JP5100545B2 - Polymerization curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerization-curable composition giving a cured body exhibiting good photochromic characteristics with high coloring density and quick decoloring rate, further excellent in basic characteristics of the cured body such as hardness, heat resistance and impact resistance, as well as enough strength (toughness) to be used for rimless glasses. <P>SOLUTION: This polymerization-curable composition comprises a mixture containing a specific multifunctional polymerizable monomer having such a hard molecular structure that a polymer obtained by homopolymerization thereof gives &ge;60 Rockwell hardness in L-scale, and a multifunctional monomer or a multifunctional oligomer having a value (M/v) of dividing its molecular weight (M) by the number (v) of polymerizable groups existing in the molecule of 300 or more, respectively at specific proportions, combined with a photochromic compound and a photopolymerization initiator. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

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.

  Photochromic glasses are lenses that quickly color and function as sunglasses when exposed to light containing ultraviolet rays such as sunlight. These glasses function as glasses, and their demand is increasing in recent years.

  As one method for producing a plastic lens having photochromic properties, 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) is 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 expressed 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 resin 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 the monomer solution, and the structural change is likely to be constrained. This is especially true for resin matrices with high hardness and heat resistance. This tendency is remarkable when a photochromic compound having a molecular weight is dispersed. For example, when a photochromic compound having a molecular weight of 300 or more is dispersed in a resin 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 speed in the resin matrix is 50 times or more than the fading speed in the monomer solution.

  As a resin composition that gives a photochromic cured product having no such problem, that is, excellent photochromic properties and high hardness and heat resistance, (A) L scale Rockwell hardness of the polymer obtained when homopolymerized Is a polymerizable monomer having an L scale Rockwell hardness of 60 or more, and (C) a polymer obtained by homopolymerization. A polymerization curable composition (hereinafter also referred to as conventional composition) comprising a bifunctional polymerizable monomer having a combined L-scale Rockwell hardness of 60 or more and (D) a photochromic compound is known (Patent Document 1). reference).

International Publication No. 01/05854 Pamphlet

  The above-mentioned conventional composition is extremely useful as a raw material composition for producing a photochromic plastic lens by a kneading method, but a rimless eyeglass that has recently been popularized as a cured product obtained by curing the composition. When it is intended to be used for (glasses without edges with a hole in the lens and a frame fixed), when drilling with a drill, or when there is no particular problem during drilling However, it has become clear that when a load is applied to the fixed frame, the lens of the fixed part is damaged.

  Therefore, the present invention exhibits excellent photochromic properties such as high color density and fast fading speed, and has excellent substrate properties such as high hardness and heat resistance, and at the same time, strength (toughness) that can be used for rimless glasses. An object is to provide a photochromic plastic lens having both of the above.

  The present inventors diligently studied to achieve the above object. As a result, it was found that about 3% of unpolymerized monomer remained in the cured product obtained by curing the conventional composition. Therefore, it is thought that the cause of the above problem is due to the presence of unpolymerized monomers, and the polymer obtained when homopolymerized as a monomer constituting a crosslinking point has a L-scale Rockwell hardness of 60 or more and a trifunctional or more functional polymerization. Monomer (using the component (B) in the conventional composition and having a reasonably long molecular chain between the functional groups (polymerizable groups) as the polyfunctional monomer constituting the molecular chain connecting the crosslinking points) Therefore, if the cross-linking points are composed of highly rigid molecular chains and the distance between the cross-linking points is a moderately long cross-linked body, the photochromic properties are not affected by the rigidity of the molecular chains between the cross-linking points. Free space can be secured, and at the same time, the number of polymerizable groups (functional groups) that cannot react due to steric hindrance can be reduced, resulting in a reduction in the amount of residual monomers. It was carried out various studies on the basis of the hypothesis that either does not kill for. As a result, a desired photochromic cured product can be obtained by using a specific monomer and a polyfunctional monomer having a reasonably long functional group in the component (B) in combination, and uniformly polymerizing by photopolymerization. As a result, the present invention has been completed.

  That is, the present invention provides (I) the following formula (1)

{In the formula, R ¹ represents a hydrogen atom or a methyl group, and the group —R ² — 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 3} is 3 to 6 valent organic residue, a is an integer from 0 to 3, b is an integer from 3 to 6. }
A polyfunctional polymerizable monomer represented by
(II) The value (M / v) obtained by dividing the molecular weight (M) by the number of polymerizable groups (v) present in the molecule is 300 or more, and the following formula (2)

{In the formula, R ⁴ and R ⁵ are each independently a hydrogen atom or a methyl group; R ⁶ and R ⁷ 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 —; And m and n are integers such that m + n is 6-30. }
A bifunctional polymerizable monomer represented by:
(III) a photochromic compound and (IV) an acyl phosphine oxide-based compound as a photopolymerization initiator, and the above-mentioned many compounds based on all polymerizable monomers contained in the polymerization-curable composition. A polymerization curable composition in which the content of the functional polymerizable monomer (I) and the bifunctional polymerizable monomer (II) is 10 to 60% by weight and 20 to 90% by weight, respectively.
The fading half-life of the photochromic compound (III) in the cured product is within 10 times the fading half-life of the photochromic compound in the polymerization curable composition, and the tensile strength defined below of the cured product is 20 kgf It is a polymerization curable composition characterized by becoming above.

