JP2005239887A - Polymerizable curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable curable composition giving a photochromic plastic lens which exhibits an excellent photochromic characteristic of a fast fading rate, has practical levels of hardness, heat resistance and water absorption resistance and also possesses a drilling-resistant strength strong enough for the composition to be used for low refractive rimless glasses. <P>SOLUTION: A specific amount of a photochromic compound is mixed with a polymerizable monomer component containing, in a specific ratio, a specific bifunctional monomer having a structure in which two phenylene groups such as 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane are bonded via a specific group, a polymerizable propylene glycol monomer such as tripropylene glycol dimethacrylate, a multifunctional monomer such as trimethylolpropane trimethacrylate and a monomer other than these monomers. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polymerization curable composition that provides a novel photochromic cured product having both excellent photochromic properties and excellent strength properties and excellent water absorption resistance.

  Photochromic glasses are lenses that quickly color and function as sunglasses when exposed to light containing ultraviolet rays such as sunlight. Demand for spectacles that function as spectacles, especially those made of plastic, has been increasing in recent years.

  As a method for producing a plastic spectacle lens having a photochromic property (plastic photochromic spectacle lens), there is a method of directly obtaining a photochromic lens by dissolving a photochromic compound in a monomer and polymerizing it (hereinafter referred to as a kneading method). Are known. In this method, the photochromic property is imparted at the same time as the molding of the lens, and a photochromic plastic lens is obtained in one step as compared with a method in which the lens is once molded and then processed to impart the photochromic property. Has the advantage of being

  Photochromic properties are manifested when a photochromic compound absorbs light energy and causes a reversible structural change. However, in a photochromic plastic lens obtained by a kneading method, the photochromic compound is dispersed in a cured matrix. Therefore, in many cases, the characteristics inherent to the photochromic compound cannot be exhibited sufficiently with respect to the photochromic characteristics such as the color density and the fading speed. This is because the free space is overwhelmingly smaller in such a matrix than in a solution, and this structural change is likely to be constrained, especially in a hardened matrix with high hardness and heat resistance. This tendency is remarkable when a high molecular weight photochromic compound is dispersed. For example, when a photochromic compound having a molecular weight of 300 or more is dispersed in a cured composition that is widely used as a plastic lens base material, the photochromic compound has a significantly longer fading half-life (a fading speed is greatly reduced). The fading half-life in the cured product matrix may be 50 times or longer than the fading half-life in the solution.

  As a cured product composition that provides a photochromic cured product having no such problems, that is, excellent photochromic properties and high hardness and heat resistance, (A) L scale Rockwell of a polymer obtained by homopolymerization A polymerizable monomer having a hardness of 40 or less, (B) a tri- or more functional polymerizable monomer having an L-scale Rockwell hardness of 60 or more, and (C) a polymer obtained by homopolymerization; A polymer curable composition (hereinafter also referred to as a conventional composition) comprising a bifunctional polymerizable monomer having an L scale Rockwell hardness of 60 or more and (D) a photochromic compound is sometimes known. (See Patent Document 1).

International Publication No. 01/05854 Pamphlet

  The above composition is extremely useful as a raw material composition for producing a photochromic plastic lens by a kneading method, but rimless eyeglasses that have recently been popularized as a cured product obtained by curing the composition ( When an arm member for hooking a lens in use and a lens having a screw hole are to be used for eyeless glasses connected via a hinge screwed to the lens), a drill is used. It is clear that there is a problem that the lens of the fixed part may be damaged if a load is applied to the fixed arm member even if there is a crack when drilling using, or there is no particular problem during drilling became.

  Therefore, as a result of examining the composition ratio of the conventional composition in order to investigate the cause of the decrease in strength after drilling or after processing (hereinafter also referred to as anti-piercing strength), in particular, the aforementioned homopolymerization was performed. When the amount of the tri- or higher functional polymerizable monomer (hereinafter also referred to as polyfunctional monomer) having an L-scale Rockwell hardness of 60 or more in the obtained polymer is large, the piercing resistance of the cured product is high. Was found to be significantly reduced. From this, it is thought that the amount of polyfunctional monomer should be reduced in order to improve the puncture resistance, but the trade-off is that it becomes difficult to obtain excellent photochromic properties if the amount of polyfunctional monomer added is too small. It became clear that there was a relationship. Further investigations were made based on this finding, and the blending ratio of the polyfunctional monomer contained in the polymerization curable composition was set within a specific range, and two phenylene groups were specified as the bifunctional polymerizable monomer. A photochromic curable composition (hereinafter also referred to as an improved composition) using a specific amount of a specific polymerizable monomer having a structure bonded through a group of the above-mentioned groups can satisfy the above-mentioned characteristics. (Japanese Patent Application 2003-208784).

