JP2003105227A - Bluing agent for plastic optical material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a bluing agent for a plastic optical material which is necessary for obtaining the material excellent in colorless transparency, a monomer composition for a plastic optical material in which the agent is dispersed, and a plastic optical material. SOLUTION: The bluing agent in which a surface of a pigment represented by Na6 Al6 Si6 O24 Sx (provided that X is 2-4) is subjected to a hydrophobic silica coating treatment, the monomer composition to which the bluing agent is added and the plastic optical material obtained by curing the composition are provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a bluing agent for a plastic optical material necessary for obtaining a plastic optical material having excellent colorless transparency, a monomer composition for a plastic optical material in which the bluing agent is dispersed, And a plastic optical material.

[0002]

2. Description of the Related Art In recent years, in the field of optical materials used for lenses and the like, lightness, safety, fashionability, etc. have become more and more important, and materials have been changed from conventional inorganic glass to synthetic resin. I'm doing it. Polydiethylene glycol bisallyl carbonate (hereinafter abbreviated as PADC) is well known as a representative synthetic resin material. Further, as a plastic lens having a higher refractive index and excellent optical characteristics, a copolymer of diallyl isophthalate and diethylene glycol bisallyl carbonate is disclosed in JP-A-62-23.
JP-A-5-501 discloses a copolymer of diallyl phthalate and an unsaturated dibasic acid diester having an aromatic ring in the ester group for the purpose of further increasing the refractive index.
Japanese Patent No. 213 discloses a resin of diallyl terephthalate oligomer. In addition to the allyl type monomer, a thiourethane resin composed of a copolymer of bisphenol A derivative dimethacrylate and styrene in JP-A-55-13747 and a thiourethane resin composed of polyisocyanate and polythiol in JP-A-62-267316. Is disclosed. These optical materials are molded by adding a curing agent and heat curing.

However, when these materials are molded by thermosetting, there is a problem that the resin after curing takes on a slight yellow color. As a method for improving the yellowness of the lens, Japanese Patent Application Laid-Open No. 5-195446 discloses a bluing method in which a blue pigment and a red pigment are added to an aromatic diallyl ester to cure. However, according to the method disclosed in JP-A-5-195446, it is not only difficult to obtain a lens of uniform color because the dispersibility of the pigment is not good, but also a filter for separating the pigment dyeing agent from the monomer and removing impurities. There is a problem that it becomes difficult to adjust the color tone of the lens due to the loss of light.

[0004]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a bluing agent for a plastic optical material which is necessary for obtaining a plastic optical material having excellent colorless transparency, and a single bluing agent for a plastic optical material in which the bluing agent is dispersed. To provide a monomer composition and a plastic optical material.

[0005]

The present invention is the following inventions. (1) Na ₆ Al ₆ Si ₆ O ₂₄ Sx (where X is 2 to 4
Is. ) A bluing agent for plastic optical materials, wherein the surface of the pigment represented by (4) is subjected to hydrophobic silica coating treatment. (2) Average particle size is 0.4 μm or less and particle size is 0.5 μm
The bluing agent for plastic optical materials according to the above (1), wherein the particle size distribution of particles of m or less is 60% by weight or more. (3) A monomer composition for a plastic optical material, to which the bluing agent for a plastic optical material according to the above (1) or (2) is added.

(4) The monomer composition for a plastic optical material according to the above (3), which contains an allyl compound. (5) The monomer composition for a plastic optical material according to the above (3), which contains a methacrylic compound or an acrylic compound. (6) The monomer composition for a plastic optical material according to (3), which contains a compound having a thiol group and / or a compound having an isocyanate group.

(7) The monomer composition for a plastic optical material according to the above (3), which contains a reaction product of a compound having a thiol group and a compound having an isocyanate group. (8) A plastic optical material obtained by curing the monomer composition for a plastic optical material according to any one of (3) to (7).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The bluing agent for a plastic optical material of the present invention is Na ₆ Al ₆ Si ₆ O ₂₄ Sx (X is 2).
The surface of the pigment represented by (4 to 4) is subjected to a hydrophobic silica coating treatment. Dispersing this bluing agent in the monomer composition for plastic optical materials,
By curing it, coloring can be prevented (blueing effect), and a plastic optical material excellent in colorless and transparent can be obtained.