  Tensile strength: after forming a disk-shaped test piece having a thickness of 2 mm and a diameter of 5 cmφ using the cured body, a diameter of 2 mmφ centered at a point of 4 mm from the periphery on a line that becomes the diameter of the disk-shaped test piece. These two holes were drilled, and a stainless steel rod with a diameter of 1.6 mmφ was passed through each of the two drilled holes, and these two rods were pulled through the test piece. Tensile strength when fixed to upper and lower chucks and subjected to a tensile test at a speed of 5 mm / min.

  By photopolymerizing the polymerizable composition of the present invention, a cured product having excellent characteristics such as high photochromic properties, hardness and strength (toughness) can be obtained. Such an excellent feature is that the resin matrix has a sufficient free space that does not deteriorate the photochromic properties of the photochromic compound (for example, does not increase the half-life of the color fading corresponding to the color fading speed), and the vicinity of the bridge is rigid. It is derived from a unique structure consisting of molecular chains and very low residual monomer content, but unfortunately it is difficult to identify such structures directly using currently available analytical tools. Yes, it must be specified using physical properties. A cured product having such a unique structure has not been known so far, and it is considered that the cured product itself has patentability.

  The polymerization curable composition of the present invention has excellent photochromic properties such as a high color density and a fast fading rate, and also has excellent substrate properties such as hardness, heat resistance, and impact resistance, and at the same time strength that can be used for rimless glasses. A photochromic cured body having both (toughness) can be obtained.

  (I) used in the polymerization curable composition of the present invention (1)

{In the formula, R ¹ represents a hydrogen atom or a methyl group, and the group —R ² — 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, R3 is trivalent to hexavalent organic residue, a is an integer from 0 to 3, b is an integer from 3 to 6. }
The polyfunctional polymerizable monomer represented by the formula (B) in the conventional composition disclosed in Patent Document 1, that is, the L-scale Rockwell hardness of the polymer obtained by homopolymerization is 60 or more. This corresponds to a tri- or higher functional polymerizable monomer.

  Specific examples of the polyfunctional polymerizable monomer represented by the formula (1) that can be suitably used include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, and tetramethylolmethane. Triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol Tetramethacrylate, pentaerythritol trimethacrylate, pentaerythritol Lumpur tetramethacrylate, caprolactam modified ditrimethylolpropane tetraacrylate, caprolactam modified ditrimethylolpropane tetramethacrylate, mention may be made of caprolactam modified dipentaerythritol hexaacrylate.

  In addition, L scale Rockwell hardness here is a value determined based on JIS K7202, and specifically, using an indenter made of a hard sphere having a diameter of 6.350 mm on the surface of the cured body test piece, When 10 kggf which is a reference load is added, and then 60 kgff which is a test load is added and returned to the reference load again, from the difference h (in mm) of the indenter penetration depth between the two reference loads before and after, 130-500 h It is the value calculated | required by the calculation formula.

The content of component (I) in the composition of the present invention needs to be in the range of 10 to 60% by weight based on the total weight of all polymerizable monomers and polymerizable oligomers contained in the composition. When the content of component (I) is less than 10% by weight, sufficient photochromic properties cannot be obtained, and when the content exceeds 60% by weight, the strength (toughness) required for rimless glasses. Cannot be obtained. Considering the balance between the two, the content of component (I) is 10 to 30% by weight, particularly 15 to 25% by weight, when R ^{1 in the} formula (1) is a methyl group and a is 0. In other cases, it is preferably 30 to 60% by weight, particularly 40 to 60% by weight.

  The composition of the present invention is a polyfunctional polymerizable compound having a molecular weight (M) divided by the number (v) of polymerizable groups present in the molecule (M / v) of 300 or more as component (II). Contains monomers or polyfunctional polymerizable oligomers. By using component (I) and component (II) in combination, the free space can be widened while maintaining high strength, and the amount of functional groups (polymerizable groups) that cannot be polymerized due to steric hindrance is reduced, and the residual monomer The amount can be reduced.