On the other hand, plastic lenses are often used with a hard coat in order to increase their scratch resistance. However, if the water absorption rate of the lens before the hard coat application is high, a hard coat solution is applied and heat is applied. When cured, there may be a crack at the end of the lens.
Furthermore, plastic spectacle lenses are characterized by a wide range of refractive indexes of the lenses, and the demands of each customer are taken into consideration, such as the severity of myopia and the lightness or strength of the lens. Those having a refractive index corresponding to the above are appropriately selected. For example, when the severity of myopia is low, in order to obtain a spectacle lens having an appropriate thickness and sufficient strength for practical use, the refractive index is in the range of 1.500 to 1.530. Some so-called low-refractive lenses are often used (high-refractive lenses often have low impact resistance, and the lens price is considerably higher than low-refractive lenses, so if myopia is serious. Often used only). Therefore, it is desirable to provide a low refractive lens as one of the lineups in the improved composition, but when adjusting the monomer composition to lower the refractive index, photochromic properties, puncture resistance, There is a problem that any physical property of the water absorption rate is lowered and a lens having a good balance of physical properties cannot be obtained.

  SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problem of reduction in punching resistance and to provide a low refractive index photochromic plastic spectacle lens with low water absorption.

  The present inventor has intensively studied on this problem. As a result, the inventors have found that the above-mentioned problems can be solved by blending a specific polymerizable propylene glycol monomer into the improved composition and further optimizing the composition, thereby completing the present invention.

That is, the present invention
(I): (I-1) 7 to 20% by mass of a component composed of a bifunctional polymerizable monomer represented by the following formula (1), (I-2) bifunctional represented by the following formula (2) 10 to 60% by mass of a component composed of a polymerizable monomer, (I-3) 1 to 15% by mass of a component composed of a polyfunctional polymerizable monomer represented by the following formula (3), and (I-4) 100 parts by mass of a polymerizable monomer composition comprising 5 to 82% by mass of a component comprising a polymerizable monomer not corresponding to any of (I-1) to (I-3) and (II): photochromic compound 0 It is a polymerization curable composition characterized by containing 0.001-5 mass parts.

{In the formula, R ¹ and R ² are each independently a hydrogen atom or a methyl group; R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 2 carbon atoms; A group represented by O—, —S—, —S (═O) ₂ —, —C (═O) —O—, —CH ₂ —, —CH═CH— or —C (CH ₃ ) ₂ —; M and n are integers in which m + n is 2 to 30. }

{In formula, R < ⁵ > and R < ⁶ > are respectively independently a hydrogen atom or a methyl group, and p is an integer of 1-4. }

{In the formula, R ⁷ represents a hydrogen atom or a methyl group, and the group —R ⁸ — represents —CH ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) O— or —C (═O) CH ₂ CH ₂ a CH ₂ CH ₂ CH ₂ O-, a group represented by, ^{R 9} is a trivalent to hexavalent organic residue, a is an integer from 0 to 3, b is an integer from 3 to 6. }

  The polymerization curable composition of the present invention exhibits excellent photochromic properties such as a fast fading speed, and has practical levels of hardness, heat resistance, and water absorption resistance, and sufficient perforation resistance sufficient for use in rimless glasses. And a cured product having a lower refractive index. Therefore, the spectacle lens of the present invention obtained by curing the polymerization curable composition of the present invention has an appropriate thickness and mechanical strength when used as a spectacle lens for correcting vision of a myopic patient with low severity. Will have. That is, the spectacle lens of the present invention is particularly excellent as a photochromic spectacle lens for correcting visual acuity of a myopic patient with low severity.

  The polymerization curable composition of the present invention comprises a specific polymerizable monomer composition (I) and a photochromic compound (II). By using the above-mentioned specific polymerizable monomer composition (I) as the polymerizable monomer component, the cured product has high puncture-resistant strength, low water absorption, and good photochromic properties. Hereinafter, the polymerizable monomer composition (I) will be described first.

