JP6723260B2 - Eyeglass lens - Google Patents

Description

The present invention relates to a spectacle lens.

Conventionally, from the viewpoint of preventing scratches on the surface, a self-repairing resin film has been provided on the surface of various members in various fields such as touch panel screens and casings of mobile phones and personal computers, eyeglass lenses and the like. (For example, patent document 1).

Patent No. 4724503

The present disclosure includes a lens base material and a resin film disposed on the lens base material, and the resin film includes a polyol component (A) and a polyisocyanate component (B), and the polyol component (A). A polyrotaxane having two or more hydroxyl groups is contained therein, and a film formed using a composition in which the number of hydroxyl groups of the polyrotaxane is 10 to 70% of the total number of hydroxyl groups of the polyol component (A) is included. Regarding spectacle lenses.

It is a schematic sectional drawing which shows the structure of 1st Embodiment of a spectacle lens. It is a schematic sectional drawing which shows the structure of 2nd Embodiment of a spectacle lens.

In recent years, in a spectacle lens in which a resin film is provided on a lens base material, not only the above-mentioned self-repairing property is further improved but also other performances are strongly demanded. For example, since the wiping operation is frequently performed on the spectacle lens, it is required to further improve the adhesion between the lens base material and the resin film.
The resin film described in Patent Document 1 cannot satisfy the above characteristics, and further improvement has been demanded.
Therefore, in view of the above situation, the present embodiment provides a spectacle lens having a resin film having excellent self-repairing property and having excellent adhesion between the lens base material and the resin film.

Below, the suitable aspect of a spectacle lens is explained in full detail.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In the present specification, the term “(meth)acryloyl group” is used to mean either one or both of an acryloyl group and a methacryloyl (methacryloyl) group.

In the present specification, the self-healing property means a property of restoring a strain (scratch) formed by stress on the surface of the resin film when the stress is unloaded, and the scratch resistance is a surface when the surface of the resin film is slid. Means the degree of haze.
In addition, in the present specification, having a self-healing property, a brass brush (manufactured by As One Co., Ltd., standard type 4 line B-3014) is used to apply a resin film at a speed of 60 mm/sec while applying a load of 200 g. When the presence of scratches immediately after rubbing 10 times is visually confirmed, it is intended that the scratches are recovered within 1 minute after being scratched in an environment of 20 to 25° C.

<First Embodiment>
FIG. 1 is a schematic sectional view of a first embodiment of a spectacle lens.
The spectacle lens 10 shown in FIG. 1 includes a lens base material 12 and a resin film 14 disposed on the lens base material 12. As described later in detail, the surface 14a of the resin film 14 (the surface on the side opposite to the lens substrate 12 side) exhibits a predetermined contact angle of water, and contacts when a predetermined rubbing treatment is performed. The reduction width of the corner is small.
In addition, in FIG. 1, the lens base material 12 and the resin film 14 are arranged so as to be in direct contact with each other. A layer (for example, an adhesive layer) may be arranged. That is, the resin film 14 may be disposed directly on the lens substrate 12 or indirectly via another layer.
Hereinafter, each member included in the spectacle lens 10 will be described in detail.

(Lens base material)
The lens substrate is a member that supports a resin film described below.
The type of lens base material is not particularly limited, and ordinary lens base materials such as plastic and inorganic glass can be used, and among them, the plastic lens base material is preferable because it is excellent in handleability.
The material of the plastic lens substrate is not particularly limited, and examples thereof include acrylic resin, thiourethane resin, methacrylic resin, allyl resin, episulfide resin, polycarbonate resin, polyurethane resin, polyester resin, polystyrene resin. , Polyethersulfone resin, poly 4-methylpentene-1 resin, diethylene glycol bisallyl carbonate resin (CR-39), polyvinyl chloride resin, halogen-containing copolymer, sulfur-containing copolymer and the like. ..
As the lens base material, finished products with desired optical surfaces on both sides (eyeglass lenses), semi-finished products with convex surfaces finished in the desired shape (semi-finished lenses), lens processing such as grinding and polishing It may be a lens blank which is not formed.

The thickness of the lens substrate is not particularly limited, and is often about 1 to 30 mm from the viewpoint of handleability.
Further, the lens substrate does not have to be transparent as long as it has translucency, and may be colored.
Further, although the surface shape of the lens substrate 12 is a flat surface in FIG. 1, the surface shape is not limited and may be selected from any shape such as a convex surface or a concave surface.

<Resin film>
The resin film is a film disposed on the lens base material, and is a film having excellent self-repairing property and also excellent adhesion to the lens base material. Further, as will be described later, in the present embodiment, since the water/oil repellent component (C) is used when forming the resin film, the obtained resin film also exhibits water/oil repellency. The water/oil repellent component (C) is an optional component.
The initial contact angle of water on the surface of the resin film (the surface on the side opposite to the lens substrate side) is not particularly limited, but is preferably 100° or more, and among them, the scratch resistance of the spectacle lens is more excellent. In this respect, 103° or more is more preferable, and 105° or more is still more preferable. The upper limit is not particularly limited, but is often 150° or less.
As a method for measuring the contact angle of water, a fully automatic contact angle meter (Model DM500, Kyowa Interface Science Co., Ltd.) is placed horizontally under a dry state (20 to 25° C., 30 to 70% RH). Water (pure water) is dropped from the microsyringe on the formed resin film surface to form water droplets, and the tangent to the water droplet surface and the resin at the point where the resin film surface and the water droplets contact each other. The angle between the surface of the membrane and the side containing the water droplets is measured.

The reduction rate of the contact angle of water on the surface of the resin film after the glasses cloth was reciprocated 1000 times while pressing the glasses cloth on the surface of the resin film with a load of 200 g (hereinafter, the treatment with the glasses cloth is also simply referred to as "rubbing treatment"). Is preferably less than 10%, and above all, 5% or less is more preferable and 3% or less is still more preferable from the viewpoint that the abrasion resistance of the spectacle lens is more excellent. The lower limit is not particularly limited, but may be 0%.
As a method for measuring the reduction rate of the contact angle of water, first, the contact angle of water on the resin film surface before the rubbing treatment with a glass cloth is measured by the method described above, and the resin film surface before the rubbing treatment is measured. Obtain the contact angle θ0 of water. Next, a rubbing treatment is performed in which the eyeglass cloth (Kanebo Dot Clean (manufactured by Pearl Co.)) is pressed against the surface of the resin film with a load of 200 g/2.25 cm ² and reciprocated 1000 times. Then, the contact angle of water on the surface of the resin film that has been rubbed is measured by the method described above, and the contact angle θ1 of water on the surface of the resin film after the rubbing treatment is obtained. Using the obtained contact angles θ0 and θ1, the contact angle reduction rate D (%) is calculated by the following equation (1).
Formula (1) Contact angle decrease rate D(%)={(θ0−θ1)/θ0}×100

The resin film preferably has a surface resistivity of less than 10 ¹³ (Ω/□) from the viewpoint of preventing adhesion of dirt such as dust which causes deterioration of scratch resistance. As a method of lowering the surface resistivity, as will be described later, a method of including an ionic compound, a conductive polymer, and conductive fine particles in the composition can be mentioned.

The resin film preferably has antireflection properties. Examples of the method of imparting antireflection property to the surface of the resin film include a method of adding hollow silica to the resin film and a method of adding a fluorine compound to the resin film.

The average thickness of the resin film is preferably 5 to 30 μm, and more preferably 10 to 20 μm, from the viewpoint of more excellent self-repairing property and scratch resistance.
As a method of measuring the above average thickness, the thickness of any 5 points of the resin film is measured, and the arithmetic mean of them is obtained.

The resin film is a film formed using a composition containing a polyol component (A), a polyisocyanate component (B), and a water/oil repellent component (C) (also referred to as “third composition”). is there.
As will be described later in detail, the resin film contains polyurethane obtained by reacting the polyol component (A) with the polyisocyanate component (B). The repeating unit derived from the polyol component (A) is contained in the polyurethane, and the repeating unit derived from the polyrotaxane described later is contained in the repeating unit derived from the polyol component (A) in a predetermined amount. When the water- and oil-repellent component (C) contains a functional group X described later, the structure derived from the water- and oil-repellent component (C) is included in the polyurethane.
Hereinafter, various components contained in the third composition will be described in detail.

