JP5521333B2 - Cleaning agent and cleaning method for composition containing sulfur and selenium atoms - Google Patents

Description

  The present invention relates to a cleaning agent and a cleaning method for a composition for an optical material obtained by using an inorganic compound having a sulfur atom and / or a selenium atom, which is a raw material of an optical material having a high refractive index and Abbe number. This composition for optical materials is useful for optical products such as plastic lenses, prisms, optical fibers, information recording substrates, filters, and adhesives, especially for plastic lenses for spectacles.

  In recent years, plastic materials have been widely used in various optical materials, particularly eyeglass lenses, because they are light and tough and easy to dye. The main performance most required for optical materials, particularly spectacle lenses, is a high refractive index, and the lens becomes thinner as the refractive index increases. In recent years, optical materials using inorganic compounds having sulfur atoms and / or selenium atoms for the purpose of increasing the refractive index have been reported (Patent Documents 1 to 3). However, a specific organic sulfur compound is used from the viewpoint of solubility when cleaning the devices used for the preparation of these optical material compositions. For example, bis (2-mercaptoethyl) sulfide and 1,2-ethanedithiol have a strong odor and thus have a poor working environment. Further, in order to treat exhaust gas, it is necessary to provide a special exhaust device such as an alkali scrubber. . Furthermore, it is necessary to ensure the stability of the waste liquid after washing, and so far no cleaning agent has been clarified in consideration of the safety of the waste liquid. When the stability of the waste liquid is poor, precipitates are generated during storage, and general waste liquid treatment may not be possible.

Japanese Patent No. 3738817 JP 2002-82203 A JP 2002-122701 A

  Detergent and cleaning method with good cleaning properties and high stability of waste liquid after cleaning for a composition for optical materials using an inorganic compound having a sulfur atom and / or selenium atom capable of increasing the refractive index I will provide a.

  As a result of intensive studies to solve the problems of the present invention, the present inventor, when washing a composition for optical materials containing an inorganic compound having a sulfur atom and / or selenium atom, (A) a compound having a lactam and (B)) The present inventors have found a cleaning agent and a cleaning method for an optical material composition characterized by containing an acidic compound.

That is, the present invention is as follows.
1. A cleaning agent for removing a composition for an optical material containing an inorganic compound having a sulfur atom and / or a selenium atom, the compound having (A) one or more lactams selected from N-methylpyrrolidone and N-ethylpyrrolidone And (B) a cleaning agent for removing the composition for optical materials, comprising an acidic compound.
2 . (B) an acidic compound, washing cleaning agent of paragraph 1 wherein the acidic organic compound.
3 . (B) an acidic compound, washing cleaning agent of paragraph 1, wherein the acidic phosphoric acid esters and / or acidic phosphite esters.
4 . (A) An optical system comprising an inorganic compound having a sulfur atom and / or a selenium atom in a cleaning agent containing a compound having one or more lactams selected from N-methylpyrrolidone and N-ethylpyrrolidone and (B) an acidic compound A cleaning method for removing the composition for materials.
5 . (B) washing method of paragraph 4 wherein the acidic compound is an acidic organic compound.
6 . (B) an acidic compound, the fourth term washing method wherein the acidic phosphoric acid esters and / or acidic phosphite esters.

  When cleaning a composition for an optical material containing an inorganic compound having a sulfur atom and / or a selenium atom, the optical material is obtained by using (A) a compound having a lactam and (B) a cleaning agent using an acidic compound. The composition for washing can be washed and removed, and the waste liquid after washing has high stability, and general waste liquid treatment becomes possible.

  The compound having (A) lactam used in the present invention is a compound having a bond formed by dehydration condensation of a carboxyl group and an amino group in the same molecule and forming a ring. Among various lactams, a lactam having 3 to 8 carbon atoms is preferable, a γ-lactam is more preferable, and an N-alkylpyrrolidone is further preferable. Particularly preferred specific examples are N-methylpyrrolidone, N-ethylpyrrolidone and N-propylpyrrolidone, and the most preferred specific example is N-methylpyrrolidone. These lactams may be used alone or in combination of two or more.

