JP6579837B2 - Photochromic composition - Google Patents

Description

  The present invention relates to a novel photochromic composition. Specifically, the present invention relates to a photochromic composition having excellent photochromic properties such as color density.

  Photochromic compounds represented by chromene compounds, fulgide compounds, spirooxazine compounds, etc., change color quickly when irradiated with light containing ultraviolet rays such as sunlight or light from mercury lamps. It has the property of returning to its original color (photochromic property), and is used for various uses, particularly for optical materials, taking advantage of this property.

  For example, photochromic eyeglass lenses that have been provided with photochromic properties through the use of photochromic compounds can quickly color and function as sunglasses outdoors exposed to light containing ultraviolet rays such as sunlight. Indoors where there is no color, it functions as normal glasses that fade and become transparent, and in recent years, its demand has increased.

  In order to impart photochromic properties to optical materials, photochromic compounds are generally used in combination with plastic materials. Specifically, the following means are known.

(A) A method of directly molding an optical material such as a lens by dissolving a photochromic compound in a polymerizable monomer and polymerizing it.
This method is called a kneading method.

(B) A method in which a resin layer in which a photochromic compound is dispersed is provided on the surface of a plastic molded product such as a lens by coating or cast polymerization.
This method is called a lamination method.

(C) Bonding two optical sheets with an adhesive layer formed of an adhesive resin in which a photochromic compound is dispersed.
This method is called a binder method.

  By the way, the following characteristics are required for optical materials such as optical articles to which photochromic properties are imparted.

(I) The coloring degree (initial coloring) in the visible light region before irradiation with ultraviolet rays is low.
(II) The coloring degree (color density) when irradiated with ultraviolet rays is high.
(III) The speed (fading speed) from when the irradiation of ultraviolet rays is stopped until it returns to the original state is high.
(IV) Good durability against reversible action of color development to fading.
(V) High storage stability.
(VI) It must be easy to mold into various shapes.
(VII) Photochromic properties are imparted without lowering the mechanical strength.

  Accordingly, various proposals have been made to satisfy the above-mentioned requirements when producing optical materials having photochromic properties by the means (a) to (c) described above. The present situation is that further excellent photochromic properties are demanded with respect to the color fading speed and the like.

  For example, the kneading method described above has the advantage that a photochromic plastic lens can be produced in large quantities at low cost using a glass mold, and many photochromic plastic lenses are currently produced by this method. .

  However, since the kneading method requires strength for the lens substrate, it is necessary to increase the mechanical strength of the matrix resin in which the photochromic compound is dispersed. For this reason, it is difficult to develop excellent photochromic properties. That is, since the degree of molecular freedom of the photochromic compound present in the matrix resin is reduced, the photochromic reversible reaction is impaired.

  For example, regarding such a kneading method, Patent Document 1 describes a method of adding a photochromic compound to a monomer composition containing an isocyanate monomer and a thiol monomer. Patent Document 2 discloses a photochromic curable composition containing a specific (meth) acryl polymerizable monomer and a photochromic compound.

  However, photochromic lenses formed by polymerizing and curing these compositions are unsatisfactory in terms of photochromic properties, particularly fading speed, although they have high mechanical strength.

  On the other hand, in the laminating method and the binder method, the photochromic property is expressed in a thin layer formed on the surface of various base materials as compared with the kneading method described above, so that the coloring density equivalent to the kneading method is expressed. It is necessary to dissolve the photochromic compound at a high concentration. In that case, depending on the type of the photochromic compound, there are problems such as insufficient solubility and precipitation during storage. Moreover, since the layer which expresses photochromic property is thin, the durability of the photochromic compound may be inferior.

  For example, Patent Document 3 discloses a method of forming a photochromic coating layer by applying a photochromic curable composition onto a plastic lens by spin coating and photocuring (this laminating method is also known as a coating method). be called).

  Further, Patent Document 4 uses a member such as an elastomer gasket, an adhesive tape, or a spacer to secure a gap between the plastic lens and the glass mold, and a photochromic curable composition is poured into the gap to polymerize and cure. A method for forming a photochromic layer (hereinafter also referred to as a two-stage polymerization method) is shown.

  Furthermore, Patent Document 5 discloses a method for producing a laminated sheet in which a transparent carbonate sheet is bonded with a polyurethane resin adhesive layer containing a photochromic compound (binder method).

  However, in any method of Patent Documents 3 to 5, the photochromic property is expressed by the thin layer in which the photochromic compound is blended. Therefore, when a photochromic compound having low solubility is used, the color density tends to be low. Further, the durability of the photochromic compound may be inferior.

  Thus, in the currently known technology, either the color density or the fading speed tends to be unsatisfactory.

WO2012 / 176439 WO2009 / 075388 WO2011-12595 WO2003 / 011967 WO2013 / 099640

  Accordingly, an object of the present invention is to provide a photochromic composition capable of imparting excellent photochromic properties to both the color density and the fading speed.

  Another object of the present invention is to provide a photochromic composition capable of forming a photochromic cured product having excellent moldability in addition to photochromic properties.

  The present inventors have made extensive studies to solve the above problems. As a result, the present inventors have succeeded in solving such a problem by combining a photochromic compound with a graft polymer having a polymerizable functional group introduced in the side chain and a polymerizable monomer.

  That is, according to the present invention, (A) a graft polymer in which a polymerizable functional group is introduced into a side chain, (B) a polymerizable monomer, and (C) a photochromic compound are included. A photochromic composition is provided.

  In the present invention, (A) the graft polymer in which a polymerizable functional group is introduced into the side chain is different from a polymer (hereinafter also referred to as a main chain or a trunk polymer) as a side chain. (Hereinafter also referred to as a branch polymer), and those having a polymerizable functional group in the side chain of the polymer.

The photochromic composition of this invention can take the following aspect suitably.
(1) The polymerizable functional group is introduced into the side chain (A) per 100 parts by mass in total of the graft polymer in which the polymerizable functional group is introduced into the side chain (A) and the polymerizable monomer (B). 1-50 mass parts of graft polymers are contained.
(2) (C) The photochromic compound is contained in an amount of 0.0001 to 20 parts by mass per 100 parts by mass in total of the graft polymer into which the polymerizable functional group is introduced and (B) the polymerizable monomer. thing.
(3) Further, it contains a polymerization hardening accelerator (D).

  According to the present invention, there is also provided a photochromic composition comprising (A) a graft polymer having a polymerizable functional group introduced into a side chain, (B) a polymerizable monomer, and (C) a photochromic compound. A photochromic cured product obtained by curing is provided.

  By using the photochromic composition of the present invention, it is possible to develop photochromic properties in which both the color developability and the fading speed are improved, as shown in Examples described later.

  The expression of the photochromic property as described above is due to the use of a graft polymer in which a polymerizable functional group is introduced in the side chain together with the photochromic compound. I think so.

  That is, when the side chain of the graft polymer having a polymerizable functional group introduced into the side chain is cross-linked, the reversible structural change of the photochromic compound existing in the vicinity of the highly flexible side chain is further improved. It is believed that it will occur quickly.

  Therefore, even when a polymerizable monomer or the like is blended in this photochromic composition and this is polymerized and cured to form a cured product, a plurality of the above-mentioned main chain and the polymerized side chain terminal portion are present. The flexible (deformable) side chain forms a space that does not disturb the reversible structural change of the photochromic compound, resulting in an improvement in fading speed and color density.

  As understood from this, in the photochromic composition of the present invention, for example, when molding a photochromic lens by a kneading method, the mechanical strength is improved without impairing the photochromic properties (color density and fading speed). Can be achieved. Further, even when a layer exhibiting photochromic properties is formed by a lamination method or a binder method, a sufficient color density can be ensured.

  The photochromic composition of the present invention is characterized by comprising (A) a graft polymer having a polymerizable functional group introduced in the side chain, (B) a polymerizable monomer, and (C) a photochromic compound. . Hereinafter, each component which comprises the photochromic composition of this invention is demonstrated.

<(A) Graft polymer having a polymerizable functional group introduced in the side chain>
The photochromic composition of the present invention is characterized by containing (A) a graft polymer in which a polymerizable functional group is introduced into the side chain (hereinafter also referred to as “polymerizable functional group-containing graft polymer”). In the cured product obtained by curing the photochromic composition of the present invention by introducing a polymerizable functional group into the side chain of the graft polymer to form a bond with a side chain of another graft polymer or a polymerizable monomer. A moderate space is more reliably formed. With this space, it is possible to reliably ensure a gap that allows a reversible reaction of the photochromic compound molecules, and to exhibit excellent photochromic properties. Moreover, a crosslinked structure can be formed in such a side chain, and the mechanical strength of the photochromic hardening body formed by this can be improved.

  In general, a graft polymer refers to a polymer having a structure in which a polymer different from the main chain is bonded to the main chain as a side chain. In other words, the graft polymer has a structure formed of a main chain and a side chain branched from the main chain, and as described above, the reversible reaction of the photochromic compound can be allowed by the presence of the side chain. Space is secured, and high color density and fast fading speed can be obtained.

  The two polymers have different properties and characteristics, so that they can provide functions not found in a single polymer. This graft polymer is composed of a single monomer or a plurality of monomers, and in the case of a plurality of monomers, the graft polymer is composed of a plurality of types of monomers such as a random graft polymer, a block graft polymer, and a gradient graft polymer. The arrangement may or may not be regular.

  Here, the molecular weight of the polymerizable functional group-containing graft polymer is not particularly limited, but if it is too large, the compatibility with other components, for example, (C) a polymerizable monomer that is appropriately blended tends to be poor. If it is too small, the photochromic property tends to decrease. From such a viewpoint, the weight average molecular weight Mw of the polymerizable functional group-containing graft polymer is preferably in the range of 1000 to 300,000, particularly 5,000 to 200,000.

  Further, in the present invention, the polymerizable functional group-containing graft polymer can form an appropriate space between the main chain and the side chain, or between the side chains, and the gap that allows the reversible reaction of the photochromic compound molecule. Can be ensured, and excellent photochromic properties can be exhibited. Thereby, the photochromic physical property of the photochromic hardening body formed using the photochromic composition of this invention can be improved.

  The blending amount of the polymerizable functional group-containing graft polymer of the present invention is 1 to 50 parts by mass per 100 parts by mass in total of (A) polymerizable functional group-containing graft polymer and (B) polymerizable monomer described later from the viewpoint of photochromic properties. The range of 4 to 30 parts by mass is preferable because a higher color density and good moldability are preferable.

