JPH09113701A - Optical product made of plastic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent antidazzle characteristic and to obtain a light- controlling function which changes transmittance of light according to the quantity of incident light by forming a light-controlling resin layer containing a photochromic compd. on the surface of a resin base body prepared by incorporating a specified proportion of ionic metal component comprising neodymium ion into a specified acryl copolymer. SOLUTION: A light-controlling resin layer containing a photochromic compd. is formed on the surface of a resin base body. This resin base body consists of 100 pts.mass copolymer obtd. by copolymn. of 5-90mass% monomers containing phosphate groups and 95-10mass% monomers which are copolymerizable with the monomers above described and 0.1-20 pts.mass ionic metal component comprising neodymium ion. In formula I, R is a polymerizable functional group expressed by formula II and n is 1 or 2. In formula II, X is a hydrogen atom or methyl group and m is an integer 0 to 5.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic optical product, and more specifically, it has a property of absorbing light in a specific wavelength region in a visible light region, has an antiglare property, and is dependent on the amount of incident light. The present invention relates to a plastic optical product having a light control function in which light transmittance changes.

[0002]

2. Description of the Related Art Neodymium ions are known to have absorption characteristics near a wavelength of 580 nm, and conventionally, as an optical material having an antiglare property, neodymium ions have been contained in an inorganic glass in a dispersed state. Optical materials that utilize the light absorption characteristics of neodymium ions are being developed.
The glass-made optical material containing such neodymium ions is used, for example, in sunglasses and spectacle lenses. Thus, in the above optical product, in order to obtain sufficient antiglare properties even when used in a place where the amount of incident light is large, for example, outdoors where sunlight is radiated, neodymium ions are contained at a considerably large ratio. It is necessary to use the contained optical material.

However, such an optical material has an extremely small transmittance for light from a light source such as a sodium lamp used as illumination in a tunnel. Therefore, for example, when driving a car using sunglasses or glasses made of the above-mentioned optical material and entering a tunnel, the brightness of the field of view becomes extremely low, which is very dangerous.

Further, the optical products made of glass have drawbacks in mechanical properties such as high specific gravity, heavy weight and brittleness,
In manufacturing, it also has a drawback that molding, cutting, polishing, etc. are difficult.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made based on the above circumstances, and its object is to provide:
An object of the present invention is to provide a plastic optical product having excellent antiglare property and having a light control function of changing the light transmittance depending on the amount of incident light.

[0006]

The plastic optical product of the present invention comprises a phosphoric acid group-containing monomer represented by the following formula (1) in an amount of 5 to 90% by mass and a monomer 95 copolymerizable therewith.
On the surface of a resin substrate composed of 100 parts by mass of a copolymer obtained by copolymerizing a mixed monomer composed of 10 to 10% by mass and 0.1 to 20 parts by mass of an ionic metal component composed of neodymium ions, It is characterized in that a dimming resin layer containing a photochromic compound is formed.

[0007]

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In the plastic optical product of the present invention, the resin substrate preferably has a light transmittance of 10 to 80% for light having a wavelength of 580 nm, and the dimming resin layer has a thickness of 0.1. It is preferably about 3.0 mm.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The plastic optical product of the present invention will be described in detail below. The plastic optical product of the present invention is a preparation containing a photochromic compound on the surface of a resin substrate containing an ionic metal component consisting of neodymium ions in a specific acrylic copolymer in a specific ratio. A light-sensitive resin layer is formed.

The acrylic copolymer constituting the resin substrate is a phosphoric acid group-containing monomer represented by the above formula (1) (hereinafter, also referred to as "specific phosphoric acid group-containing monomer") and Monomer copolymerizable with this (hereinafter, "copolymerizable monomer")
Also called. ) Is obtained by copolymerizing a monomer mixture consisting of

In formula (1) showing the molecular structure of a specific phosphoric acid group-containing monomer, the group R is an acryloyloxy group (X is hydrogen) to which an ethylene oxide group is bonded, as shown in formula (2). Atom) or a methacryloyloxy group (when X is a methyl group). Here, the repeating number m of the ethylene oxide group is an integer of 0 to 5. When the value of m exceeds 5, the resulting copolymer has a significantly reduced hardness, and thus lacks practicability as an optical product.

In the formula (1), the number of hydroxyl groups n is 1
Or 2, a specific phosphoric acid group-containing monomer in which the value of n is 1 and a specific phosphoric acid group in which the value of n is 2 depending on the characteristics of the resulting resin substrate, the molding method and the purpose of use. Either one or both of the contained monomers can be used,
When both are used, the mixing ratio can be selected.

More specifically, the specific phosphoric acid group-containing monomer in which the value of n is 1 has 2 radical-polymerizable ethylenically unsaturated bonds bonded to the phosphorus atom, and thus is cross-linked. On the other hand, the specific phosphoric acid group-containing monomer having a value of n of 2 has the number of the ethylenically unsaturated bonds of 1 and has an ionic metal component such as neodymium ion described later. The bondability of is large.

