256
The difference (Pmax−Pmin) between the maximum phase difference value Pmax and the minimum phase difference value Pmin of the obtained phase difference frequency distribution curve was obtained.
(4) Measurement of dynamic friction coefficient Using a continuous weight type surface property measuring machine TYPE: 22H manufactured by Shinto Kagaku Co., Ltd., the average dynamic friction coefficient at a moving distance of 20 mm was measured three times, and the average value was calculated.
(5) Durability Evaluation Using the apparatus shown in FIG. 2, the surface of a plastic lens having a water repellent film was rubbed back and forth 3600 times with a lens cleaning cloth (trade name: HOYA Clearcloth) under a load of 500 g (25 ° C. The relative contact angle with respect to water was measured by the method described in (1).
(6) Appearance It was visually examined whether there was any color unevenness or interference color change in the interference color, and it was evaluated whether the appearance could be used as a spectacle lens.
The above evaluation results are shown in Table 2.

As shown in Table 2, Samples 1 to 3 had different slip feelings although the same results were obtained in any evaluation of appearance, contact angle, durability, and dynamic friction coefficient. On the other hand, the smaller the value of Pmax-Pmin, the better the slip feeling. From the above results, it was shown that there is a good correlation between the phase change measured by the atomic force microscope and the slip feeling.
Evaluation criteria can be created based on the above evaluation results. In the above example, for example, a reference value may be set between the (Pmax-Pmin) value of the sample 1 and the (Pmax-Pmin) value of the sample 2, or the (Pmax-Pmin) value of the sample 2 And a reference value may be set between the (Pmax−Pmin) value of the sample 3. Specifically, for example, the value of (Pmax-Pmin) is set to 0.5 between the value of (Pmax-Pmin) of sample 1 and the value of (Pmax-Pmin) of sample 2 (that is, 0.5). If it is determined as follows, it is possible to determine that only the sample 1 is a non-defective product, and it is possible to mechanically evaluate the slip feeling that has been difficult until now.

  The evaluation method of the present invention is suitable as a method for evaluating the slipperiness of the water-repellent film.

It is explanatory drawing of the frequency distribution curve of the phase difference obtained by the measurement by an atomic force microscope. It is the schematic which shows the durability test apparatus used in the Example.

Explanation of symbols

1: Lens 2: Lens cleaning cloth 3: Hexahedral plate

Claims (8)

A phase change is measured by scanning the surface of the spectacle lens having a vapor deposition film on a substrate while vibrating a probe of an atomic force microscope, and the surface of the vapor deposition film is measured based on the measured phase change. It is a deposited film evaluation method for evaluating the slipperiness of
The vapor deposition film evaluation method, wherein the vapor deposition film is a water-repellent film located on the outermost surface of the spectacle lens . The deposited film evaluation method according to claim 1, wherein the scanning is performed by intermittently bringing a probe into contact with the surface of the deposited film. The deposited film evaluation method according to claim 1, wherein the scanning is performed with the surface of the deposited film and the probe in a non-contact state. The vapor deposition film according to any one of claims 1 to 3, wherein the vapor deposition film to be evaluated is a vapor deposition film formed by depositing a vapor deposition material containing a fluorine-substituted alkyl group-containing organosilicon compound on a substrate. Evaluation method. The vapor deposition film evaluated is a vapor deposition film formed by vapor-depositing the vapor deposition material containing the following component (A)-(C) on a base material, The vapor deposition of any one of Claims 1-4 Membrane evaluation method.
Component (A): a fluorine-substituted alkyl group-containing organosilicon compound represented by the general formula (I)

(In the general formula (I), Rf includes a unit represented by the formula: — (C _k F _2k O) — (k is an integer in the range of 1 to 6), and is a straight chain having no branch. R is a monovalent hydrocarbon group having 1 to 8 carbon atoms, X is a hydrolyzable group or a halogen atom, and n and n ′ are each a divalent group having a perfluoropolyalkylene ether structure. Each independently represents an integer ranging from 0 to 2, m and m ′ each independently represent an integer from 1 to 5, and a and b each independently represent 2 or 3.
Component (B): Silane compound R′—Si (OR ″) ₃ and / or Si (OR ″) ₄ represented by the following general formula (II) (II)
(In the general formula (II), R ′ is an organic group and R ″ is an alkyl group.)
Component (C): Modified silicone oil represented by the following general formula (III)

(In the general formula (III), c is an integer of 1 or more, X _{1 to} X ₆ are each independently an organic group, and X ₁ and X ₅ and / or X ₂ and X ₄ are each a methyl group. Have) A step of producing a plurality of spectacle lenses having a vapor deposition film by vapor-depositing a vapor deposition material on a plurality of substrates;
For at least one of a plurality of spectacle lenses to be manufactured, the step of slipping feeling of the deposited film surface to which the spectacle lens has to evaluate the method according to any one of claims 1 to 3, the deposition here The film is a water-repellent film located on the outermost surface of the spectacle lens ,
Determining a spectacle lens to be shipped as a product based on the evaluation results;
Of eyeglass lenses including The method for manufacturing a spectacle lens according to claim 6, wherein the vapor deposition material is a vapor deposition material containing a fluorine-substituted alkyl group-containing organosilicon compound. The method for manufacturing a spectacle lens according to claim 6 or 7, wherein the vapor deposition material is a vapor deposition material containing the following components (A) to (C).
Component (A): a fluorine-substituted alkyl group-containing organosilicon compound represented by the general formula (I)

(In the general formula (I), Rf includes a unit represented by the formula: — (C _k F _2k O) — (k is an integer in the range of 1 to 6), and is a straight chain having no branch. R is a monovalent hydrocarbon group having 1 to 8 carbon atoms, X is a hydrolyzable group or a halogen atom, and n and n ′ are each a divalent group having a perfluoropolyalkylene ether structure. Each independently represents an integer ranging from 0 to 2, m and m ′ each independently represent an integer from 1 to 5, and a and b each independently represent 2 or 3.
Component (B): Silane compound R′—Si (OR ″) ₃ and / or Si (OR ″) ₄ represented by the following general formula (II) (II)
(In the general formula (II), R ′ is an organic group and R ″ is an alkyl group.)
Component (C): Modified silicone oil represented by the following general formula (III)

(In the general formula (III), c is an integer of 1 or more, X _{1 to} X ₆ are each independently an organic group, and X ₁ and X ₅ and / or X ₂ and X ₄ are each a methyl group. Have)

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