JPS59193924A - Composition for optical material - Google Patents

Abstract

PURPOSE:To obtain a composition for optical material, capable of giving a hardened product such as lens, optical disk, etc. having excellent water and oil repellancy, weather resistance, stain resistance and resistance to water absorption, by adding a fluorine-containing polymerizable unsaturated compound to the components. CONSTITUTION:The objective composition is composed of (A) one or more compounds selected from (i) a polyvalent allyl compound (e.g. diallyl phthalate, trially isocyanurate, etc.), (ii) a polyvalent (meth)acryl compound [e.g. ethylene glycol di(meth)acrylate] and a compound having >=2 unsaturated cycloacetal groups per one molecule (e.g. diallylidene pentaerythritol), (B) a polyvalent mercaptan compound (e.g. dipentene mercaptan) and (C) a fluorine-containing polymerizable unsaturated compound [e.g. the compound of formula I (m and n are 0-18; X is H or CH3) or II, etc. in an amount of 0.1-30wt% based on the sum of the other components] and if necessary, (D) a polymerization catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a composition for optical materials that can produce a cured product having water repellency, oil repellency, weather resistance, stain resistance, and water absorption resistance. By curing it, it is possible to provide optical materials, especially excellent lenses, prisms, and optical discs.

It is known that polyvalent allylic compounds, polyvalent (meth)acrylic compounds, unsaturated cycloacecool compounds, and polyvalent mercaptan compounds are polymerized in the presence of an appropriate catalyst to produce polymers. The polymerization rate of this composition is fast, and the cured product has excellent adhesion, transparency, chemical resistance, etc.
It is used in cast products, molded products, paints, adhesives, etc.

However, the cured product has good wettability with water,
As an optical material, it has a major drawback in that it has high water absorption, and for example, when immersed in water, it absorbs about 1% by weight of water, which causes a change in its refractive index. Furthermore, if exposed outdoors for a long period of time, the surface will be eroded and dirt will accumulate significantly.

For example, a compound having at least two unsaturated cycloacetic groups per molecule, or a compound having at least two unsaturated cycloacetal groups per molecule and a compound having at least two mercapto groups per molecule. Although compositions consisting of the following are known and have various excellent properties, as mentioned above, these compositions have these drawbacks.

As a result of intensive research into improving this drawback, the present inventors found that
It has been found that by adding a polymerizable fluorine-containing unsaturated compound, the above drawbacks can be improved without impairing the excellent properties of the composition, and the composition can exhibit excellent optical properties. Moreover, it has been found that the curing time is not delayed compared to the case where the fluorine-containing unsaturated compound is not added, and excellent effects can be obtained.

Polymerizable fluorine-containing unsaturated compounds used in the present invention or acrylic esters or methacrylic esters of alcohols having an alkylene group are mentioned. Substituted, and the total number of carbon atoms of alkyl groups, alkylene groups, or these side groups in one molecule is 1 to 30
Acrylic esters or methacrylic esters of alcohols, such as the following compounds.

CF3-(CF2)n-(CH2)m-000-〇-C
H2ORX R'X R'X (In the above formula, m = -0-18, n =, o ~ 18. R
=H or 0H300-1X=H or CH3, R'=
Represents H or OH3(C■-■2)n-. ) Also, aromatic fluorine-containing monomers such as the following can also be used.

These alcohol acrylic esters or methacrylic esters and aromatic fluorine-containing monomers having 7-nominated alkyl groups and/or alkylene groups are
It has excellent curing properties and has a relatively low water absorption rate.

The blending amount of the polymerizable fluorine-containing unsaturated compound is at least one selected from polyvalent allyl compounds, polyvalent (meth)acrylic compounds, and compounds having at least two unsaturated 7-chloroacetal groups per molecule. It is preferable that the weight ratio is 0.01 to 30% based on the total weight of the compound and the polyvalent mercaptan compound.

The polyvalent allyl compound used in the present invention includes:
It is a compound having two or more allyl groups in the molecule, and specific examples include diallyl phthalate, diallylinophthalate, triallyl isocyanurate, and the like.