Therefore, when a resin substrate is obtained by an injection molding method or an extrusion molding method, which is a general molding method for thermoplastic resins, a specific phosphoric acid group-containing monomer having a value of n is 2 It is preferable to use one having a large mixing ratio.
On the other hand, when a resin substrate having a large surface hardness is obtained by the casting method while ensuring the bondability with an ionic metal component such as neodymium ion, a specific phosphate group-containing unit whose value of n is 1 is obtained. It is preferable to use one having a large mixing ratio of the monomers. The method for obtaining the resin substrate is not limited to the above method.

Further, the specific phosphoric acid group-containing monomer having an n value of 1 and the specific phosphoric acid group-containing monomer having an n value of 2 are in substantially equimolar amounts. When used in a ratio such as a molar ratio of 45 to 55:55 to 45, suitable mechanical strength is obtained, and the solubility of a metal compound such as a neodymium compound described later in the monomer mixture is high. It is more preferable because it is high and neodymium ions can be uniformly contained in the obtained copolymer.

In the monomer mixture for obtaining the acrylic copolymer constituting the resin substrate, a copolymerizable monomer is used together with the above specific phosphoric acid group-containing monomer. The copolymerizable monomer may be (1) uniformly mixed with the specific phosphate group-containing monomer to be used, or (2) radically copolymerized with the specific phosphate group-containing monomer to be used. There is no particular limitation as long as the polymerizability is satisfactory and (3) an optically transparent copolymer is obtained.

Specific examples of the copolymerizable monomer include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, lower alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, or lower alkyl methacrylate, ethoxyethyl acrylate. , A modified alkyl acrylate or a modified alkyl methacrylate in which an alkyl group is substituted with a glycidyl group such as a lower alkyl acrylate or a lower alkyl methacrylate, glycidyl acrylate, or glycidyl methacrylate having a lower alkyl group through an ethylene oxide group such as ethoxyethyl methacrylate Mention may be made of monofunctional acrylates or monofunctional methacrylates such as

Also, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1,4
-Butanediol diacrylate, 1,4-butanediol dimethacrylate, 2,2-bis [4-acryloxyethoxyphenyl] propane, 2,2-bis [4-methacryloxyethoxyphenyl] propane, trimethylolpropane triacrylate It is also possible to use polyfunctional acrylates or polyfunctional methacrylates such as trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and the like. These compounds can be used alone or in combination of two or more.

In the above-mentioned monomer mixture, the specific phosphoric acid group-containing monomer is used in an amount of 5 to 90% by mass, particularly 1
It is preferably from 0 to 90% by mass. If this ratio is less than 5% by mass, it will be difficult to contain an ionic metal component such as neodymium ion described below in a sufficiently dispersed state in the obtained acrylic copolymer,
A resin substrate having excellent antiglare properties may not be obtained in some cases. On the other hand, when this ratio exceeds 90% by mass, the monomer mixture has low polymerizability, and it is difficult to obtain a high yield, and the obtained acrylic copolymer is Various properties such as refractive index, heat resistance, impact resistance, and moisture absorption resistance may be low.

The acrylic copolymer constituting the resin substrate can be obtained by radical polymerization of a monomer mixture containing the above-mentioned specific phosphoric acid group-containing monomer and a copolymerizable monomer. . The radical polymerization method is not particularly limited, and it is possible to use a known method such as a bulk (cast) polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, or the like, using an ordinary radical polymerization initiator. You can

The resin substrate used in the present invention comprises the above acrylic copolymer containing an ionic metal component consisting of neodymium ions.

The ionic metal component composed of such neodymium ions can be prepared by adding an appropriate neodymium compound to the above acrylic copolymer, or by adding it to the monomer thereof and polymerizing it. It can be contained in the acrylic copolymer.

Various compounds can be used as the neodymium compound, and examples thereof include neodymium acetate, neodymium chloride, neodymium nitrate, neodymium oxide, neodymium-2,4-pentanedionate, and neodymium trifluoropentanedio. Examples thereof include anhydrides and hydrates such as nate, neodymium fluoride, and neodymium sulfate. The neodymium compound is not limited to these compounds.

In addition to the neodymium ion, the resin substrate may contain other metal ion as a part of the ionic metal component. As the metal compound for giving such other metal ions, compounds based on metal ions such as sodium, potassium, calcium, iron, manganese, cobalt, magnesium and nickel can be used.

As described above, when a metal ion other than neodymium ion is contained as a part of the ionic metal component, the proportion of neodymium ion in all metal ions is preferably 50% by mass or more. When the proportion of neodymium ions in the total ionic metal component is less than 50% by mass, it may be difficult to obtain an optical product having excellent antiglare properties.

The content ratio of the ionic metal component is such that the total of neodymium ions and other metal ions is 0.1 to 20 parts by mass with respect to 100 parts by mass of the acrylic copolymer. When this ratio is less than 0.1 part by mass, the resin substrate obtained has insufficient light absorption characteristics in the vicinity of a wavelength of 580 nm. On the other hand, when this ratio exceeds 20 parts by mass, it becomes difficult to uniformly contain the ionic metal component containing neodymium ions as a main component in the acrylic copolymer. Further, in order to contain the ionic metal component in such a ratio, the use ratio of the metal compound based on the neodymium compound and other metal ions is 0.2 to 50 parts by mass with respect to 100 parts by mass of the acrylic copolymer. It is particularly preferably 0.5 to 30 parts by mass.

