JPH093486A - Cleaner for removing deposits on lens molding glass molds - Google Patents

Abstract

PURPOSE: To obtain the subject detergent which comprises a water-soluble amide compound or a water-soluble lactone compound, completely removes monomers, polymers, adhesives or the like attached to a glass forming frame, and minimizes an influence on the environment, paying a due attention to the safety. CONSTITUTION: This detergent comprises (A) 65-95wt.% of a water-soluble amide compound or a water-soluble lactone compound, (B) 0.01-15wt.% of an alkanolamine or a quaternary ammonium hydroxy compound represented by the formula (R<1> to R<4> are each a 1-6C alkyl, an aryl, an aralkyl, or a cycloalkyl with a provise that R<1> to R<4> are not methyl at the same time), (C) 0-30wt.% of a 10C or less aromatic hydrocarbon and (D) 0-20wt.% of water. Preferably, the component A is a water-soluble compound such as 2-pyrrolidone, N-methyl-2- pyrrolidone, etc., and the component B is a compound such as monoethanolamine, diethanolamine, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to cleaning used for peeling and removing adhesives and lens forming raw materials adhering to glass molds produced when manufacturing eyeglass lenses, contact lenses and industrial lenses and prisms. Regarding agents.

[0002]

2. Description of the Related Art Conventionally, plastic lenses used for manufacturing eyeglass lenses, contact lenses, industrial lenses and prisms, etc. are manufactured by so-called cast polymerization. That is, in a lens molding die, that is, in a mold, in which a liquid monomer such as diethylene glycol bisallyl carbonate is assembled with the resin gasket 3 shown in FIG. 1 and two glass plates 1 and 2 (glass frame). And the liquid monomer injected into the mold is polymerized in a heating furnace. If you make the cavity of the mold to make the contour of the lens,
The lens can be obtained virtually immediately after polymerization.

A method different from the above thermal polymerization method, that is,
A method for producing a plastic lens by irradiating a photopolymerizable monomer with an active energy ray from a high-pressure mercury lamp, a metal halide lamp or the like to produce a plastic lens has been proposed (Japanese Patent Laid-Open No. 61-194401). Kaisho 63
-207632, JP-A-3-193313, JP-A-4-265713, JP-A-5-8230). According to these methods, it is possible to complete the polymerization in a short time or at a low temperature as an attribute unique to the polymerization by the active energy ray, as compared with the case of the thermal polymerization.

Transparent glass is used for the glass molds 1 and 2 of such a mold in order to complete the irradiation of the active energy rays 5, the polymerization and the curing of the liquid monomer, and is used as the resin of the material of the gasket 3. For example, polyvinyl chloride, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, etc. are used. Glass formwork 1, 2 and gasket 3
As the adhesive 4, a liquid epoxy resin, α-cyanoacrylate, methylcyanoacrylate, ethylcyanoacrylate, or the like is used. The photopolymerizable monomer filled in the mold is one having two or more ethylenically unsaturated bonds which gives a polymer having a high refractive index and / or a high Abbe number, or A comonomer having two or more ethylenically unsaturated bonds is used in combination.

Examples of such photopolymerizable monomers include the following. These can be used together within a group and / or between groups. In addition, "(meth) acryloyl" and "(meth) acrylate" are generic terms for acryloyl and methacryloyl, and acrylate and methacrylate. (A) Sulfur-containing di (meth) acrylates, for example, p-bis [β- (meth) acryloyloxyethylthio] xylylene, m-bis [β-
(Meth) acryloyloxyethylthio] xylylene,
p-bis [β- (meth) acryloyloxyethyloxyethylthio] xylylene, m-bis [β- (meth) acryloyloxyethyloxyethylthio] xylylene, 4,4′-bis [β- (meth) acrylol (B) alkylene glycol di (meth) acrylates such as yloxyethylthio] diphenyl sulfide, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylate, hexanediol di (meth)
(C) Bisphenol A skeleton-containing di (meth) acrylates such as acrylates, for example, 2,2-bis [4-
(Meth) acryloyloxyphenyl] propane, its halogen-substituted derivatives, 2,2-bis [4- (2-meth)]
(Acryloyloxyethoxy) phenyl] propane, halogen-substituted derivatives thereof, and the like, (d) styrene compounds, for example, m-bis [(4-vinylphenyl) methylthio]
Xylylene, β, β′-bis [(4-vinylphenyl)
Methylthio] diethyl ether and the like, and (e) lens monomers other than the above, which are photopolymerizable with a photopolymerization initiator, such as urethane acrylate and epoxy acrylate.