The polymerizable monomer composition (I) used in the present invention comprises the following components (I-1), (I-2), (I-3) and (I-4) (the sum of these components is 100% by mass).
(I-1) 7 to 20% by mass of a component composed of a bifunctional polymerizable monomer represented by the formula (1),
(I-2) 10 to 60% by mass of a component composed of a bifunctional polymerizable monomer represented by the formula (2),
(I-3) 1 to 15% by mass of a component composed of the polyfunctional polymerizable monomer represented by the formula (3) and (I-4) any of the following (I-1) to (I-3) 5 to 82% by mass of a component composed of a polymerizable monomer not corresponding to

In the above formulas (1) to (3), R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a methyl group, and R ³ and R ⁴ each independently A hydrogen atom or a C1-C2 alkyl group (namely, a methyl group or an ethyl group) is meant. In addition, the group —X— is —O—, —S—, —S (═O) ₂ —, —C (═O) —O—, —CH ₂ —, —CH═CH— or —C (CH ₃ ) means a group represented by _2- , and the group —R ⁸ — represents —CH ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) O— or —C (═O) CH ₂ CH ₂ CH _2. means CH ₂ CH ₂ O-group represented by. R ⁹ means a trivalent to hexavalent organic residue. Examples of the 3- to 6-valent organic residue include those shown below.

  Furthermore, m and n mean an integer where m + n is 2 to 30, p means an integer of 1 to 4, a and b mean an integer of 0 to 3 and an integer of 3 to 6, respectively.

  When the m + n is less than 8, the bifunctional polymerizable monomer represented by the formula (1) constituting the component (I-1) (C) in the conventional composition disclosed in Patent Document 1 ) Component, that is, a polymerizable monomer (monomer) included in a bifunctional polymerizable monomer having an L-scale Rockwell hardness of 60 or more obtained by homopolymerization, and m + n is 8 or more. In the case of (1), the polymerizable monomer (monomer) contained in the polymerizable monomer (A) in the conventional composition, that is, the L-scale Rockwell hardness of the polymer obtained when homopolymerized is 40 or less. It is. The L scale Rockwell hardness referred to here is a value determined based on JIS K7202, and specifically, using a indenter made of a hard sphere having a diameter of 6.350 mm on the surface of the cured body test piece, When a load of 10 kgf is added, then a test load of 60 kgf is added, and then returned to the reference load again, the difference in penetration depth h (in mm) between the front and rear two times of the indenter is 130-500 h. It is a value obtained by a calculation formula.

  Specific examples of the bifunctional monomer (I-1) that can be suitably used in consideration of availability are 2,2-bis [4- (methacryloyloxypolyethoxy) phenyl. ] Propane (m + n average value of 2), same (m + n average value of 2.6), same (m + n average value of 4), same (m + n average value of 10) (M + n having an average value of 30), 2,2-bis [4- (acryloyloxypolyethoxy) phenyl] propane (m + n having an average value of 4), 2,2-bis [4- (Methacryloyloxypolypropoxy) phenyl] propane (m + n having an average value of 4), the same (m + n having an average value of 10), bis [4- (methacryloyloxypolyethoxy) phenyl] methane (m + n (Average value is 4), screw [4- Methacryloyloxy polyethoxy) phenyl] sulfone (m + average value of n is that of 4), and the like. These may be used alone or in combination of two or more.

  The content of the component (I-1) in the polymerizable composition (I) needs to be in the range of 7 to 20% by mass based on the total mass of all the monomer components contained in the composition (I). is there. When the content of the component is less than 7% by mass, the strength (toughness) required for the rimless glasses cannot be obtained. On the other hand, when the content exceeds 20% by mass, the refractive index of the cured product is 1.530. It becomes difficult to adjust to the following. For these reasons, the content of the component (I-1) is preferably 10 to 18% by mass on the basis of the above.

  Component (I-2) consisting of a bifunctional monomer represented by the formula (2) functions to adjust the refractive index of the cured product to 1.530 or less, preferably 1.528 or less, and also absorbs water from the cured product. It works to reduce. The bifunctional monomer corresponds to the component (C) of the conventional composition. Among the monomers represented by the formula (2), specific examples of monomers that can be suitably used in consideration of availability are tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, and the like. . These may be used alone or in combination of two or more.

  The content of the component (I-2) in the polymerizable composition (I) needs to be in the range of 10 to 60% by mass based on the total mass of all the monomer components contained in the composition (I). is there. When the content of the component (B) is less than 10% by mass, it becomes difficult not only to adjust the refractive index of the cured product to 1.530 or less, preferably 1.528 or less, but also sufficiently low water absorption. Cannot be obtained. On the other hand, if it exceeds 60% by mass, the strength (toughness) required for rimless glasses cannot be obtained. The content of the component (I-2) is preferably 20 to 55% by mass on the basis of the above.