The method for producing the acrylic copolymer containing the ionic metal component in the present invention is not particularly limited, but the following two methods can be mentioned as preferable methods.

(1) Before radical polymerization of the monomer mixture, the metal compound is added to the monomer mixture to dissolve the monomer compound therein, whereby the unit amount of the metal compound and the specific phosphate group is contained. A method of preparing a monomer composition comprising a polymer and a copolymerizable monomer, and subjecting this monomer composition to radical polymerization treatment.

(2) A method in which the above-mentioned metal compound is added and mixed into an acrylic copolymer obtained by subjecting a monomer mixture to radical polymerization. In the method (2), specifically, a) a method in which an acrylic copolymer is melted by heating, and the metal compound is added to and mixed with this, and b) an acrylic copolymer is dissolved in an organic solvent or the like. The method of adding and mixing the metal compound to this solution, and the like can be used.

By the method as described in (1) or (2) above, a resin material made of an acrylic copolymer containing an ionic metal component made of neodymium ions can be obtained.
The resin substrate can be manufactured by molding, polishing or cutting the resin material into a plate shape, a sheet shape, a film shape, a disk shape, a lens shape, or the like depending on the purpose and application.

The resin substrate thus obtained preferably has a central portion having a thickness of 0.2 to 10 mm. If this thickness is less than 0.2 mm, sufficient antiglare properties may not be obtained. On the other hand, this thickness is 10
If the thickness exceeds mm, the weight of the entire optical product becomes large, so that the characteristics of the optical product made of plastic are lost when it is used for, for example, sunglasses.

The resin substrate preferably has a light transmittance of 10 to 80% for light having a wavelength of 580 nm. If the light transmittance is less than 10%, sufficient transmittance for light from a light source such as a sodium lamp cannot be obtained. Therefore, for example, when the optical product is used as sunglasses or spectacle lenses, Below, it is not suitable because the brightness of the field of view cannot be secured sufficiently. On the other hand, if the light transmittance exceeds 80%, sufficient antiglare properties cannot be obtained.

In the plastic optical product of the present invention, a dimming resin layer containing a photochromic compound is formed on the surface of the above resin substrate.

The resin component constituting the light control resin layer is not particularly limited as long as it has excellent transparency, but a polymer of a monomer capable of casting polymerization is used. It is preferable to use a polymer that does not impair the durability of photochromism of the photochromic compound, for example, a polymer of a monomer that does not contain a heavy atom such as a halogen atom or a metal atom.

Specific examples of the monomer for obtaining the resin component constituting the light control resin layer (hereinafter, also referred to as "monomer for forming light control resin layer") include diethylene glycol bisallyl carbonate and the like. Allyl carbonates of polyols, methacrylates such as methyl methacrylate, isobutyl methacrylate, isobonyl methacrylate, benzyl methacrylate and ethylene glycol dimethacrylate, and aromatic vinyl monomers such as styrene, α-methylstyrene and divinylbenzene. You can Further, it is preferable to use 2-ethylhexyl methacrylate, lauryl methacrylate, or the like having a low glass transition temperature (Tg) in combination, whereby the rate of change in coloring and fading based on the light control effect can be improved.
Further, a reaction product of a hydroxyl group-containing acrylate or methacrylate and a polyisocyanate can be used, whereby the moldability of the light control resin layer is increased,
And the performance of the obtained light control resin layer can be improved.

As the photochromic compound contained in the light control resin layer, it is preferable to use a spirooxazine compound, a chromene compound or a fulgide compound from the viewpoint of excellent durability against repeated photochromism.

As the spirooxazine compound, it is preferable to use a compound represented by the following formula (3).

[0038]

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Specific examples of such spirooxazine compounds include 1,3,3-trimethylspiro [indoline-2,3 '-(3H) -naphtho (2,1-b) (1,
4) Oxazine], 5-methyl-1,3,3-trimethylspiro [indoline-2,3 '-(3H) -naphtho (2,1-b) (1,4) oxazine], 4-trifluoromethyl -1,3,3-Trimethyl-6 '-(1-piperidinyl) spiro [indoline-2,3'-(3H)
-Naphtho (2,1-b) (1,4) oxazine], 5,
6,7-Trifluoro-1,3,3-trimethyl-6 '
-(1-Piperidinyl) spiro [indoline-2,3 '
-(3H) -naphtho (2,1-b) (1,4) oxazine], 1- (2-phenoxyethyl) -3,3-dimethylspiro [indoline-2,3 '-(3H) -naphtho ( 2,1-b) (1,4) oxazine], 1,3-dimethyl-3-ethylspiro [indoline-2,3 ′-(3
H) -naphtho (2,1-b) (1,4) oxazine],
1,3,3-Trimethyl-6 '-(1-piperidinyl)
Spiro [indoline-2,3 '-(3H) -naphtho (2,1-b) (1,4) oxazine], 8'-hydroxy-1,3-dimethyl-3-ethyl spiro [indoline-2,3'] -(3H) -naphtho (2,1-b) (1,
4) Oxazine], 1,3,3-trimethylspiro [indoline-2,3 '-(3H) -pyrido (3,2-f)
(1,4) benzoxazine], 1-isopropyl-
3,3-Dimethylspiro [indoline-2,3 '-(3
H) -pyrido (3,2-f) (1,4) benzoxazine],