Na ₆ Al ₆ Si ₆ O ₂₄ Sx used in the present invention
As a pigment represented by, there is ultramarine blue (X is 4, CI number: 77007), and CAS No. 57455
-37-5 and CAS No. 12769-96-9 is mentioned. As a method of performing the hydrophobic silica coating treatment, a method of treating the surface of the amorphous silica-coated ultramarine disclosed in Japanese Patent Publication No. 5-25912 with a silane coupling agent is preferable. Further, as a method of obtaining an amorphous silica-coated ultramarine, an alkali silicate and an acid disclosed in JP-A-61-111366 are previously reacted in an aqueous medium, and the resulting activated silica gel is brought into contact with ultramarine particles to obtain ultramarine blue. A method of depositing silica on the surface of particles and the method disclosed in JP
In US Pat. No. 1235, alkali silicate is previously ion-exchanged with a water-insoluble acid having an acidic ion-exchange capacity in the aqueous medium, and the resulting activated silica gel is brought into contact with ultramarine particles to deposit silica on the ultramarine particle surfaces. A method etc. can be mentioned. The surface of the pigment after silica coating is
It is preferably hydrophobic enough to completely repel water.
If it is hydrophilic, the pigment cannot be dispersed in the monomer composition for plastic optical materials, and the bluing effect cannot be sufficiently exhibited.

The size of the bluing agent for plastic optical materials of the present invention is a pigment having an average particle size of 0.4 μm or less and a particle size distribution of particles having a particle size of 0.5 μm or less is 60% or more. preferable. If the average particle size exceeds 0.4 μm, it tends to be difficult to obtain a plastic optical material having a stable hue, and if the particle size distribution of particles exceeding 0.5 μm is 60% or more, the plastic optical material The hue of the material tends to be non-uniform. The bluing agent for plastic optical materials of the present invention may be of one type, but 2
It is also possible to use a mixture of more than one type of pigment.

The concentration of the bluing agent of the present invention is in the range of 5 to 150 ppm, preferably 10 to 90 ppm in the monomer composition for plastic optical materials. If it is 5 ppm or less, the bluing effect is weak, and if it is 150 ppm or more, the cured product tends to be blue or purple. When the bluing agent is dispersed, the bluing agent may be directly dispersed in the monomer composition to be cured at the above concentration, but once the bluing agent is dispersed.
The masterbatch may be prepared at a high concentration of 1 to 3.0%, and the masterbatch may be dispersed in the monomer composition to be cured at the above concentration. The monomer composition used when preparing the masterbatch may be the same as or different from the monomer composition to be cured.

The monomer composition for a plastic optical material to which the bluing agent of the present invention is added is an allyl compound, a methacrylic compound or an acrylic compound, a compound having a thiol group and / or a compound having an isocyanate group,
Alternatively, it is preferably a monomer composition for a plastic optical material containing a reaction product of a compound having a thiol group and a compound having an isocyanate group. Examples of the allyl compound include allyl benzoate, diallyl diphenate, diallyl phthalate, diallyl ester oligomer represented by the following formula (1), diallyl polyethylene glycol carbonate represented by the following formula (2) and 2,2-bis. (Allyloxycarbonate ethoxyphenyl) propane, 2,
2-bis (allyloxycarbonate ethoxy-3,5
-Dibromophenyl) propane and the like. These diallyl compounds may be used alone or as a mixture of two or more kinds. Further, among these allyl compounds, dimethylmalate, diethylmalate, dipropylmalate, dibutylmalate, dimethoxyethylmalate, dibenzylmalate, diethylfumarate, dibutylfumarate, dibenzylfumarate, It may contain other unsaturated compounds such as dibenzyl itaconate.

CH ₂ = CH-CH ₂ OC (= O) -Ph-C (= O) O- (R ¹ OC (= O) -Ph-C (= O) O-) _x CH ₂ -CH = CH ₂ ------ (1) (In the formula, R ¹ represents an alkylene group having 1 to 4 carbon atoms, and P 1
h represents a phenylene group, and x represents an integer of 1 to 20. )

CH ₂ = CH-CH ₂ OC (= O) O-[(CH ₂ CH ₂ O) _y C (= O) O-] _z -CH ₂ -CH = CH ₂ ------ ( 2) (In the formula, y represents an integer of 2 to 5, and z represents an integer of 1 to 4.)