  Component (I-3) comprising the polyfunctional monomer represented by the formula (3) is component (B) in the conventional composition disclosed in Patent Document 1, that is, a polymer obtained by homopolymerization. This corresponds to a trifunctional or higher functional polymerizable monomer having an L scale Rockwell hardness of 60 or higher. By using the polymerizable monomer (monomer), it is possible to obtain a cured product having excellent photochromic characteristics, particularly represented by a half life of fading. Specific examples of the specific polyfunctional monomer that can be suitably used in consideration of easy availability are trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane. Triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol Tetramethacrylate, pentaerythritol trimethacrylate, pentaerythris Tall tetramethacrylate, caprolactam modified ditrimethylolpropane tetraacrylate, caprolactam modified ditrimethylolpropane tetramethacrylate, mention may be made of caprolactam modified dipentaerythritol hexaacrylate. These may be used alone or in combination of two or more.

  The content of the polyfunctional monomer of the component (I-3) in the composition of the present invention is 1 to 15% by mass, preferably 5 to 10%, based on the total weight of all the monomer components contained in the composition (I). It must be in the range of mass%. When the content of the component (I-3) is less than 1% by mass, sufficient photochromic properties cannot be obtained. On the other hand, when the content exceeds 15% by mass, the strength (toughness) required for rimless glasses is obtained. I can't get it.

  The polymerizable monomer composition (I) further comprises a polymerizable monomer (hereinafter referred to as other monomer) that does not fall under any of the above (I-1) to (I-3) as the component (I-4). 5) to 82 mass%, preferably 17 to 65 mass%. As the other monomer, for example, the component (A) and the component (C) used in the curable composition (conventional composition) disclosed in Patent Document 1 (WO01 / 05854). Among these monomers, those not corresponding to the above (I-1) to (I-3) can be preferably used, but from the viewpoint of effects, the component (I-4) is used (I -1) Depending on the type of component, the polymerizable monomer composition (I) is selected so that all components (A), (B) and (C) of the conventional composition are included. Is preferred.

  Specific examples of suitable monomers as the component (I-4) include polyethylene glycol methacrylate having an average molecular weight of 526, polyethylene glycol methacrylate having an average molecular weight of 360, and methyl ether polyethylene having an average molecular weight of 475. Glycol methacrylate, methyl ether polyethylene glycol methacrylate with an average molecular weight of 1000, polypropylene glycol methacrylate with an average molecular weight of 375, polypropylene glycol methacrylate with an average molecular weight of 430, stearyl methacrylate, lauryl methacrylate, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, tetraethylene glycol diacrylate , Nonaethylene glycol diacrylate etc. are used That.

  Moreover, as what corresponds to (C) component, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, nonaethylene glycol dimethacrylate, nonapropylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, 1, 4 -Butylene glycol dimethacrylate, 1,9-nonylene glycol dimethacrylate, neopentylene glycol dimethacrylate and the like can be used.

  Further, as other monomers, polymerizable monomers other than the components (A) and (C) include polyallyl compounds such as diallyl phthalate, diallyl isophthalate and diallyl tartrate; glycidyl acrylate, glycidyl methacrylate, methyl acrylate, Acrylic acid ester compounds such as methyl methacrylate and benzyl methacrylate and methacrylic acid ester compounds; vinyl compounds such as styrene, chlorostyrene, methylstyrene, vinylnaphthalene, α-methylstyrene dimer, bromostyrene, and divinylbenzene can also be used.

  The polymerization curable composition of the present invention contains a photochromic compound as component (II). As the photochromic compound, known photochromic compounds such as a chromene compound, a fulgimide compound, and a spirooxazine compound can be used without particular limitation. However, when a high molecular weight photochromic compound having a molecular weight of 200 or more, particularly 500 or more, is used. It is preferable to use such a photochromic compound since the effect (particularly, the effect of exhibiting good photochromic characteristics when used as a cured product) is remarkable. Among these photochromic compounds, chromene compounds are particularly suitable because they have higher photochromic properties than other series of compounds and are excellent in color density, fading speed and the like. Specific examples of photochromic compounds that can be suitably used in the present invention include the following. These compounds can be used alone, but are usually used in combination with one or more other photochromic compounds (including the following compounds and other photochromic compounds) in order to adjust the color tone during color development. There are many cases.

  Molecular weight 376

  Molecular weight 515

  Molecular weight 522

  Molecular weight 547

  Molecular weight 561

  Molecular weight 568

  Molecular weight 673

Molecular weight 681
The amount of the photochromic compound in the curable composition of the present invention needs to be 0.001 to 5 parts by mass with respect to 100 parts by mass of the polymerizable monomer composition (I). When the content of the photochromic compound is less than 0.001 part by mass based on the above criteria, a sufficient color density cannot be obtained, and when it exceeds 5 parts by mass, it is difficult to uniformly disperse. From the viewpoint of color density and uniform dispersibility, the content of the photochromic compound is preferably 0.01 to 2 parts by mass based on the above criteria.