5-Methyl-1,3,3-trimethylspiro [indoline-2,3 '-(3H) -pyrido (3,2
-F) (1,4) benzoxazine], 1,3,3-trimethylspiro [indoline-2,3 '-(3H) -pyrido (3,4-f) (1,4) benzoxazine], 1
-(N-hexyl) -3,3-dimethylspiro [indoline-2,3 '-(3H) -pyrido (3,4-f)
(1,4) benzoxazine], 1- (n-hexyl)
-3-methyl-3-ethylspiro [indoline-2,
3 '-(3H) -pyrido (3,4-f) (1,4) benzoxazine], 1-cyclohexyl-3,3-dimethylspiro [indoline-2,3'-(3H) -pyrido (3,3 4-f) (1,4) benzoxazine], 1-cyclohexylmethyl-3,3-dimethylspiro [indoline-2,3 '-(3H) -pyrido (3,4-f)
(1,4) benzoxazine], 1- (2-ethylhexyl) -3,3-dimethylspiro [indoline-2,
3 '-(3H) -pyrido (3,4-f) (1,4) benzoxazine], 5-methoxy-1- (n-hexyl)
-3,3-Dimethylspiro [indoline-2,3'-
(3H) -pyrido (3,4-f) (1,4) benzoxazine], 1- (n-dodecyl) -3,3,5-trimethylspiro [indoline-2,3 '-(3H) -pyrido (3,4-f) (1,4) benzoxazine], 1-dodecyl-3,3-dimethylspiro [indoline-2,
3 '-(3H) -pyrido (3,4-f) (1,4) benzoxazine], 1- (n-docosanyl) -3,3-dimethylspiro [indoline-2,3'-(3H)- Pyrido (3,4-f) (1,4) benzoxazine], 8 ′
-Hydroxy-1- (n-hexyl) -3,3-dimethylspiro [indoline-2,3 '-(3H) -pyrido (3,4-f) (1,4) benzoxazine] and the like can be mentioned.

As the chromene compound, it is preferable to use a compound represented by the following formula (4) or the following formula (5), in view of its excellent weather resistance against photochromism.

[0042]

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Specific examples of such a chromene compound include 3,3-diphenyl-3H-naphtho [2,1-b].
Pyran, 2,2-diphenyl-2H-naphtho [1,2-
b] diallyl naphthopyran such as pyran, 3- (2-fluorophenyl) -3- (4-methoxyphenyl) -3H
-Naphtho [2,1-b] pyran, 3- (2-methyl-4)
-Methoxyphenyl) -3- (4-ethoxyphenyl)
-3H-naphtho [2,1-b] pyran and other phenyl ring-substituted derivatives, in which a heterocycle was introduced in place of the phenyl ring 3-
(2-furyl) -3- (2-fluorophenyl) -3H
-Naphtho [2,1-b] pyran, 3- (2-thienyl)
-3- (2-fluoro-4-methoxyphenyl) -3H
-Naphtho [2,1-b] pyran, 3- {2- (1-methylpyrrolyl)}-3- (2-methyl-4-methoxyphenyl) -3H-naphtho [2,1-b] pyran and the like. To be In addition, spiro [bicyclo [3.3.1] nonane-
Also use 9,3′-3H-naphtho [2,1-b] pyran, spiro [bicyclo [3.3.1] nonane-9-2′-3H-naphtho [2,1-b] pyran and the like. You can

As the fulgide compound, a compound represented by the following formula (6) is preferably used.

[0045]

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The above photochromic compounds can be used alone or in combination of two or more kinds. For example, a mixture of 2 to 5 kinds can be used to develop a desired color such as gray or brown. .

The light control resin layer may contain an antioxidant, an ultraviolet absorber, a light stabilizer, etc., if necessary. Specific examples of the light stabilizer include bis (1,2,2,2)
6,6-pentamethyl-4-piperidyl) sebacate,
Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, di (1,2,2,6,6-pentamethyl-4-piperidyl) -butyl (3 ', 5'-di-te
rt-butyl-4-hydroxybenzyl) malonate,
1- [2- {3- (3,5-di-tert-butyl-4
-Hydroxyphenyl) propionyloxy} ethyl]
-4- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} -2,2
6,6-Tetramethylpiperidine, poly [[6-
{(1,1,3,3-tetramethylbutyl) amino}-
1,3,5-triazine-2,4-diyl] [1,6-
{2,2,6,6-tetramethyl-4-piperidinyl}
Aminohexamethylene]], poly [{6- (morpholino) -S-triazine-2,4-diyl} {1,6-
(2,2,6,6-tetramethyl-4-piperidinyl)
Amino} hexamethylene], 4-hydroxy-2,2
Examples thereof include dimethyl succinate polymer of 6,6-tetramethyl-1-piperidinethanol.