The methacrylic compound or acrylic compound means, for example, (meth) acrylic acid (meaning methacrylic acid or acrylic acid; hereinafter the same) and methyl (meth) acrylate (methyl methacrylate or methyl acrylate). The same shall apply hereinafter), ethyl (meth)
Acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate , Polyethylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2
-Bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2
-Bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyethoxycarbonyloxyphenyl)
Propane, dimethylol-tricyclodecanedi (meth)
Acrylate, trimethylpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and the like can be mentioned, and one or a mixture of two or more can be used. A third component such as styrene or chlorostyrene may be added together with the methacrylic compound or the acrylic compound for adjusting the refractive index. Further, a polymerization regulator such as α-methylstyrene dimer can be added.

Examples of the compound having a thiol group include 2,2'-thiodiethanethiol and the like, and they can be used alone or in a mixture of two or more kinds. As the compound having an isocyanate group, tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylidene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, 3- Isopropenyl-α,
α-dimethylbenzyl isocyanate and the like, and 1
It can be used in one kind or a mixture of two or more kinds. The above-mentioned thiol and isocyanate can be contained in the monomer composition for plastic optical materials either alone or as a mixture. Examples of the reaction product of the compound having a thiol group and the compound having an isocyanate group include a reaction product represented by the following formula (3).

[0017]

[Chemical 1]

(In the formula, n represents an integer of 1 to 4. R¹Is
-Ph-C (CH₃)₂-Or-CO ₂CH₂CH₂Indicates −
You R²Represents -Ph- or -Ph-Ph-. Ph
Is a phenylene group. )

Examples of the compound include those represented by the following formula (4)
To (10). [CH ₂ = C (CH ₃ ) -Ph-C (CH ₃ ) ₂ -NH-C (= O) -S (CH ₂ ) ₂ S (CH ₂ ) _2- ] ₂ Ph ------ ( 4) [CH ₂ = C (CH ₃ ) -Ph-C (CH ₃ ) ₂ -NH-C (= O) -S (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) _2- ] ₂ Ph ------ (5) [CH ₂ = C (CH ₃ ) -Ph-C (CH ₃ ) ₂ -NH-C (= O) -S (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) _2- ] ₂ (Ph) ₂ ------ (6) [CH ₂ = C (CH ₃ ) -Ph-C (CH ₃ ) ₂ -NH-C (= O) -S ( CH ₂ ) _2- S (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) _2- ] ₂ Ph --- --- (7) [CH ₂ = C (CH ₃ ) -C (= O ) O- (CH ₂ ) ₂ -NH-C (= O) -S (CH ₂ ) ₂ S (CH ₂ ) _2- ] ₂ Ph ------ (8) [CH ₂ = C (CH ₃ ) -C (= O) O- (CH ₂ ) ₂ -NH-C (= O) -S (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) _2- ] ₂ Ph ----- -(9) [CH ₂ = C (CH ₃ ) -CO _2- (CH ₂ ) ₂ -NH-C (= O) -S (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) _2- ] ₂ (Ph) ₂ ------ (10)

As a method for synthesizing such a compound, for example, first, 3-isopropenyl-α, α-dimethylbenzyl isocyanate or isocyanate ethyl methacrylate and ethanedithiol, 2,2'-thiodiethanethiol or An equimolar amount of dithiol such as dimercaptotriethylenedisulfide, triethylenediamine,
1,8-diazabicyclo (5,4,0) undecene-7
Addition reaction is carried out in the presence of a catalyst such as dibutyltin dilaurate or the like to synthesize an intermediate compound. The reaction can be performed at room temperature to 80 ° C. for 10 minutes to 3 hours. Next, a radical initiator may be added to 2 mol of the intermediate compound and 1 mol of divinylbenzene or divinylbiphenyl and reacted at a reaction temperature of 30 to 100 ° C. for 1 to 8 hours to obtain a target compound.

