JPH0441785A - Production of dyed resin having high refractive index and dyed plastic lens obtained from the same resin - Google Patents

Abstract

PURPOSE:To obtain the title resin having high refractive index, excellent heat resistance and cutting processing by adding a polymerization initiator to a polymerizable monomer component having a specific composition, subjecting the blend to cast polymerization to give a polymer and immersing the polymer in a dyeing solution containing disperse dye and an aromatic compound. CONSTITUTION:(A) 5-94.5 wt.% one or more polymerizable polymers selected from polyfunctional (meth)acrylates shown by formula I [R<1> and R<2> are H or CH3; X is group shown by formula II to formula V, etc., (R<3> is H, CH3 or OH; (l) and (m) are 2-14)] and formula IV (R<4> is H or CH3; R<5> is saturated aliphatic hydrocarbon which may contain ether or ester of q-valence; (q) is 2-6) is blended with (B) 5-99.5wt.% polymerizable monomer of styrene and/or alpha-methylstyrene and (C) 0.5-40wt.% polymerizable monomer of unsaturated nitrile to give a polymerizable monomer component, which is mixed with a polymerization initiator and subjected to cast polymerization to give a polymer. The polymer is uniformly dyed with a dyeing solution which contains 0.05-50g/l disperse dye and 0.001-10g aromatic compound. The dyed polymer is useful as lens for glasses (dyed plastic lens).

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a manufacturing method for easily obtaining a φg bright phase resin that has a high refractive index and is evenly dyed, and a dyed plastic lens obtained thereby. .

[Conventional technology]

In recent years, transparent plastics have come to be widely used as optical components such as lenses, prisms, and optical waveguides, mirror components, and decorative components or glazing in fields such as vehicles, ships, and architecture.

In general, plastic optical materials have superior characteristics compared to inorganic glass, such as being lightweight, resistant to breakage, and easy to dye, and are widely used, especially in eyeglass lenses that require fashionability. Diethylene glycol bisallyl carbonate resin is widely used as plastic lenses for eyeglasses, and although it can be easily dyed with various dyes, it has a low refractive index of 1.50 (although it is made of materials with a high refractive index). The drawback was that the edge and center thickness of the lens was thicker than that of conventional lenses.

Therefore, it is desired to have a transparent ♂- that has a high refractive index and is dyed evenly. Polycarbonate is known as an optical material with a high refractive index. Polycarbonate has a high refractive index of 1.59;
Although thinner lenses can be obtained than lenses made of diethylene glycol bisallyl carbonate resin of 1.52 or crown glass of 1.52, polycarbonate resin cannot be beaded and is difficult to dye, making it unsuitable for eyeglass lenses that require fashionability. There's a problem.

Therefore, it is desired to develop dyed high refractive index resins and plastic lenses that have the above-mentioned drawbacks improved.

[Means and effects for solving the problem] The present inventors
As a result of intensive studies in view of the current situation, we found that a polymer obtained by adding a polymerization initiator to a polymerizable monomer component of a specific composition and performing cast polymerization is immersed in a liquid composition of a specific composition. The present invention was completed by discovering a method for producing a dyed high refractive index transparent resin.

That is, the present invention provides a specific polymer obtained by adding a polymerization initiator to a polymerizable monomer component having a specific composition and casting the resulting polymer into water with a specified amount of a disperse dye and an aromatic compound. The present invention relates to a method for producing a dyed high refractive index transparent resin, which is characterized by immersion in a liquid composition of the same composition, and a dyed plastic lens obtained thereby.・ .

The polymerizable monomer component having a specific composition used in the present invention is a polyfunctional (
Polymerizable monomer consisting of one or more types selected from meth)acrylates [115 to 94.5% by weight, polymerizable monomer consisting of styrene and/or α-methylstyrene [formerly 5 to 94.5% by weight] % by weight and 0.5 to 40% by weight of a polymerizable monomer [111] consisting of unsaturated nitrile as an essential component.

(Note) General formula (1) (However, R3 is H, CH, or OH, and ρ and m are 2 to
an integer of 14; n is an integer of 4 to 14; ) represents. ] General formula (2) (wherein R4 represents H or CH, R' represents a saturated aliphatic hydrocarbon group which may contain an ether or ester with a valence of q, and q represents an integer of 3 to 6. The polymerizable monomer III used in the present invention is not particularly limited as long as it is represented by the general formula (1) or (2), and examples thereof include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate. (meth)acrylate, tetraethylene glycol di(meth)acrylate,
Nonaethylene glycol di(meth)acrylate, Tetradecaethylene glycol di(meth)acrylate, Dibrobylene glycol di(meth)acrylate, Nonabrobylene glycol di(meth)acrylate, Butanediol(meth)acrylate, Bentanediol(meth)acrylate ) acrylate, alkylene glycol di(meth)acrylates such as neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, dodecanediol di(meth)acrylate; trimethylolpropane tri(meth)acrylate, pentaerythritol tetra (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(,y'5ri'>age'IJ l/-t,
dipentaerythritol tetra(meth)acrylate,
Examples include trimethylolethane tri(meth)acrylate, and one or more of these may be used.

