JPH05194616A - Bluing of plastic lens - Google Patents

Abstract

PURPOSE:To carry out a bluing process for the production of colorless transparent plastic lens by adding a combination of specific pigment-based dyeing agents to a compound containing radical-polymerizable unsaturated double bond and polymerizing and curing the composition. CONSTITUTION:The objective bluing process is carried out by incorporating (A) 100 pts.wt. of an aliphatic, alicyclic or aromatic compound having one or more radical-polymerizable unsaturated double bonds in the molecule (e.g. diethylene glycol bisallylcarbonate) with (B) 0.0001-0.1 pts.wt. of a pigment-based dyeing agent selected from ultramarine and phthalocyanine blue [preferably Pigment Blue 29 (an ultramarine) or Pigment Blue 16 (a non-metallic phthalocyanine)] and (C) 0.0001-0.1 pts.wt. of a dyeing agent selected from quinacridone red pigment and azo red pigment [preferably Pigment Red 214 (a condensed polyazo pigment), etc.] to form a solution, adding an organic peroxide, azo-type polymerization initiator and/or photo-polymerization initiator suiting the radical polymerization of the component A to the solution and pouring the mixture into a glass mold, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a manufacturing method for obtaining a plastic lens having excellent heat resistance, surface hardness, chemical resistance and transparency, and having an excellent appearance.

[0002]

2. Description of the Related Art Plastic lenses are widely used in optical products because of their features such as easy molding and light weight. Above all, since transparent plastics used as spectacle lenses are required to have heat resistance and chemical resistance, thermosetting plastics such as polydiethylene glycol bisallyl carbonate (CR-39) are used instead of thermoplastics such as polymethylmethacrylate and polystyrene. Has been used. However, in recent years, since CR-39 has a low refractive index, many attempts have been made to develop a new transparent plastic having a high refractive index. In order to obtain a plastic lens having a high refractive index, it is common to introduce a halogen atom other than fluorine, an aromatic group and a sulfur atom into the molecular structure.

[0003]

However, in the conventional method of polymerizing these polymerizable monomers containing CR-39 in a mold glass to obtain a plastic lens, the degree of polymerization of these monomers is increased. Accordingly, there has been a drawback that the yellowness of the lens of the product is increased and the appearance of the lens is deteriorated. Further, the higher the refractive index of the lens composition, the greater the problem of yellowing. As one of the methods for solving the problem of yellowing, a method of bluing a lens can be considered. However, a dye-based bluing agent that blues a thermoplastic resin is a radical of a polymerizable monomer. Decomposes during polymerization and turns yellow or red,
There were problems such as not being able to bluing. Furthermore, there is a method of preventing yellowing by suppressing the degree of polymerization of the polymerizable monomer to a low level. In this method, the impact resistance, heat resistance, surface hardness, chemical resistance, etc. required for the lens are Not enough performance. The present invention has been made in the background described above, and an object of the present invention is a method for producing a plastic lens having a good appearance and excellent impact resistance, heat resistance, surface hardness, and chemical resistance.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the combination of a specific pigment-based dyeing agent gives a colorless and transparent appearance,
Further, they have found that a plastic lens having excellent impact resistance, heat resistance, surface hardness, and chemical resistance can be obtained, and the present invention has been completed.

That is, the plastic lens bluing method of the present invention comprises (A) at least one aliphatic, alicyclic or aromatic compound having at least one radically polymerizable unsaturated double bond in the molecule. To the compound,
(B) at least one pigment-based dyeing agent selected from ultramarine blue and phthalocyanine-based blue, (C) at least one dyeing agent selected from quinacridone-based red and azo-based red, and then polymerized and cured. To do.

Examples of the radically polymerizable unsaturated double bond contained in the polymerizable compound as the component (A) include methacryloyl group, acryloyl group, allyl group, methallyl group, vinyl group, and the like. After adding an organic peroxide or an active energy ray-sensitive catalyst to one or a mixture of two or more compounds having a group, an appropriate amount of the bluing agent of the present invention is added, followed by heating or irradiation with active energy rays. By carrying out the polymerization, a colorless and transparent plastic lens can be obtained in appearance.

Next, each component will be described. The aliphatic, alicyclic or aromatic compound having at least one radically polymerizable unsaturated double bond in the molecule of the component (A) is manufactured by a known method and is commercially available. (Aliphatic, alicyclic or aromatic alcohol mono (meth) acrylates, polyols poly (meth))
(Meth) acrylate monomers such as acrylate, polyester poly (meth) acrylate, epoxy poly (meth) acrylate, urethane poly (meth) acrylate, polyether poly (meth) acrylate, etc., aliphatic, alicyclic or aromatic carvone Mono-, di- or triallyl esters of acids, aliphatic, alicyclic or aromatic carboxylic acid mono-, di- or trimethallyl esters, aliphatic, alicyclic or aromatic alcohol mono-, di- or triallyl carbonates, fats Examples thereof include mono-, di- or trimetallyl carbonates of group, alicyclic or aromatic alcohols.