  In the above curable composition, an additive is added for the purpose of improving the durability of the photochromic compound, improving the color development speed, improving the fading speed, and improving the moldability within the range not impairing the effects of the present invention. Further, it can be added. Additives that can be suitably used include surfactants, antioxidants, radical scavengers, UV stabilizers, UV absorbers, mold release agents, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, etc. Can be mentioned.

  The addition amount of the surfactant is preferably 0 to 20 parts by mass with respect to 100 parts by mass of the total polymerizable monomer, and is an antioxidant, radical scavenger, ultraviolet stabilizer, ultraviolet absorber, release agent. The addition amount of the mold agent, anti-coloring agent, antistatic agent, fluorescent dye, dye, pigment, and fragrance is preferably 0 to 2 parts by mass with respect to 100 parts by mass of the total polymerizable monomer, respectively. .

  The method for producing a cured product by curing the curable composition is not particularly limited, and after preparing a polymerization curable composition of the present invention by weighing out a predetermined amount of each component and mixing them appropriately, thermal polymerization and / or Alternatively, it may be cured by photopolymerization. At this time, a polymerization initiator may be used as necessary.

  Although it does not restrict | limit especially about the polymerization initiator used for hardening by heat, Specifically, diacyl peroxides, such as a benzoyl peroxide, p-chloro benzoyl peroxide, a decanoyl peroxide, a lauroyl peroxide, an acetyl peroxide; Peroxyesters such as t-butylperoxy-2-ethylhexanoate, t-butylperoxydicarbonate, cumylperoxyneodecanate, t-butylperoxybenzoate, t-butylperoxyisobutyrate; diisopropyl Percarbonates such as peroxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-sec-butyloxycarbonate; 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-dimethyl) Reronitoriru), 2,2'-azobis (2-methylbutyronitrile), mention may be made of 1,1'-azobis (cyclohexane-1-carbonitrile) azo compounds such like.

  Further, the polymerization initiator used for curing by light is not particularly limited. Specifically, benzoin, benzoin methyl ether, benzoin butyl ether, benzophenol, acetophenone, 4,4′-dichlorobenzophenone, diethoxyacetophenone, 2 -Hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2 -Isopropylthioxanthone, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, and the like.

  The amount of the polymerization initiator is not particularly limited, but it is 0 with respect to 100 parts by mass of the total polymerizable monomer from the viewpoint of sufficiently allowing the polymerization to proceed and not leaving an excessive polymerization initiator in the cured product. 0.001 to 10 parts by mass, particularly 0.01 to 3 parts by mass is preferred.

The cured product obtained by curing the polymerization curable composition of the present invention has excellent characteristics when it has high photochromic properties, hardness and strength (toughness). Since the cured product has such excellent characteristics, it can be particularly suitably used as a photochromic plastic lens substrate for optical articles, particularly rimless spectacles. When the cured product of the present invention is used for such applications, a lens base material molded and processed into an appropriate shape can be used as a lens as it is, but the lens is subjected to surface processing as necessary. It can also be. That is, treatment with a silane coupling agent and a hard coating agent mainly composed of sol components such as silicon, zirconium, antimony, aluminum, tin, and tungsten, and vapor deposition of a thin film of metal oxide such as SiO ₂ , TiO ₂ , and ZrO ₂ Or an antireflection treatment by applying a thin film of an organic polymer, etc., to give a lens.

  The photochromic plastic lens made of a cured product of the polymerization curable composition of the present invention is a spectacle lens made of a molded product in which a photochromic compound is dispersed in a polymer matrix, and the spectacle lens has the following excellent characteristics. Have. That is, the half-life of fading is 4 minutes or less, preferably 2 minutes or less, and the water absorption is 3% or less, preferably when the spectacle lens is irradiated with ultraviolet rays to stop the ultraviolet irradiation after the photochromic compound is brought into a colored state. Is 2.5% or less, the refractive index is 1.518 to 1.530, preferably 1.520 to 1.528, and the tensile strength defined below is 15 Kgf or more.

  Here, the term “fading half-life” means “when the UV irradiation is stopped after the photochromic compound is irradiated by irradiating the spectacle lens with ultraviolet rays, the absorbance at the maximum wavelength during color development is ½ of that during color development. It is a value that is an index of the fading speed, which is one of the most important characteristics among the photochromic characteristics. In the spectacle lens of the present invention, the fading half-life of the photochromic compound is within 10 times, preferably within 7 times, particularly preferably within 5 times the fading half-life of the photochromic compound in the solution, and the fading half-life in the lens is Within 4 minutes, preferably within 2.5 minutes. In addition, although the solvent of the said photochromic compound solution is not specifically limited, As a standard solvent, ethylene glycol dimethyl ether can be mentioned.