(Polyol component (A))
The polyol component (A) is generally a compound having two or more hydroxyl groups in one molecule. In the present embodiment, the polyol component (A) contains a predetermined amount of polyrotaxane having two or more hydroxyl groups. That is, a polyrotaxane having two or more hydroxyl groups and a polyol other than the above polyrotaxane are used in combination.
Below, the component which comprises a polyol component (A) is explained in full detail first.

As the polyol component (A), a polyrotaxane having two or more hydroxyl groups (in other words, a polyol containing a rotaxane structure) is included. Since the polyrotaxane contains two or more hydroxyl groups in one molecule, it is included as one kind of the polyol component (A).
The polyrotaxane is, for example, both ends of a pseudo-polyrotaxane in which the opening of a cyclic molecule such as cyclodextrin is pierced by a linear molecule in a skewered manner, and a plurality of cyclic molecules include the linear molecule (the linear molecule is It is a molecular complex in which a blocking group is arranged at both ends) so that the cyclic molecule is not released, and includes those having improved compatibility and solubility by modifying the cyclic molecule such as cyclodextrin.
In the present specification, with polyrotaxane, in addition to the above-mentioned molecular complex, a cross-linked body in which the above-mentioned molecular complexes are cross-linked with a cyclic molecular portion, and the above-mentioned molecular complex and other monomers or polymers are polymerized. It is a concept including a polymer.

Polyrotaxane contains two or more hydroxyl groups. The number of hydroxyl groups is not particularly limited, but is preferably 100 or more from the viewpoint of reactivity with the polyisocyanate component (B) described later.
The hydroxyl group contained in polyrotaxane is contained in a linear molecule, one directly linked to a cyclic molecule (for example, a hydroxyl group derived from cyclodextrin), and introduced into the side chain end of the cyclic molecule by chemical modification. Things are included. Above all, in consideration of the reaction with polyisocyanate, it is preferable that a hydroxyl group is introduced at the side chain terminal of the cyclic molecule by chemical modification.

The linear molecule constituting the polyrotaxane is a molecule or substance that is included in a cyclic molecule and can be integrated non-covalently with the cyclic molecule, and is not particularly limited as long as it is a linear molecule. ..
Further, the “linear chain” of the “linear molecule” means substantially “linear chain”. That is, the linear molecule may have a branched chain as long as the cyclic molecule that is the rotor can rotate or the cyclic molecule can slide on the linear molecule. The length of the “straight chain” is not particularly limited as long as the cyclic molecule can slide or move on the straight chain molecule.

Examples of the linear molecule forming the polyrotaxane include polycaprolactone, styrene-butadiene copolymer, isobutene-isoprene copolymer, polyisoprene, natural rubber (NR), polyethylene glycol, polyisobutylene, polybutadiene, polypropylene glycol, One or more of polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, ethylene-polypropylene copolymer and the like can be mentioned. Among them, polyethylene glycol, polypropylene glycol, polytetrahydrofuran, polyalkylene glycol such as a copolymer of polyethylene glycol and polypropylene glycol, polyisoprene, polyisobutylene, polybutadiene, polydimethylsiloxane, polyethylene and polypropylene are preferable.
Examples of the blocking group that blocks both ends of the linear molecule include one or more of dinitrophenyl groups, adamantyl groups, trityl groups, fluoresceins, and pyrenes.

As the cyclic molecule constituting the polyrotaxane, any cyclic molecule can be used as long as it is a cyclic molecule capable of including the above linear molecule.
As the cyclic molecule, for example, various cyclodextrins (for example, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, dimethylcyclodextrin and glucosylcyclodextrin, derivatives or modified products thereof, etc.), crown ethers, Examples thereof include benzocrownes, dibenzocrownes, dicyclohexanocrownes, and derivatives or modified products thereof.

The weight average molecular weight of the polyrotaxane is not particularly limited, but is preferably 10,000 to 1,000,000, more preferably 100,000 to 1,000,000.
Specific examples of the polyrotaxane include "Cerm (registered trademark) superpolymer" commercially available from Advanced Soft Materials Co., Ltd. and the like. The "Cerm (registered trademark) superpolymer" has improved compatibility and solubility so that it can be used in various industrial applications by chemically modifying a cyclic molecule. Specifically, a part of the hydroxyl groups of cyclodextrin, which is a cyclic molecule constituting polyrotaxane, is chain-extended with polycaprolactone and a hydroxyl group or a (meth)acryl group is introduced at the terminal. In the present embodiment, it is preferable to use a polyrotaxane having a hydroxyl group introduced at the side chain end of a cyclic molecule.
For example, in the case of a polyrotaxane in which cyclodextrin is used as the cyclic molecule, and a hydroxyl group is introduced at the end of the side chain end of the cyclic molecule which is chain-extended by chemical modification, the hydroxyl group existing in the molecule is newly introduced. There are hydroxyl groups and residual hydroxyl groups that are not chemically modified and are directly linked to cyclodextrin. The residual hydroxyl group directly linked to the cyclodextrin is not necessarily highly reactive due to steric hindrance, and it is presumed that the hydroxyl group introduced into the cyclic molecule preferentially reacts.
As the polyrotaxane, only one kind may be used, or two or more kinds may be used in combination.

The proportion of polyrotaxane in the polyol component (A) is such that the number of moles of hydroxyl groups in the polyrotaxane (the number of moles of hydroxyl groups contained in the polyrotaxane) is 10 to 70% with respect to the total number of moles of hydroxyl groups in the polyol component (A). In other words, the proportion of polyrotaxane in the polyol component (A) is 10 to 70% in terms of molar amount of hydroxyl groups. Among them, at least one of the superior adhesiveness of the resin film, the superior water/oil repellency, and the superior self-healing property (hereinafter also simply referred to as “the superior effect”) 50) to 70% is preferable.
If the proportion of polyrotaxane in the polyol component (A) is less than 10%, the self-repairing property of the resin film is poor, and if it exceeds 70%, the adhesion between the lens substrate and the resin film is poor.

The ratio of the number of moles of hydroxyl groups of the polyrotaxane to the total number of moles of hydroxyl groups of the polyol component (A) is calculated using the value of the hydroxyl number measured by the potentiometric titration method described later. That is, the hydroxyl value of each component is calculated by the potentiometric titration method described below, and the mixing ratio of each component is determined using the hydroxyl value. The number of moles of hydroxyl groups in the polyrotaxane and the total number of moles of hydroxyl groups in the polyol component (A) correspond to the number of moles of hydroxyl groups capable of reacting with the acetylating reagent used in the potentiometric titration method described later.
When a polyrotaxane X having a hydroxyl value of x (mgKOH/g) is used as m (g) and a polyol Y other than the polyrotaxane having a hydroxyl value of y (mgKOH/g) is used as n (g) as the polyol component (A), The ratio of the number of moles of hydroxyl groups of the polyrotaxane to the total number of moles of hydroxyl groups of the polyol component (A) is calculated by xm/(xm+yn)×100(%).
As the value of the hydroxyl value, a value measured by a potentiometric titration method specified in JIS-K0070 (1992) can be adopted. The specific measurement method is as follows.