<Main chain (backbone polymer)>
In such a polymerizable functional group-containing graft polymer, various types can be used as the main chain, but a homopolymerized polymer or a copolymerized polymer can be used.
Examples of the polymer that forms such a main chain portion include polyvinyl alcohol, polyvinyl pyrrolidone, cellulose resins (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal, Polyvinyl methyl ether, polyamine, polyethyleneimine, polyacrylonitrile, polyoxazoline, casein, gelatin, starch, olefin resins (polyethylene, polypropylene, etc.), polyester resins (polyethylene terephthalate, poly-ε-caprolactone, poly α-acetyl-γ) -Butyrolactone), polyvinyl chloride, styrene resin (polystyrene, acryloni) Ril-styrene copolymer resin), acrylic resin (poly (meth) acrylic acid, polymethyl (meth) acrylate, polycyano (meth) acrylate, polyhydroxyethyl (meth) acrylate, acrylonitrile-methylacrylate copolymer resin, etc.) ), Polycarbonate, polyurethane, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamide (such as nylon), polyimide, polydiene (poly) Isoprene, polybutadiene, etc.), polysiloxane resins (polydimethylsiloxane, polydiphenylsiloxane, polyphenylvinylsiloxane, etc.), polycarbonate resins (polyethylene, etc.) Ren carbonate, poly propylene carbonate), it polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, poly ketone polyphenylene, be mentioned polyhaloolefins like. These polymers may be random copolymers or block copolymers as appropriate, or may be modified. These polymers may have a polymerizable and / or non-polymerizable substituent.
In the present invention, olefin-based resins, styrene-based resins, acrylic resins, and polysiloxane-based resins are preferable as the polymer that forms the chain portion, and acrylic resins are most preferable.

<Side chain (branched polymer)>
In the above-mentioned polymerizable functional group-containing graft polymer of the present invention, as the polymer that forms the side chain portion, those mentioned as the polymer that forms the main chain portion can be used. Among them, olefin-based resins, styrene-based resins, acrylic resins, polyester-based resins, and polysiloxane-based resins are preferable as the polymer that forms a side chain. Polyester resins are most preferred because they easily introduce polymerizable functional groups into the chain. Of the polyester resins, polycaprolactone is most preferable because it exhibits photochromic properties excellent in color density and fading speed.

  The side chains are preferably formed by repeating organic chains having 3 to 20 carbon atoms, and the average weight molecular weight of such side chains is 300 to 10,000, preferably It is in the range of 350 to 8,000. That is, if the side chain is too small, the function of ensuring a gap that can allow the reversible reaction of the photochromic compound molecule is insufficient, and if the side chain is too large, the photochromic compound described later is uniformly mixed into the graft polymer. As a result, it tends to be difficult to fully utilize the space secured by the graft polymer.

  The side chain as described above can be introduced by polymerizing a monomer starting from a functional group of the main chain, or by using a macromonomer used for main chain formation. The number of side chains that can be introduced per molecule of the graft polymer is such that when monomers are polymerized starting from the functional group of the main chain, the reactivity of the side chain that is present in the polymer (main chain) can be formed. This is the number of functional groups (hereinafter also referred to as side chain introduction functional groups). When a macromonomer is used, the number of macromonomer introductions. In the present invention, in order to sufficiently exhibit the function of the side chain described above, when the total number of unit monomer units (repeating units) of the main chain is 100, 0.01 to 100 unit monomer units are It preferably has a side chain.

<Polymerizable functional group>
In the present invention, by introducing a polymerizable functional group into the side chain of the graft polymer, an appropriate space can be more reliably formed along with the formation of a bond with a side chain of another graft polymer or a polymerizable monomer. Therefore, it is possible to reliably ensure a gap that allows the reversible reaction of the photochromic compound molecules, and to exhibit excellent photochromic properties. Moreover, a crosslinked structure can be formed in such a side chain, and the mechanical strength of the photochromic hardening body formed by this can be improved.

  The position of introduction of the polymerizable functional group introduced into the polymerizable functional group-containing graft polymer in the present invention is not limited to either the polymer end of the side chain or in the chain, but the functional group at the polymer end of the side chain is defined as What is introduced by use is easy in synthesis. In this case, as a functional group for introducing a polymerizable functional group, a group suitable for introducing a polymerizable functional group described below may be appropriately used.

The polymerizable functional group is typically a radical polymerizable group such as a (meth) acryl group, a vinyl group or an allyl group, but depending on the type of the (B) polymerizable monomer, an epoxy group, a hydroxyl group, A thiol group, amino group (—NH ₂ ), episulfide group, thietanyl group, isocyanate group, or thioisocyanate group also functions as a polymerizable functional group.

For example, an epoxy group, an episulfide group, and a thietanyl group react with an amino group and an isocyanate group that (B) the polymerizable monomer has.
The hydroxyl group or thiol group reacts with the isocyanate group or thioisocyanate group (B) polymerizable monomer to form a urethane bond or thiourethane bond.
The isocyanate group or thioisocyanate group reacts with the hydroxyl group, thiol group, or amino group of the (B) polymerizable monomer.

  Among the polymerizable functional groups introduced into the above-mentioned polymerizable functional group-containing graft polymer in the present invention, a urethane bond and a thiourethane bond can be formed because of the excellent effect of improving the photochromic property particularly in the kneading method. A hydroxyl group or a thiol group is preferred.

<(A) Method for Producing Polymerizable Functional Group-Containing Graft Polymer>
The (A) polymerizable functional group-containing graft polymer in the present invention can be produced by a known method. Graft polymers are generally synthesized by (1) a method of homopolymerizing a macromonomer or copolymerizing with a comonomer, (2) a method of increasing another polymer chain (side chain) from the polymerization start point of the main chain, and (3) polymerization. A method of reacting a main chain having a polymerizable functional group with a branch polymer such as a polymer having a polymerizable functional group at the terminal or a living polymer is known, and the polymerizable functional group-containing graft polymer of the present invention is the above-mentioned It can be manufactured by any method.

(1) Method of homopolymerizing a homomonomer or copolymerizing with a comonomer Here, the macromonomer is a high molecular weight monomer containing a polymerizable group at one end in a narrow sense, but in a broad sense, a telepolymer having both ends polymerizable. Rick macromonomer, as well as polyfunctional macromonomer containing many polymerizable groups. A graft polymer can be obtained by homopolymerizing the macromonomer by radical polymerization or the like or copolymerizing with a comonomer (low molecular weight monomer).

(2) Method of increasing another polymer chain (side chain) from polymerization start point of main chain A polymer having a reactive functional group (hereinafter also referred to as a side chain introduction functional group) in the main chain is used. A monomer having a side chain introduction functional group is first polymerized under the condition that the side chain introduction functional group does not initiate polymerization to obtain a polymer (main chain). Subsequently, polymerization is performed based on the side chain-introducing functional group in the obtained main chain to form a side chain, whereby a graft polymer can be obtained.
Examples of the side chain-introducing functional group include an alkoxysilyl group, a carbon-bromine bond, and a thioester group. The polymerization method for introducing the side chain is not particularly limited, but living radical polymerization is preferable because a polymer having a uniform length can be easily introduced at a high density.

(3) A method of reacting a main chain having a polymerizable functional group with a polymer having a polymerizable functional group at the end As a method of reacting a branch polymer with the main chain polymer, a backbone polymer having a polymerizable functional group, and a terminal A method of reacting a branched polymer such as a polymer having a polymerizable functional group or a living polymer can also be used. As this method, a method using a dynamic covalent bond method using 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), a click chemistry method, or the like can be applied.

  In addition, as a polymerization method for producing the polymerizable functional group-containing graft polymer, a known method such as a chemical method using radical polymerization, cationic polymerization, chemical polymerization, or a physical method using radiation is adopted. I can do it.

<(B) Polymerizable monomer>
The photochromic composition of the present invention contains (B) a polymerizable monomer in order to suppress the increase in viscosity of the photochromic composition and to more effectively exhibit the effect of improving photochromic properties by the (A) polymerizable functional group-containing graft polymer. Blend. Examples of such polymerizable monomers include (B1) radical polymerizable monomers, (B2) epoxy polymerizable monomers, (B3) urethane or urea polymerizable monomers capable of forming urethane bonds or urea bonds, and (B4). ) Other polymerizable monomers can be mentioned, and in particular, (A) a polymerizable monomer capable of reacting with a polymerizable group introduced into a side chain of the polymerizable functional group-containing graft polymer is preferably used.

  As described above, there are a kneading method, a laminating method, and a binder method as methods for imparting photochromic properties to an optical material. However, in the kneading method in which both the thermal polymerization method and the photopolymerization method are easy to apply, (B1) radical A polymerizable monomer, and (B3) a urethane or urea-based polymerizable monomer, (B1) is a radically polymerizable monomer in a laminating method to which a photopolymerization method is easily applied, and (B3) in a binder method to which a thermal polymerization method is easily applied. ) It is preferred to use urethane or urea polymerizable monomers.

<(B1) radical polymerizable monomer>
The (B1) radical polymerizable monomer is preferably used particularly when a radical polymerizable functional group is introduced into the side chain of the (A) polymerizable functional group-containing graft polymer. And a (meth) acrylic polymerizable monomer, a vinyl polymerizable monomer having a vinyl group, an allyl polymerizable monomer having an allyl group, and a silsesquioxane polymerizable monomer. The specific example is shown below.

(Meth) acrylic polymerizable monomers;
The (meth) acrylate polymerizable monomer is cured by radical polymerization. These compounds can also be used for adjusting the lens hardness. The following can be illustrated as the specific example.
(Meth) acrylate compounds; ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol Dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, polypropylene glycol Dimethacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, 2,2-bis (4-acryloxyethoxyphenyl) propane 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2, 2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (4-methacryloylio) Sidipropoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,1-bis (4-acryloxyethoxyphenyl) methane, 1,1-bis (4-methacryloxyethoxyphenyl) methane, 1,1- Bis (4-acryloxydiethoxyphenyl) methane, 1,1-bis (4-methacryloxydiethoxyphenyl) methane, dimethyloltricyclodecane diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate , Ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate Relate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, xylylenedithiol diacrylate, xylylenedithiol dimethacrylate, mercaptoethylsulfide diacrylate, mercaptoethylsulfide dimethacrylate, bifunctional urethane acrylate, 2 Functional urethane methacrylate.