In the composition containing the compound having a thiol group or the compound having an isocyanate group or a reaction product thereof, another copolymerizable vinyl monomer may be contained. Examples of other vinyl monomers include styrene, halogen nucleus-substituted styrene, methyl nucleus-substituted styrene,
Divinylbenzene, vinylnaphthalene, methyl (meth)
Acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) Acrylate, various urethane poly (meth) acrylate, various urethane poly (meth) acrylate, diallyl phthalate, glyceroyl (meth) acrylate, (meth) acrylic acid, (meth) acrylic acid amide, N, N-dimethylacrylamide and the like can be mentioned. . One or two kinds of these mixed monomers can be appropriately selected and used according to need, for example, depending on the refractive index and the like.

To cure a monomer composition for plastic optical materials containing an allyl compound, a methacrylic compound, and an acrylic compound, a radical polymerization initiator is added as a curing agent, and then a heat curing method or an active energy method is used. It is cured by the line curing method. The radical polymerization initiator is used to cure vinyl monomers, for example, benzoyl peroxide, lauroyl peroxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, t-butyl peroxy-2-ethylhexa. Noate, t-butyl peroxypivalate, t-butyl peroxy neodecanoate, t-butyl peroxydiisobutyrate, t-butyl peroxyisopropyl carbonate, azobisisobutyronitrile, azobisdimethylvaleronitrile and the like. . These can be used alone or in combination of two or more. The addition amount of the radical polymerization initiator is usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the monomer composition for plastic optical materials. 0.01% by weight
If it is less than 10% by weight, curing is insufficient, and if it exceeds 10% by weight, the cured product tends to be distorted. The vinyl monomer composition for plastic optical materials may contain other copolymerizable vinyl monomers. Examples of other vinyl monomers include styrene, halogen nucleus-substituted styrene, methyl nucleus-substituted styrene, and vinylnaphthalene.

When a monomer composition for a plastic optical material containing a compound having a thiol group and a compound having an isocyanate group is to be cured, a metal salt or a basic substance is added as a curing agent and then a heat curing method is used. A cured product can be obtained by curing. As the curing agent, triethylenediamine, 1,8-diazabicyclo (5,4,4)
0) Undecene-7, dibutyltin dilaurate and the like can be mentioned. The amount added is usually 10 to 1000 ppm, preferably 10 to 500 ppm. 10 ppm
If it is less than 1,000, the curing is insufficient, and if it exceeds 1000 ppm, the cured product tends to be distorted. Further, when the monomer composition containing a compound having a thiol group and a compound having an isocyanate, a monomer composition having a polymerizable group is contained,
A cured product can be obtained by using the above-mentioned curing agent and a radical polymerization initiator in combination.

Further, in the monomer composition for plastic optical materials of the present invention, in addition to the above respective components, if necessary, an ultraviolet absorber, an antioxidant, a colorant, a release agent, a surfactant,
Additives such as antibacterial agents can be used within the range usually used. For example, a benzotriazole-based UV absorber,
It can be used in the range of 0.05 to 2% by weight based on the whole.

The lens as an optical material of the present invention is prepared by adding a curing agent to a monomer composition for a plastic optical material and then injecting it into a casting of a desired lens shape made of metal, glass, plastic or the like. , Heat cure. Then, it can be obtained by demolding. The cured resin is a colorless transparent cross-linking resin that is insoluble in a solvent. As the curing conditions, the polymerization temperature is 30 to 120 ° C., preferably the temperature is raised within the temperature range, and the polymerization time is 5 to 72 hours, preferably 10 to 36 hours. After demolding, it is desirable to further anneal at a temperature of 80 to 120 ° C. for 1 to 5 hours in a nitrogen or air atmosphere. Further, as another method, it can be obtained by directly cutting the cured product into a desired lens shape.

As the lens as the optical material of the present invention, the lens obtained by the above-mentioned preparation method can be used as it is, but if necessary, a hard coat treatment for improving the surface hardness and imparting fashionability are imparted. It is also possible to perform a coloring treatment with a disperse dye or a photochromic dye. The bluing agent for plastic optical materials of the present invention can be used in thermoplastic resins such as polycarbonate in addition to the above thermosetting resins.

[0027]

EXAMPLES The present invention will now be described in detail based on Examples and Comparative Examples, but the present invention is not limited to these.