Among the above, cyclohexyl (meth)
Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, biphenyl (meth) acrylate, thiophenyl (meth) acrylate, thiobiphenyl (meth) acrylate, 2,2-bis (methacryloxyethoxyphenyl) propane, 2,2-bis (methacryloxyethoxy-3,5-dibromophenyl) propane, bis (methacryloxydiethoxyphenyl) sulfide, bis (methacryloxydiethoxyphenyl) sulfone, Epoxy di (meth) acrylate obtained by reacting bisphenol A type diepoxy with (meth) acrylic acid, and epoxy di (wherein tetrabromobisphenol A type diepoxy is reacted with (meth) acrylic acid ( Data) acrylate, tolylene diisocyanate and 2-hydroxypropyl (meth) urethane di reacted acrylate (meth) acrylate,
Urethane di (meth) reacted with xylylene diisocyanate and 2-hydroxypropyl (meth) acrylate
Acrylate, orthodiallyl phthalate, metadiallyl phthalate, orthodimethallyl phthalate, 2,2-
Diallyl biphenylate, 4,4-diallyl biphenylate, diethylene glycol bisallyl carbonate,
It is preferable to use 2,2-bis (allyloxycarbonatoethoxyphenyl) propane, 2,2-bis (allyloxycarbonatoethoxy-3,5-dibromophenyl) propane, or the like. These monomers may be used alone or in combination of two or more.

At least one pigment-based dyeing agent selected from the ultramarine and phthalocyanine-based blue of the component (B) is
By adding an appropriate amount to the lens-constituting monomer of the component (A), blue dyeing is performed to cancel the yellowing. Specific examples of the component (B) include chemical formulas: Na _6-8 Al ₆ O ₂₄ S _2-4
, C.I. I. Number: 77007 (Pigment Blue 29) ultramarine blue, represented by the following chemical formula, C.I.
I. No .: 74100 (Pigment Blue 16), metal-free phthalocyanine, C.I. I. Number: 74160
(Pigment Blue 15) copper phthalocyanine, C.I.
I. No .: 74180 (Pigment Blue 17), copper phthalocyanine sulfonic acid barium salt, and the like.

[0010]

[Chemical 1] These are preferably used alone or in combination of two or more.

Among the above, C.I. I. Number: 77
Ultramarine blue of 007 (Pigment Blue 29), or C.I. I.
It is particularly preferable to use a metal-free phthalocyanine of No. 74100 (Pigment Blue 16). The blending ratio of the component (B) is 0. 100 parts by weight of the component (A).
0001 to 0.1 part by weight. The addition amount of the component (B) is preferably adjusted according to the degree of yellowing when the component (B) is not added. It is preferably 0.0002 to 0.005 parts by weight.

At least one of the dyes selected from quinacridone red and azo red as the component (C) is
The bluing effect is increased by adding an appropriate amount to the lens-constituting monomer of the component (A) together with the blue dyeing agent of the component (B). When the component (C) is not added,
The yellow color of the component (A) and the blue color of the component (B) make the lens green. A red color is needed to counteract this.
Specific examples of the component (C) include the following chemical formulas.

[0013]

[Chemical 2] (R ₁ and R ₂ represent a hydrogen atom or a methyl group, and X ₁ and X ₂ represent hydrogen, chlorine, bromine or iodine.),
C. I. Number; 73915 (Pigment Red 12
Quinacridone magenta of 2) (R ₁ and R ₂ are both methyl groups), C.I. I. No .; 73900 (Pigment Violet 19), quinacridone red (both R ₁ and R ₂ are hydrogen atoms), C.I. I. No .; 73905 (Pigment Red 209), quinacridone red E, Pigment Red 214, Pigment Red 242, and other condensed polyazo red dyes. These are preferably used alone or in combination of two or more. Among the above, C.I. I. No .: 73915 (Pigment Red 122), quinacridone magenta (R ₁ and R ₂ are both methyl groups), and Pigment Red 214 (condensed polyazo red dye) are particularly preferable. The mixing ratio of the component (C) is 0.0001 to 100 parts by weight of the component (A).
0.1 parts by weight. 1 for the added amount of component (B) 1
It is better to use ~ 1/3 amount. Preferably 0.000
It is 1 to 0.005 parts by weight. The plastic lens of the present invention may contain various additives such as an antioxidant, an anti-yellowing agent and an ultraviolet absorber, if necessary.

In carrying out the present invention, after adjusting the monomer mixture of the component (A) according to the desired lens performance,
Mix components (B) and (C). Since the components (B) and (C) are pigments, they cannot be easily dissolved in the component (A).
It is advisable to uniformly disperse the resulting mixture in the monomer mixture by subjecting it to a general kneading process to form ultrafine particles. After the components (A), (B) and (C) are brought into a solution state, an organic peroxide or an azo-based initiator which is adjusted to the radical polymerizability of the component (A),
Alternatively, an appropriate amount of a photopolymerization initiator is added, and desired glass such as glass is injected to carry out polymerization. As the organic peroxide, benzoyl peroxide, diisopropyl peroxypercarbonate,
Examples of azo initiators such as t-butylperoxyisobutyrate and t-butylperoxy-2-ethylhexanoate include 2,2′-azobisisobutyronitrile and 2,2′-azobisisobutyronitrile.
2'-azobis (2,4-dimethylvaleronitrile)
Examples of the photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one, methylphenylglyoxylate, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. These are used alone or in a mixture of two or more.