Vinyl polymerizable monomers;
Examples of vinyl polymerizable monomers having a vinyl group include methyl vinyl ketone, ethyl vinyl ketone, ethyl vinyl ether, styrene, vinyl cyclohexane, butadiene, 1,4-pentadiene, divinyl sulfide, divinyl sulfone, 1,2-divinylbenzene, , 3-Divinyl-1,1,3,3-tetramethylpropanedisiloxane, diethylene glycol divinyl ether, divinyl adipate, divinyl sebacate, ethylene glycol divinyl ether, divinyl sulfoxide, divinyl persulfide, dimethyl divinyl silane, 1,2 , 4-trivinylcyclohexane, methyltrivinylsilane, styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, 3,9-divinyls Lobby (m-dioxane), can be mentioned α- methyl styrene and α- methylstyrene dimer.

Allylic polymerizable monomers;
Examples of the allyl polymerizable monomer having an allyl group include the following.
Allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate, methoxypolyethylene glycol allyl ether, diethylene glycol bisallyl carbonate, methoxypolyethylene glycol allyl ether (especially average molecular weight 550) ), Methoxy polyethylene glycol allyl ether (especially average molecular weight 350), methoxy polyethylene glycol allyl ether (especially average molecular weight 1500), polyethylene glycol allyl ether (especially average molecular weight 450), methoxy polyethylene glycol-polypropylene glycol allyl ether (especially average molecular weight 750). ), Butoxypolyethylene glycol-polypropylene Recall allyl ether (especially average molecular weight 1600), methacryloyloxypolyethylene glycol-polypropylene glycol allyl ether (especially average molecular weight 560), phenoxypolyethylene glycol allyl ether (especially average molecular weight 600), methacryloyloxypolyethylene glycol allyl ether (especially average molecular weight 430) Acryloyloxypolyethylene glycol allyl ether (especially average molecular weight 420), vinyloxypolyethylene glycol allyl ether (especially average molecular weight 560), styryloxypolyethylene glycol allyl ether (especially average molecular weight 650), methoxypolyethylene thioglycol allylthioether (especially average) Molecular weight 730).

  The allyl polymerizable monomer can improve the photochromic properties (color density, fading speed) of the photochromic composition by acting as a chain transfer agent.

Silsesquioxane polymerizable monomer;
The silsesquioxane polymerizable monomer has various molecular structures such as a cage shape, a ladder shape, and a random shape, and has a radical polymerizable group such as a (meth) acryl group.
Examples of such silsesquioxane polymerizable monomers include those represented by the following formula (1).

{Wherein n is a degree of polymerization and is an integer of 3 to 100, and a plurality of R1s may be the same or different from each other, and are a radical polymerizable group, an organic group containing a radical polymerizable group, hydrogen An organic group containing an atom, alkyl group, cycloalkyl group, alkoxy group, phenyl group, hydroxyl group and / or thiol group, and at least one R1 is a radical polymerizable group or an organic group containing a radical polymerizable group . }
Here, the radical polymerizable group represented by R1 or the organic group containing a radical polymerizable group includes (meth) acryl group; (meth) acryloyloxypropyl group, (3- (meth) acryloyloxypropyl) dimethylsiloxy An organic group having a (meth) acryl group such as an allyl group; an allyl group; an organic group having an allyl group such as an allylpropyl group or an allylpropyldimethylsiloxy group; a vinyl group; a vinyl group such as a vinylpropyl group or a vinyldimethylsiloxy group. The organic group etc. which have are mentioned.

In the present invention, other radical polymerizable monomers other than (C1) to (C4) mentioned above can also be used.
Examples of such other radical polymerizable monomers include γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and the like.

<(B2) Epoxy polymerizable monomer>
This polymerizable monomer has an epoxy group in the molecule as a polymerizable group, and is cured by ring-opening polymerization. In particular, it is particularly suitable when a hydroxyl group, an amino group, or an isocyanate group is introduced as a polymerizable functional group into the side chain of the polymerizable functional group-containing graft polymer (A). Such epoxy-based polymerizable monomers are roughly classified into aliphatic epoxy compounds, alicyclic epoxy compounds, and aromatic epoxy compounds, and specific examples thereof include the following.

Aliphatic epoxy compounds; ethylene oxide, 2-ethyloxirane, butylglycidyl ether, phenylglycidyl ether, 2,2′-methylenebisoxirane, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, Triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, nonapropylene Glycol diglycidyl ether, neopentyl glycol diglycy Diether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, diglycidyl ether of tris (2-hydroxyethyl) isocyanurate, tris (2-hydroxyethyl) isocyanurate Triglycidyl ether of alicyclic epoxy compound; isophoronediol diglycidyl ether, bis-2,2-hydroxycyclohexylpropane diglycidyl ether aromatic epoxy compound; resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl Ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ester, pheno Le novolak polyglycidyl ether, cresol novolak polyglycidyl ether

In addition to the above, an epoxy compound having a sulfur atom in the molecule can be used together with the epoxy group. Such a sulfur-containing atom epoxy compound particularly contributes to the improvement of the refractive index, and includes a chain aliphatic type and a cycloaliphatic type. Specific examples thereof are as follows.
Chain aliphatic sulfur-containing atom epoxy compounds; bis (2,3-epoxypropyl) sulfide, bis (2,3-epoxypropyl) disulfide, bis (2,3-epoxypropylthio) methane, 1,2- Bis (2,3-epoxypropylthio) ethane, 1,2-bis (2,3-epoxypropylthio) propane, 1,3-bis (2,3-epoxypropylthio) propane, 1,3-bis ( 2,3-epoxypropylthio) -2-methylpropane, 1,4-bis (2,3-epoxypropylthio) butane, 1,4-bis (2,3-epoxypropylthio) -2-methylbutane, , 3-bis (2,3-epoxypropylthio) butane, 1,5-bis (2,3-epoxypropylthio) pentane, 1,5-bis (2,3-epoxypropylthio) 2-methylpentane, 1,5-bis (2,3-epoxypropylthio) -3-thiapentane, 1,6-bis (2,3-epoxypropylthio) hexane, 1,6-bis (2,3- Epoxypropylthio) -2-methylhexane, 3,8-bis (2,3-epoxypropylthio) -3,6-dithiaoctane, 1,2,3-tris (2,3-epoxypropylthio) propane, 2 , 2-bis (2,3-epoxypropylthio) -1,3-bis (2,3-epoxypropylthiomethyl) propane, 2,2-bis (2,3-epoxypropylthiomethyl) -1- ( 2,3-epoxypropylthio) butane cycloaliphatic sulfur-containing atom epoxy compound; 1,3-bis (2,3-epoxypropylthio) cyclohexane, 1,4-bis (2,3-epoxy (Lopylthio) cyclohexane, 1,3-bis (2,3-epoxypropylthiomethyl) cyclohexane, 1,4-bis (2,3-epoxypropylthiomethyl) cyclohexane, 2,5-bis (2,3-epoxypropyl) Thiomethyl) -1,4-dithiane, 2,5-bis [<2- (2,3-epoxypropylthio) ethyl> thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epoxy Propylthiomethyl) -2,5-dimethyl-1,4-dithiane

<(B3) Urethane or urea-based polymerizable monomer>
In this polymerizable monomer, the repeating unit of polymerization is linked by a urethane bond or a urea bond, and in particular, (A) as a polymerizable functional group on the side chain of the graft polymer in which the polymerizable functional group is introduced into the side chain. This is effective when an epoxy group, episulfide group, thietanyl group, hydroxyl group, thiol group, amino group, isocyanate group or thioisocyanate group is introduced.
For example, a urethane bond is formed by a reaction between a polyol and a polyisocyanate, and in this urethane bond, a reaction between a polyol and a polyisothiocyanate, or a reaction between a polythiol and a polyiso (thio) isocyanate. Thiourethane bond formed

  The urea bond is formed by the reaction of polyamine and polyisocyanate, and this urea bond includes the thiourea bond formed by the reaction of polyamine and polyisothiocyanate.

As understood from the above description, in the present invention, the urethane or urea-based polymerizable monomer is selected from poly (thi) ol compounds, polyiso (thio) cyanate compounds, polyamine compounds, epoxy compounds, and carboxylic acid compounds. A plurality of types of compounds are selected and used so that the urethane bond (thiourethane bond) or urea bond (thiourea bond) is formed.
Moreover, when a hydroxyl group, a thiol group, an amino group, an isocyanate group, an isothiocyanate group, an epoxy group, a carboxylic acid group, or the like is introduced as a polymerizable group in the side chain of the above-described polymerizable functional group-containing graft polymer. Is preferred because the side chain is incorporated into the polymer chain formed by such urethane or urea-based polymerizable monomer.
Specific examples of the compound used as one of such urethane or urea polymerizable monomers include the following.

Poly (thi) ol compounds;
When a poly (thi) ol compound is used, a rigid cured body having a network structure having a (thio) urethane bond is formed by a reaction between the polyiso (thio) cyanate compound and the poly (thi) ol compound. This is preferable because a photochromic cured product having excellent mechanical strength can be obtained. Among the poly (thi) ol compounds, as the polyol compound, for example, di-, tri-, tetra-, penta-, hexa-hydroxy compounds, polyester containing two or more OH groups in one molecule (polyester) Polyol) polyether containing two or more OH groups in one molecule (hereinafter referred to as polyether polyol), polycarbonate containing two or more OH groups in one molecule (polycarbonate polyol), 1 A typical example is polycaprolactone (polycaprolactone polyol) containing two or more OH groups in the molecule, and an acrylic polymer (polyacryl polyol) containing two or more OH groups in the molecule.

Specific examples of the poly (thi) ol compound are as follows.
Polyethylene polyol, polycaprolactone polyol, polycarbonate polyol, trimethylolpropane, pentaerythritol, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), Dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), 1,4-butanediol bis (3-mercaptopropionate), 1,6-hexane Diol bis (3-mercaptopropionate), 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, 2,2-bis (mercaptomethyl) -1,4-butanedithiol, 1, 4-bis (mercaptopropyl) Omethyl) benzene, 2,5-bis (mercaptomethyl) -1,4-dithiane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 1,1,1,1-tetrakis (mercaptomethyl) Methane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- Mercaptoethanol, tris-{(3-mercaptopropionyloxy) -ethyl} -isocyanurate

A polyiso (thio) cyanate compound;
The polyiso (thio) cyanate compound is a compound having two or more isocyanate groups and / or isothiocyanate groups in one molecule.

  Among the above polyiso (thio) cyanate compounds, polyisocyanate compounds include aliphatic isocyanates, alicyclic isocyanates, aromatic isocyanates, sulfur-containing aliphatic isocyanates, aliphatic sulfide isocyanates, aromatic sulfide isocyanates, aliphatic sulfones. Examples include isocyanates, aromatic sulfone isocyanates, sulfonate ester isocyanates, aromatic sulfonic acid amide isocyanates, and sulfur-containing heterocyclic isocyanates.