As the photopolymerization initiator blended with the monomer, one selected from the following group is used. (I) Acylphosphine oxide and acylphosphinic acid esters, for example, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-
Trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, etc.
(Ii) Acetophenone compounds, for example 1-phenyl-
2-hydroxy-2-methylpropan-1-one, 1-
Hydroxycyclohexyl phenyl ketone, 4-diphenoxydichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, and (iii)
Benzophenone compounds such as benzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 3,3'-dimethyl-
4-methoxybenzophenone, diphenoxybenzophenone and the like.

To mold a lens, a cavity of the mold is filled with a predetermined monomer in an inert gas atmosphere or in air, and an active energy ray 5 is irradiated to start photopolymerization. The active energy ray is preferably an active energy ray having a wavelength of 200 to 600 nm, and as a light source, a known chemical lamp, xenon lamp, low pressure mercury lamp, high pressure mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp or the like is applied. Irradiation may be carried out with the same energy intensity, or the energy intensity may be changed over time, for example, the polymerization may be started at a low energy intensity, and the energy intensity may be increased in the latter stage of the polymerization to complete the polymerization. . Irradiation is generally performed at room temperature.

Since the mold used for molding the lens is reused, the burrs of the attached resin, the adhesive, the unreacted monomer, the pitch, the tar, etc. are peeled off and removed by the cleaning agent. Freon, trichlene, methylene chloride, kerosene, etc. have been used as such detergents. At present, the use of CFCs and chlorine-based solvents has become a serious problem because of their safety and environmental impact, and their use is being restricted. In addition, flammable organic solvents, which have a low boiling point and are highly flammable, are extremely important in terms of safety, and those that cause photochemical smog and the like are used, which is a major problem. Cleaning agents are needed.

[0009]

DISCLOSURE OF THE INVENTION The present invention has the effect of improving the performance of removing the deposits on the lens-molded glass mold, which occurs during lens molding, and reduces the impact on the environment.
Moreover, it aims at providing the cleaning agent which considered safety.

[0010]

The present invention provides (a) a water-soluble amide compound or a water-soluble lactone compound.
65-95% by weight (b) Alkanolamine or general formula (I)

[0011]

Embedded image (In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an aryl group, an aralkyl group or a cycloalkyl group, provided that R ¹ , R ² , R
Not all ³ and R ⁴ are methyl groups. ) Quaternary ammonium hydroxy compound 0.01 to 1
A cleaning agent for removing deposits on a lens-molded glass mold containing 5% by weight (c) aromatic hydrocarbon having 10 or less carbon atoms 0 to 30% by weight (d) water 0 to 20% by weight. is there. Hereinafter, the present invention will be described in detail.

(Summary of the Invention) Adhesives on glass molds As the adhering substances, a monomer of the above-mentioned plastic lens material, a burr of a polymer obtained by thermosetting or photocuring the same, a pitch tar for polishing (asphalt) Examples include materials such as a resin, a wood-based material, a resin-based material or a sticking (resin-based) material, and a photo-curable cyanoacrylate-based (instant adhesive) or a thermosetting epoxy-based material as an adhesive.

Cleaning Agent The cleaning agent is (a) a water-soluble amide compound or a water-soluble lactone compound.
65 to 95% by weight, preferably 80 to 95% by weight (b) Alkanolamine or quaternary ammonium hydroxy compound 0.01 to 15% by weight, preferably 0.
05-10 wt% (c) Aromatic hydrocarbon having 10 or less carbon atoms 0-30 wt%, preferably 5-15 wt% (d) Water 0-20 wt%.

(A) Water-soluble amide compound or water-soluble lactone compound: The water-soluble amide compound has a molecular weight of 2
50 or less, N, N'-dimethylformamide (DMF), N, N'-diethylformamide (D
EF), N, N'-dimethylacetamide (DMAC)
Chain amide compounds such as and cyclic amide compounds such as pyrrolidone compounds are used.

