EP0332670A1 - Farbloses transparentes polymermaterial - Google Patents

Farbloses transparentes polymermaterial

Info

Publication number
EP0332670A1
EP0332670A1 EP19880907237 EP88907237A EP0332670A1 EP 0332670 A1 EP0332670 A1 EP 0332670A1 EP 19880907237 EP19880907237 EP 19880907237 EP 88907237 A EP88907237 A EP 88907237A EP 0332670 A1 EP0332670 A1 EP 0332670A1
Authority
EP
European Patent Office
Prior art keywords
polymer material
methacrylate
material according
component
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19880907237
Other languages
German (de)
English (en)
French (fr)
Inventor
Nanning Arfsten
Karl Heinz Wiesner
Birgit Lintner
Helmut Dislich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Schott AG
Carl Zeiss AG
Original Assignee
Carl Zeiss AG
Schott Glaswerke AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Carl Zeiss AG, Schott Glaswerke AG filed Critical Carl Zeiss AG
Publication of EP0332670A1 publication Critical patent/EP0332670A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof

Definitions

  • the present invention relates to transparent plastics which are suitable for applications in optics.
  • transparent plastics the low density and better breaking strength are significant advantages over glasses, but in terms of optical data and other physical properties, glasses are superior to the previously known transparent plastics.
  • glass Due to the wide range of possible combinations, glass enables the desired optical data to be achieved in a wide range.
  • the most important physical variables are the refractive index and the Abbe number, with the combination of high refractive indexes and high Abbe number being particularly noteworthy.
  • the disadvantages of glasses are the high densities and the associated high weight and the critical breaking strength, so that glass is increasingly being replaced by plastic in many areas.
  • CR 39 has been used increasingly for spectacle lenses.
  • n D 1.498
  • a disc of the plastic to be tested is rubbed with sandpaper under defined and reproducible conditions.
  • the smudge resistance is determined by volumetric determination of the amount of abrasion.
  • New plastics are usually classified between CR 39 and PMMA.
  • the wiping resistance of PMMA represents an average value that is necessary in order to exceed the wiping resistance level of CR 39 by means of a wiping layer (today's state of the art). If the substrate is significantly more sensitive to wiping than PMMA, this fails because the layer is "pushed through" by the abrasive.
  • the solarization stability of new plastics is determined similarly pragmatically by comparison with CR 39 in field trials or in a xenotest device. The solarization stability can be determined in the xenon test device (DIN 53387, draft 1987) under defined and reproducible conditions by artificially irradiating the test specimens with filtered xenon arc radiation.
  • Patent EP 0 027 857 A3 describes ionically crosslinked polymers which are produced by direct copolymerization of acrylic or methacrylic acid. According to this, it is known that crosslinked polymers generally have a higher mechanical strength, an increased
  • the polymers are prepared either by dissolving or technically accessible metal salts of acrylic or methacrylic acids in a monomer mixture, but in most cases by dissolving metal salts in a mixture of acrylic or methacrylic acid and a monomer mixture.
  • the metal compound is used in such an amount that the charge equivalents of the metal cations are the same as the acid equivalents of acrylic or methacrylic acid.
  • the polymers are produced in a single process step and by bulk polymerization.
  • a mixture is prepared from copolymerizable vinyl monomers, aromatic and aliphatic carboxylic acids and one or more metal compounds, which is then after heat treatment and optionally distilling off the resulting by-products can be polymerized. An excess of carboxylic acid is always used.
  • Patent BE 770 192 describes terpolymers of (methyl) styrene and / or (cyclo) aliphatic methacrylate with acrylic acid and an epoxy ester of an epoxy carboxylic acid. These polymers have good smudge resistance and high transmission. However, optical data such as refractive index and Abbe number are not described.
  • EP 126 397 describes naphthyl-containing polymers which can be used for optical purposes. These polymers, which can also contain acrylic groups, have a high refractive index of, for example, 1.58; Abbe numbers are not given. However, high refractive indices due to a high aromatic content are related to low Abbe numbers of approx. 30.
  • transparent polymers are described which contain norbonane, narbonan derivatives, decahalopenticyclodecyl groups and adamantane as molecular building blocks. The compounds used have in common that they are all very expensive and are therefore unsuitable as raw materials for a mass product.
  • the object of the present invention is to provide a colorless, transparent polymer material with a refractive index n D ⁇ 1.55 and an Abbe number v D ⁇ 35, as well as a smudge resistance which is at least equal to or greater than that of PMMA (poly (methyl methacrylate )) and a solarization stability that at least corresponds to that of the CR 39.
  • the polymer material to be created should also have an increased breaking strength compared to the previously known materials, and should be inexpensive and easy to manufacture. In addition, the use of environmentally harmful substances should be avoided in the production of this material.
  • aliphatic contains and in the components except a) the molar ratio of the functionalities aromatic: aliphatic is 2 - 1.4, with a naphthyl radical being weighted by a factor of 1.3 to 1.5 compared to the phenyl radical, and the polymer material having a refractive index n D ⁇ 1.55 and an Abbe number v D ⁇ 35.