[Method of measuring hydroxyl value]
(1. Reagent)
1) As the acetylating reagent, acetic anhydride (about 12.5 g, about 11.8 ml) is taken, and pyridine is added to make the total amount to 50 ml. Alternatively, about 25 g (about 23.5 ml) of acetic anhydride is taken, pyridine is added thereto to make the total volume 100 mL, and the mixture is sufficiently stirred before use.
2) A 0.5 mol/l potassium hydroxide ethanol solution is used as a measuring reagent.
3) In addition, prepare toluene, pyridine, ethanol and distilled water.
(2. Operation)
1) About 2 g of a sample is accurately weighed in a flat-bottomed flask, 5 ml of an acetylating reagent and 10 ml of pyridine are added, and an air cooling tube is attached.
2) After heating the above flask in a bath at 100° C. for 70 minutes, allowing it to cool, adding 35 ml of toluene as a solvent from the upper part of the cooling tube and stirring, and then adding 1 ml of distilled water and stirring to remove acetic anhydride. Disassemble. Heat again in the bath for 10 minutes to complete decomposition and allow to cool.
3) Wash the cooling tube with 5 ml of ethanol and remove it. Then, 50 ml of pyridine as a solvent is added and stirred.
4) Add 25 mL of 0.5 mol/l potassium hydroxide ethanol solution using a whole pipette.
5) Perform potentiometric titration with 0.5 mol/l potassium hydroxide ethanol solution. The end point is the inflection point of the obtained titration curve.
6) In the blank test, the above 1) to 5) are performed without inserting a sample.
(3. Calculation)
The hydroxyl value is calculated by the following formula.
Hydroxyl value (mgKOH/g)=[(b−c)×f×28.05]/s+d
here,
b: amount of 0.5 mol/l potassium hydroxide ethanol solution used in blank test (ml),
c: amount of 0.5 mol/l potassium hydroxide ethanol solution used for the sample (ml),
f: 0.5 mol/l potassium hydroxide ethanol solution factor (titer),
s: mass of sample (g),
d: acid value,
28.05: 1/2 of molecular weight 56.11 of potassium hydroxide

The polyol component (A) includes a polyol other than the above polyrotaxane (hereinafter, also referred to as “polyol not containing a rotaxane structure”).
Examples of such polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, glycerin, pentaerythritol, and trimethylol. Propane, a relatively low molecular weight polyhydric alcohol such as trimethylolethane, or a relatively high molecular weight such as polyether polyol, polyester polyol, polyether ester polyol, polyalkylene polyol, polycarbonate polyol, polycaprolactone polyol, polyurethane polyol Examples thereof include polyols, polycarbonate-modified polyols obtained by modifying these polyols, polyene-modified polyols, caprolactone-modified polyols, and bisphenol-modified polyols.
The molecular weight of the polyol other than polyrotaxane and the number of hydroxyl groups are not particularly limited, the adhesion between the resin film and the lens substrate, the hardness and self-repairing property of the resin film, and the viscosity as a resin film forming composition, An optimum value is appropriately selected from the viewpoint of stability and the like.
As one of preferred embodiments of polyols other than polyrotaxane, (meth)acrylic polyol having a relatively low Tg and easy adhesion to a lens substrate, and a relatively high Tg, resulting in a high resin film hardness. Examples thereof include easy-to-use polycarbonate-modified polyester polyols, and these may be used in combination.

(Polyisocyanate component (B))
The polyisocyanate component (B) is a compound that reacts with the above-mentioned polyol component (A). Polyurethane is produced by reacting the polyisocyanate component (B) and the polyol component (A).
The type of the polyisocyanate component (B) is not particularly limited as long as the resin film having the above-mentioned characteristics can be obtained. For example, polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate and other aromatic polyisocyanates; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, Aliphatic or alicyclic polyisocyanates such as dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethyl xylylene diisocyanate can be used. Above all, it is more preferable to use an aliphatic or alicyclic polyisocyanate called non-yellowing type.
The polyisocyanate component (B) may be used alone or in combination of two or more.
In order to provide the composition with storage stability, it is preferable to use, as the polyisocyanate component (B), a blocked polyisocyanate having an isocyanate group masked (sealed) with a blocking agent.
The type of blocking agent is not particularly limited as long as a resin film having the above-mentioned characteristics can be obtained. For example, MEK oxime, amines, active methylene and the like can be used.

(Water- and oil-repellent component (C))
The water/oil repellent component (C) is a component that imparts water/oil repellency to the surface of the resin film, and is an arbitrary component as described above. It is also required that the resin film exhibit water and oil repellency from the viewpoint of easily wiping off stains on the eyeglass lens.
The type of the water/oil repellent component (C) is not particularly limited as long as the resin film having the above-mentioned characteristics can be obtained. Examples thereof include a fluorine-containing compound, a silicone compound, and a compound having a long-chain alkyl group, and a fluorine-containing compound and a silicone compound are preferable from the viewpoint of more excellent effect.

The fluorine-containing compound and the silicone compound preferably have a functional group X that reacts with the above-described polyol component (A) and/or polyisocyanate component (B) from the viewpoint of more excellent effect. Examples of such a functional group X include an amino group, a mercapto group, a (meth)acryloyl group, a hydroxyl group, a carboxyl group and an epoxy group, and an amino group, a mercapto group, a (meth)acryloyl group and a hydroxyl group are preferable. ..

The fluorine-containing compound and the silicone compound may contain an alkoxysilyl group.
The alkoxysilyl group is not particularly limited as long as it has 1 to 3 alkoxy groups bonded to the silicon atom. Examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group. When the number of alkoxy groups bonded to the silicon atom is 1 or 2, examples of groups other than the alkoxy groups bonded to the silicon atom include non-hydrolyzable groups such as a methyl group and an ethyl group. An alkyl group is mentioned. Examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethylsilyl group, a dimethoxyethylsilyl group, a diethoxymethylsilyl group, and a diethoxyethylsilyl group.

The fluorine-containing compound is a compound containing a fluorine atom. Examples of the fluorine-containing compound include a perfluoroalkyl group-containing compound and a perfluoropolyether group-containing compound.
The structure of the perfluoroalkyl group is not particularly limited. That is, the perfluoroalkyl group is straight-chain structure (e.g. _{-CF 2 CF 3, -CH 2 (} CF 2) 4 H, -CH 2 (CF 2) 8 CF 3, -CH 2 CH 2 (CF 2) 4 be H, or the like), a branched structure (e.g. _{-CH (CF 3) 2, -CH} 2 CF (CF 3) 2, -CH (CH 3) CF 2 CF 3, -CH (CH 3) (CF 2 ) ₅ CF ₂ H, etc.), alicyclic structure (preferably 5-membered ring or 6-membered ring, for example, perfluorocyclohexyl group, perfluorocyclopentyl group or alkyl group substituted with these) May be
The perfluoropolyether group is a perfluoroalkyl group having an ether bond, and its structure is not particularly limited. That is, as the perfluoropolyether group, _{e.g., -CH 2 OCH 2 CF 2 CF} 3, -CH 2 CH 2 OCH 2 C 4 F 8 H, -CH 2 CH 2 OCH 2 CH 2 C 8 F 17, - _{CH 2 CH 2 OCF 2 CF 2} OCF 2 CF 2 H, fluorocycloalkyl group having 4 to 20 carbon atoms and having a fluorine atom 5 or more can be mentioned. Examples of the perfluoropolyether group include (CF ₂ ) _x O(CF ₂ CF ₂ O) _y , [CF(CF ₃ )CF ₂ O] _x —[CF ₂ (CF ₃ )], (CF _{2 CF 2 CF 2 O) x} , and the like _{(CF 2 CF 2 O) x} . Here, x and y are arbitrary natural numbers.
In addition, it is preferable that the fluorine-containing compound contains the functional group X or the alkoxysilyl group described above from the viewpoint that the effect is more excellent.

Examples of the silicone compound include compounds having a repeating unit represented by the following formula (X) (organopolysiloxane).
Formula ^{(X) - (Si (R} 1) (R 2) O) n -
In the formula, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group (preferably an alkyl group or a phenyl group), n represents the number of repeating units, and preferably an integer of 10 to 10000. ..
Further, the silicone compound may contain the above-mentioned functional group X and/or alkoxysilyl group.
When the above-mentioned functional group X or alkoxysilyl group is introduced into the silicone compound, it may be introduced into the terminal or the side chain. When introduced into the side chain, for example, a group having the functional group X or an alkoxysilyl group is included instead of R ¹ and R ² in the above formula (X).

Although the molecular weight of the water/oil repellent component (C) (for example, the above-mentioned fluorine-containing compound or silicone compound) is not particularly limited, it is preferably 1000 or more, and more preferably 3000 or more in terms of excellent water/oil repellency and excellent effect. More preferable. The upper limit is not particularly limited, but in terms of handleability, it is often 100,000 or less.