  Polyisothiocyanate compounds include aliphatic isothiocyanate, alicyclic isothiocyanate, aromatic isothiocyanate, heterocycle-containing isothiocyanate, sulfur-containing aliphatic isothiocyanate, sulfur-containing aromatic isothiocyanate, and sulfur-containing heterocycle isothiocyanate. Etc. Specific examples of these polyiso (thio) cyanate compounds include the following compounds.

Pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, 2,5-bis (isocyanatemethyl) -bicyclo [2,2,1] -heptane, 2,6-bis (isocyanate) Methyl) -bicyclo [2,2,1] -heptane, 1,2-bis (2-isocyanato-ethylthio) ethane, xylene diisocyanate (o-, m-, p-), 2,4-tolylene diisocyanate, 2 , 6-tolylene diisocyanate and 4,4′-diphenylmethane diisocyanate In addition, as the polyiso (thio) cyanate compound, one or more of isocyanate groups and / or isothiocyanate groups are blocking agents. Protected poly blocks iso (thio) cyanate compound may be used. The polyblock iso (thio) cyanate compound is a compound in which an iso (thio) cyanate group (—NCO and —NCS) is blocked by a thermally detachable protecting group.

  As a blocking agent for the polyiso (thio) cyanate compound, known ones can be selected and used. For example, methanol, ethanol, isopropanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, cyclohexanol Alcohols such as phenol, phenol, o-nitrophenol, p-chlorophenol, o-cresol, lactams such as ε-caprolactam, oximes such as acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, pyrazole, Pyrazoles such as 3,5-dimethylpyrazole and 3-methylpyrazole, thiols such as dodecanethiol and benzenethiol, dimethyl malonate, acetoacetate ester, dinitrate malonate, acetylacetone, methylene Sulfone, dibenzoylmethane, dipivaloylmethane include active methylene compounds such as acetone dicarboxylic acid diester.

Polyamine compounds;
A polyamine compound is a compound having two or more amino groups (—NH ₂ ) in one molecule, which forms a urea bond by reaction with polyisocyanate, and forms a thiourea bond by reaction with polyisothiocyanate. To do. These monomers may be added for adjusting the hardness. Specific examples thereof include the following compounds.

  Ethylenediamine, hexamethylenediamine, isophoronediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylenediamine, 1,3-propanediamine, putrescine, 2- (2-aminoethylamino) ethanol, diethylenetriamine, p-phenylenediamine, m-phenylenediamine, melamine, 1,3,5-benzenetriamine

Epoxy compounds;
The epoxy compound has an epoxy group in the molecule as a polymerizable group, and is cured by ring-opening polymerization. These compounds may be added for adjusting the refractive index and adjusting the lens hardness. Such an epoxy compound is roughly classified into an aliphatic epoxy compound, an alicyclic epoxy compound, and an aromatic epoxy compound, and specific examples thereof include the following.

Aliphatic epoxy compounds; ethylene oxide, 2-ethyloxirane, butylglycidyl ether, phenylglycidyl ether, 2,2′-methylenebisoxirane, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, Triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, nonapropylene Glycol diglycidyl ether, neopentyl glycol diglycy Diether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, diglycidyl ether of tris (2-hydroxyethyl) isocyanurate, tris (2-hydroxyethyl) isocyanurate Triglycidyl ether of alicyclic epoxy compound; isophoronediol diglycidyl ether, bis-2,2-hydroxycyclohexylpropane diglycidyl ether aromatic epoxy compound; resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl Ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ester, pheno Le novolak polyglycidyl ether, cresol novolak polyglycidyl ether

In addition to the above, an epoxy compound having a sulfur atom in the molecule can be used together with the epoxy group. Such a sulfur-containing atom epoxy compound particularly contributes to the improvement of the refractive index, and includes a chain aliphatic type and a cycloaliphatic type. Specific examples thereof are as follows.
Chain aliphatic sulfur-containing atom epoxy compounds; bis (2,3-epoxypropyl) sulfide, bis (2,3-epoxypropyl) disulfide, bis (2,3-epoxypropylthio) methane, 1,2- Bis (2,3-epoxypropylthio) ethane, 1,2-bis (2,3-epoxypropylthio) propane, 1,3-bis (2,3-epoxypropylthio) propane, 1,3-bis ( 2,3-epoxypropylthio) -2-methylpropane, 1,4-bis (2,3-epoxypropylthio) butane, 1,4-bis (2,3-epoxypropylthio) -2-methylbutane, , 3-bis (2,3-epoxypropylthio) butane, 1,5-bis (2,3-epoxypropylthio) pentane, 1,5-bis (2,3-epoxypropylthio) 2-methylpentane, 1,5-bis (2,3-epoxypropylthio) -3-thiapentane, 1,6-bis (2,3-epoxypropylthio) hexane, 1,6-bis (2,3- Epoxypropylthio) -2-methylhexane, 3,8-bis (2,3-epoxypropylthio) -3,6-dithiaoctane, 1,2,3-tris (2,3-epoxypropylthio) propane, 2 , 2-bis (2,3-epoxypropylthio) -1,3-bis (2,3-epoxypropylthiomethyl) propane, 2,2-bis (2,3-epoxypropylthiomethyl) -1- ( 2,3-epoxypropylthio) butane cycloaliphatic sulfur-containing atom epoxy compound; 1,3-bis (2,3-epoxypropylthio) cyclohexane, 1,4-bis (2,3-epoxy (Lopylthio) cyclohexane, 1,3-bis (2,3-epoxypropylthiomethyl) cyclohexane, 1,4-bis (2,3-epoxypropylthiomethyl) cyclohexane, 2,5-bis (2,3-epoxypropyl) Thiomethyl) -1,4-dithiane, 2,5-bis [<2- (2,3-epoxypropylthio) ethyl> thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epoxy Propylthiomethyl) -2,5-dimethyl-1,4-dithiane

Carboxylic acid compounds;
The carboxylic acid compound is a compound having a COOH group in the molecule, and forms a thiourethane bond by a reaction with a polyisothiocyanate which forms a urethane bond by a reaction with a polyisocyanate. These monomers may be added for adjusting the hardness. Specific examples thereof include the following compounds and acid anhydrides thereof.

  Aliphatic polycarboxylic acid; succinic acid, adipic acid, maleic anhydride, sebacic acid, dimer acid, aromatic polycarboxylic acid; orthophthalic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid and terephthalic acid

  The aforementioned (B3) urethane or urea-based polymerizable monomer is used in combination so as to form a urethane bond or a urea bond by polymerization.

<(B4) Other polymerizable monomer>
In the present invention, in addition to the above-described polymerizable monomers (B1) to (B3), other polymerizable monomers can be blended. As other polymerizable monomers, episulfide polymerizable monomers and thietanyl polymerizable monomers can be used for the purpose of improving the refractive index, and monofunctional polymerizable monomers and composites for the purpose of improving photochromic properties. A type polymerizable monomer can also be used.

Episulfide polymerizable monomers;
This polymerizable monomer is a compound having two or more episulfide groups in one molecule, and is cured by ring-opening polymerization. In particular, it is suitable when an SH group is introduced as a polymerizable functional group into the side chain of the (A) polymerizable functional group-containing graft polymer. Specifically, the following compounds can be exemplified.

  Bis (1,2-epithioethyl) sulfide, bis (1,2-epithioethyl) disulfide, bis (2,3-epithiopropyl) sulfide, bis (2,3-epithiopropylthio) methane, bis (2,3 -Epithiopropyl) disulfide, bis (2,3-epithiopropyldithio) methane, bis (2,3-epithiopropyldithio) ethane, bis (6,7-epithio-3,4-dithiaheptyl) sulfide, bis (6,7-epithio-3,4-dithiaheptyl) disulfide, 1,4-dithian-2,5-bis (2,3-epithiopropyldithiomethyl), 1,3-bis (2,3-epithio) Propyldithiomethyl) benzene, 1,6-bis (2,3-epithiopropyldithiomethyl) -2- (2,3-epithiopropyldithioethylthio) ) -4-thiahexane, 1,2,3-tris (2,3-epithiopropyldithio) propane, 1,1,1,1-tetrakis (2,3-epithiopropyldithiomethyl) methane, 1,3 -Bis (2,3-epithiopropyldithio) -2-thiapropane, 1,4-bis (2,3-epithiopropyldithio) -2,3-dithiabutane, 1,1,1-tris (2,3 -Epithiopropyldithio) methane, 1,1,1-tris (2,3-epithiopropyldithiomethylthio) methane, 1,1,2,2-tetrakis (2,3-epithiopropyldithio) ethane, , 1,2,2-tetrakis (2,3-epithiopropyldithiomethylthio) ethane, 1,1,3,3-tetrakis (2,3-epithiopropyldithio) propane, 1,1,3,3- Tetrachi (2,3-epithiopropyldithiomethylthio) propane, 2- [1,1-bis (2,3-epithiopropyldithio) methyl] -1,3-dithietane, 2- [1,1-bis (2 , 3-Epithiopropyldithiomethylthio) methyl] -1,3-dithietane

Thietanyl polymerizable monomer;
This polymerizable monomer is effective when an SH group is introduced as a polymerizable functional group in the side chain of the (A) polymerizable functional group-containing graft polymer, and two or more thietanyl groups are contained in one molecule. And is cured by ring-opening polymerization. These compounds may be added to increase the refractive index. Some of these thietanyl compounds have an episulfide group together with a plurality of thietanyl groups, which are listed in the above section on episulfide compounds. Other thietanyl compounds include a metal-containing thietane compound having a metal atom in the molecule and a non-metal thietane compound not containing a metal. Here, in the metal-containing thietane compound, in the molecule, as a metal atom, a group 14 element such as Sn atom, Si atom, Ge atom or Pb atom; a group 4 element such as Zr atom or Ti atom; Al atom Group 13 elements such as Zn; or group 12 elements such as Zn atoms; and the like. As specific examples of such thietanyl compounds, the following can be exemplified.