The polymerizable monomer [II] used in the present invention is styrene and α
- methylstyrene, each of which is used alone or as a mixture of the two. When used as a mixture,
There is no particular restriction on the usage ratio.

The polymerizable monomer [111] used in the present invention is acrylonitrile and methacrylonitrile, each of which is used alone or as a mixture of the two, but acrylonitrile is usually used.

The polymerizable monomer components in the dyed high refractive index transparent resin of the present invention are polymerizable monomers El], [II] and [I
If necessary, other polymerizable monomers [IVl may be used as a copolymerization component, or other polymerizable monomers that can be used may be used for the purpose of imparting other physical properties. The polymerizable monomer [IVl] is not particularly limited as long as it can be copolymerized with at least one of the polymerizable monomers [1], [II] and [1+1]; Monofunctional monomers that do not fall under any of the above, polymerizable monomers [polymerizable polymers collectively referred to as polyfunctional monomers that do not fall under 11, stupid oligomers] can be used. Specific examples of such polymerizable monomers llTl include, for example,
Methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 4-t-butylcyclohexyl methacrylate, 2,3-dibromopropyl methacrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-methacryloyloxymethylthiophene, 3-methacryloyl Oxymethylthiophene, 2-(2-methacryloyloxyethyl)thiophene, 2-tricyclo[5,2,1,0''1]-3-decenyloxyethyl methacrylate, methyl-2-chloroacrylate, methyl-2- Bromoacrylate, cyclohexyl-2-chloroacrylate, cyclohexyl-
2-bromoacrylate, 2-tricyclo[5,2,1
,0"・6]-3-decenyloxyethyl-2-chloroacrylate and other monofunctional (meth)acrylic esters; (meth)allyl benzoate, di(meth)allyl phthalate, diethylene glycol bisallyl carbonate , 2゜(meth)allyl esters such as 2-bis(4-allyloxycarbonyloxyethoxy-3,5-dibromophenyl)propane, 2.2-bis(4-allyloxy-3,5-dibromophenyl)propane, Allyl carbonate, allyl ethers; epoxy (meth)acrylate,
Polyester (meth)acrylate, urethane (meth)
Mention may be made of reactive oligomers such as acrylates.

In the present invention, the polymerizable monomer [11] imparts a crosslinked structure to the high refractive index resin, which has excellent heat resistance and prevents fusion and clogging during cutting and machining, allowing resin components to adhere to processing tools. It is used to obtain a heat resistant, high refractive index resin that does not cause any oxidation. In order to exhibit such characteristics, the amount of polymerizable monomer [11] used is 5 to 94.5% by weight, preferably 10 to 90% by weight, in the polymerizable monomer component. If the amount is 5% by weight without grooves, the crosslinking density will be small and the effect on improving heat resistance, cutting workability, soil tank workability, impact resistance, etc. will be small, and if the amount exceeds 94.5% by weight, the resulting resin will be The refractive index becomes smaller.

The polymerizable monomer [II] is used to impart a high refractive index to the resulting resin. In order to sufficiently express such characteristics, the amount of the polymerizable monomer [11J] is 5 to 94.5% by weight, preferably 10 to 90% by weight in the polymerizable monomer component. be. An amount of 5% by weight of non-vortex has a small contribution to the change in the refractive index of the resulting resin (,9
If the amount exceeds 4.5% by weight, the amount of polymerizable monomer [11] will not reach the specified amount, the crosslinking density will decrease, and the properties such as heat resistance, cutting workability, earth tank workability, impact resistance, etc. will decrease. Mechanical properties tend to deteriorate.

The polymerizable monomer [101] is used to dramatically improve the impact resistance of the resulting high refractive index resin. In order to fully express these characteristics, polymerizable monomer [1
1 is gz using an amount of 0.5 to 40% by weight in the polymerizable monomer component, preferably 2 to 30% by weight. 0
．． If the amount is 5% by weight, the effect on improving the impact resistance of the resulting high refractive index resin will be small, and if the amount exceeds 40% by weight, the heat resistance of the resulting resin will be low.