(Amine compound (D) and metal oxide (E))
The third composition contains the above-mentioned polyol component (A), polyisocyanate component (B), and water- and oil-repellent component (C). An alkoxysilyl group is used as the water- and oil-repellent component (C). When the compound containing (fluorine-containing compound or silicone compound) is used, at least one of the amine compound (D) and the metal oxide (E) is preferably contained in the third composition.
By using at least one of the amine compound (D) and the metal oxide (E), the hydrolysis reaction and condensation reaction of the alkoxysilyl group are promoted, and the adhesiveness and water/oil repellency of the resin film are more excellent. Will be things.

The amine compound (D) is a compound having an amino group. In addition, it is a compound different from the water- and oil-repellent component (C) described above.
As the amine compound (D), a silane coupling agent having an amino group is preferable because the effect is more excellent.
The silane coupling agent having an amino group is a hydrolyzable group (for example, an alkoxy group such as a methoxy group and an ethoxy group; an acyloxy group such as an acetoxy group; a halogen group such as a chloro group; and the like), and at least an amino group. A silane compound having two different reactive groups.
Examples of the silane coupling agent having an amino group include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2. -(Aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, Examples thereof include N-phenyl-3-aminopropyltrimethoxysilane and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane.

As the metal oxide (E), for example, an oxide of at least one metal selected from Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti is suitable. Can be mentioned. Among them, particles of oxides containing Ti (titanium oxide particles) are preferable because they are more effective.
The metal oxide (E) may contain only one kind of metal (metal atom) exemplified above, or may contain two or more kinds of metal (metal atom).
The average particle size of the metal oxide (E) is not particularly limited, but is preferably 100 nm or less, more preferably 30 nm or less.
The average particle size is obtained by measuring the diameters of 100 or more metal oxides with a transmission microscope and arithmetically averaging them. If the metal oxide is not a perfect circle, the major axis is the diameter.

(Other ingredients)
In addition to the above, the third composition contains a solvent, an ionic compound, a conductive polymer, conductive fine particles, a surfactant, a deblocking catalyst, a curing catalyst, a light stabilizer, an ultraviolet absorber, an antioxidant, and a coloring agent. Various additives such as inhibitors and dyes may be included.
The solvent may be water or an organic solvent.
The type of organic solvent is not particularly limited, and examples thereof include ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; ether solvents such as diethyl ether, tetrahydrofuran and ethylene glycol dimethyl ether; methyl acetate; butyl acetate. , Benzyl benzoate, dimethyl carbonate, ethylene carbonate, γ-butyrolactone, ester solvents such as caprolactone, hydrocarbon solvents such as benzene, toluene, ethylbenzene and tetralin, halogenated hydrocarbon solvents such as dichloromethane, trichloroethane and chlorobenzene, Amides or cyclic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone (N-methyl-2-pyrrolidone), sulfone solvents such as dimethyl sulfone, and sulfoxides such as dimethyl sulfoxide. Examples include system solvents and the like.

The ionic compound (ionic liquid) is a “salt” that exists in a liquid state even at around room temperature. Ionic compounds generally maintain a liquid state even in a temperature range of -30°C to +300°C, and have an extremely low vapor pressure. The ionic liquid is generally non-volatile and has a low viscosity.
Examples of the cation of the ionic compound include ammonium-based ions such as imidazolium salts and pyridinium salts, phosphonium-based ions, and Li ions. Examples of anions include halogen-based ions such as triflate (SO ₃ CF ₃ ⁻ ), phosphorus-based ions such as hexafluorophosphate (PF ₆ ⁻ ), and boron-based ions such as tetraphenylborate.

Examples of the conductive polymer include polyacetylene, polythiophene, polyaniline, carbon nanotubes and fullerenes.
Examples of the conductive fine particles include conductive oxide fine particles (ITO, ATO, SnO ₂ ) and the like.

(Content of each component in the third composition)
The content of the polyol component (A) in the third composition is not particularly limited, but is preferably 20 to 75% by mass, and more preferably 30 to 60% by mass based on the total mass of the third composition.
The content of the polyisocyanate component (B) in the third composition is not particularly limited, but is preferably 20 to 75 mass% and more preferably 25 to 55 mass% with respect to the total mass of the third composition.
The content of the water/oil repellent component (C) in the third composition is not particularly limited, but is preferably 0.1 to 10% by mass, and 0.2 to 2% by mass with respect to the total mass of the third composition. Is more preferable.
The content of the amine compound (D) in the third composition is preferably 10% by mass or less and more preferably 3% by mass or less based on the total mass of the third composition. The lower limit is not particularly limited, but is often 0.1% by mass or more.
The content of the metal oxide (E) in the third composition is preferably 1% by mass or more and more preferably 5% by mass or more based on the total mass of the third composition. The upper limit is not particularly limited, but is often 50% by mass or less.

<Method for manufacturing eyeglass lens>
The method for manufacturing the above-mentioned spectacle lens is not particularly limited, and a known method can be adopted. Among them, in terms of excellent productivity, the above-mentioned third composition is applied onto a lens substrate to form a coating film, and the coating film is subjected to a curing treatment to form a resin film on the lens substrate. The method of forming may be mentioned.

The method for applying the third composition onto the lens substrate is not particularly limited, and known methods (for example, screen printing method, dip coating method (dipping method), spray coating method, spin coating method, inkjet method, pad printing) are used. Law, etc.) can be adopted.
The thickness of the coating film formed on the lens substrate is not particularly limited, and a thickness that is the above-mentioned thickness of the resin film is appropriately selected.
If necessary, the solvent may be removed by applying a drying treatment after applying the third composition to the lens substrate. By removing the remaining solvent, it is possible to suppress the generation of minute cracks and voids in the resin film due to the vaporization and expansion of the solvent in the curing treatment described later, which is preferable.
A warm air dryer or the like can be used as a method of the drying treatment, and the heating treatment may be performed at a temperature of 30 to 70°C.

The method of curing treatment is not particularly limited, but usually heat treatment or light irradiation treatment (for example, UV treatment) is performed.
The conditions of the heat treatment are not particularly limited, and the optimum conditions are appropriately selected depending on the material used, but from the viewpoint of tack-free property and productivity, low temperature and short time are preferable. Further, it is preferable to divide the curing process into a plurality of times (preliminary curing and main curing). Pre-curing is preferably carried out at 100° C. or lower within 1 hour (preferably 90° C. or lower within 40 minutes) and main curing is carried out at 150° C. or lower within 4 hours (preferably 130° C. or lower within 2 hours).

<<Second Embodiment>>
Below, 2nd Embodiment of a spectacle lens is described with reference to drawings.
The spectacle lens 100 includes a lens base material 12 and a resin film 114 arranged on the lens base material 12, and the resin film 114 includes a lower layer film 16 and an upper layer film 18.
The spectacle lens 100 shown in FIG. 2 has the same layers as the spectacle lens 10 shown in FIG. 1 except that the resin film 114 has a two-layer structure. The reference numeral is given, and the description thereof is omitted. In the following, the configuration of the resin film 114 will be described in detail.

The resin film 114 contains a polyol component (A) and a polyisocyanate component (B), and contains a polyrotaxane having two or more hydroxyl groups in the polyol component (A), and the number of moles of hydroxyl groups of the polyrotaxane is the polyol component (A). The lower layer film 16 formed by using the first composition whose amount is 10 to 70% of the total number of moles of hydroxyl groups, and the second composition which is disposed on the lower layer film 16 and includes the water/oil repellent component (C). And an upper layer film 18 formed by using an object.
The lower layer film contains polyurethane obtained by reacting the polyol component (A) and the polyisocyanate component (B). The polyurethane contains a repeating unit derived from the polyol component (A), and the repeating unit derived from the polyol component (A) contains a predetermined amount of the repeating unit derived from a polyrotaxane. Further, although the upper layer film contains the water/oil repellent component (C), when the water/oil repellent component (C) contains the functional group X described later, the polyurethane in the lower layer film and the water repellent in the upper layer film are contained. It may be combined with the oil repellent component (C).