The “tensile strength” is an index of the anti-drilling strength, and “the two straight lines that pass through the center of gravity of the spectacle lens or its vicinity and cross the lens substrate and the periphery of the lens substrate. Two holes with a diameter of 2 mmφ are drilled in the lens centering on two points on the straight line 4 mm inside from the intersection point, respectively, and then the obtained two holes are made of stainless steel with a diameter of 1.6 mmφ. It means “tensile strength when these two bars are fixed to the upper and lower chucks of the tensile tester after the bars are penetrated and a tensile test is performed at a speed of 5 mm / min”. Since the spectacle lens is a board body with a surface area of 10 to 40 cm ² which may be curved, usually having a thickness of 1 to 5 mm, the tensile strength is such that a test piece is prepared, The test piece has a diameter of 2 mmφ centered at two points on the straight line 4 mm inside each of the two intersections of the arbitrary line that passes through or near the center of gravity of the test piece and crosses the test piece and the periphery of the substrate. Two holes are drilled by drilling, and then a stainless steel rod having a diameter of 1.6 mmφ is passed through each of the two drilled holes, and then the two rods are fixed to the upper and lower chucks of the tensile tester. It can be said that the tensile strength is obtained when the tensile test is performed at a speed of 5 mm / min. In such tensile strength tests, specimen breakage usually occurs in the vicinity of a drilled hole, and for those normally used as spectacle lenses, the tensile strength is hardly affected by the shape of the substrate. . However, when the tensile strength is used as an index of the perforation-proof strength of an actual spectacle lens, when a rimless frame (that is, an arm member connected to a hinge) is attached to the spectacle lens processed into an actually used shape, It is preferred to drill one of the two holes so that they are at the same or nearly the same position and perform a tensile test.

  The tensile strength that can be used for the rimless glasses is 15 kgf or more, preferably 20 kgf or more, and the tensile strength of 15 kgf or more shows good results in the use of the rimless glasses monitor, and at any position on the substrate. When drilling a hole with a diameter of 2 mmφ violently at a rotation speed of 2100 rpm (as a guide, at a speed of 1 hole / second), no large cracks are generated (the length of the crack is within 0.4 mm). It corresponds to that.

  The water absorption rate is an index representing the water absorption rate of a substance, and is measured as follows. That is, the surface water of the wet sample is completely wiped off to make the surface dry and saturated, and the mass (A) at that time is measured. Then, the sample is dried at a temperature of 100 to 110 ° C. until a constant mass is obtained. The mass (B) of the state (absolute dry state) is measured, and is obtained according to the following formula.

Water absorption rate = {(BA) / A} × 100 (%)
The wet state refers to a state in which moisture is attached to the entire surface of the sample, and a state in which the wet surface water is completely wiped off is a surface dry saturated state. Moreover, an absolute dry state means the state which dried the sample of the surface dry saturated state until it became a constant mass at the temperature of 100-110 degreeC.
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. The abbreviations and names of the compounds used in the examples are shown below.

(I-1) component bifunctional monomer BPE100: 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane (average of m + n is 2.6)
BPE200: 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane (average value of m + n is 4)
BPE500: 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane (average value of m + n is 10).

(I-2) Component bifunctional monomer 3PGX: tripropylene glycol dimethacrylate 4PGX: tetrapropylene glycol dimethacrylate.

(I-3) Component polyfunctional monomer TMPT: trimethylolpropane trimethacrylate TMPT3EO: ethoxylated trimethylolpropane trimethacrylate.

(I-4) Monomer corresponding to component (A) A200: Tetraethylene glycol diacrylate A400: Nonaethylene glycol diacrylate (C) Component corresponding to KT-04: Tetraethylene glycol dimethacrylate (A) Component, corresponding to monomer other than component (C) M90G: Methyl ether polyethylene glycol methacrylate GMA: glycidyl methacrylate αMS: α-methylstyrene MSD: α-methylstyrene dimer having an average molecular weight of 475.

(II) Photochromic compound chromene 1: Compound having the following structure (the fading half-life of the compound in an ethylene glycol dimethyl ether (EGDME) solution is 0.4 minutes)

Chromene 2: Compound having the following structure (the fading half-life of the compound in an ethylene glycol dimethyl ether (EGDME) solution is 0.3 minutes)

(III) Additive Tween 20: Polyoxyethylene (20) sorbitan monolaurate.