The compositions of Examples 1-54 and Comparative Examples 1-7 are shown in Tables 1-6. Abbreviations in the table indicate the following compound names. (Polymerization component) DAIP; diallyl isophthalate, DATP; diallyl terephthalate, P-DAIPE; isophthalic acid-diallyl ester of ethylene glycol polyester oligomer (x = 1: 70% by weight in the formula (1), x = 2: 20% by weight) , X = 3: 1
0% by weight), P-DATAPB; terephthalic acid-1,4-butanediol polyester oligomer diallyl ester (in the formula (1), x = 1: 86% by weight, x = 2: 11% by weight,
x = 3: 3% by weight), P-DAIPP; diallyl ester of isophthalic acid-propylene glycol polyester oligomer (formula (1)
Medium, x = 1: 82% by weight, x = 2: 13% by weight, x =
3: 5 wt%), CR-39; diethylene glycol bisallyl carbonate (manufactured by Asahi Pen Chemical Co., Ltd., in the formula (2), y = 2,
z = 1: 89% by weight, z = 2: 7% by weight, z = 3: 4% by weight),

DMM: dimethylmalate, DBM: di-n-butylmalate, DMEM: dimethoxyethylmalate, DBzM: dibenzylmalate, St: styrene, DVB: divinylbenzene, BzMA: benzylmethacrylate, 1G: ethyleneglycoldimethacrylate , 2G; diethylene glycol dimethacrylate, BPE-2E; 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, BPE-4E; 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane, BPE-6E; 2,2-bis (4-methacryloyloxytriethoxyphenyl) propane, BPA-4E; 2,2-bis (4-acryloyloxydiethoxyphenyl) propane, HE-BP; 2,2-bis (4-methac) Liloyloxyethoxycarbonyloxyphenyl) propane, PETM; pentaerythritol trimethacrylate, TMPT; trimethylolpropane trimethacrylate, MSDM; α-methylstyrene dimer, TDET; 2,2′-thiodiethanethiol PETMP; pentaerythritol Tetrakismercaptopropionate, PETMA; pentaerythritol tetrakismercaptoacetate, XDI; xylylene diisocyanate, NDI; naphthalene diisocyanate, IDMBI; 3-isopropenyl-α, α-dimethylbenzyl isocyanate, TMDSDB; ethanedithiol and 3 -Addition product of isopropenyl-α, α-dimethylbenzyl isocyanate and divinylbenzene, TMTSDB; 2,2′-thiodiethanethio Le and 3
Addition product of isopropenyl-α, α-dimethylbenzyl isocyanate and divinylbenzene, MMTSDB; Addition product of 2,2′-thiodiethanethiol, isocyanate ethylmethacrylate and divinylbenzene,

(Ultraviolet absorber) S-MBT; 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, S-BMBT; 2- (2'-hydroxy-3'-t-butyl-) 5'-methylphenyl) -5-chlorobenzotriazol, S-OBT; 2- (2'-hydroxy-5'-t-octylphenyl) -benzotriazole, (basic catalyst) TEA; triethylenediamine (Metal salt catalyst) BTL; n-butyltin laurate.

Production Example 1 (Hydrophobic silica coating treated pigment) An ultramarine pigment (trade name SM-
V10, manufactured by Daiichi Kasei Kogyo Co., Ltd., was classified and adjusted to the particle size and particle size distribution shown in Tables 1 to 6. The surface of the adjusted ultramarine was coated with amorphous silica using alkali silicate and sulfuric acid, and glycidylsilane, which is a silane coupling agent, was added dropwise to the surface of the ultramarine blue for hydrophobic silica coating. It was confirmed that each hydrophobic silica-coated pigment after production floated in water and the surface was hydrophobic. Note that the hydrophilic ultramarine pigment settled in water under the present experimental conditions.