The surface 114a of the resin film 114 (the surface on the side opposite to the lens base material 12 side) exhibits a predetermined contact angle of water, like the resin film 14, and is water when a predetermined rubbing treatment is performed. The reduction range of the contact angle is small. More specifically, the contact angle of water on the surface 114a of the resin film 114 (the surface on the side opposite to the base material side) is 100° or more, and a glass cloth is loaded on the surface 114a of the resin film 114 with a load of 200 g. The reduction rate of the contact angle of water on the surface 114a of the resin film 114 after reciprocating 1000 times while being pressed by is less than 10%. The evaluation method and the preferred range of the contact angle and the rate of decrease of the contact angle are the same as the evaluation method and the preferred range described in the first embodiment.
Further, the resin film 114 preferably exhibits a predetermined surface resistivity, like the resin film 14 of the first embodiment.
In addition, the resin film 114 preferably exhibits antireflection properties, like the resin film 14 of the first embodiment.

As described above, the lower layer film contains the polyol component (A) and the polyisocyanate component (B), and the polyrotaxane having two or more hydroxyl groups is contained in the polyol component (A), and the number of moles of hydroxyl groups in the polyrotaxane is the polyol. It is a film|membrane formed using the 1st composition which is 10-70% with respect to the total number of moles of hydroxyl groups of a component (A).
The definitions of the polyol component (A), polyisocyanate component (B), and polyrotaxane are as described above.
The range of the content of each component in the first composition (for example, the content of the polyol component (A), the content of the polyisocyanate component (B), the content of the polyrotaxane in the polyol component (A)) Is synonymous with the range of the content of each component in the third composition described in the first embodiment.
The method for producing an underlayer film using the first composition is not particularly limited, and for example, a method of applying the first composition on a lens substrate to form a coating film and subjecting the coating film to a curing treatment. Are listed. As the coating method and the curing treatment, the coating method and the curing treatment in the case of using the third composition described above are appropriately performed.
The film thickness of the lower layer film is preferably 5 to 30 μm, and more preferably 10 to 20 μm, from the viewpoint of more excellent effect. Within the above range, not only the self-repairing property of the resin film is excellent, but also the film thickness uniformity of the resin film is excellent.
As a method of measuring the average thickness, the thickness of the underlayer film is measured at arbitrary 5 points and arithmetically averaged to obtain them.

As described above, the upper layer film is a film formed by using the second composition containing the water/oil repellent component (C). The definition of the water/oil repellent component (C) is as described above.
Further, the range of the content of the water- and oil-repellent component (C) in the second composition is not particularly limited, but when the second composition contains a solvent, it is 0 with respect to the total mass of the second composition. 0.01 to 10 mass% is preferable, and 0.1 to 5 mass% is more preferable.
The method for producing the upper layer film using the second composition is not particularly limited, and, for example, a method of applying the second composition on the lower layer film to form a coating film, and subjecting the coating film to a curing treatment is known. Can be mentioned. As the coating method and the curing treatment, the coating method and the curing treatment in the case of using the third composition described above are appropriately performed.
The average thickness of the upper layer film is not particularly limited, but is preferably 0.1 μm or less, and more preferably 0.05 μm or less, from the viewpoint of more excellent effect. The lower limit is not particularly limited, but is more than 0 μm.

The first composition contains the polyol component (A) and the polyisocyanate component (B), and the second composition contains the water- and oil-repellent component (C). When a compound containing an alkoxysilyl group (a fluorine-containing compound or a silicone compound) is used as a), the amine compound (D) and the metal oxide (E) are added to either the first composition or the second composition. It is preferable that at least one of the above is included.
Among them, it is preferable that the first composition contains at least one of the amine compound (D) and the metal oxide (E) described above because the effect is more excellent.
Further, the content of the amine compound (D) in the first composition is preferably 10% by mass or less and more preferably 3% by mass or less based on the total mass of the first composition. The lower limit is not particularly limited, but is often 0.1% by mass or more.
The content of the metal oxide (E) in the first composition is preferably 1% by mass or more and more preferably 5% by mass or more based on the total mass of the first composition. The upper limit is not particularly limited, but is often 50% by mass or less.

In addition, the first composition and the second composition, if necessary, are optional components that may be included in the third composition (corresponding to the components described in the above (other components). For example, a solvent and the like). May be included.

Hereinafter, the present embodiment will be described in more detail by way of examples, but the present embodiment is not limited to these.

<Example 1>
A polyrotaxane having two or more hydroxyl groups (one kind of polyol component (A)) (manufactured by Advanced Soft Materials Co., Ltd., Celm (registered trademark) superpolymer, SH3400P, hydroxyl value 62) (5.8 parts by mass), Contains a rotaxane structure and a polyol not containing a rotaxane structure (a kind of polyol component (A)) (manufactured by Sumika Bayer Urethane Co., Ltd., polycarbonate modified polyester polyol, Desmophen C1100, hydroxyl value 112) (10.8 parts by mass). Polyol (one kind of polyol component (A)) (Sumitomo Bayer Urethane Co., Ltd., acrylic polyol, Desmophen A870BA, hydroxyl value 98) (21.6 parts by mass) and block polyisocyanate (polyisocyanate component (B)) 1) (blocked hexamethylene diisocyanate manufactured by Sumika Bayer Urethane Co., Ltd. (blocking agent is a pyrazole derivative), Desmodur BL3575/1) (27.3 parts by mass), and butyl acetate (33.1 parts by mass) A surfactant (3M, FC-4432) (0.2 parts by mass) and a deblocking catalyst (Tokyo Kasei Kogyo Co., Ltd., dibutyltin dilaurate) (0.2 parts by mass) were added to the mixed solution of , And an ionic compound (IL-M22 manufactured by Koei Chemical Industry Co., Ltd.) (0.5 parts by mass) were mixed to prepare a composition (corresponding to the first composition). The prepared composition was applied onto a polydiethylene glycol bisallyl carbonate (CR-39) substrate (corresponding to a lens substrate) by a dipping method to form a coating film. Then, the coating film was cured by heating at 130° C. for 1 hour to form a lower layer film having a thickness of 12 μm.
Next, a composition in which a water- and oil-repellent component (C) (manufactured by Shin-Etsu Chemical Co., Ltd., amino-modified silicone compound, KF-869) (0.3 parts by mass) and n-hexane (99.7 parts by mass) are mixed. The material (corresponding to the second composition) was applied on the lower layer film by a dipping method to form a coating film. Then, the coating film was cured by heating at 100° C. for 15 minutes to form an upper layer film and a resin film having a two-layer structure of a lower layer film and an upper layer film.

<Example 2>
A polyrotaxane having two or more hydroxyl groups (one kind of polyol component (A)) (Celm (registered trademark) superpolymer, SH3400P) (16.7 parts by mass) and a polyol not containing a rotaxane structure (polyol component (A)). 1 type) (desmophen C1100) (8.1 parts by mass), a polyol not containing a rotaxane structure (1 type of polyol component (A)) (desmophen A870BA) (16.2 parts by mass), and a blocked polyisocyanate (polyene). One kind of isocyanate component (B) (Desmodur BL3575/1) (28.5 parts by mass) and butyl acetate (29.0 parts by mass) were mixed in a solution, and a surfactant (3M, FC -4432) (0.2 parts by mass), a deblocking catalyst (Tokyo Chemical Industry Co., Ltd., dibutyltin dilaurate) (0.2 parts by mass), and an ionic compound (Koei Chemical Industry Co., Ltd., IL-M22). ) (0.5 parts by mass) was mixed to prepare a composition (corresponding to the first composition). The prepared composition was applied onto a polydiethylene glycol bisallyl carbonate (CR-39) substrate (corresponding to a lens substrate) by a dipping method to form a coating film. Next, the coating film was cured by heating at 130° C. for 1 hour to form a lower layer film having a film thickness of 13 μm.
Next, according to the same procedure as in Example 1, an upper layer film was formed.