The polyvalent (meth)acrylic compound used in the present invention is a compound having two or more (meth)acryloyl groups in the molecule, such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, Examples include aliphatic polyvinyl compounds such as trimethylolpropane trimethacrylate and pentaerythritol tetraacrylate.

The polyvalent (meth)acrylic compounds may be used alone or in combination of two or more.

The compound having at least two unsaturated cycloacetal groups per molecule used in the present invention refers to an unsaturated cycloacetal group represented by (unsaturated dioxane type) and/or (unsaturated dioxane type). Typical examples of unsaturated cycloacetal compounds having at least two molecules in one molecule are diarylidene pentaerythritol, triarylidene rubitol, and diarylidene-2,2,6,6-titramethylolcyclohexanone. can be a mixture of these.

Polyvalent allylic compounds, polyvalent (meth)acrylic compounds, and compounds having at least two unsaturated cycloacecool groups per molecule may be used alone or mixed by straining. Good too. The mixing ratio is arbitrary.

The polyvalent mercaptan compound used in the present invention is
At least two meJ17 capto groups ()- per molecule
aliphatic or aromatic mercapcones having IS-), such as dipentene dimercaptan, ethylchlorohexyl dimercaptan, 1,6-hexane dimercaptan, as well as mercapto compounds and polyhydric alcohol ester compounds having carboxyl groups; , for example, esters of thioglycolic acid, β-mercaptopropionic acid, mercaptoconocarboxylic acid and polyhydric alcohols, such as noesters of trimethylolpropane or trimethylolethane, esters of pentaerythritol or dipene querrythritol, Examples include a compound having a hydroxyl group at the carbon atom at the β-position with respect to a mercapto group, a compound obtained by a reaction between an epoxy resin and hydrogen sulfide, and a compound obtained by a reaction between an epoxy resin and thioglycolic acid.

Mixing ratio of the polyvalent mercaptan compound and at least one compound selected from polyvalent allyl compounds, polyacrylic compounds, and unsaturated compounds having at least two unsaturated cycloacetal groups per molecule The ratio of the latter compound to 1 equivalent of the former compound is 0. An amount of 6 to 1 is desirable. In particular, the blending ratio of the compound having at least two unsaturated cycloacetal groups per molecule and the polyvalent mercaptan compound may take a long time to cure if the blending amount of the compound having unsaturated cycloacetal groups is large. On the other hand, if the amount of the polyvalent mercaptan compound is extremely large, unpleasant odor and physical properties will decrease, so the equivalent ratio is approximately 1:1.
-05 is preferable.

1. What is the number of unsaturated/chloroacetal groups per molecule of a compound having an unsaturated/chloroacetal group and M per molecule of a polymercaptan compound? Combined with the number of mercapto groups, 4
It is necessary that the number is 5 or more, preferably 5 or more.

Obtaining an optical material from the composition of the present invention will be explained using Plastinocre/Z as an example.
A method in which the lens is injected into a lens mold with a specific shape designed in advance with the shape of the final product in mind and cured into the desired shape, and a method in which it is cured into an arbitrary shape without using a specific mold. After that, any known method may be used, such as cutting into a desired shape.

Acid catalysts, radical generators, active energy rays, etc. can be used to cure the composition injected into molds for producing plastic lenses or molds of arbitrary shapes. Curing by using them together is also possible. Examples of acid catalysts include polyphosphoric acid, phosphoric acid, trifluoro-p-toluenesulfonic acid, boron trifluoride complex, and metal chlorides such as tin chloride and zinc chloride, but in general, radical generators are used. Can be used as a hardening agent. As a radical generator,
As a thermal polymerization catalyst, benzoyl peroxide, di-t-butyl hydroperoxide, dicumyl peroxide, silauryliver oxide, azobisisobutyronitrile, etc. are used. As the photopolymerization catalyst, benzoin, benzyl, benzophenone, 2-hydroxy-3-benzoylpropane, 2-oxy-4-methoxybenzophenone, penzoin ingropyl ether, etc. are used. The amount added is 0.01 to 5 to the composition.