Production Example 2 (TMDSDB) A 100 cc four-necked flask equipped with a thermometer, a dropping funnel and a stirrer was charged with 0.2 mol of ethanedithiol and 400 ppm of triethylenediamine and stirred to make 20 reaction systems.
While keeping the temperature at 0 ° C., 3-isopropenyl-α, α-dimethylbenzyl isocyanate was added dropwise from the dropping funnel over 1 hour for reaction. After completion of the reaction, toluene was removed from the reaction solution by vacuum distillation. The obtained intermediate compound is
Infrared absorption spectrum analysis shows that the absorption derived from the isocyanate group at 2250 cm ^-1 has disappeared to 1733 cm.
The absorption derived from the urethane bond of ^-1 was confirmed. To 0.2 mol of the obtained intermediate compound and 0.1 mol of divinylbenzene, 1% by weight of t-butylperoxy-2-ethylhexanoate was added as a radical initiator, and the mixture was reacted at 60 ° C. for 3 hours. The resulting compound derived from benzene ring 1630～1570Cm ^-1 in an infrared absorption spectrum _{analysis, CH 2 = C (CH 3} ) to 1,695 cm ^-1 - derived base, 1
At 730 cm ^-1 , derived from C = O group of thiourethane, 1535
from -CN group cm ^-1, can be confirmed each absorption by -NH groups 3330cm ^-1, CH of 990 cm ^-1 ₂ = CH-
It was confirmed that the absorption derived from the group and from the —SH group at 2540 cm ⁻¹ was disappeared. Therefore, the compound obtained by the reaction is
The compound of interest can be identified as the compound of the following formula (11). [CH ₂ = C (CH ₃ ) −Ph-C (CH ₃ ) _2- NH-C (= O) −S (CH ₂ ) ₂ S (CH ₂ ) _2- ] ₂ Ph ------ ( 11) The compound of formula (11) is abbreviated as TMDSDB (the same applies below).

Production Example 3 (TMTSDB) Similarly, 3-isopropenyl-α, α-dimethylbenzyl isocyanate and 2,2'-thiodiethanethiol were reacted to obtain intermediates, respectively, and then divinyl. Benzene was reacted with a radical initiator to obtain a compound of the following formula (12). [CH ₂ = C (CH ₃ ) −Ph-C (CH ₃ ) _2- NH-C (= O) −S (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) _2- ] ₂ Ph- ----- (12) The compound of formula (12) is abbreviated as TMTSDB (the same applies below).

Production Example 3 (MMTSDB) Similarly, isocyanate ethyl methacrylate and 2,2 '
-Thiodiethanethiol was reacted to obtain each intermediate, and divinylbenzene was further reacted with a radical initiator to obtain a compound of the following formula (13). _{[CH 2 = C (CH 3} ) -CO 2 - (CH 2) 2 -NH-C (= O) -S (CH 2) 2 S (CH 2) 2 S (CH 2) 2 -] 2 Ph - ---- (13) The compound of formula (13) is abbreviated as MMTSDB (the same applies below).

Evaluation Test The properties of the pigment used and the properties of the resin plate obtained were evaluated by the following test methods. The results are shown in Examples 1 to 54 and Comparative Examples 1 to 7. (1) Average particle size and particle size distribution of pigment The average particle size and particle size distribution were measured using a particle size distribution measuring device (manufactured by Horiba, Ltd.), and the proportion of particles having a particle size of 0.5 μm or less was obtained. (2) Light transmittance and yellowness transmittance of the cured product Photometer (manufactured by Nippon Denshoku Industries Co., Ltd.)
The light transmittance was measured according to K 7105. At the same time, the yellowness (YI value) was also measured. (3) Refractive index of cured product and Abbe number 25 using an Abbe refractometer (DR-M2 manufactured by Atago Co., Ltd.)
A test piece of 1 cm × 1.5 cm was cut out from the cured resin plate at 0 ° C. and measured. (4) Specific gravity of cured product According to JIS K 7112, the test piece was measured at 25 ° C by an underwater displacement method. (5) Impact resistance of cured product A steel ball having a weight of 16 g was naturally dropped onto a resin plate from a height of 127 cm, and the one that did not damage the resin plate was marked with ◯, and the one that damaged was marked with x. (6) A 1 cm × 4 cm plate was cut out from the heat-resistant resin plate of the cured product, and Leovibron (DDV-III-EP manufactured by Toyo Baldwin Co., Ltd.)
The dynamic viscoelasticity was measured by the method, and the temperature showing the maximum TANδ was taken as the glass transition temperature (Tg) and used as an index of heat resistance. (7) The dyeability test piece of the cured product is dipped in a brown dyeing bath at 90 ° C. for 10 minutes, and the light transmittance after dyeing is measured by a luminosity transmittance measuring device (MODEL304 manufactured by Asahi Spectroscopy Co., Ltd.). did. (8) Color unevenness of the cured product The color unevenness of the cured product was visually observed, and those with no color unevenness were evaluated as ◯, those with a little color unevenness as Δ, and those with severe color unevenness as x.