<Example 3>
A polyrotaxane having two or more hydroxyl groups (one kind of polyol component (A)) (Celm (registered trademark) superpolymer, SH3400P) (27.0 parts by mass) and a polyol not containing a rotaxane structure (polyol component (A)). 1 type) (desmophen C1100) (5.6 parts by mass), a polyol not containing a rotaxane structure (1 type of polyol component (A)) (desmophen A870BA) (11.2 parts by mass), and a block polyisocyanate (polyene). Isocyanate component (B) (1 type) (Desmodur BL3575/1) (29.7 parts by mass) and butyl acetate (25.0 parts by mass) were mixed with a solution of a surfactant (3M, FC -4432) (0.2 parts by mass), a deblocking catalyst (Tokyo Chemical Industry Co., Ltd., dibutyltin dilaurate) (0.2 parts by mass), and an ionic compound (Koei Chemical Industry Co., Ltd., IL-M22). ) (0.5 parts by mass) was mixed to prepare a composition (corresponding to the first composition). The prepared composition was applied onto a polydiethylene glycol bisallyl carbonate (CR-39) substrate (corresponding to a lens substrate) by a dipping method to form a coating film. Next, the coating film was cured by heating at 130° C. for 1 hour to form a lower layer film having a film thickness of 14 μm.
Next, according to the same procedure as in Example 1, an upper layer film was formed.

<Example 4>
A polyrotaxane having two or more hydroxyl groups (one kind of polyol component (A)) (Celm (registered trademark) superpolymer, SH3400P) (36.7 parts by mass) and a polyol not having a rotaxane structure (polyol component (A)) 1 type) (Desmophen C1100) (3.3 parts by mass), a polyol not containing a rotaxane structure (1 type of polyol component (A)) (Desmophen A870BA) (6.6 parts by mass), and a blocked polyisocyanate (polyene). Isocyanate component (B) (1 type) (Desmodur BL3575/1) (30.8 parts by mass) and butyl acetate (21.3 parts by mass) were mixed in a solution, and a surfactant (3M, FC -4432) (0.2 parts by mass), a deblocking catalyst (Tokyo Chemical Industry Co., Ltd., dibutyltin dilaurate) (0.2 parts by mass), and an ionic compound (Koei Chemical Industry Co., Ltd., IL-M22). ) (0.5 parts by mass) was mixed to prepare a composition (corresponding to the first composition). The prepared composition was applied onto a polydiethylene glycol bisallyl carbonate (CR-39) substrate (corresponding to a lens substrate) by a dipping method to form a coating film. Then, the coating film was cured by heating at 130° C. for 1 hour to form a lower layer film having a film thickness of 15 μm.
Next, according to the same procedure as in Example 1, an upper layer film was formed.

<Example 5>
Instead of the blocked polyisocyanate of Example 1 (one kind of polyisocyanate component (B)) (Desmodur BL3575/1) (27.3 parts by mass), a blocked polyisocyanate (one kind of polyisocyanate component (B)) ( A lower layer film was formed according to the same procedure as in Example 1 except that blocked hexamethylene diisocyanate (blocking agent methyl ethyl ketoxime, Desmodur BL3175) manufactured by Sumika Bayer Urethane Co., Ltd. (26.4 parts by mass) was used. ..
Next, according to the same procedure as in Example 1, an upper layer film was formed.

<Example 6>
Instead of the blocked polyisocyanate of Example 2 (one kind of polyisocyanate component (B)) (Desmodur BL3575/1) (28.5 parts by mass), a blocked polyisocyanate (one kind of polyisocyanate component (B)) ( An underlayer film was formed according to the same procedure as in Example 2 except that Desmodur BL3175) (27.5 parts by mass) was used.
Next, according to the same procedure as in Example 1, an upper layer film was formed.

<Example 7>
Instead of the blocked polyisocyanate of Example 3 (one kind of polyisocyanate component (B)) (Desmodur BL3575/1) (29.7 parts by mass), a blocked polyisocyanate (one kind of polyisocyanate component (B)) ( An underlayer film was formed according to the same procedure as in Example 3 except that Desmodur BL3175) (28.7 parts by mass) was used.
Next, according to the same procedure as in Example 1, an upper layer film was formed.

<Example 8>
Instead of the blocked polyisocyanate of Example 4 (one kind of polyisocyanate component (B)) (Desmodur BL3575/1) (30.8 parts by mass), a blocked polyisocyanate (one kind of polyisocyanate component (B)) ( An underlayer film was formed in the same procedure as in Example 4 except that Desmodur BL3175) (29.7 parts by mass) was used.
Next, according to the same procedure as in Example 1, an upper layer film was formed.

<Example 9>
The coating film was cured according to the same procedure as in Example 3 except that butyl acetate (62.0 parts by mass) was used instead of butyl acetate (25.0 parts by mass) in Example 3 to give a film thickness of 7.5 μm. An underlayer film was formed.
Next, according to the same procedure as in Example 1, an upper layer film was formed.

<Example 10>
A lower layer film was formed according to the same procedure as in Example 3.
Next, a composition in which a water- and oil-repellent component (C) (manufactured by Shin-Etsu Chemical Co., Ltd., mercapto-modified silicone compound, KF-2001) (0.3 parts by mass) and n-hexane (99.7 parts by mass) are mixed. The material (corresponding to the second composition) was applied on the lower layer film by a dipping method to form a coating film. Then, the coating film was cured by heating at 100° C. for 15 minutes to form an upper layer film and a resin film having a two-layer structure of a lower layer film and an upper layer film.

<Example 11>
A polyrotaxane having two or more hydroxyl groups (one type of polyol component (A)) (Celm (registered trademark) superpolymer, SH3400P) (27.1 parts by mass) and a polyol not containing a rotaxane structure (polyol component (A)). 1 type) (desmophen C1100) (5.6 parts by mass), a polyol not containing a rotaxane structure (1 type of polyol component (A)) (desmophen A870BA) (11.3 parts by mass), and a block polyisocyanate (polyene). One type of isocyanate component (B)) (Desmodur BL3575/1) (29.8 parts by mass) and water/oil repellent component (C) (manufactured by Shin-Etsu Chemical Co., Ltd., KY-1203, acrylic modified fluorine compound). (0.5 parts by mass) and butyl acetate (25.0 parts by mass) in a solution mixed with a surfactant (3M, FC-4432) (0.2 parts by mass) and a deblocking catalyst (Tokyo). Kasei Kogyo Co., Ltd. dibutyltin dilaurate) (0.2 parts by mass) and an ionic compound (Koei Chemical Co., Ltd. IL-M22) (0.5 parts by mass) are mixed to form a composition (No. Corresponding to 3 compositions) were prepared. The prepared composition was applied onto a polydiethylene glycol bisallyl carbonate (CR-39) substrate (corresponding to a lens substrate) by a dipping method to form a coating film. Then, the coating film was cured by heating at 130° C. for 1 hour to form a single-layer film having a film thickness of 12 μm.

<Example 12>
A polyrotaxane having two or more hydroxyl groups (one kind of polyol component (A)) (Celm (registered trademark) superpolymer, SH3400P) (26.6 parts by mass) and a polyol not containing a rotaxane structure (polyol component (A)). 1 type) (desmophen C1100) (5.5 parts by mass), a polyol not containing a rotaxane structure (1 type of polyol component (A)) (desmophen A870BA) (11.1 parts by mass), and a block polyisocyanate (polyene). One type of isocyanate component (B)) (Desmodur BL3575/1) (29.2 parts by mass) and amine compound (D) (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-903, amino group-containing silane coupling agent). (2.4 parts by mass) and butyl acetate (25.0 parts by mass) were mixed in a solution, and a surfactant (manufactured by 3M, FC-4432) (0.2 parts by mass) and a deblocking catalyst ( Tokyo Chemical Industry Co., Ltd. dibutyltin dilaurate) (0.2 parts by mass) and an ionic compound (Koei Chemical Industry Co., Ltd. IL-M22) (0.5 parts by mass) are mixed to obtain a composition ( Corresponding to the first composition) was prepared. The prepared composition was applied onto a polydiethylene glycol bisallyl carbonate (CR-39) substrate (corresponding to a lens substrate) by a dipping method to form a coating film. Next, the coating film was cured by heating at 130° C. for 1 hour to form a lower layer film having a film thickness of 14 μm.
Then, a water- and oil-repellent component (C) (manufactured by Shin-Etsu Chemical Co., Ltd., alkoxysilyl group-containing fluorine compound, KY-130) (0.3 parts by mass) and n-hexane (99.7 parts by mass) were mixed. The composition (corresponding to the second composition) was applied on the lower layer film by a dipping method to form a coating film. Then, the coating film was cured by heating at 100° C. for 15 minutes to form an upper layer film and a resin film having a two-layer structure of a lower layer film and an upper layer film.