A zero weight factor is used. Active energy rays include sunlight, carbon arcs, xenon lamps, high-pressure mercury lamps, which are widely used in paints and inks made from unsaturated polyester resins and acrylic resins, and photopolymerization type paint instant drying equipment such as the pulse method. Things are good. When cured by active energy rays, the composition of the present invention includes:
There is no need to add a photosensitizer, but it expands the sensitization range and
In addition, in order to shorten the curing time, the above ketone compound,
It is preferable to use a disulfide compound or a diazo compound in an amount of 0.01 to 10 parts per 100 parts of the composition. When carrying out the present invention, it is particularly preferable to use active energy rays from the viewpoint of productivity.

In addition, the composition of the present invention may contain a polymerization accelerator, as desired.
Polymerization regulators, antifogging agents, mold release agents and other additives can be added.

When the composition is cured by heating, light irradiation, ultraviolet ray irradiation, radiation irradiation, etc., it is preferable to cure the composition in the air or in an inert gas atmosphere at a temperature in the range of room temperature to 150°C.

Colored plastic lenses can be produced by adding dyes or pigments to the compositions of the invention or by dyeing the plastic lenses after they are formed.

The optical materials obtained by using the composition of the present invention are characterized by high surface hardness, abrasion resistance, scratch resistance, heat resistance, chemical resistance, impact resistance, light transmittance, dyeability, etc. It is excellent in that it has extremely low absorbency and has extremely good cutting and polishing properties during processing.

Optical materials obtained from the composition of the present invention are useful as lenses, prisms, optical discs, and the like.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Diarylidenepentaerythritol 25 cupentaerythritol tet 2 thioglycolate 252 trimethylolpropane triacrylate 4720F5(O
F2) After uniformly mixing and dissolving 60H20000H=0H23y2-hydroxy-3-benzoylpropane 0.911, the mixture was poured into a lens mold and irradiated with ultraviolet rays for 20 seconds at a distance of 15 cTn using a 30 W/cm high pressure mercury lamp. fully cured.

When demolded, a lens with a refractive index of 1530 was obtained.

This lens received a 1.1 rating in the Sunshine Weatherometer test.
No change was observed at 00 hours.

Example 2 Diallynotalate 5o-trimethylolpropane trithioglycolate
47? Pentafluorostyrene 1
1 Benzoyl peroxide 0.2
Mix and dissolve f uniformly and pour this into a prism mold. ,
did. The temperature was kept at 80° C. for 2 hours, then the temperature was increased at a rate of 5° C./10 minutes, and the temperature was kept at 120° C. for 5 hours for complete polymerization. When the mold was removed, a transparent prism with a refractive index of 1568 was obtained.

This prism passed the Sunshine Weatherometer Test 1.
No change was observed at 000 hours.

Example 3 aF' 3- (OF 2) 5- OH2-OH2-
0000H=CI-122t triethylene glycol dimethacrylate 431 bentaerythritol tetrameccrylate 78y trimethylolpropane trithioglycolate 120 F diisopropyl baroxodicarbonate 1.85'2-(2'-Hydro*C5'-
methylphenyl)be/citriazole (ultraviolet absorber)
o, osr were uniformly mixed and dissolved and poured into a lens mold. After maintaining the temperature at 90°C for 2 hours, the temperature was increased at a rate of 5°C/30 minutes, and the temperature was maintained at 120°C for 5 hours for complete polymerization. Upon removal, a transparent lens with a refractive index of 1495 was obtained.

This lens tested 1.0 on the Sunshine Weatherometer.
No change was observed at 00 hours.

Patent applicant: Showa Denko Co., Ltd. Showa Kobunshi Co., Ltd. Representative Patent Attorney Sei Kikuchi

Claims (1)

[Claims] At least one compound selected from polyvalent allyl compounds, polyvalent (meth)acrylic compounds, and compounds having at least two unsaturated cycloacetal groups per molecule, a polyvalent mercaptan compound, and a polymerizable fluorine-containing compound. A composition for optical materials comprising an unsaturated compound and optionally containing a polymerization catalyst.