Metal-containing thietane compounds; alkylthio (thietanylthio) tin; methylthiotris (thietanylthio) tin, ethylthiotris (thietanylthio) tin, propylthiotris (thietanylthio) tin, isopropylthiotris (thietanylthio) tin bis (alkylthio) bis (thietanylthio) tin Bis (methylthio) bis (thietanylthio) tin, bis (ethylthio) bis (thietanylthio) tin, bis (propylthio) bis (thietanylthio) tin, bis (isopropylthio) bis (thietanylthio) tin alkylthio (alkylthio) bis (thietanylthio) tin Ethylthio (methylthio) bis (thietanylthio) tin, methylthio (propylthio) bis (thietanylthio) tin, isopropylthio (methylthio) bis (thie Nylthio) tin, ethylthio (propylthio) bis (thietanylthio) tin, ethylthio (isopropylthio) bis (thietanylthio) tin, isopropylthio (propylthio) bis (thietanylthio) tin non-metallic thietane compounds; bis (3-thietanyl) disulfide, bis (3-thietanyl) sulfide, bis (3-thietanyl) trisulfide, bis (3-thietanyl) tetrasulfide, 1,4-bis (3-thietanyl) -1,3,4-trithiabutane, 1,5-bis ( 3-thietanyl) -1,2,4,5-tetrathiapentane, 1,6-bis (3-thietanyl) -1,3,4,6-tetrathiahexane, 1,6-bis (3-thietanyl) -1,3,5,6-tetrathiahexane, 1,7-bis (3-thietanyl) -1,2,4 5,7-pentathiaheptane, 1,7-bis (3-thietanylthio) -1,2,4,6,7-pentathiaheptane, 1,1-bis (3-thietanylthio) methane, 1,2-bis (3-thietanylthio) ethane, 1,2,3-tris (3-thietanylthio) propane,

Monofunctional polymerizable monomer;
This monomer is a compound having one hydroxyl group or thiol group in one molecule (hereinafter also referred to as mono (thio) ol compound), and in addition to the poly (thio) ol compound, this monomer is further used. When the photochromic composition is cured, a rigid cured body having a network structure having a (thio) urethane bond is obtained by a reaction between the polyiso (thio) cyanate compound and the poly (thi) ol compound. Since the mono (thi) ol compound having a terminal-free structure is taken into the network structure, a flexible space is formed around the mono (thi) ol compound. Accordingly, since a reversible structural change of the photochromic compound existing in the vicinity of the space is generated more rapidly, it is possible to produce a photochromic cured product having excellent photochromic properties (color density, fading speed).

  Furthermore, since the mono (thi) ol compound has only one hydroxyl group or thiol group, it has fewer hydrogen bonds than the poly (thi) ol compound, and as a result, the viscosity of the photochromic composition can be reduced. It is possible and the handling performance at the time of casting can be improved. Specific examples of the mono (thi) ol compound used in the photochromic composition of the present invention include the following compounds.

One hydroxyl compound in one molecule; polyethylene glycol monooleyl ether, polyoxyethylene oleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol mono-4-octylphenyl ether, linear polyoxy Ethylene alkyl ether (polyethylene glycol monomethyl ether, polyoxyethylene lauryl ether, polyoxyethylene-2-ethylhexyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether), 5 to 5 carbon atoms 30 saturated alkyl alcohols having a linear or branched structure, one thiol compound per molecule; 3-methoxybutyl thioglycolate, 2-ester Tylhexyl thioglycolate, 2-mercaptoethyl octanoate, 3-mercaptopropionate-3-methoxybutyl, ethyl 3-mercaptopropionate, 2-octyl 3-mercaptopropionate, n-octyl-3-mercaptopropio , Methyl-3-mercaptopropionate, tridecyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, saturated alkyl thiol having a linear or branched structure having 5 to 30 carbon atoms Preferred examples of the (thi) ol compound include polyethylene glycol monooleyl ether, polyethylene glycol monolaurate, polyethylene glycol monostearate, 1-dodecanethiol, stearyl-3-mercaptopropionate, n-Octyl-3-mercaptopropionate is preferred.

Composite polymerizable monomer;
This polymerizable monomer has a plurality of different types of polymerizable groups in the molecule, and various physical properties can be adjusted by using such a polymerizable monomer.

Examples of such a complex polymerizable monomer include the following compounds.
Radical polymerization / epoxy-type polymerizable monomer; glycidyl methacrylate, glycidyloxymethyl methacrylate, polyethylene glycol glycidyl methacrylate Radical polymerization / OH-type polymerizable monomer; 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate radical polymerization / Isocyanate type polymerizable monomer; 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate

  In the present invention, (A) a polymerizable functional group introduced into the side chain of the polymerizable functional group-containing graft polymer in order to maximize the photochromic effect of the polymerizable functional group-containing graft polymer. A hydroxyl group and / or a thiol group, (B) a polymerizable monomer, (B3) a urethane or urea-based polymerizable monomer, a urethane bond, a thiourethane bond, a urea bond or a thiourea bond, particularly a urethane bond or a thiourethane bond) Most preferably, they are used in combination so that is formed.

<(C) Photochromic compound>
As the photochromic compound exhibiting photochromic properties, those known per se can be used, and these can be used alone or in combination of two or more.

  Typical examples of such photochromic compounds are fulgide compounds, chromene compounds and spirooxazine compounds. For example, JP-A-2-28154, JP-A-62-228830, WO94 / 22850 pamphlet, WO96. / 14596 pamphlet and other documents.

  In the present invention, among known photochromic compounds, indeno [2,1-f] naphtho [1,2-b] pyran skeleton from the viewpoint of photochromic properties such as color density, initial colorability, durability, and fading speed. It is more preferable to use a chromene compound having a molecular weight of 540. Particularly, a chromene compound having a molecular weight of 540 or more is preferably used because it is particularly excellent in color density and fading speed.

  The following chromene compounds are examples of chromene compounds that are particularly preferably used in the present invention.

<Preferred composition of photochromic composition>
In the photochromic composition of the present invention having the above-mentioned (A) polymerizable functional group-containing graft polymer and (C) photochromic compound as essential components, usually 0.0001 to 20 parts by mass per 100 parts by mass of the graft polymer (A) The amount of the photochromic compound (B) is used, and the preferred amount of use varies depending on the photochromic expression method.

For example, when the photochromic property is expressed by a kneading method, it is preferably used in an amount of 0.001 to 2 parts by mass. When the photochromic property is expressed by a lamination method, an amount of 0.01 to 10 parts by mass. Is preferably used.
Moreover, when making photochromic property express by a binder method, it is preferable to use it in the quantity of 0.5-20 mass parts.

<(D) Polymerization curing accelerator, (E) Internal mold release agent>
In the present invention, in addition to the components (A), (B), and (C), for the purpose of improving moldability and adjusting the hardness of the cured product, (D) a polymerization curing accelerator, (E) An internal mold release agent may further be included. These will be described.

(D) a polymerization curing accelerator;
In the photochromic composition of the present invention, depending on the type of the polymerizable functional group introduced into the side chain of the (A) polymerizable functional group-containing graft polymer and the type of the polymerizable monomer (B), the polymerization curing is promptly performed. Various polymerization curing accelerators can be used to promote the polymerization.

For example, when used for the reaction of a hydroxyl group and a thiol group with an isocyanate group and an isothiocyanate group, a reaction catalyst or condensing agent for urethane or urea is used as a polymerization curing accelerator.
When an episulfide compound, a thietanyl compound, or an epoxy compound is used, an epoxy curing agent or a cationic polymerization catalyst for ring-opening polymerization of an epoxy group is used as a polymerization curing accelerator.
When a radical polymerizable monomer containing a (meth) acryl group or vinyl group is contained, a radical polymerization initiator is used as a polymerization curing accelerator.

<Reaction catalyst for urethane or urea>
This reaction catalyst is used in poly (thio) urethane bond formation by reaction of polyiso (thia) cyanate with a polyol or polythiol. These polymerization catalysts can include tertiary amines and the corresponding inorganic or organic salts, phosphines, quaternary ammonium salts, quaternary phosphonium salts, Lewis acids, or organic sulfonic acids. As specific examples, the following can be exemplified. Further, when the catalytic activity is too high depending on the kind of the above-mentioned compound to be selected, it is possible to suppress the catalytic activity by using a mixture of a tertiary amine and a Lewis acid.

Tertiary amines; triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, triethylamine, hexamethylenetetramine, N, N-dimethyloctylamine, N, N, N ′, N '-Tetramethyl-1,6-diaminohexane, 4,4'-trimethylenebis (1-methylpiperidine), 1,8-diazabicyclo- (5,4,0) -7-undecene phosphines; trimethylphosphine, Triethylphosphine, tri-n-propylphosphie, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tribenzylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,2-bis (dimethylphosphine) Fino) ethane Quaternary ammonium salts Tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide quaternary phosphonium salts; tetramethylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide Lewis acid; triphenylaluminum, dimethyltin dichloride, dimethyltin bis (isooctyl) Thioglycolate), dibutyltin dichloride, dibutyltin dilaurate, dibutyltin maleate, dibutyltin maleate polymer, dibutyltin diricinolate, dibutyltin bis (dodecyl mercaptide), dibutyltin bis (isooctylthioglycolate), dioctyltin dichloride, Dioctyltin maleate, Dioctyltin maleate polymer, Diocti Tin bis (butyl maleate)
Various metal salts; copper oleate, copper acetylacetonate, iron acetylacetonate, iron naphthenate, iron lactate, iron citrate, iron gluconate, potassium octoate, 2-ethylhexyl titanate organic sulfonic acid; methanesulfonic acid, benzenesulfone Acid, p-toluenesulfonic acid

<Condensation agent>
Specific examples of the condensing agent include the following.
Inorganic acids; hydrogen chloride, hydrogen bromide, sulfuric acid, phosphoric acid, etc. Organic acids; p-toluenesulfonic acid, camphor-sulfonic acid, etc. Acidic ion exchange resins; Amberlite, Amberlyst, etc. Carbodiimides; Dicyclohexylcarbodiimides, 1-ethyl -3- (3-Dimethylaminopyrrolyl) -carbodiimide

<Epoxy curing agent>
Specific examples of the epoxy curing agent include the following.
Amine compounds and salts thereof; 2-methylimidazole, 2-ethyl-4-methylimidazole, 1,8-diaza-bicyclo (5,4,0) undecene-7-trimethylamine, benzyldimethylamine, triethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, 2- (dimethylaminomethyl) phenol quaternary ammonium salt; tetramethylammonium chloride, benzyltrimethylammonium bromide, tetrabutylammonium bromide organic phosphine compound; tetra-n-butyl Phosphonium benzotriazolate, tetra-n-butylphosphonium-o, o-diethyl phosphorodithioate metal carboxylate; chromium (III) tricarboxylate, tin octylate acetylacetone chelate compound; Muacetylacetonate

<Cationic polymerization catalyst>
Specific examples of the cationic polymerization catalyst include the following.
Lewis acid catalyst; BF ₃ / amine complex, PF ₅ , BF ₃ , AsF ₅ , SbF _5, etc. Thermosetting cationic polymerization catalyst; Phosphonium salt, quaternary ammonium salt, sulfonium salt, benzylammonium salt, benzylpyridinium salt, benzyl Sulfonium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester, amine imide UV curable cationic polymerization catalyst; diaryliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate

<Radical polymerization initiator>
The polymerization initiator includes a photopolymerization initiator and a thermal polymerization initiator.
Specific examples of the photopolymerization initiator are as follows.
Acetophenone compounds; 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one α -Dicarbonyl compounds; 1,2-diphenylethanedione, methylphenylglycoxylate acylphosphine oxide compounds; 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphinic acid methyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide Note that a photopolymerization initiator is used. The case can also be used in combination known polymerization curing accelerator aid such tertiary amines.