[0015]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples. Example 1 ( Preparation of dyeing agent solution) (1) 50 g of diethylene glycol bisallyl carbonate (trade name, CR-39, manufactured by PPG), diallyl phthalate prepolymer (trade name, Daiso Dup A,
(Manufactured by Daiso Co., Ltd.) 50 g, C.I. I. Number: 770
07 (Pigment Blue 29) ultramarine, 60 g, quinacridone magenta [C. I. No .; 73915 (Pigment Red 122)] 40 g was mixed and well kneaded with a three-roll to prepare a thick dyeing agent solution. (This is referred to as dyeing agent solution I.) (2) Next, 1 g of the above dyeing agent solution I was mixed with 90 g of diethylene glycol bisallyl carbonate and 10 g of diallyl phthalate prepolymer to obtain a dyeing agent concentration of 0.
A 5 wt% dye solution was prepared. (This is a stain solution
II. (Production of lens) Diethylene glycol bisallyl carbonate 100 g, dye solution I, 3 g, 2- (5-methyl-2-hydroxyphenyl) benzotriazole (trade name, Tinuvin P, manufactured by Ciba Geigy) 0.1 g,
After mixing 3 g of diisopropyl peroxypercarbonate and stirring well at room temperature, the pressure was reduced to 50 mmHg and degassing was performed for 10 minutes. This composition has a mirror-finished diameter of 70
Two pieces of glass having a thickness of 2 mm were combined so as to have a thickness of 2 mm, and the glass was poured into a mold surrounded by a polyvinyl chloride gasket. Then at 45 ° C for 10 hours and 60 ° C for 3 hours.
The molded product was held at 80 ° C. for 3 hours and at 95 ° C. for 3 hours. The lens was removed from the mold and heated at 120 ° C. for 1 hour to be annealed. The flat plate thus produced is colorless and transparent in appearance and has a visible light transmittance of 88% as measured according to ASTM D-1003, ASTM D-1.
Y. 925. I. (Yellowness) is 0.5
Met.

Example 2 70 g of 2,2-bis (methacryloxyethoxyphenyl) propane (trade name, NK ester, BPE-100, Shin-Nakamura Chemical Co., Ltd.), benzyl methacrylate (trade name,
Acryester BZ, Mitsubishi Rayon Co., Ltd.) 30 g, Staining agent solution II prepared in Example 1, 3 g, 2- (5-methyl-2-hydroxyphenyl) benzotriazole (trade name, Tinuvin P, Ciba Geigy) 0 .1 g, methylphenylglyoxylate (trade name, Vicure 55,
Stopher Co., Ltd.) 0.05 g and t-butylperoxyisobutyrate (trade name, Kayaester i, Kayaku Akzo Co., Ltd.) 0.1 g were mixed and well stirred at room temperature, then 50
The pressure was reduced to mmHg and degassing was performed for 10 minutes. Two pieces of glass with a diameter of 70 mm obtained by mirror-finishing this composition had a thickness of 2 mm.
And were poured into a mold surrounded by a polyvinyl chloride gasket. Then, 10 J / cm ² of ultraviolet rays were irradiated from both sides of the mold by a 2 kw high-pressure mercury lamp and then heated at 120 ° C. for 2 hours. After that, the lens was removed from the mold and heated at 120 ° C. for 1 hour for annealing treatment. The thus-prepared flat plate is colorless and transparent in appearance, has a visible light transmittance of 88% measured according to ASTM D-1003, and a Y.V. measured according to ASTM D-1925. I. (Yellowness) was 0.9.

Comparative Example 1 A flat plate was produced in the same manner as in Example 1 except that 3 g of the dye solution II was not added. The obtained flat plate was slightly yellowed, and the visible light transmittance measured according to ASTM D-1003 was 90%.
The Y.I. measured according to STM D-1925. I. (Yellowness) was as high as 2.1.

Comparative Example 2 A flat plate was produced in the same manner as in Example 2 except that 3 g of Dyeing Agent Solution II was not added. The obtained flat plate was slightly yellowed, and the visible light transmittance measured according to ASTM D-1003 was 89%.
Y.M. measured according to MD-1925. I. (Yellowness)
Was as high as 3.7.

[0019]

As described above, the method of bluing a plastic lens of the present invention is colorless and transparent in appearance, and has impact resistance, heat resistance, surface altitude, resistance to abrasion, by combining with a specific pigment dyeing agent. It is possible to obtain a plastic lens having excellent chemical properties.

Claims (1)

[Claims] 1. At least one compound of (A) an aliphatic, alicyclic or aromatic compound having at least one radically polymerizable unsaturated double bond in the molecule, and (B) an ultramarine blue or phthalocyanine compound. A method for bluing a plastic lens, which comprises polymerizing and curing after adding at least one pigment-based dyeing agent selected from blue, (C) at least one dyeing agent selected from quinacridone red and azo red. ..