Examples of the pyrrolidone compound include 2-pyrrolidone and N-alkyl-2-pyrrolidone (for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone,
N-propyl-2-pyrrolidone), 5-alkyl-2-
Pyrrolidone (eg, 5-methyl-2-pyrrolidone, 5
-Ethyl-2-pyrrolidone, 5-propyl-2-pyrrolidone), N-vinyl-2-pyrrolidone and the like are exemplified, but N-methyl-2-pyrrolidone is particularly effective. As the water-soluble lactone compound, γ-butyrolactone (G
BL) and tetrahydrofuran (THF).

These components may be used alone or in combination of two or more. In the cleaning agent, (a)
If the amount of the component is less than 65% by weight, the swelling action of the adhered matter becomes small, and the effect of removing the adhered matter adhered to the lens mold is weakened. On the other hand, when the amount exceeds 95% by weight, only the swelling action of the adhering matter precedes, and the adhering matter adhering to the lens mold is hardly peeled off.

(B) Alkanolamine or quaternary ammonium hydroxy compound: Examples of the alkanolamine include monoethanolamine, diethanolamine and triethanolamine. Specific examples of the quaternary ammonium hydroxy compound represented by the formula (I) include tetraethylammonium hydroxide, tetrabutylammonium hydroxide, tetraoctylammonium hydroxide, triethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, Examples thereof include triethylbenzylammonium hydroxide, tribenzylmethylammonium hydroxide, tetrabenzylammonium hydroxide, trimethylcyclohexylammonium hydroxide and tributylcyclohexylammonium hydroxide.

The component (b) is 0.01 to 15 in the detergent.
% By weight. When the amount is less than 0.01% by weight, the degree of curing that hardens the adhered material that has been subjected to the swelling action by the component (a) and makes it easier to peel off from the lens mold is reduced. Fifteen
If the content exceeds 10% by weight, the effect of curing the adhered material is too strong, and the adhered material is less likely to peel off from the lens mold.

(C) Aromatic hydrocarbon solvent having 10 or less carbon atoms: As the aromatic hydrocarbon having 10 or less carbon atoms,
Examples thereof include benzene, toluene, ethylbenzene, xylene, propylbenzene, isopropylbenzene, ethyltoluene, trimethylbenzene, polymethylbenzene, propyltoluene, cymene, diethylbenzene, dimethylbenzene and dimethyl-ethylbenzene. This hydrocarbon solvent is particularly effective when an epoxy resin is used as an adhesive. (D) Water: Water is added to prevent flammability of the detergent. Cleaning method

For cleaning the glass mold for lens molding and the gasket, for example, a cleaning liquid is charged in a cleaning tank, and the temperature is from room temperature to 60 ° C.
The temperature is raised to a certain degree and the lens-molded glass mold with the adhered matter is immersed in it for ultrasonic cleaning, or the lens-molded glass mold with the adhered matter is fixed to a tank surrounded by spray cleaning. After washing, water rinsing and drying are performed to remove the detergent adhering to the lens forming glass mold.

[0021]

【Example】

Lens Production Example 1 In a 200 ml flask, p- was added as a photopolymerizable monomer.
100 parts of bis (β-methacryloyloxyethylthio) xylylene and 0.03 part of 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photopolymerization initiator were added and mixed well, and nitrogen substitution was performed to form a lens. A monomer composition for use was prepared. This was injected into a mold formed by a glass mold and a polyvinyl chloride gasket in a nitrogen gas atmosphere with a syringe in a nitrogen gas atmosphere. The glass frame and the gasket were bonded using an α-cyanoacrylate adhesive.

In the first step, two high-pressure mercury lamps were used to obtain a maximum illuminance of 25 mW / cm from both upper and lower surfaces.
^2. Irradiation with active energy rays having an irradiation energy amount of 0.5 joule. Then, after the second stage of irradiation in which the maximum illuminance is less than 10 mW / cm ² and the irradiation energy amount is 0.1 joule, as the third stage, the maximum illuminance of 20 mW / c
Polymerization was carried out by irradiating with an active energy ray having m ² and an irradiation energy amount of 2.0 joules. After demolding, 100 ℃
Annealing was performed for 2 hours to obtain a lens.