<Example 13>
A polyrotaxane having two or more hydroxyl groups (one type of polyol component (A)) (Celm (registered trademark) superpolymer, SH3400P) (20.4 parts by mass) and a polyol not containing a rotaxane structure (polyol component (A)). 1 type) (desmophen C1100) (4.2 parts by mass), a polyol not containing a rotaxane structure (1 type of polyol component (A)) (desmophen A870BA) (8.5 parts by mass), and a blocked polyisocyanate (poly). One type of isocyanate component (B) (Desmodur BL3575/1) (22.4 parts by mass) and metal oxide (E) (manufactured by JGC Catalysts & Chemicals Co., Ltd., OPTOLAKE 6320Z, MIBK dispersed TiO ₂ sol) (25. 3 parts by mass) and butyl acetate (18.9 parts by mass) are mixed in a solution, and a surfactant (manufactured by 3M, FC-4432) (0.1 parts by mass) and a deblocking catalyst (Tokyo Kasei Kogyo). Co., Ltd., dibutyltin dilaurate) (0.3 parts by mass) and an ionic compound (Koei Chemical Industry Co., Ltd., IL-M22) (0.3 parts by mass) are mixed to form a composition (first composition). Corresponding to the product) was prepared. The prepared composition was applied onto a polydiethylene glycol bisallyl carbonate (CR-39) substrate (corresponding to a lens substrate) by a dipping method to form a coating film. Then, the coating film was cured by heating at 130° C. for 1 hour to form a lower layer film having a film thickness of 10 μm.
Next, according to the same procedure as in Example 12, an upper layer film was formed.

<Comparative Example 1>
A polyol not containing a rotaxane structure (one kind of polyol component (A)) (desmophen C1100) (12.2 parts by mass) and a polyol not containing a rotaxane structure (one kind of polyol component (A)) (desmophen A870BA) ( 24.4 parts by mass, block polyisocyanate (one kind of polyisocyanate component (B)) (Desmodur BL3575/1) (26.7 parts by mass), and butyl acetate (35.4 parts by mass) are mixed. Into the prepared solution, a surfactant (3M, FC-4432) (0.2 parts by mass), a deblocking catalyst (Tokyo Chemical Industry Co., Ltd., dibutyltin dilaurate) (0.2 parts by mass), and ions A compound (corresponding to the first composition) was prepared by mixing with a volatile compound (IL-M22, manufactured by Koei Chemical Industry Co., Ltd.) (0.5 parts by mass). The prepared composition was applied onto a polydiethylene glycol bisallyl carbonate (CR-39) substrate by a dipping method to form a coating film. Then, the coating film was cured by heating at 130° C. for 1 hour to form a lower layer film having a thickness of 12 μm.
Next, according to the same procedure as in Example 1, an upper layer film was formed.
In Comparative Example 1, polyrotaxane having two or more hydroxyl groups is not used.

<Comparative example 2>
Polyol containing rotaxane structure (one kind of polyol component (A)) (Celme (registered trademark) superpolymer, SH3400P) (45.8 parts by mass) and polyol not containing rotaxane structure (one kind of polyol component (A)) ) (Desmophen C1100) (1.1 parts by mass), a polyol not containing a rotaxane structure (a kind of polyol component (A)) (desmophen A870BA) (2.1 parts by mass), and a blocked polyisocyanate (polyisocyanate component). One kind of (B)) (Desmodur BL3575/1) (31.7 parts by mass) and butyl acetate (17.7 parts by mass) were mixed in a solution, and a surfactant (manufactured by 3M, FC-4432). ) (0.2 parts by mass), a deblocking catalyst (manufactured by Tokyo Chemical Industry Co., Ltd., dibutyltin dilaurate) (0.2 parts by mass), and an ionic compound (manufactured by Koei Chemical Industry Co., Ltd., IL-M22) ( 0.5 parts by mass) was mixed to prepare a composition (corresponding to the first composition). The prepared composition was applied onto a polydiethylene glycol bisallyl carbonate (CR-39) substrate by a dipping method to form a coating film. Then, the coating film was cured by heating at 130° C. for 1 hour to form a lower layer film having a film thickness of 15 μm.
Next, according to the same procedure as in Example 1, an upper layer film was formed.

<Comparative example 3>
Polyol containing rotaxane structure (one kind of polyol component (A)) (Celme (registered trademark) superpolymer, SH3400P) (50.4 parts by mass) and blocked polyisocyanate (one kind of polyisocyanate component (B)) ( Desmodur BL3575/1) (32.3 parts by mass) and butyl acetate (15.9 parts by mass) were mixed in a solution, and a surfactant (manufactured by 3M, FC-4432) (0.2 parts by mass) was added. And a deblocking catalyst (dibutyltin dilaurate manufactured by Tokyo Chemical Industry Co., Ltd.) (0.2 parts by mass) and an ionic compound (IL-M22 manufactured by Koei Chemical Industry Co., Ltd.) (0.5 parts by mass). A composition (corresponding to the first composition) was prepared by mixing. The prepared composition was applied onto a polydiethylene glycol bisallyl carbonate (CR-39) substrate by a dipping method to form a coating film. Next, the coating film was cured by heating at 130° C. for 1 hour to form a lower layer film having a thickness of 16 μm.
Next, according to the same procedure as in Example 1, an upper layer film was formed.

<Comparative example 4>
Instead of the blocked polyisocyanate (one kind of polyisocyanate component (B)) (Desmodur BL3575/1) (26.7 parts by mass) of Comparative Example 1, a blocked polyisocyanate (one kind of polyisocyanate component (B)) ( An underlayer film was formed in the same procedure as in Comparative Example 1 except that Desmodur BL3175) (25.7 parts by mass) was used.
Next, according to the same procedure as in Example 1, an upper layer film was formed.

<Comparative Example 5>
Instead of the blocked polyisocyanate of Comparative Example 2 (one type of polyisocyanate component (B)) (Desmodur BL3575/1) (31.7 parts by mass), one type of blocked polyisocyanate (one type of polyisocyanate component (B)) ( An underlayer film was formed according to the same procedure as in Comparative Example 2 except that Desmodur BL3175) (30.8 parts by mass) was used.
Next, according to the same procedure as in Example 1, an upper layer film was formed.

<Comparative example 6>
Instead of the blocked polyisocyanate of Comparative Example 3 (one kind of polyisocyanate component (B)) (Desmodur BL3575/1) (32.3 parts by mass), a blocked polyisocyanate (one kind of polyisocyanate component (B)) ( An underlayer film was formed in the same procedure as in Comparative Example 3 except that Desmodur BL3175) (31.3 parts by mass) was used.
Next, according to the same procedure as in Example 1, an upper layer film was formed.

<Various evaluations>
(Adhesion evaluation)
Adhesion of the resin film was evaluated by the cross-cut method (JIS K5400-8.5 reference), and peeling along the squares (inward 0.1 mm or less) was 5/100 squares or less, "○", squares If the number of peelings (inward 0.1 mm or less) was greater than 5/100 squares, or if the amount was more than 0.1 mm inward, it was evaluated as "x".
The inner 0.1 mm means an inner portion of the score line and a distance of 0.1 mm from the score line.