Further, the dimming resin layer may contain a singlet oxygen quencher in order to remove the influence of oxygen.
Thereby, the weather resistance of photochromism in the spirooxazine compound in the light control resin layer can be improved. Such singlet oxygen quenchers include β-carotene, various Schiff base nickel (II) complexes, 1,4
-Amines such as diazabicyclo [2.2.2] octane and triethylamine, phenols and the like can be used, and particularly amines and phenols that have small absorption in the visible light region can be preferably used. This singlet oxygen quencher is contained, for example, in the dimming resin layer in an amount of 0.1% by mass, preferably 0.5 to 50% by mass.

The thickness of such a light control resin layer is preferably 0.1 to 3.0 mm. When the thickness of the light control resin layer is less than 0.1 mm, the weather resistance of the light control function tends to be low. On the other hand, when the thickness of the dimming resin layer exceeds 3.0 mm, it is not effective because the degree of color development due to the dimming action does not improve in proportion to the size of the thickness, and the photochromic compound used Depending on the type, some of them may be deteriorated by ultraviolet rays and discolor to red, so that the light transmittance may be low in a state where the dimming effect is not exhibited.

The method for forming the dimming resin layer on the surface of the resin substrate is not particularly limited, but the following two methods (1) and (2) can be mentioned as preferable methods. .

(1) In this method, the resin substrate is directly used as a molding plate, and a dimming resin layer molding mold plate is provided on one surface side of the resin substrate, the molding surface of which is one surface of the resin substrate. The resin substrate and the dimming resin layer molding mold plate are arranged so as to face each other, and in this state, an appropriate sealing and fixing member is provided so as to commonly cover the side surfaces of the resin substrate and the dimming resin layer molding plate. A cavity for dimming resin layer molding is formed between the dimming resin layer molding mold plate, and in the dimming resin layer molding cavity,
A method of forming a dimming resin layer by polymerizing a dimming resin layer forming material.

In the above-mentioned method, the mold plate for molding the dimming resin layer has a shape whose molding surface conforms to the shape of one surface of the resin substrate, that is, a shape in a specific relationship in which both are in close contact with each other. It is preferable to use it, and thereby a dimming resin layer having a uniform thickness is formed.

When the resin substrate is manufactured by the cast polymerization method using a mold composed of a pair of mold plates, the resin substrate obtained after the polymerization treatment is held in one mold. In this state, the other mold plate is detached to form a resin substrate composite body in which the resin substrate is held on one mold plate, and this resin substrate composite body is used as it is as one mold plate for dimming. It is preferable to use for forming the functional resin layer. In this case, the other mold plate used in the production of the resin substrate and removed can be used as a mold plate for dimming resin layer molding.

As the sealing and fixing member, for example, a gasket made of ethylene-vinyl acetate copolymer or ethylene-ethyl acrylate copolymer, or an appropriate adhesive tape can be used. It is preferable to use the pressure-sensitive adhesive tape because it can be applied regardless of the thickness of the light-controllable resin layer.

As the material for forming the dimming resin layer, a material containing the above-mentioned monomer for forming the dimming resin layer and the photochromic compound is used. This light control resin layer forming material can contain the above-mentioned light stabilizer, antioxidant, ultraviolet absorber, singlet oxygen quencher, and other additives.

In the above-mentioned formation of the dimming resin layer, it is preferable to treat one surface of the resin substrate with a silane coupling agent or with ultraviolet rays, whereby the dimming resin formed with the resin substrate is formed. The adhesion with the layer can be improved. Further, in order to enhance the adhesion between the resin substrate and the light control resin layer, the polymerization treatment may be stopped before all the monomers in the light control resin layer forming material completely react with the polymer. It is valid.

(2) A cast body for a light control resin layer is produced by casting polymerization of the above-mentioned light control resin layer forming material,
A method of laminating and adhering the molded body for a light control resin layer on a resin substrate. In this method, when the resin base and the light control resin layer molded body are bonded with an adhesive or a pressure sensitive adhesive,
A thermosetting or photocurable adhesive having excellent transparency, for example, an epoxy-based, urethane-based or acrylic-based adhesive, or an acrylic pressure-sensitive adhesive excellent in transparency and weather resistance is preferable. Can be used.

By the method as described in (1) and (2) above, the light control resin layer is formed on the surface of the resin substrate, so that the plastic optical product of the present invention can be obtained.

In the plastic optical product of the present invention, a colorant such as a dye or a pigment may be contained in the resin substrate or the light control resin layer within a range not impairing the antiglare property and the light control property. . The method of incorporating such a colorant is not particularly limited, and for example, a colorant is added to the monomer mixture or the dimming resin layer forming material for obtaining the acrylic copolymer constituting the resin substrate. And a method of polymerizing them, or a method of adding a colorant after polymerizing the monomer mixture or the light control resin layer forming material.