  Examples of the acidic compound (B) used in the present invention include carboxylic acids, phenols, acidic phosphoric esters, acidic phosphites, organic sulfonic acids, silicon halides, tin halides, inorganic acids and the like. These may be used alone or in combination of two or more. Of these, (A) an acidic organic compound that cannot decompose a compound having a lactam is preferable. More preferred are acidic phosphates and acidic phosphites that are easy to handle with less unpleasant odor. Particularly preferred are acidic phosphites.

(B) The addition amount of an acidic compound can be changed as desired, and (A) 0.1-100 weight part can be added with respect to 100 weight part of cleaning agents containing the compound which has a lactam. More preferably, it is 0.2-70 weight part, More preferably, it is 0.5-50 weight part.

  In the present invention, a mixture of (A) a lactam-containing compound and (B) an acidic compound is used as a cleaning agent. However, a diluent can be used as long as the object of the present invention is not impaired. It is desirable to use a diluent that can be mixed uniformly with the agent. Specific examples include water, hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ethers, and ketones. Specific examples include hydrocarbons such as normal pentane, normal hexane, normal heptane, cyclopentane, cyclohexane, cycloheptane; benzene, toluene, 1,2- or 1,3- or 1,4-xylene, ethylbenzene, isopropylbenzene Aromatic hydrocarbons such as naphthalene; halogenated hydrocarbons such as dichloromethane, chloroform, chlorobenzene, 1,2- or 1,3- or 1,4-dichlorobenzene; methanol, ethanol, normal propanol, isopropanol, etc. Alcohols; ethers such as diethyl ether, tetrahydrofuran, dioxane, diphenyl ether; ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, cyclohexanone, etc. may be used together. No. Aromatic hydrocarbons, ethers, and halogenated hydrocarbons are preferable.

In the present invention, a mixture of (A) a lactam-containing compound and (B) an acidic compound is used as a cleaning agent, so long as the object of the present invention is not impaired, a surfactant, an antioxidant, an ultraviolet absorber, It is also possible to add known additives such as a rust inhibitor.

  The composition for an optical material containing an inorganic compound having a sulfur atom and / or selenium atom to be cleaned in the present invention is reacted with the inorganic compound in an amount of 1 to 50% by weight of the inorganic compound having a sulfur atom and / or selenium atom. It is a composition containing 50 to 99% by weight of a possible compound and, if necessary, other known compounds, catalysts, ultraviolet absorbers, antioxidants, dyes, release agents and the like. Examples of inorganic compounds having a sulfur atom and / or selenium atom include sulfur, carbon disulfide, phosphorus sulfide, selenium sulfide, metal sulfide and metal hydrosulfide, selenium, carbon diselenide, phosphorus selenide, metal selenide More preferred are sulfur, carbon disulfide and selenium sulfide, and particularly preferred is sulfur. These inorganic compounds having a sulfur atom and a selenium atom may be used alone or in combination of two or more. The compound capable of reacting with an inorganic compound having a sulfur atom and / or selenium atom is not particularly limited as long as it can become a resin by polymerization and curing, but has a sulfur atom and / or selenium atom. One or more organic compounds selected from organic compounds are preferred for making the optical material obtained by polymerization and curing have a higher refractive index. Specifically, mercaptans, sulfides, polysulfides, thioketones, thioisocyanates, thiolsulfinates, thiolsulfonates, sulfilimines and derivatives thereof, sulfonium salts, sulfonium ylides, sulfones , Sulfoximines and derivatives thereof, sulfinic acids and derivatives thereof, sulfonic acids and derivatives thereof, preferably mercaptans, sulfides, polysulfides, and more preferably episulfide compounds in sulfides. A more preferred specific example is a compound having a structure represented by the following formula (1):

（式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは各々独立で０〜３の整数を表す。）
特に好ましくは、ビス（β−エピチオプロピル）スルフィドおよびビス（β−エピチオプロピル）ジスルフィドである。

(Wherein, a, b, c, d, e and f each independently represent an integer of 0 to 3)
Particularly preferred are bis (β-epithiopropyl) sulfide and bis (β-epithiopropyl) disulfide.