(Self-healing evaluation)
Using a brass brush (manufactured by AS ONE Co., Ltd., standard type 4 lines B-3014), a resin film was rubbed 10 times at a speed of 60 mm/sec while applying a load of 200 g, and the presence of scratches immediately after rubbing was visually confirmed. At that time, in the environment of 20 to 25°C, "○" indicates that the wound is recovered within 1 second after the wound is made, and "" indicates that the wound is recovered within 30 seconds longer than 1 second. ◯”, the case where the scratch was recovered within 1 minute for more than 30 seconds was evaluated as “Δ”, and the case where the scratch was not recovered within 1 minute was evaluated as “x”.

(Water and oil repellency evaluation (contact angle evaluation))
The contact angle of water is an angle formed by the tangent to the water droplet surface and the surface of the resin film including the water droplet at the point where the resin film surface and the water droplet contact each other, and the dry state ( Using a fully automatic contact angle meter (Kyowa Interface Science Co., Ltd. DM500 type) at 20 to 25° C. and 30 to 70% RH, water (pure water) from a microsyringe was placed on the surface of the resin film arranged horizontally. ) Was added dropwise to form water droplets, and the measurement was performed.

(Contact angle test after durability test)
The contact angle of water on the surface of the resin film before the rubbing treatment with the eyeglass cloth was measured by the above-mentioned method to obtain the contact angle of water on the surface of the resin film before the rubbing treatment θ0. Next, a rubbing treatment was performed in which the eyeglass cloth (Kanebo Dot Clean (manufactured by Pearl Co.)) was pressed against the surface of the resin film at a load of 200 g/2.25 cm ² and reciprocated 1000 times. Then, the contact angle of water on the surface of the rubbing-treated resin film was measured by the method described above, and the contact angle θ1 of water on the surface of the rubbing-treated resin film was obtained.

(BAYER evaluation)
The BAYER test is a comparison of the degree of wear between a reference lens (CR-39 lens not coated) which is an ISO standard lens and a test lens (lens having a resin film), and a test lens holder is provided with a curved surface of the lens. Was placed on the bottom of the tray so as to face upward, and sand made by Taber was put in the tray and reciprocated at a distance of 4 inches back and forth for 4 minutes at 150 cycles per minute. Then, the reference lens and the test lens were taken out from the tray and evaluated by the amount of change in haze, which is the degree of wear measured by a haze meter. When the ratio for comparing the increase in haze between the ISO reference lens and the test lens is 10 or more, "◎", when 5 to less than 10, "○", when 2 to less than 5, "△", when less than 2, "×" Was evaluated.

(Surface resistivity evaluation)
The surface resistivity is measured in a surface resistivity mode using a “HIRESTA MCP HT450” URS probe manufactured by Mitsubishi Chemical Analytech Co., Ltd., and a resin film having a surface resistivity of less than 10 ¹³ Ω/□ is indicated by “◯”, The resin film having a surface resistivity of 10 ¹³ Ω/□ or more was evaluated as “x”.

The results of the above various evaluations are summarized in Table 1.

As shown in Table 1, it was confirmed that the spectacle lens of this example exhibited excellent self-healing property, water and oil repellency, and adhesion.
On the other hand, in Comparative Examples 1 to 6 in which the predetermined amount of polyrotaxane was not used, the desired effect was not obtained.

As described above, the present inventor, as a result of diligent studies, has a resin film having excellent self-repairing property by using a resin film obtained from a composition containing predetermined components, and a lens substrate and a resin film. It has been found that it is possible to provide a spectacle lens having excellent adhesion with.
That is, it has been found that a spectacle lens satisfying the above characteristics can be provided by the following configuration.

(1) a lens substrate,
A resin film disposed on the lens substrate,
The resin film contains the polyol component (A) and the polyisocyanate component (B), and the polyrotaxane having two or more hydroxyl groups is contained in the polyol component (A), and the number of moles of hydroxyl groups of the polyrotaxane is equal to that of the polyol component (A). A spectacle lens including a film formed by using a composition having a total hydroxyl group mole number of 10 to 70%.
(2) The resin film contains a polyol component (A) and a polyisocyanate component (B), and the polyol component (A) contains a polyrotaxane having two or more hydroxyl groups, and the number of moles of hydroxyl groups of the polyrotaxane is the polyol component ( An underlayer film formed using the first composition, which is 10 to 70% based on the total number of moles of hydroxyl groups of A),
The spectacle lens according to (1), which has an upper layer film formed on the lower layer film by using a second composition containing a water- and oil-repellent component (C).
(3) The resin film contains a polyol component (A), a polyisocyanate component (B), and a water- and oil-repellent component (C), and the polyol component (A) contains a polyrotaxane having two or more hydroxyl groups, The spectacle lens according to (1), which is a resin film formed using a composition in which the number of moles of hydroxyl groups of polyrotaxane is 10 to 70% with respect to the total number of moles of hydroxyl groups of the polyol component (A).
(4) The spectacle lens according to (2), wherein the film thickness of the lower layer film is 5 to 30 μm.
(5) The spectacle lens according to (3), wherein the resin film has a thickness of 5 to 30 μm.
(6) A fluorine-containing compound or silicone compound, wherein the water- and oil-repellent component (C) has at least one functional group selected from the group consisting of an amino group, a mercapto group, a (meth)acryloyl group, and a hydroxyl group. The spectacle lens according to any one of (2) to (5).
(7) One of the first composition and the second composition further contains at least one of the amine compound (D) and the metal oxide (E),
The spectacle lens according to (2) or (4), wherein the water/oil repellent component (C) contains an alkoxysilyl group-containing fluorine compound.
(8) The composition further contains at least one of the amine compound (D) and the metal oxide (E), and the water/oil repellent component (C) contains an alkoxysilyl group-containing fluorine compound (3) or ( The spectacle lens according to 5).

According to the above embodiment, it is possible to provide a spectacle lens having a resin film having excellent self-repairing property and having excellent adhesion between the lens substrate and the resin film.
Further, according to the above-described embodiment, it is possible to further provide a spectacle lens having a resin film having water and oil repellency.

10,100 Eyeglass lens 12 Lens base material 14,114 Resin film 16 Lower layer film 18 Upper layer film

Claims (8)

A lens substrate,
A resin film disposed on the lens substrate,
The resin film contains a polyol component (A) and a polyisocyanate component (B), and the polyrotaxane having two or more hydroxyl groups is contained in the polyol component (A), and the number of moles of hydroxyl groups of the polyrotaxane is the polyol component. A spectacle lens comprising a film formed using the composition of (A) in an amount of 10 to 70% based on the total number of moles of hydroxyl groups. The resin film is disposed on the lens substrate, contains a polyol component (A) and a polyisocyanate component (B), and contains a polyrotaxane having two or more hydroxyl groups in the polyol component (A), An underlayer film formed using a first composition in which the number of moles of hydroxyl groups of polyrotaxane is 10 to 70% with respect to the total number of moles of hydroxyl groups of the polyol component (A),
The spectacle lens according to claim 1, further comprising an upper layer film disposed on the lower layer film and formed using a second composition containing a water- and oil-repellent component (C). The resin film contains a polyol component (A), a polyisocyanate component (B) and a water/oil repellent component (C), and the polyrotaxane having two or more hydroxyl groups is contained in the polyol component (A), The spectacle lens according to claim 1, which is a resin film formed using a composition in which the number of moles of hydroxyl groups of polyrotaxane is 10 to 70% with respect to the total number of moles of hydroxyl groups of the polyol component (A). The spectacle lens according to claim 2, wherein the thickness of the lower layer film is 5 to 30 μm. The spectacle lens according to claim 3, wherein the resin film has a thickness of 5 to 30 μm. The water- and oil-repellent component (C) contains a fluorine-containing compound or a silicone compound having an amino group, a mercapto group, a (meth)acryloyl group, and at least one functional group selected from the group consisting of a hydroxyl group. The spectacle lens according to any one of claims 2 to 5. One of the first composition and the second composition further contains at least one of an amine compound (D) and a metal oxide (E),
The spectacle lens according to claim 2, wherein the water- and oil-repellent component (C) contains an alkoxysilyl group-containing fluorine compound. 6. The composition according to claim 3, wherein the composition further contains at least one of an amine compound (D) and a metal oxide (E), and the water/oil repellent component (C) contains an alkoxysilyl group-containing fluorine compound. The described spectacle lens.