(IV) Thermal polymerization initiator perbutyl ND: t-butylperoxyneodecanoate.
Perocta O: 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate Perbutyl O: t-butyl peroxy-2-ethylhexanoate

  Below, the photochromic characteristic of the obtained hardening body, the intensity | strength characteristic, and the evaluation method of water absorption are shown.

(1) Strength characteristics After forming a disk-shaped test piece having a thickness of 2 mm and a diameter of 5 cmφ using the obtained cured body, a point about 4 mm from the periphery is centered on a line that becomes the diameter of the disk-shaped test piece. Two holes with a diameter of 2mmφ were drilled by drilling, and a stainless steel rod with a diameter of 1.6mmφ was passed through each of the two drilled holes, and each of these two rods was subjected to a tensile test while passing through the test piece. The tensile strength when the tensile test was carried out at a speed of 5 mm / min was fixed to the upper and lower chucks of the machine.

(2) Water absorption The obtained cured product is put into a container containing distilled water, the container is heated to 70 ° C. in an air circulation oven, the cured product is taken out, the mass is measured, and the mass becomes constant. The heating was stopped, the mass of the cured product was measured, and the water absorption was determined from the mass of the cured product before being put into the container.

(3) Refractive index The refractive index at 20 ° C. was measured using an Abbe refractometer manufactured by Atago Co., Ltd. Bromonaphthalene was used as the contact liquid.

(4) Photochromic characteristics A xenon lamp L-2480 (300W) SHL-100 made by Hamamatsu Photonics was applied to the obtained cured body (disk shape having a thickness of 2 mm and a diameter of 5 cm) through an aeromass filter (manufactured by Corning). The sample was irradiated for 120 seconds at a temperature of ± 1 ° C. and a beam intensity of 365 nm = 2.4 mW / cm ² and 245 nm = 24 μW / cm ² on the polymer surface, and the photochromic characteristics of the sample were measured. Each photochromic characteristic was evaluated by the following method.

  (i) Maximum absorption wavelength (λmax): This is the maximum absorption wavelength after color development determined by a spectrophotometer (instant multichannel photodetector MCPD1000) manufactured by Otsuka Electronics Co., Ltd. The maximum absorption wavelength is related to the color tone at the time of color development.

  (ii) Color density {ε (120) −ε (0)}: The difference between the absorbance {ε (120)} after 120 seconds of light irradiation and the above ε (0) at the maximum absorption wavelength. It can be said that the higher this value, the better the photochromic properties.

(iii) Fading half-life [t _1/2 (min.)]: When light irradiation is stopped after 120 seconds of light irradiation, the absorbance of the sample at the maximum wavelength is {ε (120) −ε (0) }, The time required to drop to 1/2. It can be said that the shorter the time, the faster the fading speed and the better the photochromic property.

Example 1
BPE100: 17 parts by mass, 3PGX: 55 parts by mass, TMPT: 5 parts by mass, A200: 5 parts by mass, GMA: 10 parts by mass, αMS: 7 parts by mass, MSD: 1 part by mass were sufficiently mixed. To this, 0.03 part by mass of chromene 1, 1 part by mass of perbutyl ND as a thermal polymerization initiator, and 0.1 part by mass of perocta O were added and mixed thoroughly. This mixed solution was poured into a mold composed of a glass mold and a gasket made of an ethylene-vinyl acetate copolymer. After thermal polymerization at 90 ° C. for 2 hours, the cured product was removed from the mold glass mold. Next, the photochromic properties and strength properties of the obtained cured body, and further water absorption were evaluated. The results are shown in Table 1. In Table 1, the fading half-life of the EGDME solution was obtained by separately preparing EGDME having the same concentration.

Example 2
BPE100: 17 parts by mass, 3PGX: 50 parts by mass, TMPT: 5 parts by mass, M90G: 5 parts by mass, A200: 5 parts by mass, GMA: 10 parts by mass, αMS: 7 parts by mass, MSD: 1 part by mass did. To this, 0.03 part by mass of chromene 1, 1 part by mass of perbutyl ND as a thermal polymerization initiator, and 0.1 part by mass of perocta O were added and mixed thoroughly. This mixed solution was poured into a mold composed of a glass mold and a gasket made of an ethylene-vinyl acetate copolymer. After thermal polymerization at 90 ° C. for 5 hours, the cured product was removed from the mold glass mold. Subsequently, the photochromic characteristics and strength characteristics of the obtained cured body were evaluated. The results are also shown in Table 1.