  The content of component (II) in the composition of the present invention is the total weight of all polymerizable monomers and polymerizable oligomers contained in the composition from the viewpoint of ensuring the strength (toughness) required for rimless glasses. It is preferable that the content is in the range of 20 to 90% by weight, particularly 40 to 80% by weight based on the above.

  The polyfunctional polymerizable monomer or oligomer contained in component (II) has a value (M / v) obtained by dividing its molecular weight (M) by the number (v) of polymerizable groups present in the molecule, of 300 or more. The following can be used. Such a polyfunctional polymerizable monomer or oligomer having (M / v) of 300 or more may be used alone, or two or more kinds may be used in combination. The L scale Rockwell hardness when the polyfunctional polymerizable monomer or oligomer corresponding to (II) is homopolymerized is not particularly limited, but the L scale lock when homopolymerizing the monomer corresponding to (II) is not limited. The well hardness is often 40 or less (that is, it corresponds to the component (A) of the conventional composition).

  As the polyfunctional polymerizable monomer or oligomer (II), the following formula (2) is obtained because it is easy to obtain and a cured product having excellent strength (toughness) can be obtained.

{In the formula, R ⁴ and R ⁵ are each independently a hydrogen atom or a methyl group; R ⁶ and R ⁷ 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 —; And m and n are integers such that m + n is 6-30. }
The bifunctional polymerizable monomer represented by these is contained.

  Specific examples of those that can be suitably used include 2,2-bis [4- (methacryloyloxypolyethoxy) phenyl] propane (m + n having an average value of 10), and the same (m + n having an average value of 30). ), 2,2-bis [4- (acryloyloxypolyethoxy) phenyl] propane (m + n having an average value of 10), 2,2-bis [4- (methacryloyloxypolypropoxy) phenyl] Propane (m + n having an average value of 10), bis [4- (methacryloyloxypolyethoxy) phenyl] methane (m + n having an average value of 10), bis [4- (methacryloyloxypolyethoxy) phenyl] And sulfone (m + n having an average value of 10).

  These may be used alone or in combination of two or more.

  Moreover, as a polyfunctional polymerizable monomer or oligomer (II), 2-6 functional polymerizable polyurethane oligomers, 2-2 from the reason that the hardened | cured material excellent also in the availability and especially strength (toughness) is obtained. A hexafunctional polymerizable polyester oligomer can also be preferably used.

  The 2-6 functional polymerizable polyurethane oligomer here is a product obtained by adding hydroxyacrylic acid or hydroxymethacrylic acid to an isocyanate group remaining in a polyurethane skeleton synthesized from various diisocyanates and polyols. Specific examples of the diisocyanate include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, and the like. Specific examples of the polyol include polypropylene oxide diol, copolyethylene oxide-propylene oxide diol, polytetramethylene oxide diol, ethoxylated bisphenol A, ethoxylated bisphenol S spiro glycol, caprolactone-modified diol, carbonate diol, polyester diol, and the like. Can be mentioned.

  The 2-6 functional polymerizable polyurethane oligomer may be used alone or in combination of two or more.

  Next, the 2-6 functional polymerizable polyester oligomer referred to here is a product obtained by condensing acrylic acid or methacrylic acid to a hydroxyl group remaining in a polyester skeleton synthesized from various polyols and polybasic acids. Specific examples of polyols include diethylene glycol, triethylene glycol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, and the like. Specific examples of polybasic acids include phthalic anhydride, adipic acid, trimellitic acid, and the like. Is mentioned.

  A 2-6 functional polymerizable polyester oligomer may be used individually, and may mix and use two or more types.

  The bifunctional polymerizable monomer represented by the above formula (2), the 2-6 functional polymerizable polyurethane oligomer, and the 2-6 functional polymerizable polyester oligomer described above may be used alone or in combination. You may mix and use the above. That is, a combination of a bifunctional polymerizable monomer represented by the above formula (2) and a 2-6 functional polymerizable polyurethane oligomer, a bifunctional polymerizable monomer represented by the above formula (2) and a 2-6 functional polymerizable polyester Combination of oligomer, combination of 2-6 functional polymerizable polyurethane oligomer and 2-6 functional polymerizable polyester oligomer, bifunctional polymerizable monomer represented by the above formula (2), 2-6 functional polymerizable polyurethane oligomer, and 2- It is a combination of hexafunctional polymerizable polyester oligomers. Among these, from the viewpoint of the balance between photochromic properties and strength (toughness) that can be used for rimless glasses, the combination of the bifunctional polymerizable monomer represented by the above formula (2) and the 2-6 functional polymerizable polyurethane oligomer is the most. preferable.

  Next, in the component (II), in addition to the bifunctional polymerizable monomer represented by the above formula (2) (m + n is 6 to 30), those having m + n of 0 to 5 are combined at a predetermined ratio. Thus, a cured product having a better balance between photochromic properties and strength (toughness) that can be used for rimless glasses can be obtained.