  • the weight ratio of the aromatic to aliphatic components according to b) and c) is correspondingly 1.4 - 0.6.
  • the plastics according to the invention differ from earlier plastics in that, in addition to excellent mechanical properties, they also have a high refractive power and a high Abbe number, so that they are particularly suitable for optical moldings, in particular spectacle lenses.
  • organic dyes can be copolymerized directly, which is problematic when using peroxides.
  • plastics in the stated composition ranges of the monomer mixture have a clear advantage over the plastics described in the common literature due to the advantageous properties of the very simple implementation of the polymerization, the optical data and the use of common and inexpensive starting monomers .
  • the polymerization is carried out in bulk and by customary methods. For example, an amount of 0.01 to 5 parts by weight of radical-forming initiators such as dibenzoyl peroxide, diluroyl peroxide, tert-butyl perbenzoate, peroctate or percarbonate, cumene hydroperoxide, dicyclohexyl peroxide dicarbonate etc. and preferably Azobisi sobutyronitrile are used. Depending on the decomposition temperature of the initiator, the polymerization temperatures range between 30 ° C and 120 ° C.
  • radical-forming initiators such as dibenzoyl peroxide, diluroyl peroxide, tert-butyl perbenzoate, peroctate or percarbonate, cumene hydroperoxide, dicyclohexyl peroxide dicarbonate etc. and preferably Azobisi sobutyronitrile are used.
  • the polymerization temperatures range between 30 ° C and 120 ° C.
  • the metal ester used can have an accelerating effect on the initiator, so that the polymerization starts even at lower temperatures than in the absence of the metal compound.
  • the polymerization is preferably carried out in lens molds which are made up of two ground moldings at a distance of 2 to 20 mm and a circumferential elastic sealing ring. Both the molded parts and the sealing cords are made of a material which is inert to the monomer mixture.
  • the zirconium (iv) acrylic compound used as component a) is between 20 and 40% by weight. -% based on the total weight of the monomer solution (and thus also the finished polymer) contained in this.
  • Zirconium methacrylate is advantageously used, preferably in an amount of 28 to 32% by weight. % is particularly preferred an amount of 31.5 wt. -%
  • Zirconium methacrylate is distinguished from other salts of methacrylic acid in that it
  • polymerized under UV radiation does not tend to discolouration or induces effects of a similar nature in the polymer.
  • the metal esters are prepared by dissolving the metal starting compounds in a mixture of methacrylic acid and water. The volatile constituents are distilled off from the clear solutions thus prepared and evaporated to dryness. This gives colorless powders which dissolve very well in organic monomers and monomer mixtures, as in the compounds contained in components b), c) and d) of claim 1.
  • the polymerizable aromatic compounds used in component b) are in the monomer mixture with a proportion of 20 to 50 wt. -% contain, preferably from 30 to 45 wt. -%
  • Aromatic compounds with a vinyl function are preferably used for b). Styrene is preferred because of its low price. However, other compounds which contain the aromatic function and at least one function capable of polymerization can also be used, for example vinyltoluene, methylstyrene, divinylbenzene, diphenyldi (methacryloxy) silane, with diphenyl ether substituted by the function (s) capable of polymerization.
  • Component c) contains at least one aliphatic methacrylic acid ester in the monomer mixture, in a proportion of 20 to 40% by weight, based on the total weight of the monomer mixture, preferably in a proportion of 25 to 40% by weight.
  • Compounds which can be used individually or in combination for component c) are:
  • components b) and c) can be realized in one compound by using aromatic methacrylic acid esters, such as, for example, ⁇ -naphthyl methacrylate, benzyl methacrylate, phenyl methacrylate, phenooxyphenyl methacrylate and similar compounds.
  • aromatic methacrylic acid esters such as, for example, ⁇ -naphthyl methacrylate, benzyl methacrylate, phenyl methacrylate, phenooxyphenyl methacrylate and similar compounds.
  • unsaturated monomers which are not mentioned here and which are known as free-radically polymerizable or mixed-polymerizable monomers can also be used.
  • the optical properties of this polymer are determined by the nature of the monomers used and the resulting bond ratios and superordinate structures in the polymer.
  • An advantage of the invention is the possibility, owing to the very wide miscibility of the "basic system" of zirconium methacrylate / styrene, to copolymerize it with a wide variety of methacrylates. This possibility makes it possible to produce optical moldings in the interesting optical areas, in particular with regard to refractive index and Abbe number.
  • the ratio of the aromatic to the aliphatic proportions must be kept largely constant; the molar ratio of the functionalities aromatic: aliphatic must be in the range from 2 to 1.4. It must be taken into account that, for example, a naphthyl radical should be weighted approximately by a factor of 1.3 - 1.5 when calculating the aromatic proportion compared to the phenyl radical.
  • Examples 2 and 4 clearly show how a reduced proportion of styrene is compensated for by adding an aromatic methacrylic acid ester, namely ⁇ -naphthyl methacrylate, so that the required optical data are retained.
  • the wiping resistance is between that of PMMA and CR 39.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP19880907237 1987-08-28 1988-08-25 Farbloses transparentes polymermaterial Withdrawn EP0332670A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873728720 DE3728720A1 (de) 1987-08-28 1987-08-28 Farbloses, transparentes polymermaterial
DE3728720 1987-08-28