Examples 1 to 12 Each monomer, ultraviolet absorber and pigment were mixed so as to have the composition of each example in Table 1. The pigment was prepared in advance as a concentrated solution and mixed. That is, 100 g of C
To R-39, 1 g of the ultramarine blue pigment produced in Production Example 1 and subjected to the silica coating treatment was added, and the mixture was mixed in a ball mill at room temperature for 3 days.
A thick solution prepared by mixing for 0 minutes was added. After stirring and mixing, a monomer composition was obtained through a nylon filter (5 μm) to remove impurities. The stability of the monomer composition is
The rate of change in pigment concentration before and after filtration with a filter was measured from visible light transmittance (460 nm). In addition, Example 1
Even when the monomer composition for a plastic optical material prepared in any of 12 to 12 was left at 40 ° C. for 30 days, the pigment concentration was stable and stable. Then, 20 g of the raw material mixture was used as a polymerization initiator
Add 0.64 g or 0.70 g of PP or NPP,
The composition was poured into a casting mold composed of two glass disks having a diameter of 7 cm and a gasket made of ethylene-propylene rubber having a thickness of 2 mm. After that, in a hot air bath with a program temperature controller, change the temperature from 30 ℃ to 100 ℃.
The temperature was raised over time. Subsequently, the casting was held at 100 ° C. for 2 hours. Then, the casting was cooled to 40 ° C. over 2 hours. The composition in the casting was cured, and a disk-shaped resin was obtained by demolding. The resin mass is further heated at 100 ° C for 2
Annealing treatment was performed over time to obtain a resin plate. In addition, the resin plates cured in Examples 1 to 12 were colorless, and even after being left for 2 years, almost no yellowing change was observed.

Examples 13 to 21 The respective monomers, the ultraviolet absorbers and the pigments were mixed so as to have the compositions of the respective examples in Table 2. Next, 1.0% by weight of t-butylperoxyneodecanoate as a polymerization initiator was added to 20 g of the raw material mixture, and the composition was mixed with two glass disks having a diameter of 7 cm and an ethylene-propylene rubber having a thickness of 2 mm. It was poured into a casting consisting of a gasket made of steel. After that, the temperature was raised from 30 ° C. to 100 ° C. in 18 hours in a hot air thermostat with a program temperature controller. Subsequently, the casting was held at 100 ° C. for 2 hours. Then, the casting was cooled to 40 ° C. over 2 hours. The composition in the casting was cured, and a disk-shaped resin was obtained by demolding. The resin block was further annealed at 100 ° C. for 2 hours to obtain a resin plate. In addition, the resin plates cured in Examples 13 to 21 were colorless, and even after being left for 2 years, almost no yellowing change was observed.

Examples 22 to 30 Monomers, ultraviolet absorbers and pigments were mixed so as to have the compositions of Examples in Table 3. Next, 1000 ppm of dibutyltin dilaurate was added as a curing agent to 20 g of the raw material mixture, and the composition was poured into a casting mold composed of two glass disks having a diameter of 7 cm and an ethylene-propylene rubber gasket having a thickness of 2 mm. After that, the temperature was raised from 30 ° C. to 100 ° C. in 18 hours in a hot air thermostat with a program temperature controller. Continue casting at 100 ° C for 2
Held for hours. Then, the casting was cooled to 40 ° C. over 2 hours. The composition in the casting was cured, and a disk-shaped resin was obtained by demolding. The resin mass is further heated to 100 ° C.
Annealing treatment was performed for 2 hours to obtain a resin plate. In addition, the resin plates cured in Examples 22 to 30 were colorless, and even after left for 2 years, almost no yellowing change was observed.