  That is, the following formula (3)

{In the formula, R ⁸ and R ⁹ are each independently a hydrogen atom or a methyl group; R ¹⁰ and R ¹¹ 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 such that m ′ + n ′ is 0-30. }
A mixture of a plurality of bifunctional polymerizable monomers each having a different value of m ′ + n ′, wherein m ′ + n ′ occupies 0 to 5 in the mixture (II′− The ratio (a1 / a2) between the total number of moles (a1) of 1) and the total number of moles (a2) of the bifunctional polymerizable monomer (II′-2) having a molecular weight of 600 or more in which m ′ + n ′ is 6-30 Is a mixture of bifunctional polymerizable monomers having 0 to 3.0.

  In the present invention, a specific example of a bifunctional polymerizable monomer in which m ′ + n ′ is 0 to 5 (many of which corresponds to the component C of the conventional composition) is 2,2-bis [4- (methacrylic). Leuoxy) phenyl] propane (m + n = 0), 2,2-bis [4- (methacryloyloxyethoxy) phenyl] propane (m + n = 2), 2,2-bis [4- (methacryloyl) Roxydiethoxy) phenyl] propane (m + n is 4), 2,2-bis [4- (acryloyloxyethoxy) phenyl] propane (m + n is 2), 2,2-bis [4- (methacrylic) Leuoxypropoxy) phenyl] propane (m + n is 2), bis [4- (methacryloyloxydiethoxy) phenyl] methane (m + n is 4), bis [4- (methacryloyloxy) Ethoxy) phenyl] sulfone (m + n is a two) and the like.

  In the component (II), the total number of moles (a1) of the bifunctional polymerizable monomer in which m ′ + n ′ is 0 to 5 in the mixture and the bifunctional polymerizable monomer in which m ′ + n ′ is 6 to 30 The ratio (a1 / a2) to the total number of moles (a2) is preferably 0 to 3.0. If it exceeds 3.0, the free space in the cured product becomes narrower, so the photochromic properties tend to decrease, and the number of polymerizable groups (functional groups) that cannot react due to steric hindrance increases, so that it can be used as rimless glasses. (Toughness) may not be obtained. In addition, in the combination represented by the above formula (1) and the above formula (3), glycidyl methacrylate and glycidyl acrylate, which are other components described later, are 5 to 20 based on the total weight of all polymerizable monomers or oligomers. It is particularly preferable that the content is by weight from the viewpoint of a balance between photochromic properties and strength (toughness) as rimless glasses.

  In addition to the components (I) and (II), the composition of the present invention contains a polymerizable monomer (other monomer) not corresponding to these for the purpose of preventing decomposition of the photochromic compound. Also good. The content of the other monomer is preferably 0 to 50% by weight, particularly 5 to 30% by weight, based on the total weight of all polymerizable monomers or oligomers contained in the composition.

  Specific examples of other monomers suitably used in the present invention include glycidyl methacrylate, glycidyl acrylate, etc. used for the purpose of preventing the decomposition of photochromic compounds; used for the purpose of improving photochromic properties. Methoxynonaethylene glycol methacrylate, stearyl methacrylate, phenoxyhexaethylene glycol acrylate, lauryl acrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, nonaethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol di Acrylate, nonaethylene glycol diacrylate, tripropylene glycol diacrylate, etc. .

  In the composition of the present invention, the composition of all polymerizable monomers or oligomers contained in the cured product from the viewpoint of the balance of physical properties of the resulting cured product is 10 to 40% by weight of component (I), 20 to 20% of component (II). 90% by weight, preferably 0-50% by weight of other monomers, especially 15-25% by weight of component (I), 50-80% by weight of component (II), 5-30% by weight of other monomers Is preferred.

  The photochromic compound used as component (III) in the composition of the present invention is not particularly limited, and a known photochromic compound can be used, but 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. The upper limit of the molecular weight of the photochromic compound is not particularly limited, but is preferably 800.

  For example, a chromene compound, a fulgimide compound, a spirooxazine compound and the like can be used without any limitation as those that can be suitably used as the component (D) of the conventional composition. Among these, 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 usually a plurality of compounds are often used in combination in order to adjust the color tone at the time of color development.

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 (III) photochromic compound contained in the composition of the present invention is not particularly limited, but from the viewpoint of uniform dispersibility, 0.001 to 5 weights with respect to 100 parts by weight of the total polymerizable monomer or oligomer in the composition. Parts, especially 0.01 to 2 parts by weight.

  The photopolymerization initiator used as component (IV) in the composition of the present invention is not particularly limited, and a known photopolymerization initiator can be used. Specific examples of photopolymerization initiators that can be suitably used in the present invention include 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. Among them, acylphosphine oxides such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide are available. preferable.