Specific examples of the thermal polymerization initiator are as follows.
Diacyl peroxide; benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide acetyl peroxide peroxy ester; t-butyl peroxy-2-ethyl hexanate, t-butyl peroxy neodecanate , Cumylperoxyneodecanate, t-butylperoxybenzoate percarbonate; diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate azo compound; azobisisobutyronitrile Each of the accelerators may be used alone or in combination of two or more, but the amount used may be a so-called catalytic amount. For example, (A) the polymerizable functional group-containing graft polymer and (B ) Polymerizable monomer The range of 0.001 to 10 parts by mass, particularly 0.01 to 5 parts by mass is sufficient for a total of 100 parts by mass.

<(E) Internal mold release agent>
As an example of the internal mold release agent used in the present invention, any can be used as long as it has a release effect and does not impair the physical properties such as transparency of the resin, but preferably a surfactant is used. Is done. Of these, phosphate ester surfactants are preferred. The internal mold release agent herein includes those exhibiting a mold release effect among the above-mentioned various catalysts, and may include, for example, quaternary ammonium salts and quaternary phosphonium salts. These internal mold release agents are appropriately selected from the combination with monomers, polymerization conditions, economy, and ease of handling. Specific examples of the internal release agent of the phosphate ester are as follows.

Alkyl acid phosphate; mono-n-butyl phosphate, mono-2-ethylhexyl phosphate, mono-n-octyl phosphate, mono-n-butyl phosphate, bis (2-ethylhexyl) phosphate, di ( 2-ethylhexyl), di-n-octyl phosphate, di-n-butyl phosphate, butyl acid phosphate (mono-, di-mixture), ethyl acid phosphate (mono-, di-mixture), butoxyethyl acid phosphate ( Mono-, di-mixture), 2-ethylhexyl acid phosphate (mono-, di-mixture), isotridenic acid phosphate (mono-, di-mixture), tetracosyl acid phosphate (mono-, di-mixture), stearyl Acid phosphate (mono-, di-mixture)
Other phosphate esters; oleyl acid phosphate (mono-, di-mixture), dibutyl pyrophosphate, ethylene glycol acid phosphate (mono-, di-mixture), butoxyethyl acid phosphate (mono-, di-mixture) it can.

  Each of the various (E) internal mold release agents described above can be used alone or in combination of two or more, but the amount used can be small, for example, the sum of (A) and (B). It can use in the quantity of 0.001 mass part-20 mass parts with respect to 100 mass parts.

<Other ingredients>
The photochromic composition of the present invention has various compounding agents known per se within a range not impairing the effects of the present invention, such as an ultraviolet absorber, an antistatic agent, an infrared absorber, an ultraviolet stabilizer, an antioxidant, and an anti-coloring agent. Various stabilizers such as additives, antistatic agents, fluorescent dyes, dyes, pigments, and fragrances, additives, solvents, leveling agents, and thiols such as t-dodecyl mercaptan are added as polymerization regulators as needed. can do.

  Among these, use of an ultraviolet stabilizer is preferable because durability of the photochromic compound can be improved. As such an ultraviolet stabilizer, a hindered amine light stabilizer, a hindered phenol antioxidant, a sulfur-based antioxidant, and the like are known. Particularly suitable UV stabilizers are as follows.

  Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Adeka Stub LA-52, LA-57, LA-62, LA-63, LA-67 manufactured by Asahi Denka Kogyo Co., Ltd. LA-77, LA-82, LA-87, 2,6-di-t-butyl-4-methyl-phenol, ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m -Tolyl) propionate], IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565 manufactured by Ciba Specialty Chemicals.

  The amount of the ultraviolet stabilizer used is not particularly limited as long as the effect of the present invention is not impaired, but is usually 0.001 with respect to a total of 100 parts by mass of (A) and (B). The range is from 10 to 10 parts by mass, particularly from 0.01 to 1 part by mass. In particular, when a hindered amine light stabilizer is used, there is a difference in durability improvement effect depending on the type of photochromic compound. The amount per unit is 0.5 to 30 mol, more preferably 1 to 20 mol, still more preferably 2 to 15 mol.

  Antistatic agents include alkali metal or alkaline earth metal salts, quaternary ammonium salts, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants). ), And ionic liquids (salts that exist as liquids at room temperature and exist as pairs of cations and anions). Specific examples are as follows.

Alkali metal or alkaline earth metal salt; alkali metal (such as lithium, sodium and potassium) or alkaline earth metal (such as magnesium and calcium) and organic acid [mono- or dicarboxylic acid having 1 to 7 carbon atoms (formic acid, acetic acid, Salt of propionic acid, oxalic acid, succinic acid, etc.), sulfonic acid having 1 to 7 carbon atoms (methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, etc.) and thiocyanic acid], and said organic acid and inorganic Salts of acids [hydrohalic acids (hydrochloric acid and hydrobromic acid, etc.), perchloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.], etc. Quaternary ammonium salts; Amidinium (1-ethyl-3-methylimidazolium, etc.) Or a salt of guanidinium (2-dimethylamino-1,3,4-trimethylimidazolinium, etc.) and the organic acid or inorganic acid, etc. Sexifier: Sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, fatty acid alkanolamide, polyoxyethylene alkyl ether, alkyl glycoside, polyoxyethylene alkyl phenyl ether, higher fatty acid salt (soap) , Α-sulfo fatty acid methyl ester salt, linear alkylbenzene sulfonate, alkyl sulfate ester salt, alkyl ether sulfate ester salt, (mono) alkyl phosphate ester salt, α-olefin sulfonate, alkane sulfonate, alkyl trimethyl Ammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, N-methylbishydroxyethylamine fat, fatty acid ester / hydrochloride, alkylammonium Fatty acid salts, alkylbetaines, alkylamine oxides, etc. Ionic liquids; 1,3-ethylmethylimidazolium bistrifluoromethanesulfonimide, 1,3-ethylmethylimidazolium tetrafluoroborate, 1-ethylpyridinium bistrifluoromethanesulfonimide 1-ethylpyridinium tetrafluoroborate, 1-ethylpyridinium hexafluorophosphate, 1-methylpyrazolium bistrifluoromethanesulfonimide, etc.

<Method for producing photochromic composition>
The photochromic composition of the present invention is generally formulated with (D) a polymerization curing accelerator in addition to (A) a polymerizable functional group-containing graft polymer, (B) a polymerizable monomer, and (C) a photochromic compound. For example, it is desirable to prepare a photochromic composition by melting and kneading each component, polymerizing and curing the component, and producing a photochromic property by this cured body.

  Further, in order to improve the solubility of the constituent components and adjust the film thickness, the photochromic composition of the present invention is dispersed or dissolved in an organic solvent to prepare a coating solution, and this coating solution is applied to a transparent optical sheet or optical film. By drying, a photochromic coating layer can be formed, whereby photochromic properties can be expressed. The organic solvent to be used may be appropriately selected depending on the use, but from the viewpoint of solubility, ketones such as methyl ethyl ketone and diethyl ketone, halogens such as methylene chloride and chloroform, aromatic hydrocarbons such as toluene and xylene, It is preferable to use ethers such as dioxane and tetrahydropyran.

  The photochromic composition is polymerized and cured in order to produce a photochromic cured product. Polymerization curing is performed by radical polymerization, ring-opening polymerization, anionic polymerization or condensation by irradiation with heat or, if necessary, active energy rays such as ultraviolet rays, α rays, β rays, and γ rays, heat, or a combination of both. This is done by carrying out polymerization. That is, an appropriate polymerization means may be employed depending on the type of (B) polymerizable monomer or (D) polymerization curing accelerator and the form of the photochromic cured product to be formed.

  When the photochromic composition of the present invention is thermally polymerized, it affects the properties of the photochromic cured product from which the temperature can be obtained. This temperature condition is influenced by the type and amount of the thermal polymerization initiator and the type of polymerizable monomer, and thus cannot be limited in general. Generally, the polymerization is started at a relatively low temperature, and the temperature is slowly increased. The method is preferred. Since the polymerization time varies depending on various factors as well as the temperature, it is preferable to determine the optimal time according to these conditions in advance. Generally, the conditions are set so that the polymerization is completed in 2 to 48 hours. It is preferable to choose. When obtaining a photochromic laminated sheet, it is preferable to polymerize at a temperature at which the reaction between the polymerizable functional groups proceeds, and at that time, to determine the optimum temperature and time so as to achieve the target molecular weight.

In addition, when photopolymerizing the photochromic composition of the present invention, among the polymerization conditions, particularly the UV intensity affects the properties of the resulting photochromic cured product. This illuminance condition is influenced by the type and amount of the photopolymerization initiator and the type of the polymerizable monomer, and thus cannot be generally limited. However, in general, UV light of 50 to 500 mW / cm ² at a wavelength of 365 nm is reduced to 0. It is preferable to select conditions so that light is irradiated in a time of 5 to 5 minutes.

  In the case where the photochromic property is expressed by the kneading method using the above-described polymerization curing, the above photochromic composition is injected between the glass molds held by the elastomer gasket or the spacer, and the polymerizable monomer or the polymerization is injected. Depending on the type of curing accelerator, a photochromic cured product molded in the form of an optical material such as a lens can be obtained by casting polymerization by heating in an air furnace or irradiation with active energy rays such as ultraviolet rays. According to such a method, a spectacle lens or the like to which photochromic properties are directly imparted can be obtained.

  When photochromic properties are developed by a lamination method, a photochromic composition is appropriately dissolved in an organic solvent to prepare a coating solution, and the coating solution is applied to the surface of an optical substrate such as a lens substrate by spin coating or dipping. It is applied and dried to remove the organic solvent, and then polymerized and cured by UV irradiation or heating in an inert gas such as nitrogen, whereby a photochromic layer made of a photochromic cured product is formed on the surface of the optical substrate. Formed (coating method).