Examples 31 to 44 The respective monomers, ultraviolet absorbers and pigments were mixed so as to have the compositions of the respective examples in Table 4. Next, a predetermined amount of triethylenediamine or n-butyltin laurate as a curing agent and 1.0% by weight of t-butylperoxyneodecanoate as a polymerization initiator were added to 20 g of the raw material mixture to prepare a composition. Two glass discs with a diameter of 7 cm and a thickness of 2 m
m of ethylene-propylene rubber gasket. After that, the temperature was raised from 30 ° C. to 100 ° C. in 18 hours in a hot air thermostat with a program temperature controller. Subsequently, the casting was held at 100 ° C. for 2 hours. Then, the casting was cooled to 40 ° C. over 2 hours. The composition in the casting was cured, and a disk-shaped resin was obtained by demolding. The resin block was further annealed at 100 ° C. for 2 hours to obtain a resin plate.
The resin plates cured in Examples 31 to 44 are
It was colorless and almost no change in yellowing was observed even if left for 2 years.

Examples 45 to 54 The divinyl compound having a thiourethane bond produced in Production Examples 2 to 4 was mixed with each monomer, an ultraviolet absorber and a pigment so as to have the composition of each Example in Table 5. did. Next, t-butylperoxy neodecanoate, which is a polymerization initiator, was added to 1.0
% By weight, and the composition was poured into a casting mold composed of two glass disks having a diameter of 7 cm and a gasket made of ethylene-propylene rubber having a thickness of 2 mm. Then, in a hot air bath with a program temperature controller
The temperature was raised to 0 ° C. over 18 hours. Continue casting 10
Hold at 0 ° C. for 2 hours. Then, the casting was cooled to 40 ° C. over 2 hours. The composition in the casting was cured, and a disk-shaped resin was obtained by demolding. The resin block is further annealed at 100 ° C. for 2 hours,
A resin plate was obtained. In addition, the resin plates cured in Examples 45 to 54 were colorless and almost no change in yellowing was observed even after standing for 2 years.

Comparative Examples 1 to 7 As Comparative Examples 1 to 4, classified ultramarine pigments (trade name SM-
Examples 1 to 8 using V10, manufactured by Daiichi Kasei Kogyo Co., Ltd.
It was cured in the same manner as in (1) and the physical properties were measured. Comparative Examples 5-7
As the above, the physical properties were measured by using the same method as in Examples 1 to 8 without using a pigment. The results are shown in Table 6.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

[Table 5]

[0047]

[Table 6]

The bluing agent in which the surface of the pigment of the present invention is coated with hydrophobic silica is an allyl compound (Table 1), a methacrylic compound or an acrylic compound (Table 2), a compound having a thiol group and / or Or a compound having an isocyanate group (Table 3), a methacrylic compound or an acrylic compound, a compound having a thiol group and / or a compound having an isocyanate group (Table 4), a compound having a thiol group and a compound having an isocyanate group In the reaction product (Table 5), an excellent bluing effect was exhibited, and even if the monomer composition was cured, a plastic optical material without yellowing could be obtained.

In Comparative Examples 1 to 4, when the pigment not subjected to the hydrophobized silica coating treatment is used, color unevenness occurs, but in the present invention, it was found that this is improved.

[0050]

According to the present invention, a bluing agent for a plastic optical material required for obtaining a plastic optical material having excellent colorless transparency, a monomer composition for a plastic optical material in which a bluing agent is stably dispersed, And a plastic optical material obtained by curing the same.

Claims (8)

[Claims] 1. Na ₆ Al ₆ Si ₆ O ₂₄ Sx (provided that X
Is 2 to 4. ) A bluing agent for plastic optical materials, wherein the surface of the pigment represented by (4) is subjected to hydrophobic silica coating treatment. 2. The bluing agent for a plastic optical material according to claim 1, wherein the average particle size is 0.4 μm or less, and the particle size distribution of particles having a particle size of 0.5 μm or less is 60% by weight or more. 3. A monomer composition for a plastic optical material, to which the bluing agent for a plastic optical material according to claim 1 is added. 4. The monomer composition for a plastic optical material according to claim 3, which contains an allyl compound. 5. The monomer composition for a plastic optical material according to claim 3, which contains a methacrylic compound or an acrylic compound. 6. The monomer composition for a plastic optical material according to claim 3, which contains a compound having a thiol group or a compound having an isocyanate group. 7. The monomer composition for a plastic optical material according to claim 3, which contains a reaction product of a compound having a thiol group and a compound having an isocyanate group. 8. A plastic optical material obtained by curing the monomer composition for a plastic optical material according to any one of claims 3 to 7.