Polymerizable monomer [Tfl is used to add various properties other than those mentioned above to the high refractive index resin obtained. For example, among the above polymerizable monomers [N], (meth) The acrylic acid ester is used to supplement the polymerizable monomers 1, [formerly and [11], and is used to arbitrarily adjust the refractive index, heat resistance, moldability, etc. of the high refractive index resin obtained. The amount is preferably 1 to 50% by weight in the weight component, and
(Meth) allyl esters, allyl carbonates, and allyl ethers are useful in controlling polymerization reactions, and have the effect of increasing production stagnation, especially in cast polymerization. ~30% by weight, more preferably 0
．． Epoxy (
Reactive oligomers such as meth)acrylate, polyester(meth)acrylate, and urethane(meth)acrylate have the effect of alleviating the shrinkage rate during polymerization, improving the production yield in cast polymerization, and improving polymerizability. It is preferably used in an amount of 1 to 50% by weight, preferably 5 to 40% by weight, based on the monomer components.

Furthermore, the above polymer may appropriately contain known additives such as ultraviolet absorbers, antioxidants, drip-proofing agents, and colorants.

The present invention is a dyed high refractive index resin obtained by immersing a polymer obtained by adding a polymerization initiator into a polymerizable monomer component having a specific composition and performing cast polymerization in a liquid composition having a specific composition. This relates to a manufacturing method. The production method of the present invention is achieved by immersing the above polymer in a liquid composition prepared by blending 0.05 to 50 g of a disperse dye and 0.001 to 10 g of an aromatic compound in 1 liter of water.

The disperse dye used in the liquid composition is not particularly limited as long as it has been conventionally used in the field; specific examples include C,1, Disperse Red 13.56.
．． 112, C, 1, Disperse Yellow 3.7.31
．． 42.54.198, C, 1, Disperse Blue 1
．． 3.5.54.56.197 etc. can be mentioned.

The amount of disperse dye used in the present invention is 0.05 to 0.05 to water II2.
If the amount of disperse dye is less than 0.05 g per 12 g of water, preferably in a ratio of 0.2 to 10 g, the dyeing of the polymer may take a very long time or may only be dyed in a light color. If the amount is more than 50g, the dye will be difficult to disperse and the effect of increasing the concentration will be difficult to achieve.

The aromatic compound according to the present invention acts as a carrier for penetrating the disperse dye into the polymer, and preferred aromatic compounds include, for example, benzoic acid ester,
Examples include salicylic acid esters, phthalic acid esters, phthalic acid imides, and methylnaphthalene derivatives. Specifically, methyl benzoate, ethyl benzoate, butyl benzoate, benzyl benzoate, methyl salicylate, ethyl salicylate, butyl salicylate, dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, N-butylphthalimide, α-methyl Examples include naphthalene, β-methylnaphthalene, etc., but are not limited thereto.

The aromatic compound according to the present invention is 0.001 to 12 of water.
It is used at a rate of ~10g, preferably 0.0g.
The proportion is 1 to 5 g. If the amount of aromatic compound is less than 0,001 g per 1° C. of water, the dyeing of the polymer will take a very long time or will not be dyed at all. Also 1
If the amount is more than 0g, it may be difficult to dye uniformly,
Roughen the surface of high refractive index resin.

The liquid composition according to the present invention may consist only of water, a disperse dye, and an aromatic compound as described above, but if necessary, a water-soluble organic solvent, a pH adjuster, a wetting agent, and a surfactant may be added. , a dispersion accelerator, an antifoaming agent, and other additives may be included as appropriate.

The conditions during dipping are not particularly limited and can be set in a wide range, for example, the dipping time can be 1 to 60 minutes at a temperature of 60 to 100 ° C., and the pH range of the solution is as follows:
It is preferable to dye in a range in which the disperse dye is stable, that is, in a side-end fpH range of 2 to 8.

The dyed high refractive index resin obtained by the production method of the present invention and the dyed plastic lens obtained thereby can be used with a hard coat, an antireflection coat,
It is also possible to apply a coating to prevent water staining.

[Effects of the present invention]

The dyed high refractive index resin obtained by the production method of the present invention is uniformly dyed, has a high refractive index, and has excellent heat resistance and machinability, so it can be used for example in eyeglass lenses, color screens, etc. , which can be suitably used for decorative and building material moldings.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples. In addition, the method of physical property evaluation in Examples is as follows.

[Refractive index] Measured using an Abbe refractometer according to JIS K7105.

[Workability] A flat plate obtained by cast polymerization was polished using a polishing machine, and its condition was observed. Those with no cracks, cracks, fusion, etc. are marked with an O mark.

Example 1 40 parts by weight of tetraethylene glycol dimethacrylate, 50 parts by weight of styrene, 10 parts by weight of acrylonitrile,
A transparent polymer having a thickness of 1.5 m+a obtained by cast polymerization of a polymerizable monomer component consisting of 0.1 part by weight of 2,2°-azobis(isobutyronitrile) was dyed by the following method.

Dyanix Red AC-E (
Mitsubishi Kasei ■) 5g, 01g of methyl salicylate in 1β of water
and acetic acid was added to bring the pH to 5. 95% of this liquid
The transparent polymer was immersed for 10 minutes and dyed. The obtained high refractive index resin is uniformly dyed,
The total light transmittance in the visible light part was 36%. The results are shown in Table 1.