This lens was hardened uniformly without any striking inside, had no peeling on the surface, had good transfer accuracy, and had excellent mechanical properties. Examples 1 to 10, Comparative Examples 1 to 3 Using the cleaning agents shown in Table 1, ultrasonic oscillation (400 W, 2
8 KHz) cleaning, and the degree of cleaning of the polymer of the monomer burr adhered to the lens-molded glass mold used in Example 1, the adhesive, and pitch tar were observed and the condition after cleaning was observed.

In Table 1, the observations of the monomers, polymers, adhesives, and pitch tars adhered to the lens-molded glass mold after cleaning are shown by the following symbols. ○: Monomers, polymers, adhesives, and pitch tar are completely removed. Δ: A slight amount of monomers, polymers, adhesives, and pitch tar remained, but there was no problem in practical use. X: Most of the monomers, polymers, adhesives, and pitch tar remain. The cleaning time was 5 minutes. The results are shown in Table 1.

[0025]

[Table 1]

Production Example 2 of plastic lens Compound 40 obtained by reacting isophorone diisocyanate and 2-hydroxyethyl methacrylate at a molar ratio of 1: 2.
Parts by weight, polyethylene glycol diacrylate (“Aronix M245” manufactured by Toagosei Chemical Industry Co., Ltd.) 35
Parts by weight, 25 parts by weight of hexanediol diacrylate,
0.05 parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 0.03 parts by weight of t-butylperoxyisobutyrate, 2 (2'-hydroxy-5'-methylphenyl) benzotriazole 0.02
The parts by weight were mixed to prepare a monomer composition. This monomer composition has a mirror-finished outer diameter of 80 mm and a curvature of 386.
mm, an outer diameter of 80 mm, and a curvature of 65 mm were combined to form a concave lens having a center thickness of 1.5 mm, the periphery was surrounded by a polyvinyl chloride gasket, and the mixture was poured into this mold. A bisphenol A epoxy resin adhesive was used to bond the gasket and the glass frame.

Then, as a prepolymerization step, a pair of lamps were passed through at a speed of 2 m / min from a distance of 20 cm on both sides of the mold using a 3 KW metal halide lamp. After passing, it was left at room temperature for 20 minutes. Then, irradiation with the lamp was continuously performed for 1 minute, and curing was performed at 110 ° C. for 1 hour without removing the glass mold to complete the polymerization. Demolded to obtain a plastic lens, and then 120
Annealing was performed at 1 ° C. for 1 hour. Examples 11 to 17 and Comparative Examples 4 to 6 Cleaning was performed in the same manner as in Example 1 except that the cleaning agents shown in Table 2 were used and the lens mold used in Production Example 2 was used. Table 2 shows the results.

[0028]

[Table 2]

[0029]

EFFECTS OF THE INVENTION Monomers, polymers, adhesives, and pitch tars adhering to a glass mold for molding plastic lenses can be completely removed, so that even if reused, irregular patterns are formed on the lens surface. A plastic lens that does not generate

[Brief description of drawings]

FIG. 1 is a molding flow diagram of a plastic lens.

[Explanation of symbols]

 1 Glass Formwork 2 Glass Formwork 3 Gasket 4 Adhesive 5 Active Energy Rays 5a, 5b Light Source

Claims (2)

[Claims] 1. (a) Water-soluble amide compound or water-soluble lactone compound 65 to 95% by weight (b) Alkanolamine or general formula (I) (In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an aryl group, an aralkyl group or a cycloalkyl group, provided that R ¹ , R ² , R
Not all ³ and R ⁴ are methyl groups. ) Quaternary ammonium hydroxy compound 0.01-
15% by weight (c) A hydrocarbon having 10 or less carbon atoms 0 to 30% by weight (d) 0 to 20% by weight of water A cleaning agent for removing deposits on a lens-molded glass mold. 2. The component (a) comprises 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinylpyrrolidone, N,
It is a water-soluble compound selected from N'-dimethylacetamide, N, N'-dimethylformamide, N, N'-diethylformamide and γ-butyrolactone, and the component (b) is monoethanolamine, diethanolamine, triethanolamine. , Tetraethylammonium hydroxide, tetrabutylammonium hydroxide, tetraoctylammonium hydroxide, triethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, tribenzylmethylammonium hydroxide, tetrabenzylammonium hydroxide, trimethyl Compound selected from cyclohexyl ammonium hydroxide and tributyl cyclohexyl ammonium hydroxide Detergent for removing deposits of lens molding glass mold according to claim 1 is.