  In addition, an optical substrate such as a lens substrate is placed facing the glass mold so that a predetermined gap is formed, and a photochromic composition is injected into the gap, and in this state, polymerization curing is performed by UV irradiation or heating. A photochromic layer made of a photochromic cured product can also be formed on the surface of the optical base material by cast polymerization using an inner mold (cast polymerization method).

  When the photochromic layer is formed on the surface of the optical substrate by the above laminating method (coating method and cast polymerization method), the surface of the optical substrate is preliminarily chemically treated with an alkaline solution, an acid solution, By performing a physical treatment such as corona discharge, plasma discharge, and polishing, the adhesion between the photochromic layer and the optical substrate can be enhanced. Of course, it is also possible to provide a transparent adhesive resin layer on the surface of the optical substrate.

Furthermore, when photochromic properties are manifested by the binder method, a photochromic sheet is produced by sheet molding using a photochromic composition, and this is sandwiched between two transparent sheets (optical sheets). As a result, a photochromic laminate having the photochromic layer as an adhesive layer is obtained.
In this case, for the production of the photochromic sheet, a means of coating using a coating solution in which the photochromic composition is dissolved in an organic solvent can be employed.

  The photochromic laminate produced in this way is, for example, mounted in a mold, and thereafter, a photochromic property is imparted by injection molding of a thermoplastic resin for an optical substrate such as a lens (for example, polycarbonate). An optical substrate such as a lens having a predetermined shape is obtained, and the photochromic laminate can be adhered to the surface of the optical substrate with an adhesive or the like, whereby a photochromic lens can be obtained. .

  The photochromic composition of the present invention described above can exhibit photochromic properties with excellent color density, fading speed, etc., and is optically imparted with photochromic properties without reducing properties such as mechanical strength. It is effectively used for the production of a substrate such as a photochromic lens.

In addition, the photochromic layer and the photochromic cured body formed by the photochromic composition of the present invention are dyed using a dye such as a disperse dye, silane coupling agent, silicon, zirconium, antimony, aluminum, tin, Preparation of hard coat film using hard coat agent mainly composed of sol such as tungsten, formation of thin film by vapor deposition of metal oxide such as SiO ₂ , TiO ₂ , ZrO _2, etc., thin film by applying organic polymer It is also possible to perform post-processing such as antireflection treatment or antistatic treatment by the above.

  Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to the examples. In the following Examples and Comparative Examples, the above-described components, photochromic evaluation methods, and the like are as follows.

(A) Polymerizable functional group-containing graft polymer A-1: Hydroxyethyl methacrylate (HEMA) -polycaprolactone (PCL) -OH macromonomer (number average molecular weight 910) and methyl methacrylate (having OH groups as polymerizable functional groups) MMA) and a graft polymer having an OH group as a polymerizable functional group in the side chain (weight average molecular weight 90,000).
A-2: Copolymer of HEMA-PCL-OH macromonomer (number average molecular weight 1,800) having an OH group as a polymerizable functional group and MMA, having an OH group as a polymerizable functional group in a side chain It is a graft polymer (weight average molecular weight 135,000).
A-3: A graft polymer obtained by modifying the polymerizable functional group (OH group) of the graft polymer A-1 and introducing an acrylic group (weight average molecular weight 93,000).
A-4: A graft polymer obtained by modifying the polymerizable functional group (OH group) of the graft polymer A-2 and introducing an acrylic group (weight average molecular weight 138,000).

(B) Polymerizable monomer (meth) acrylic polymerizable monomer TMPT: trimethylolpropane trimethacrylate D-TMPT: ditrimethylolpropane tetramethacrylate 3PG: tripropylene glycol dimethacrylate BPE100: 2,2-bis [4- (methacryloyloxy) Ethoxy) phenyl] propane (average chain length of ethylene glycol chain is 2.6, average molecular weight is 478)
A400: Polyethylene glycol diacrylate (average chain length of ethylene glycol chain is 9, average molecular weight is 508)
BPE500: 2,2-bis [4- (methacryloyloxypolyethoxy) phenyl] propane (average chain length of ethylene glycol chain is 10, average molecular weight is 804)
A-BPE: 2,2-bis (4-acryloyloxypolyethoxyphenyl) proban (average repeating number of ethyleneoxy groups is 10, average molecular weight is 776)
M90G: Methoxypolyethylene glycol methacrylate (Shin Nakamura Chemical Co., Ltd. “M90G”)
14G: Polyethylene glycol dimethacrylate (average chain length of ethylene glycol chain is 14, average molecular weight is 736)
EB4858: a bifunctional urethane methacrylate manufactured by Daicel UCB (acrylic equivalent is 227)
M-1: Polycarbonate diol diacrylate Vinyl polymerizable monomer αMS: α-methylstyrene MSD: α-methylstyrene dimer Allyl polymerizable monomer MPEAE: Methoxypolyethylene glycol allyl ether (average molecular weight 550)
Poly (thi) ol compound PL1: Duranol manufactured by Asahi Kasei Chemicals Corporation (polycarbonate diol, number average molecular weight 500)
TMMP: Trimethylolpropane tris (3-mercaptopropionate)
Pemp: pentaerythritol tetrakis (3-mercaptopropionate)
Polyisocyanate compound XDI: m-xylene diisocyanate IPDI: isophorone diisocyanate polyamine compound IPDA: isophorone diamine monofunctional polymerizable monomer PLE: polyoxyethylene lauryl ether (n≈23)
Composite type polymerizable monomer GMA: Glycidyl methacrylate

(C) a photochromic compound;
PC1:

(D) polymerization curing accelerator thermal polymerization initiator;
Perbutyl ND: t-butyl peroxyneodecanate (trade name: perbutyl ND, manufactured by NOF Corporation)
Perocta O: 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanate (trade name: Perocta O, manufactured by NOF Corporation)
Photopolymerization initiator;
PI: Phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide (trade name: Irgacure 819, manufactured by BASF)
Reaction catalyst for urethane or urea>;
DBTD: Dibutyltin dilaurate

Other ingredients;
solvent;
THF tetrahydrofuran DMF: dimethyl sulfoxide IPA: isopropyl alcohol stabilizer;
HALS: bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (molecular weight 508)
HP: Ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (Irganox 245, manufactured by Ciba Specialty Chemicals)
Leveling agent;
L1: Toray Dow Corning Corporation product name; L7001

A graft polymer containing no polymerizable functional group;
F-1: Graft polymer in which a side chain polymerizable functional group (OH group) is capped with an isopropyl group

<(A) Preparation method of polymerizable functional group-containing graft polymer>
(1-1) A copolymer of a HEMA-PCL-OH macromonomer (number average molecular weight 910) having an OH group as a polymerizable functional group and methyl methacrylate (MMA), and OH as a polymerizable functional group in the side chain Graft polymer (A-1) having a weight average molecular weight of 90,000 having a group
First, a HEMA-PCL-OH macromonomer (number average molecular weight: Mw = 910) was prepared as follows.
A 100 ml toluene solution of 1.30 g (10 mmol) of distilled HEMA was gradually added dropwise to a 90 ml toluene solution of 1.14 (10 mmol) triethylaluminum while stirring in a nitrogen atmosphere. The mixture was vigorously stirred at room temperature for 30 minutes and then at 40 ° C. for 30 minutes. After generation of ethane, stirring was further performed at room temperature for 1 hour to obtain a diethylaluminum alkoxide in the system.

  Subsequently, a solution prepared by dissolving 8.0 g (70 mmol) of ε-caprolactone in 100 ml of toluene was added to the solution containing the diethylaluminum alkoxide compound at 25 ° C. and reacted for 3 hours. The alkoxide was decomposed by putting it in 2N hydrochloric acid 10 times as much as the solution. The remaining aluminum component was repeatedly extracted with a 0.1 M aqueous solution of ethylenediaminetetraacetic acid, and the polymer component was washed with water until neutral. After distilling off 2/3 amount of toluene, precipitation was performed, followed by vacuum drying to obtain 8.2 g of a HEMA-PCL-OH macromonomer. From the GPC analysis, it was found that the number average molecular weight (Mn) was 910, and the average number of ε-caprolactone units in the side chain was 6.7 per macromonomer molecule.

The above prepared HEMA-PCL-OH macromonomer (number average molecular weight: Mw = 910) 2.0 g (2.2 mmol), methyl methacrylate (MMA) 1.0 g (10 mmol) and azobisisobutyronitrile 100 mg Was dissolved in dimethylformamide (DMF) and reacted at 60 ° C. for 22 hours. After the DMF was distilled off, the polymer component was redissolved in tetrahydrofuran (THF) and reprecipitated in heptane. The precipitate was filtered and then dried under reduced pressure to obtain the desired graft polymer (A-1).
IR: 1730 cm-1 (C = O expansion and contraction),
Weight average molecular weight Mw (GPC): 90,000
The molar ratio of MMA and HEMA-PCL-OH macromonomer constituting the obtained graft polymer in ¹ H-NMR measurement is the ratio of characteristic peaks in ¹ H-NMR, that is, hydrogen at α-hydroxymethylene terminal derived from HEMA. It was calculated from the signal intensity ratio between (—OCH ₂ OH) and MMA-derived methyl ester hydrogen (—C (O) OCH ₃ ), and was found to be 89:11.

  (1-2) A copolymer of MMA and a HEMA-PCL-OH macromonomer having an OH group as a polymerizable functional group (number average molecular weight 1,800) and an OH group as a polymerizable functional group on the side chain Preparation of a graft polymer having a weight average molecular weight of 135,000 (A-2).

First, a HEMA-PCL-OH macromonomer was prepared in the following manner (number average molecular weight: Mn = 1,800);
HEMA-PCL was prepared in the same manner as in (1-1) except that 2.14 g (theoretical amount, equivalent to 10 mmol) of diethylaluminum alkoxide obtained from HEMA and 17.1 g (150 mmol) of ε-caprolactone were used. 17.4 g of —OH macromonomer was obtained. The number average molecular weight of the obtained macromonomer was 1,800, and the average ε-caprolactone unit was found to be 14.6 per macromonomer molecule.