  The amount of (IV) photopolymerization initiator contained in the composition of the present invention is not particularly limited, but the composition is sufficiently advanced from the viewpoint of allowing the polymerization to proceed sufficiently and leaving no excess photopolymerization initiator in the cured product. The amount is preferably 0.001 to 5 parts by weight, particularly 0.005 to 1 part by weight based on 100 parts by weight of the total polymerizable monomer or oligomer in the product.

  In the composition of the present invention, a photopolymerization initiator and a thermal polymerization initiator can be used in combination. Preferred thermal polymerization initiators include diacyl peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, and acetyl peroxide; t-butylperoxy-2-ethylhexa Peroxyesters such as noate, t-butylperoxydicarbonate, cumylperoxyneodecanate, t-butylperoxybenzoate, t-butylperoxyisobutyrate; diisopropylperoxydicarbonate, di-2-ethylhexyl Percarbonates such as peroxydicarbonate and di-sec-butyloxycarbonate; 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-dimethylvaleronitrile), 2,2′-azobis ( - methylbutyronitrile), mention may be made of 1,1'-azobis (cyclohexane-1-carbonitrile) azo compounds such like. The amount of the thermal polymerization initiator used when the thermal polymerization initiator is used in combination is not particularly limited, but it is a composition from the viewpoint that the polymerization proceeds sufficiently and no excessive thermal polymerization initiator is left in the cured product. The amount is preferably 0.01 to 10 parts by weight, particularly 0.05 to 3 parts by weight based on 100 parts by weight of the total polymerizable monomer or oligomer.

  In the composition of the present invention, an additive is further added in order to improve the durability of the photochromic compound, the color development speed, the fading speed and the moldability within the range not inhibiting the effects of the present invention. You can also 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 0 to 20 parts by weight with respect to 100 parts by weight of the total polymerizable monomer or oligomer in the composition, antioxidant, radical scavenger, ultraviolet stabilizer, ultraviolet absorber, release agent, The addition amount of the coloring inhibitor, antistatic agent, fluorescent dye, dye, pigment, fragrance and the like is preferably 0 to 2 parts by weight with respect to 100 parts by weight of the total polymerizable monomer or oligomer in the composition. .

  The method for producing the composition of the present invention is not particularly limited, and a predetermined amount of each component may be weighed and mixed as appropriate. The order of mixing is not particularly limited. The composition of the present invention thus prepared is a cured product having excellent characteristics when photochromic properties, hardness and strength (toughness) are high by photopolymerization or photopolymerization followed by heat polymerization. give.

  The method for curing the composition of the present invention is not particularly limited as long as it is a photopolymerization method, and can be carried out by the same method as that for producing a conventional photocurable plastic lens. For example, it can be suitably cured by the following method.

  That is, first, the polymerization curable composition of the present invention is injected between molds held by an elastomer gasket or a spacer, and then a metal halide lamp, medium pressure mercury lamp, high pressure mercury lamp, ultrahigh pressure mercury lamp, sterilization lamp, xenon lamp. It hardens | cures by irradiating an active energy ray using a tungsten lamp, a fluorescent lamp, etc. as a light source. In the irradiation of active energy rays, in order to prevent the absorption of active energy rays by the photochromic compound (generally, coloring occurs by absorbing ultraviolet rays of about 380 to 400 nm), for example, to cut wavelengths of 400 nm or less. It is preferable to use an ultraviolet cut filter.

The cured product obtained by curing the composition of the present invention in this way is a novel product of the present invention characterized by various physical properties as shown in the following [1] to [3] derived from its unique structure. Includes hardened bodies.
[1] The fading half-life of the photochromic compound in the cured product is within 10 times, preferably within 7 times, particularly preferably within 5 times the fading half-life of the photochromic compound in the polymerization curable composition. Further, the absolute value of the fading half-life of the cured product is within 4 minutes, preferably within 2 minutes. Here, the fading half-life is defined as in the examples described later. When the light irradiation is stopped after light irradiation to bring the photochromic compound into a colored state, the absorbance at the maximum wavelength is the value at the time of coloring. This means the time required to decrease to ½, and is a value that serves as an index for fading speed.
[2] The L scale Rockwell hardness of the cured body is 70 or more.
[3] The amount of the remaining polymerizable monomer contained in the cured product is 2% by weight or less, preferably 1% by weight or less.