In the plastic optical product of the present invention, the resin substrate absorbs a light beam having a wavelength in the vicinity of 580 nm, and the light control resin layer changes the light transmittance depending on the incident light amount, so that the incident light amount is large. In this case, excellent antiglare property is exhibited, and when the amount of incident light is small,
Sufficient light transmittance is obtained. Therefore, the plastic optical product of the present invention can be suitably used for sunglasses, spectacle lenses, and the like.

[0061]

The present invention will be described below with reference to examples, but the present invention is not limited by these examples. In the following, "part" means "part by mass" and "%" means "% by mass" excluding light transmittance.

Example 1 (1) Production of Resin Substrate Specific phosphoric acid group-containing monomer 3 represented by the following formula (7)
1.5 parts, 18.5 parts of a specific phosphoric acid group-containing monomer represented by the following formula (8), 29 parts of methyl methacrylate, 20 parts of diethylene glycol dimethacrylate,
A monomer mixture was prepared by thoroughly mixing 1 part of α-methylstyrene. To this monomer mixture, 2.5 parts of neodymium acetate monohydrate (the amount of which neodymium ion is 1.1 parts per 100 parts of the monomer mixture) is added, and the mixture is sufficiently stirred by mixing at room temperature. To obtain a monomer composition in which neodymium acetate monohydrate was dissolved in the monomer mixture.

[0063]

[Chemical 6]

To the monomer composition prepared as described above, 2.0 parts of t-butylperoxyoctanoate was added, mixed and deaerated. This monomer composition is -3.0
It is poured into a glass mold composed of a convex mold plate and a concave mold plate configured to obtain a 0 diopter lens, and heated at 45 ° C. for 2 hours and then at 50 ° C. for 2 hours, and then at 50 ° C. to 60 ° C. Up to 60 ° C in 6 hours
To 80 ° C. in 5 hours, then 80 ° C. to 100 ° C. in 3 hours, and heating at 100 ° C. for 2 hours to perform cast polymerization to obtain an acrylic crosslinked copolymer containing neodymium ions. A resin base body having a center portion thickness of 1.9 mm was manufactured. After that, the convex-side mold plate was removed while the resin-based substrate was held by the concave-side mold plate, to obtain a resin-base composite body in which the resin substrate was held by the concave-side mold plate.

(2) Formation of dimming resin layer 26.97 parts of 2-hydroxyethyl methacrylate,
To 23.03 parts of isophorone diisocyanate and 50 parts of 2-ethylhexyl methacrylate, 0.05 part of di-n-butyltin dilaurate as a urethanization catalyst was added, and a urethanization reaction was carried out at 60 ° C. for 3 hours. 1,3,3- as a photochromic compound was added to the reaction product.
Trimethyl-6 '-(1-piperidinyl) spiro [indoline-2,3'-(3H) -naphtho (2,1-b)
(1,4) Oxazine] 0.022 part, and bis (1,2,2,6,6-pentamethyl-4- as a light stabilizer.
0.2 parts of piperidyl sebacate was added and mixed, and further, 1.5 parts of t-butylperoxyneodecanate as a polymerization initiator was added and mixed to prepare a light control resin layer forming material.

On the convex side of the resin base in the resin base composite obtained in (1), the convex side mold plate removed in the production of the resin base is provided with its molding surface facing the convex side of the resin base in the resin base composite. Then, in this state, the outer peripheral side surfaces of both are fixed so as to be commonly covered by a sealing and fixing member made of an adhesive tape, so that the distance between the resin base and the convex side mold plate is 1.0 mm. A cavity for molding a light control resin layer was formed.

The prepared material for forming a light-controlling resin layer was injected into the cavity for molding the light-controlling resin layer, and the temperature was adjusted to 40 ° C. for 10 hours, 60 ° C. for 3 hours, 80 ° C. for 1 hour, and further 90 hours.
A dimming resin layer was formed on the surface of the resin substrate by performing the polymerization treatment by gradually increasing the polymerization temperature at 1 ° C. for 1 hour. After that, the sealing and fixing member is removed, and the concave side mold plate and the convex side mold plate are released from the mold, whereby the thickness of the dimming resin layer is 0.9 mm, and the thickness of the central portion including the dimming resin layer is 2 mm. A plastic optical product according to the present invention of 0.8 mm and -3.00 diopters was produced. This plastic optical product had a slight purple tinge.

When the light transmittance of the obtained plastic optical product was measured in a room, the total light transmittance was 85% and the light transmittance at a wavelength of 580 nm was 60%. When this plastic optical product is irradiated with ultraviolet rays, the optical product has a high purple color density, and when the light transmittance is measured after being irradiated with ultraviolet rays for 5 minutes, the total light transmittance is 70% and the wavelength is 580 nm.
The light transmittance was 40%. It was also confirmed that when the optical product was placed in a dark place, the color returned to the state before the ultraviolet irradiation in a short time, and that it had an excellent light control function.