Examples 2 to 13 and Comparative Examples 1 to 3 Transparent polymers were produced by repeating the same operations as in Example 1, except that the polymerizable monomer components in Example 1 were changed as shown in Table 1. After that, the same operations as in the example were repeated except that the disperse dye and aromatic compound were changed as shown in Table 1 to obtain a dyed high refractive index resin. The results are shown in Table 1.

Example 14 A polymerizable monomer component consisting of 40 parts by weight of tetraethylene glycol dimethacrylate, 50 parts by weight of styrene, and 10 parts by weight of acrylonitrile was added with 0.1 part by weight of lauroyl peroxide and t-butylperoxy-2-ethylhexane. Add 0.2 parts by weight of Noate and make the mixture into an inner diameter of 75 mm.
It was injected into a space made of a glass mold and a gasket made of soft polyvinyl chloride, which was designed to obtain a lens with a dioptric power of -3°00D.

This was kept at 50°C for 4 hours in a constant temperature bath, then gradually raised to 110°C over 15 hours, and further heated to 110°C for 30 hours.
Cast polymerization was carried out to maintain the polymerization temperature.Then, the glass mold and gasket were removed from the polymerized product to obtain a lens with a diameter of 75° C. and a power of −3.0 OD.

Separately, as a disperse dye, Dyanix RedAC-E
C (manufactured by Mitsubishi Kasei ■) and 0.1 g of methyl salicylate were dissolved in water IJ, and acetic acid was added to adjust the pH to 5. This solution was heated to 9t'C, and the lens Th1O obtained as above was obtained.
Dyeing was done by dipping for a minute. The obtained lens was evenly and uniformly dyed.

Examples 15 to 17 and Comparative Example 4 Lenses were produced by repeating the same operations as in Example 14, except that the polymerizable monomer components in Example 14 were changed as shown in Table 2. A dyed lens was obtained by repeating the same operation as in Example 14, except that , disperse dye, and aromatic compound were changed as shown in Table 2. The result is the second
Shown in the table.

Claims (1)

[Claims] 1. Polymerizable monomer [I] consisting of one or more selected from polyfunctional (meth)acrylates represented by the following general formulas (1) and (2) 5-94. 5% by weight, polymerizable monomer [II] consisting of styrene and/or α-methylstyrene 5 to 94.5% by weight, and polymerizable monomer [III] consisting of unsaturated nitrile 0.5 to 40% by weight A polymer obtained by adding a polymerization initiator to a polymerizable monomer component containing
A method for producing a dyed high refractive index resin, which comprises immersing the dyed resin in a liquid composition containing 0.001 to 10 g of a dyed resin and an aromatic compound. (Note) General formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 are each independently H or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas , tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R^3 is H, CH_3 or OH, l and m
is an integer of 2 to 14, and n is an integer of 4 to 14. ) represents. ] General formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^4 is H or CH_3, and R^5 is a saturated aliphatic hydrocarbon that may contain an ether or ester with a valence of q. group, and q represents an integer of 3 to 6.) 2. The polymerizable monomer component further comprises a polymerizable monomer [I],
The manufacturing method according to claim 1, further comprising another polymerizable monomer [IV] capable of radical copolymerization with at least one of [II] and [III]. 3. Polymerizable monomer [IV] is a group consisting of (meth)acrylic acid ester, (meth)allyl ester, allyl carbonate, allyl ether, epoxy (meth)acrylate, polyester (meth)acrylate, urethane (meth)acrylate The manufacturing method according to claim 2, wherein the monomer is one or more polymerizable monomers selected from the following. 4. A claim in which one or more selected from the group consisting of (meth)acrylic esters is used as the polymerizable monomer [IV] in an amount of 1 to 50% by weight based on the polymerizable monomer component. 3. The manufacturing method described in 3. 5. As the polymerizable monomer [IV], 0.1 to 30% by weight of one or more selected from the group consisting of (meth)allyl ester, allyl carbonate, and allyl ether in the polymerizable monomer component The manufacturing method according to claim 3, wherein the amount is used. 6. As the polymerizable monomer [IV], one or more selected from the group consisting of epoxy (meth)acrylate, polyester (meth)acrylate, and urethane (meth)acrylate are included in the polymerizable monomer component. 1-50% by weight
The manufacturing method according to claim 3, wherein the amount is used. 7. The manufacturing method according to claims 1 to 6, wherein at least one selected from benzoic acid ester, salicylic acid ester, phthalic acid ester, phthalic acid imide, or methylnaphthalene derivative is used as the aromatic compound. 8. A dyed plastic lens obtained by the manufacturing method according to any one of claims 1 to 7.