  That the fading half-life is within 10 times the fading half-life of the photochromic compound (including the mixture) in the polymerization curable composition is that the resin matrix in the cured product has a reversible structural change in the photochromic compound. It means having enough free space to do. The L scale Rockwell hardness correlates with the heat resistance of the cured body, and the hardness of 70 or more means that deformation in processing that requires a relatively high temperature, such as treatment of a hard coat agent described later, is caused. It means that there is little possibility of causing such problems. Moreover, the residual polymerizable monomer contained in the cured product is a cause of lowering the strength (toughness) of the cured product, and the small amount of residual polymerizable monomer means that the strength (toughness) of the cured product is inherent. It means that it can be shown. The amount of the remaining polymerizable monomer is determined by pulverizing the cured product with a ball mill or the like, extracting it with a halogen-based solvent such as methylene chloride, and then quantifying it by gas chromatography, high performance liquid chromatography, gel permeation chromatography, etc. Can be sought. Moreover, evaluation of strength (toughness) can be performed with the tensile strength defined below.

  Tensile strength: After forming a disk-shaped test piece having a thickness of 2 mm and a diameter of 5 cmφ using a cured body, a diameter of 2 mmφ centered on a point of 4 mm from the periphery on a line that becomes the diameter of the disk-shaped test piece. Two holes are drilled, and a stainless steel rod with a diameter of 1.6 mmφ is passed through each of the two drilled holes, and these two rods are pulled up and down the tensile tester with the test piece penetrating. Tensile strength when a tensile test is performed at a speed of 5 mm / min.

  The tensile strength that can be used for the rimless glasses is 20 kgf or more, preferably 25 kgf or more, and the tensile strength of 20 kgf or more shows good results in using the monitor of the rimless glasses and any of the cured products. When a hole with a diameter of 2 mmφ is drilled at a position vigorously at a rotation speed of 2100 rpm (as a guideline, at a speed of 1 hole / sec.), A large crack does not occur (the crack length is within 0.4 mm). To fit).

Since the cured product of the present invention has such excellent characteristics, it can be particularly suitably used as a photochromic plastic lens for optical articles, particularly rimless spectacles. When the cured product of the present invention is used for such applications, surface processing can be performed as necessary. That is, treatment of 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 And antireflection treatment by applying a thin film of organic polymer.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

The abbreviations and chemical names of the compounds used in the examples are shown below.
1) Polymerizable monomer and oligomer Component (I)
TMPT: trimethylolpropane trimethacrylate AD-TMP-4CL: caprolactan-modified ditrimethylolpropane tetraacrylate.

Ingredient (II)
BPE-500: 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane (m + n is 10, M / v = 402)
U-1084: Polyurethane oligomer tetraacrylate (M / v = 440)
EB-1830: Polyester oligomer hexaacrylate (M / v = 300).

Other monomer BPE-100: 2,2-bis (4-methacryloyloxyethoxyphenyl) propane (m + n is 2.6, M / v = 239)
GMA: glycidyl methacrylate.

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

3) Photopolymerization initiator Irgacure 819: bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

4) Thermal polymerization initiator perbutyl IB: t-butyl peroxyisobutyrate.

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

1) Photochromic characteristics A cured product (thickness: 2 mm), xenon lamp L-2480 (300W) SHL-100 manufactured by Hamamatsu Photonics, 20 ° C. ± 1 ° C. through an aeromass filter (manufactured by Corning), polymer The surface was irradiated with a beam intensity of 365 nm = 2.4 mW / cm 2 and 245 nm = 24 μW / cm 2 for 120 seconds to develop a color, and the photochromic characteristics of the sample were measured. Each photochromic characteristic was evaluated by the following method.

  (1) 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.

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

  (3) Fading half-life [t1 / 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)}. Time required to drop to 1/2 of It can be said that the shorter the time, the faster the fading speed and the better the photochromic property.

2) 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 2 mmφ were drilled by drilling, and a stainless steel rod with a diameter of 1.6 mmφ was passed through each of the two drilled holes. 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 testing machine.

Example 1
30 parts by weight of TMPT, 60 parts by weight of BPE-500, and 10 parts by weight of GMA were sufficiently mixed. To this, 0.04 part by weight of chromene 1 and 0.01 part by weight of Irgacure 819 as a photopolymerization initiator were added and mixed well under light shielding. This mixed solution was poured into a mold composed of a glass mold and a gasket made of an ethylene-vinyl acetate copolymer. This was irradiated with a metal halide lamp for 2 minutes. After the irradiation, the cured body was removed from the glass mold.

  Table 1 shows the evaluation results of the photochromic properties and strength properties of the obtained cured product. The residual polymerizable monomer amount of the cured product was 0.5%. Further, the fading half-life of the monomer solution in Table 1 means the fading half-life of the mixed solution (curable composition) before curing.