Example 2 (1) Manufacture of Resin Substrate A monomer composition was prepared in the same manner as in Example 1, and the monomer composition was constructed so as to obtain a lens of 0.00 diopter. A resin substrate having a central portion with a thickness of 2 mm was manufactured in the same manner as in Example 1 except that the resin was poured into a glass mold and cast polymerization was performed.

(2) Formation of dimming resin layer A dimming resin layer forming material prepared in the same manner as in Example 1 using the glass mold used in the production of the resin substrate was subjected to the same conditions as in Example 1. By performing the polymerization treatment in step 1, a molded product for a light control resin layer having a thickness of 0.9 mm was obtained.
This dimmable resin layer molding is superposed on the convex side surface of the resin substrate via an epoxy adhesive and heated at 50 ° C. for 1 hour to bond them to each other, thereby dimming the surface of the resin substrate. The thickness of the central part, which is formed of a resin layer, is 2.9 m.
m plastic optical product was obtained. This plastic optical product had a slight purple tinge.

When the light transmittance of the obtained plastic optical product was measured in a room, the total light transmittance was 82% and the light transmittance at a wavelength of 580 nm was 57%. When this plastic optical product is irradiated with ultraviolet rays, the optical product has a high purple color density, and when the light transmittance is measured after being irradiated with ultraviolet rays for 5 minutes, the total light transmittance is 70% and the wavelength is 580 nm.
The light transmittance was 42%. It was also confirmed that when the optical product was placed in a dark place, the color returned to the state before the ultraviolet irradiation in a short time, and that it had an excellent light control function.

Example 3 (1) Production of Resin Substrate Specific phosphoric acid group-containing monomer 4 represented by the above formula (7)
7.2 parts, 27.8 parts of the specific phosphoric acid group-containing monomer represented by the above formula (8), 19 parts of t-butoxyethyl methacrylate, 5 parts of diethylene glycol dimethacrylate, and α-methylstyrene. 1 part was thoroughly mixed to prepare a monomer mixture. To this monomer mixture, 10 parts of neodymium acetate monohydrate (the amount that makes the ratio of neodymium ion to 4.3 parts to 100 parts of the monomer mixture) was added, and the mixture was sufficiently dissolved by stirring and mixing at room temperature. Thus, a monomer composition was obtained in which neodymium acetate monohydrate was dissolved in the monomer mixture.

Two glass plates of 120 mm square are arranged so as to face each other at an interval of 3 mm, and the side surfaces of these two glass plates are sealed with a sealing material made of fluororubber so that the two glass plates are sealed. A cavity for casting polymerization was formed between the glass plates. By injecting the above-mentioned monomer composition into the cavity for casting polymerization and performing the casting polymerization under the same conditions as in Example 1, the acrylic cross-linked copolymer containing neodymium ions is formed. A resin substrate having a central portion having a thickness of 2.8 mm was manufactured.

(2) Formation of dimming resin layer 18.76 parts of 2-hydroxyethyl methacrylate,
Hexamethylene diisocyanate trimer (24.24 parts), n-butyl methacrylate (24 parts), α-methylstyrene (23 parts), and divinylbenzene (10 parts) were added to dilaurylate di-n-butyltin (0.1 part) as a urethane-forming catalyst. 05
Parts were added, and urethanization reaction was carried out at 60 ° C. for 3 hours.
1- as a photochromic compound was added to this reaction product.
Cyclohexylmethyl-3,3-dimethylspiro [indoline-2,3 '-(3H) -pyrido (3,4-f)
(1,4) benzoxazine] 0.5 part, 3,3-diphenyl-3H-naphtho [2,1-b] pyran 1.6 parts,
And 5,6,7-trifluoro-1,3,3-trimethyl-6 '-(1-piperidinyl) spiro [indoline-2,3'-(3H) -naphtho (2,1-b) (1,
4) Oxazine] 0.1 part, and 0.2 part of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate as a light stabilizer are added and mixed, and further t-is used as a polymerization initiator. Butyl peroxy neodecanoate 1.5
Parts were added and mixed to prepare a light control resin layer forming material.

The resin substrate obtained in (1) has a diameter of 90 mm.
Cut into a disk shape, and the disk-shaped resin base and a diameter of 90 m
A circular glass plate of m is arranged at a distance of 0.88 mm so as to face each other, and a polyethylene terephthalate tape is sealed so as to cover the outer periphery of the side surface of the resin plate. By forming a cavity for molding a light-controlling resin layer, injecting a light-controlling resin layer forming material into the cavity, and performing a polymerization treatment under the same conditions as in Example 1, the thickness of the light-controlling resin layer is reduced to 0. A plastic optical product having a thickness of 0.8 mm and a central portion including the dimming resin layer having a thickness of 3.6 mm was obtained. This plastic optical product was slightly bluish.