  A method for cleaning an optical material composition containing an inorganic compound having a sulfur atom and / or a selenium atom is obtained by using (A) a compound having a lactam and (B) an acid used for the preparation of these optical material compositions. The mixture of compounds is used with a cleaning agent. The method of contacting with the composition for optical materials is, for example, spraying a cleaning agent on the device, soaking it in a sponge or waste cloth, wiping it, filling the device with the cleaning agent, immersing the device in the cleaning agent, etc. Not limited. If necessary, simultaneous stirring, vibration, ultrasonic irradiation, air bubbling, etc. may be used. The temperature at the time of washing may be room temperature, under heating, or under cooling.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

The solubility of the composition was evaluated as follows.
A: completely dissolved and the cleaning agent became transparent B; almost dissolved but the cleaning agent became cloudy C; little dissolved but visible undissolved D; not dissolved at all

The stability of the waste liquid after washing was visually observed after being allowed to stand at 30 ° C. for 1, 7, and 30 days.
A: Clear liquid B: Slightly opaque C: Clearly opaque but no sediment D: Clearly opaque and sediment

Preparation Example of Composition for Optical Material Preparation of Composition for Optical Material Containing Inorganic Compound having Sulfur Atom and / or Selenium Atom 50 g of sulfur and 450 g of bis (thioglycidyl) sulfide were mixed and stirred at 30 ° C. in a 500 ml glass flask. . After about 3 hours, a uniform composition was obtained.

Example 1
After most of the composition was taken out from the glass flask used in the preparation of the optical material composition described in the preparation example of the optical material composition, 100 parts by weight of N-methylpyrrolidone (NMP) was added as a cleaning agent. A cleaning solution consisting of 2 parts by weight of diphenyl phosphate was sprayed at room temperature (25 ° C.). The composition was completely dissolved and the cleaning agent became clear, and the flask could be cleaned cleanly. When the waste liquid of the detergent in which the composition was dissolved was stored at 30 ° C., it was transparent for 30 days. The results are shown in Table 1.

Examples 2-14, Comparative Examples 1-5
The same operation as in Example 1 was repeated except that the cleaning agent shown in Table 1 was used. The results are shown in Tables 1 and 2.

  An optical material characterized by containing a compound having a lactam and an acidic compound when cleaning an optical material composition using an inorganic compound having a sulfur atom and / or a selenium atom capable of increasing the refractive index. By using the cleaning agent of the composition for cleaning, it is possible to provide a cleaning liquid and a cleaning method that have a high level of detergency and stability of the waste liquid after cleaning and that enable general waste liquid treatment. .

Claims (6)

A cleaning agent for removing a composition for an optical material containing an inorganic compound having a sulfur atom and / or a selenium atom, the compound having (A) one or more lactams selected from N-methylpyrrolidone and N-ethylpyrrolidone And (B) a cleaning agent for removing the composition for optical materials, comprising an acidic compound. (B) washing cleaning agent according to claim 1, wherein the acidic compound is characterized in that it is an acidic organic compound. (B) an acidic compound, washing cleaning agent according to claim 1, characterized in that the acidic phosphoric acid esters and / or acidic phosphite esters. (A) An optical system comprising an inorganic compound having a sulfur atom and / or a selenium atom in a cleaning agent containing a compound having one or more lactams selected from N-methylpyrrolidone and N-ethylpyrrolidone and (B) an acidic compound A cleaning method for removing the composition for materials. (B) washing method according to claim 4, wherein the acidic compound is an acidic organic compound. (B) washing method according to claim 4, wherein the acidic compound is an acidic phosphoric acid esters and / or acidic phosphite esters.