Example 2
25 parts by weight of TMPT, 45 parts by weight of BPE-500, 20 parts by weight of U-1084, and 10 parts by weight of GMA were sufficiently mixed. To this, 0.04 part by weight of chromene 1 and 0.01 part by weight of Irgacure 819 as a photopolymerization initiator were added and mixed well under light shielding. This mixed solution was poured into a mold composed of a glass mold and a gasket made of an ethylene-vinyl acetate copolymer. This was irradiated with a metal halide lamp for 2 minutes. After the irradiation, the cured body was removed from the glass mold.

  Table 1 shows the evaluation results of the photochromic properties and strength properties of the obtained cured product.

Example 3
25 parts by weight of TMPT, 45 parts by weight of BPE-500, 20 parts by weight of EB-1830, and 10 parts by weight of GMA were sufficiently mixed. To this, 0.04 part by weight of chromene 1 and 0.01 part by weight of Irgacure 819 as a photopolymerization initiator were added and mixed well under light shielding. This mixed solution was poured into a mold composed of a glass mold and a gasket made of an ethylene-vinyl acetate copolymer. This was irradiated with a metal halide lamp for 2 minutes. After the irradiation, the cured body was removed from the glass mold.

  Table 1 shows the evaluation results of the photochromic properties and strength properties of the obtained cured product.

Example 4
TMPT 20 parts by weight, BPE-100 30 parts by weight, BPE-500 40 parts by weight (the ratio (a1 / a2) between the number of moles of BPE-100 (a1) and the number of moles of BPE-500 (a2) is 1.26) And 10 parts by weight of GMA were mixed well. To this, 0.04 part by weight of chromene 1, 0.01 part by weight of Irgacure 819 as a photopolymerization initiator, and 0.5 part by weight of perbutyl IB as a thermal polymerization initiator were added and mixed well under light shielding. This mixed solution was poured into a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer. This was irradiated with a metal halide lamp for 2 minutes. After the irradiation, the polymer was thermally polymerized at 90 ° C. for 5 hours, and then the cured product was removed from the mold glass mold.

  Table 1 shows the evaluation results of the photochromic properties and strength properties of the obtained cured product.

Example 5
AD-TMP-4CL 50 weight part, BPE-500 40 weight part, GMA 10 weight part was fully mixed. To this, 0.04 part by weight of chromene 1, 0.01 part by weight of Irgacure 819 as a photopolymerization initiator, and 0.5 part by weight of perbutyl IB as a thermal polymerization initiator were added and mixed well under light shielding. This mixed solution was poured into a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer. This was irradiated with a metal halide lamp for 2 minutes. After the irradiation, the polymer was thermally polymerized at 90 ° C. for 5 hours, and then the cured product was removed from the mold glass mold.

  Table 1 shows the evaluation results of the photochromic properties and strength properties of the obtained cured product.

Comparative Example 1 (system not using component (II))
10 parts by weight of TMPT, 80 parts by weight of BPE-100 and 10 parts by weight of GMA were sufficiently mixed. To this, 0.04 part by weight of chromene 1 and 0.01 part by weight of Irgacure 819 as a photopolymerization initiator were added and mixed well under light shielding. This mixed solution was poured into a mold composed of a glass mold and a gasket made of an ethylene-vinyl acetate copolymer. This was irradiated with a metal halide lamp for 2 minutes. After the irradiation, the cured body was removed from the glass mold.

  Table 1 shows the evaluation results of the photochromic properties and strength properties of the obtained cured product.

Comparative Example 2 (system in which the blending ratio of component (I) and component (II) deviates from a specific ratio)
70 parts by weight of TMPT, 20 parts by weight of BPE-500, and 10 parts by weight of GMA were sufficiently mixed. To this, 0.04 part by weight of chromene 1 and 0.01 part by weight of Irgacure 819 as a photopolymerization initiator were added and mixed well under light shielding. This mixed solution was poured into a mold composed of a glass mold and a gasket made of an ethylene-vinyl acetate copolymer. This was irradiated with a metal halide lamp for 2 minutes. After the irradiation, the cured body was removed from the glass mold.

  Table 1 shows the evaluation results of the photochromic properties and strength properties of the obtained cured product.

Comparative Example 3 (system not using photopolymerization)
TMPT 20 parts by weight, BPE-100 30 parts by weight, BPE-500 40 parts by weight (the ratio (a1 / a2) between the number of moles of BPE-100 (a1) and the number of moles of BPE-500 (a2) is 1.26) And 10 parts by weight of GMA were mixed well. To this, 0.04 part by weight of chromene 1 and 0.5 part by weight of perbutyl IB as a thermal polymerization initiator were added and mixed well. This mixed solution was poured into a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer. After thermal polymerization at 90 ° C. for 15 hours, the cured product was removed from the mold glass mold.

  Table 1 shows the evaluation results of the photochromic properties and strength properties of the obtained cured product. The residual polymerizable monomer content of the cured product was 4.5%.