Publications (1)

Publication Number Publication Date
EP0332670A1 true EP0332670A1 (de) 1989-09-20

Family

ID=6334677

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19880907237 Withdrawn EP0332670A1 (de) 1987-08-28 1988-08-25 Farbloses transparentes polymermaterial

Country Status (4)

Country Link
EP (1) EP0332670A1 (enrdf_load_stackoverflow)
JP (1) JPH02501147A (enrdf_load_stackoverflow)
DE (1) DE3728720A1 (enrdf_load_stackoverflow)
WO (1) WO1989001952A1 (enrdf_load_stackoverflow)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU7469691A (en) * 1990-03-08 1991-10-10 Dsm N.V. Radiation-curable liquid composition
DE19751153A1 (de) * 1997-11-19 1999-05-20 Henkel Kgaa Polymerisierbare chromfreie organische Coilbeschichtungen
DE19923118A1 (de) 1999-05-19 2000-11-23 Henkel Kgaa Chromfreies Korrosionsschutzmittel und Korrosionsschutzverfahren
KR20040040029A (ko) * 2002-11-06 2004-05-12 정동환 선회·하향연소식 연소기
JP5754272B2 (ja) * 2011-05-17 2015-07-29 信越化学工業株式会社 嵩高い置換基を有するカルボン酸シリルエステル化合物及びその製造方法
JP6311556B2 (ja) * 2014-09-26 2018-04-18 三菱ケミカル株式会社 表面硬度向上剤、ポリカーボネート樹脂組成物および成形体

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4811355B1 (enrdf_load_stackoverflow) * 1970-07-20 1973-04-12
DE2943566A1 (de) * 1979-10-29 1981-05-07 Röhm GmbH, 6100 Darmstadt Verfahren zur herstellung eines ionisch vernetzten acrylkunststoffes
JPS56147101A (en) * 1980-04-17 1981-11-14 Seiko Epson Corp Material for plastic lens
DE3366938D1 (en) * 1982-11-01 1986-11-20 Hitachi Ltd Transparent resin material containing metal atoms
DE3479651D1 (en) * 1983-05-20 1989-10-12 Showa Denko Kk Naphthalene derivative, polymerizable composition containing the same and polymer obtainable by polymerizing this composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8901952A1 *

Also Published As

Publication number Publication date
DE3728720A1 (de) 1989-03-09
DE3728720C2 (enrdf_load_stackoverflow) 1990-11-22
WO1989001952A1 (en) 1989-03-09
JPH02501147A (ja) 1990-04-19

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