Subsequently, 2.0 g (1.1 mmol) of the preparation of the HEMA-PCL-OH macromonomer prepared above (number average molecular weight: Mn = 1,800) and 1.0 g (10 mmol) of methyl methacrylate (MMA) A graft polymer (A-2) was obtained in the same manner as in (1-1) except that it was used. It was found that the molar ratio of MMA constituting the obtained graft polymer and HEMA-PCL-OH macromonomer in ¹ H-NMR measurement was 90:10.
IR: 1731 cm-1 (C = O expansion and contraction)
Weight average molecular weight Mw (GPC): 135,000

(2-1) Preparation of graft polymer having a weight average molecular weight of 93,000 in which an acrylic group is introduced by modifying the polymerizable functional group (OH group) of graft polymer A-1 (A-3)
After adding 0.01 g of dibutylhydroxytoluene (polymerization inhibitor) to 100 g of a toluene solution of 5.0 g (0.055 mmol) of the graft polymer (A-1) prepared in (1-1) above, 2-acryloyl 0.45 g (2.9 mmol) of oxyethyl isocyanate was added dropwise. The mixture was stirred at 40 ° C. for 12 hours to obtain a toluene solution of a graft polymer in which an acrylic group was introduced at the end of polycaprolactone.

A toluene solution of this graft polymer was dropped into hexane, recovered, and dried to obtain a graft polymer (A-3) in which an acrylic group was introduced into the side chain as a polymerizable functional group. The physical properties of this graft polymer (A-3) were as follows.
IR: 1730 cm-1 (C = O expansion and contraction)
Weight average molecular weight Mw (GPC): 93,000

(2-2) Preparation of a graft polymer (A-4) having a weight average molecular weight of 138,000 in which a polymerizable functional group (OH group) of the graft polymer A-2 is modified and an acrylic group is introduced;
A graft polymer (A-4) was prepared in the same manner as in the above (2-1) except that the graft polymer (A-2) was used. The physical properties of this graft polymer (A-4) were as follows.
IR: 1730 cm-1 (C = O expansion and contraction)
Weight average molecular weight Mw (GPC): 138,000

<Preparation of Graft Polymer (F-1) Capped with Polymerizable Functional Group of Side Chain with Isopropyl Group>
A polycaprolactone macromolecule in which the end of the side chain (OH group) is capped with an isopropyl group by the method described in European Polymer Journal 41, 1187-1195, 2005 using ε-caprotactone, methacrylic acid, etc. As a monomer, α-isopropoxy, ω-methacrylate-poly (ε-caprotactone) (hereinafter also referred to as Pr-PCLMA) was obtained. Number average molecular weight = 1870 (GPC). The average number of ε-caprolactone units in the side chain was found to be 15.6 per molecule of macromonomer.

The above-prepared Pr-PCLMA (number average molecular weight: Mw = 1870) 1.0 g (1.1 mmol), methyl methacrylate (MMA) 1.0 g (10 mmol) and azobisisobutyronitrile 100 mg were mixed with dimethylformamide ( DMF) and reacted at 60 ° C. for 22 hours. After the DMF was distilled off, the polymer component was redissolved in tetrahydrofuran (THF) and reprecipitated in heptane. The precipitate was filtered and then dried under reduced pressure to obtain the desired graft polymer (F-1). The physical properties of this graft polymer (F-1) were as follows.
IR: 1731 cm-1 (C = O expansion and contraction)
Weight average molecular weight Mw (GPC): 135,000
The molar ratio of MMA constituting the main chain of the graft polymer to the polycaprolactone macromonomer is the ratio of characteristic peaks in ¹ H-NMR, that is, ester methylene hydrogen (—C (O) OCH ₂ —) derived from the polyester chain. It was calculated from the signal intensity ratio of MMA-derived methyl ester hydrogen (—C (O) OCH ₃ ) and found to be 91: 9.

<Example 1>
(A-3) 10 parts by mass, 0.5 part by mass of 14G, and 15 parts by mass of tetrahydrofuran (THF) were stirred and dissolved at 50 ° C. for 1 hour. Next, 0.3 parts by mass of PC1 (photochromic compound), 0.03 parts by mass of PI (polymerization initiator), 0.01 parts by mass of L1 (leveling agent) are added, and the mixture is stirred and mixed at 40 ° C. for 30 minutes to obtain a photochromic composition. Got.

  Using a spin coater (1H-DX2, manufactured by MIKASA), about 2 g of the photochromic composition obtained above on the surface of a glass plate having a diameter of 80 mm and a thickness of 2 mm, the number of revolutions and time are adjusted, and finally obtained. The resulting photochromic coating film was spin-coated so that the film thickness was 40 μm.

  The glass plate on which the photochromic composition was applied as described above was irradiated with light for 90 seconds in a nitrogen gas atmosphere using a metal halide lamp with an output of 200 mW / cm 2 to cure the coating film. Thereafter, the mixture was further heated at 100 ° C. for 1 hour to produce a photochromic laminate having a photochromic coating layer.

  The obtained photochromic laminate had photochromic properties with a maximum absorption wavelength of 580 nm, a color density of 0.87, and a fading speed of 38 seconds. In addition, evaluation of these photochromic properties was performed as follows.

The obtained photochromic laminate (thickness of about 2 mm) was used as a sample, and a xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics Co., Ltd. was passed through an aeromass filter (manufactured by Corning) to 20 ± 1. The photochromic laminate was measured for color development by irradiation for 120 seconds at a beam intensity of 365 nm = 2.4 mW / cm ² and 245 nm = 24 μW / cm ² on the polymer (photochromic coat layer) surface. Moreover, the moldability of the obtained photochromic cured body was also favorable. Each photochromic property and moldability were evaluated by the following methods and are shown in Table 2.

<Maximum absorption wavelength (λmax)>
It 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.
<Color density {ε (120) −ε (0)}>
Difference between absorbance {ε (120)} after light irradiation for 120 seconds and absorbance ε (0) before light irradiation at the maximum absorption wavelength. It can be said that the higher this value, the better the photochromic properties. Further, when the color was developed outdoors, the color tone was visually evaluated.
<Fade speed [t1 / 2 (sec.)]>
The time required for the absorbance at the maximum absorption wavelength of the sample to drop to ½ of {ε (120) −ε (0)} when light irradiation is stopped after light irradiation for 120 seconds. It can be said that the shorter this time is, the better the photochromic property is.
<Moldability>
The optical distortion of the molded photochromic cured product was visually observed. Evaluation was made according to the following criteria.
1: No optical distortion 2: Optical distortion observed in a part of half or less of the lens 3: Optical distortion observed in the entire lens

<Example 2 and Comparative Example 1>
A photochromic laminate was prepared and evaluated in the same manner as in Example 1 except that the photochromic composition having the composition shown in Table 1 was used. The results are shown in Table 2.

<Example 3>
The photochromic composition shown in Table 1 was poured on a glass petri dish having a diameter of about 80 mm so that the film thickness of the finally obtained photochromic film was 40 μm. Next, tetrahydrofuran was volatilized from the glass petri dish under vacuum so as not to generate bubbles in the photochromic film. Finally, thermosetting was performed at 100 ° C. for 3 hours to prepare a photochromic film. The obtained photochromic film had photochromic properties with a maximum absorption wavelength of 580 nm, a color density of 0.86, and a fading speed of 37 seconds. These evaluations were performed in the same manner as in Example 1. The results are shown in Table 2.

<Examples 4 to 10 and Comparative Examples 2 to 4>
Each component shown in Table 3 was mixed to prepare a uniform liquid (photochromic composition). The obtained uniform liquid was sufficiently degassed, and then poured into a mold comprising a mold composed of a glass mold subjected to a mold release treatment and a gasket made of an ethylene-vinyl acetate copolymer.

  Subsequently, it was cured for 15 hours while gradually raising the temperature from 30 ° C to 95 ° C. After completion of the polymerization, the photochromic cured product was removed from the glass mold. Table 4 shows each photochromic characteristic and moldability. Note that the fading rates of Comparative Examples 2 and 3 were not measurable because the color density was too low.

<Examples 11-14, Comparative Examples 5-7>
Each component shown in Table 5 was sufficiently mixed to prepare a photochromic composition. The obtained mixed liquid (photochromic composition) was poured into a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer, and substantially all of the polymerizable monomer was polymerized by cast polymerization.

  The polymerization was carried out using an air furnace and heat-cured while gradually raising the temperature from 30 ° C. to 90 ° C. over 18 hours. After completion of the polymerization, the photochromic cured product was removed from the glass mold. Table 6 shows the photochromic properties and moldability results of the obtained photochromic cured product.

<Example 15, Comparative Example 8>
Each component shown in Table 7 was sufficiently mixed to prepare a photochromic composition. Subsequently, the photochromic laminated body was obtained by the laminating method using said photochromic composition. The polymerization method is shown below.

  First, a thiourethane plastic lens having a center thickness of 2 mm and a refractive index of 1.60 was prepared as an optical substrate. This thiourethane plastic lens was previously alkali-etched at 50 ° C. for 5 minutes using a 10% aqueous sodium hydroxide solution, and then thoroughly washed with distilled water.

  Using a spin coater (1H-DX2, manufactured by MIKASA), a moisture-curing primer (product name: TR-SC-P, manufactured by Tokuyama Co., Ltd.) is applied to the surface of the plastic lens at a rotational speed of 70 rpm for 15 seconds. Subsequently, coating was performed at 1000 rpm for 10 seconds. Thereafter, about 2 g of the photochromic composition obtained above was spin-coated so that the film thickness of the photochromic coating layer was 40 μm at 40 rpm for 40 seconds and then at 600 rpm for 10 to 20 seconds.

The lens having the coating agent coated on the surface was irradiated with light for 90 seconds in a nitrogen gas atmosphere using a metal halide lamp with an output of 200 mW / cm ² to cure the coating film. Thereafter, the mixture was further heated at 110 ° C. for 1 hour to produce a photochromic laminate having a photochromic layer. Table 8 shows the results of photochromic properties and moldability of the obtained photochromic laminate.

Claims (4)

(A) a graft polymer having a polymerizable functional group introduced in the side chain;
(B) a polymerizable monomer;
(C) a photochromic composition containing a photochromic compound ,
Because
(A) A photochromic composition in which the graft polymer in which a polymerizable functional group is introduced into the side chain is a graft polymer in which a polymerizable functional group is introduced into the polymer terminal of the side chain .   1 to 50 parts by weight of the graft polymer (A) having a polymerizable functional group per 100 parts by weight of the total of (A) the graft polymer having a polymerizable functional group introduced in the side chain and (B) the polymerizable monomer The photochromic composition according to claim 1, which is contained.   (C) A photochromic compound is included in an amount of 0.0001 to 20 parts by mass per 100 parts by mass in total of the graft polymer in which a polymerizable functional group is introduced into the side chain (A) and (B) a polymerizable monomer. The photochromic composition according to claim 1.   The photochromic hardening body obtained by hardening | curing the photochromic composition of Claims 1-3.