  Thus, a cured product satisfying both physical properties of photochromic properties and strength (toughness) can be obtained by curing a polymerization curable composition containing a specific polymerizable monomer or oligomer in a specific ratio with light. I understand. On the other hand, in a polymerization curable composition that does not use a specific polymerizable monomer or oligomer, or in a polymerization curable composition that is out of a specific blending ratio even if a specific polymerizable monomer or oligomer is used, the photochromic properties are improved. Problems such as inferiority or insufficient strength (toughness) occur. In addition, even a polymerization curable composition containing a specific polymerizable monomer or oligomer in a specific ratio causes problems such as insufficient strength (toughness) when cured with heat instead of light.

Claims (2)

(I) The following formula (1)

{In the formula, R ¹ represents a hydrogen atom or a methyl group, and the group —R ² — 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 3} is 3 to 6 valent organic residue, a is an integer from 0 to 3, b is an integer from 3 to 6. }
A polyfunctional polymerizable monomer represented by
(II) The value (M / v) obtained by dividing the molecular weight (M) by the number of polymerizable groups (v) present in the molecule is 300 or more, and the following formula (2)

{In the formula, R ⁴ and R ⁵ are each independently a hydrogen atom or a methyl group; R ⁶ and R ⁷ 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 —; And m and n are integers such that m + n is 6-30. }
A bifunctional polymerizable monomer represented by:
(III) a photochromic compound and (IV) an acyl phosphine oxide-based compound as a photopolymerization initiator, and the above-mentioned many compounds based on all polymerizable monomers contained in the polymerization-curable composition. A polymerization curable composition in which the content of the functional polymerizable monomer (I) and the bifunctional polymerizable monomer (II) is 10 to 60% by weight and 20 to 90% by weight, respectively.
The fading half-life of the photochromic compound (III) in the cured product is within 10 times the fading half-life of the photochromic compound in the polymerization curable composition, and the tensile strength defined below of the cured product is 20 kgf The polymerization curable composition characterized by becoming above.
Tensile strength: after forming a disk-shaped test piece having a thickness of 2 mm and a diameter of 5 cmφ using the cured body, a diameter of 2 mmφ centered at a point of 4 mm from the periphery on a line that becomes the diameter of the disk-shaped test piece. These two holes were drilled, and a stainless steel rod with a diameter of 1.6 mmφ was passed through each of the two drilled holes, and these two rods were pulled through the test piece. Tensile strength when fixed to upper and lower chucks and subjected to a tensile test at a speed of 5 mm / min. (I) The following formula (1)

{In the formula, R ¹ represents a hydrogen atom or a methyl group, and the group —R ² — represents —CH ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) O—, or —C (═O) CH ₂ CH ₂ CH _The group represented by ₂ CH ₂ CH ₂ O—, R ³ is a 3-6 valent organic residue, a is an integer of 0-3, and b is an integer of 3-6. }
A polyfunctional polymerizable monomer represented by
(II ′) The following formula (3)

{In the formula, R ⁸ and R ⁹ are each independently a hydrogen atom or a methyl group; R ¹⁰ and R ¹¹ 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 0-30. }
A mixture of a plurality of bifunctional polymerizable monomers each having a different value of m ′ + n ′, wherein m ′ + n ′ occupies 0 to 5 in the mixture (II′− The ratio (a1 / a2) between the total number of moles (a1) of 1) and the total number of moles (a2) of the bifunctional polymerizable monomer (II′-2) having a molecular weight of 600 or more in which m ′ + n ′ is 6 to 30 A mixture of bifunctional polymerizable monomers having a 0 to 3.0,
(III) a photochromic compound and (IV) an acyl phosphine oxide-based compound as a photopolymerization initiator , and based on the total polymerizable monomer, the polyfunctional polymerizable monomer (I) and the above A polymerization curable composition in which the content of the mixture of bifunctional polymerizable monomers (II′-2) is 10 to 60% by weight and 20 to 90% by weight, respectively,
The fading half-life of the photochromic compound (III) in the cured product is within 10 times the fading half-life of the photochromic compound in the polymerization curable composition, and the tensile strength defined below of the cured product is 20 kgf A polymerization curable composition characterized by the above.
Tensile strength: after forming a disk-shaped test piece having a thickness of 2 mm and a diameter of 5 cmφ using the cured body, a diameter of 2 mmφ centered at a point of 4 mm from the periphery on a line that becomes the diameter of the disk-shaped test piece. These two holes were drilled, and a stainless steel rod with a diameter of 1.6 mmφ was passed through each of the two drilled holes, and these two rods were pulled through the test piece. Tensile strength when fixed to upper and lower chucks and subjected to a tensile test at a speed of 5 mm / min.