Examples 3-10
Similarly to Example 1, the polymerized curable composition shown in Table 1 was polymerized to obtain a cured product, and the photochromic properties and strength properties of the obtained cured product were evaluated. The results are shown in Table 1.

Comparative Example 1
BPE100: 50 parts by mass, TMPT: 5 parts by mass, KT-04: 22 parts by mass, A200: 5 parts by mass, GMA: 10 parts by mass, αMS: 7 parts by mass, MSD: 1 part by mass were sufficiently mixed. To this, 0.03 part by mass of chromene 1, 1 part by mass of perbutyl ND as a thermal polymerization initiator, and 0.1 part by mass of perocta O were added and mixed thoroughly. This mixed solution was poured into a mold composed of a glass mold and a gasket made of an ethylene-vinyl acetate copolymer. After thermal polymerization at 95 ° C. for 5 hours, the cured product was removed from the mold glass mold. The evaluation results of the photochromic properties and strength properties of the obtained cured product were performed, and the results are shown in Table 1.

Comparative Examples 2-6
In the same manner as in Comparative Example 1, polymerized curable compositions listed in Table 1 were polymerized to obtain cured products. Table 1 shows the evaluation results of the photochromic properties and strength properties of the obtained cured product.

From Table 1, the cured product obtained from the polymerization curable composition of the present invention has excellent photochromic properties and water absorption resistance, has strength that can be used for rimless glasses, and has a low refractive index of 1.500. It is adjusted to ˜1.530. On the other hand, when the blending ratio of the bifunctional monomer (I-1), the monomer (I-2), and the polyfunctional monomer (I-3) is out of the range specified in the present invention, the refractive index is It exceeds 1.530, sufficient photochromic properties cannot be obtained, water absorption is high, or strength is decreased, and as a result, a good physical property balance is not obtained.

Claims (5)

(I): (I-1) 7 to 20% by mass of a component composed of a bifunctional polymerizable monomer represented by the following formula (1), (I-2) bifunctional represented by the following formula (2) 10 to 60% by mass of a component composed of a polymerizable monomer, (I-3) 1 to 15% by mass of a component composed of a polyfunctional polymerizable monomer represented by the following formula (3), and (I-3) 100 parts by mass of a polymerizable monomer composition comprising 5 to 82% by mass of a component comprising a polymerizable monomer not corresponding to any of (I-1) to (I-3) and (II): photochromic compound 0 A polymerization curable composition comprising 0.001 to 5 parts by mass.

{In the formula, R ¹ and R ² are each independently a hydrogen atom or a methyl group; R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 2 carbon atoms; A group represented by O—, —S—, —S (═O) ₂ —, —C (═O) —O—, —CH ₂ —, —CH═CH— or —C (CH ₃ ) ₂ —; M and n are integers in which m + n is 2 to 30. }

(In the formula, R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group, and p is an integer of 1 to 4.}

{In the formula, R ⁷ represents a hydrogen atom or a methyl group, and the group —R ⁸ — represents —CH ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) O— or —C (═O) CH ₂ CH ₂ a CH ₂ CH ₂ CH ₂ O-, a group represented by, ^{R 9} is a trivalent to hexavalent organic residue, a is an integer from 0 to 3, b is an integer from 3 to 6. } A cured product obtained by polymerizing the polymerization curable composition according to claim 1. In a spectacle lens made of a molded product in which a photochromic compound is dispersed in a polymer matrix, the fading half-life defined below is 4 minutes or less, the water absorption is 3% or less, and the refractive index is 1.518 to The spectacle lens according to claim 1, wherein the spectacle lens is 1.530 and has a tensile strength defined below of 15 kgf or more.
Fading half-life: The time required for the absorbance at the maximum wavelength during color development to drop to half that during color development when UV irradiation is stopped after the photochromic compound is colored by irradiating the spectacle lens with ultraviolet rays. Intensity: The lens centered at two points on the straight line 4 mm inside each of two intersection points between an arbitrary straight line passing through or near the center of gravity of the spectacle lens and crossing the lens base and the periphery of the lens base Two holes with a diameter of 2 mmφ are drilled by drilling, and then the stainless steel rods with a diameter of 1.6 mmφ are penetrated into the two obtained drillings, respectively. Tensile strength when fixed to chuck and subjected to tensile test at 5mm / min A spectacle lens comprising the spectacle lens according to claim 3 or a surface-treated spectacle lens obtained by subjecting the spectacle lens to surface treatment, and an arm member for latching the spectacle lens during use. glasses. The spectacles according to claim 4, wherein the spectacle lens has a screw hole, and the spectacle lens and the arm member are connected via a hinge screwed to the lens.