When the light transmittance of the obtained plastic optical product was measured in a room, the total light transmittance was 80% and the light transmittance at a wavelength of 580 nm was 27%. When this plastic optical product is exposed to sunlight, the optical product develops a gray color,
When the light transmittance was measured after exposure to sunlight for 10 minutes, the total light transmittance was 55% and the light transmittance at a wavelength of 580 nm was 16%. It was also confirmed that when the optical product was placed in a dark place, the color returned to the state before exposure to sunlight in a short time, and that it had an excellent dimming function.

Example 4 5,6,7-trifluoro-1,3,3-trimethyl-as a photochromic compound
6 '-(1-piperidinyl) spiro [indoline-2,
3 '-(3H) -naphtho (2,1-b) (1,4) oxazine] 0.25 part was used as a light stabilizer.
The thickness of the dimming resin layer was 0.8 mm, and the dimming resin layer was 0.8 mm in the same manner as in Example 3 except that 0.2 part of 2,2,6,6-pentamethyl-4-piperidinyl) sebacate was used. A plastic optical product having a thickness of 3.6 mm (including the center portion of the resin substrate of 2.8 mm) was obtained.
This plastic optical product had a slight reddish purple color.

When the light transmittance of the obtained plastic optical product was measured in a room, the total light transmittance was 78% and the light transmittance at a wavelength of 580 nm was 26%. When this plastic optical product was exposed to sunlight, the optical product developed a red color, and the light transmittance was measured after exposing it to sunlight for 5 minutes,
The total light transmittance was 50%, and the light transmittance at a wavelength of 580 nm was 8%. It was also confirmed that when the optical product was placed in a dark place, the color returned to the state before exposure to sunlight in a short time, and that it had an excellent dimming function.

Example 5 (1) Manufacture of Resin Substrate The addition amount of neodymium acetate monohydrate was set to 15 parts ((the ratio of neodymium ion to 6.4 parts per 100 parts of the monomer mixture)). A monomer composition was prepared in the same manner as in Example 3 except that it was changed, and the cavity for casting polymerization was formed by setting the distance between two glass plates to 5 mm, and the same procedure as in Example 3 was performed. And made of an acrylic cross-linked copolymer containing neodymium ions, the central portion has a thickness of 4.6 mm.
The resin base of was manufactured.

(2) Formation of dimming resin layer 1-dodecyl-3,3-as a photochromic compound
Dimethylspiro [indoline-2,3 '-(3H) -pyrido (3,4-f) (1,4) benzoxazine] 0.
7 parts, spiro [bicyclo [3.3.1] nonane-9,
0.5 part of 3′-3H-naphtho [2,1-b] pyran, and 5,6,7-trifluoro-1,3,3-trimethyl-6 ′-(1-piperidinyl) spiro [indoline-
2,3 '-(3H) -naphtho (2,1-b) (1,4)
Oxazine] Example 3 except that 0.13 part was used.
A dimming resin layer forming material was prepared in the same manner as in.

A dimming resin was prepared in the same manner as in Example 3 except that the resin substrate obtained in (1) and the glass plate were separated by 0.5 mm to form a cavity for molding the dimming resin layer. A plastic optical product having a layer thickness of 0.42 mm and a central portion including the dimming resin layer having a thickness of 5.02 mm was obtained. This plastic optical product had a slight purple tinge.

When the light transmittance of the obtained plastic optical product was measured in a room, the total light transmittance was 78% and the light transmittance at a wavelength of 580 nm was 15%. When this plastic optical product was exposed to sunlight, the optical product developed a red color, and the light transmittance was measured after exposing it to sunlight for 5 minutes,
The total light transmittance was 53% and the light transmittance at a wavelength of 580 nm was 8%. It was also confirmed that when the molded product was placed in a dark place, it returned to the color before exposure to sunlight in a short time, and had an excellent light control function.

[0083]

According to the plastic optical product of the present invention, since the resin substrate contains a specific acrylic monomer and an ionic metal component consisting of neodymium ions in a specific ratio, it is 580 nm. Light having a wavelength in the vicinity is absorbed, and since the dimming resin layer is formed on the surface of this resin substrate, the light dimming resin layer changes the light transmittance according to the amount of incident light. As a result, when the amount of incident light is large, excellent antiglare property is exhibited, and when the amount of incident light is small, sufficient light transmittance is obtained.
Therefore, the plastic optical product of the present invention can be suitably used for sunglasses, spectacle lenses, and the like.

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Claims (3)

[Claims] 1. A phosphoric acid group-containing monomer represented by the following formula (1) in an amount of 5 to 90% by mass and a monomer 9 copolymerizable therewith.
On the surface of a resin substrate composed of 100 parts by mass of a copolymer obtained by copolymerizing a mixed monomer composed of 5 to 10% by mass and 0.1 to 20 parts by mass of an ionic metal component composed of neodymium ions. A plastic optical product comprising a photochromic compound-containing dimming resin layer formed thereon. Embedded image 2. The plastic optical product according to claim 1, wherein the resin substrate has a light transmittance of 10 to 80% for light having a wavelength of 580 nm. 3. The thickness of the light control resin layer is 0.1 to 3.0 m.
The optical product made of plastic according to claim 1 or 2, wherein m is m.