DE2445958A1 - METHOD OF MANUFACTURING BUTTONS, BUTTON PLATES, BUCKLES AND BIJOUTERY ITEMS - Google Patents

Description

$ 244,595

DR. WALTER NlELSCH

Patent attorney

2 Hamburg 70-Postfach 10914

Fenruf: 6529707 File: R 23 ^ 6

Process for the production of buttons, button plates, buckles and jewelry articles

HOECHST AKTIENGESELLSCHAPT, Prankfurt / Main

The present invention relates to a method for producing buttons from unsaturated polyester resin preparations, which contain polymerizable unsaturated monomers and coloring additives.

The production of button plates, buttons, buckles and jewelry items from unsaturated polyester resin preparations, which contain polymerizable vinyl monomers and coloring additives is, for example in the magazine "Reichhold-Albert-Nachrichten" September 1971, in the article "Buttons, Buckles and Jewelery items made from unsaturated polyester resins " by Rudolf H. Reiter, pages 30 to 31, and in DOS 2 402 611.

In these known processes, an unsaturated polyester resin preparation, the accelerator, is generally used and free radical generators, for example cobalt salts and contains organic peroxides, up to one

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Shore Α hardness of about 40 in the form of plate-shaped structures or cured by casting in molds after shaping. -These shaped body blanks must then be removed mechanically from the button blank bzxv relatively quickly. Molded body blank for the finished button bzvj. Shaped bodies are processed, since the polymerization in the shaped body blanks continues even when stored at room temperature. For this reason, the previous shaped body blanks must not be stored because of the risk of embrittlement. This is particularly pronounced when the molded body blanks prematurely polymerize to such an extent as a result of the heat generated during mechanical processing that they become too brittle for further processing.

So far it has not been possible to produce buttons, button plates, buckles and jewelry articles from unsaturated polyester resin preparations produce the fluorescent dyes and / or fluorescent pigments that remain lightfast contain organic basis (which already light up in daylight), as this was previously necessary for the hardening process Peroxide, more or less damage to the fluorescent dye occurs (see special print "Hostasol-Farbstoffej lightfast new fluorescent dyes and their application technology in plastics "by Dr. R. Merkle and Dr. H. Schäfer, Farbwerke Hoechst AG, 6230 Frankfurt / Main 80).

The production of lightfast fluorescent pigments on an organic basis is described in US Pat. No. 2,809,954 and US Pat. No. 2,938 and the production of lightfast fluorescent dyes is described in DT-PS 1 569 761, DT-PS 1 297 259, DT-PS 1 293 939 and DT-AS 2 046 111 described.

It is therefore an object of the invention in the method for the production of buttons, button plates, buckles and Jewelery articles made from unsaturated polyester resin preparations to use such a hardening process without doing so To use peroxides to harden the unsaturated polyester resins contained in the preparation or the plastic

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To avoid fluorescent dyes and / or fluorescent pigments on an organic basis, since in any case their -Light resistance is reduced in the previous processes.

Another object of this invention is to provide such unsaturated polyester resin preparations which are lightfast Fluorescent dyes and / or lightfast fluorescent pigments on an organic basis are available too provide in which the polymerization up to a desired point in time, for example after the shaped body blanks Shore A hardnesses of around 20 to 60 have been reached, can be broken off and these can be easily processed mechanically Shaped body blanks stored for any length of time with exclusion of light can be in order to be able to carry out the mechanical processing at any time without the Curing or the fluorescence capacity in the cured molded bodies of organic fluorescent dyes or. Fluorescent pigments on an organic basis noticeably reduced will.

It is now also possible to carry out the production of the molded body blanks and the further processing centrally to be carried out in other places, so that the invention makes it possible to sell molded body blanks as commercial goods to other places or to other countries, as there is no difficulty in packing them and to be transported so that they are not exposed to light. Since with the shaped body blanks e.g. button plates through mechanical processing for optimal manufacturing processes, e.g. when deburring, faceting, drilling, grinding, polishing and / or punching, certain mechanical Properties are decisive for the mechanical processability, it is an object of this invention, the shaped body blanks which are already fluorescent in daylight, e.g. button plates or button blanks, always to be made available in such a way that they are optimally mechanically machinable.

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The invention is a method for the production of buttons, button plates, buckles and Jewelery items made from stabilized polymerizable unsaturated polyester resin preparations, the polymerizable Contain unsaturated monomers and coloring additives by shaping and polymerizing the Shaped body up to Shore A hardness of 20 to about 60, processing of the shaped body blank to the finished shaped body by mechanical processing, characterized in that the preparation from the unsaturated polyester resin and the polymerizable unsaturated monomer has at least one lightfast fluorescent dye and / or lightfast Contains fluorescent pigments on an organic basis and a photoinitiator and the preparation after shaping is cured by dosed irradiation with UV light to the desired processing hardness and the obtained fluorescent shaped body blank for the finished shaped body is completed by mechanical processing and then, if necessary, again by irradiation is brought to the required hardness for use with UV light.

In the DT-AS 1 233 59 ** the use of compounds of the formula Ar ^ -SS-Ar ₂ as a trigger of the photochemical hardening in molding or coating compounds, the unsaturated polyester, mono-

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contain mer compounds and optionally peroxides, where Ar. and Ar _{2 are} aromatic radicals,

described. There it is stated in column 3, lines 57 to: "On the other hand, when producing molded parts it has an advantageous effect that the masses by appropriately dosed irradiation without significant Heat tint can be cured, creating crack-free molded parts. In addition, the Curing is interrupted by darkening and later using prepolymers that are darker Storage are stable, to be completed. "

However, it is also known that the curing of unsaturated polyester resins by irradiation with UV light is related to peroxide curing (see Bayer data sheet "Roskydal UV 10" p. 3, paragraph 3).

Furthermore, in "Chemiker-Zeitung" there is 96th year (1972) No. 10, page 5 ^ 3, right column, paragraph 2, stated: "The use of pigmented, light-curing lacquers has not yet been put into practice found. The pigments absorb too much light; so the penetration depth of the radiation is too small and accordingly the through-hardening speed is too slow. "

On the basis of this state of the art, it was to be expected that the curing times of the unsaturated polyester resins, which are used in the method of the present invention by those contained therein coloring additives are significantly influenced (as with peroxide hardening; e.g. also by the fact that you have to use lower peroxide concentrations (cf. the already mentioned special print "Hostasol dyes" Page 6, left column, last paragraph)).

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It is therefore to be regarded as surprising that in the Method of the present invention in curing of sensitized unsaturated polyester resins with exposure to medium to long-wave UV light (28O - 400nm) no damage to the coloring additives occurs although this UV curing is related to peroxide curing and UV curing is related to peroxide curing takes place via the formation of radicals.

The usual condensation products (cf. Johan Bjorksten, "Polyesters and their Applications ", Reinhold Publishing Corporation" New York, 1956, pages 21 to 155) understood, those from α, 8-unsaturated dicarboxylic acids and / or their anhydrides obtained by polycondensation with polyhydric alcohols used in a molar excess will. As α, 8-unsaturated dicarboxylic acids are, for example useful:

Maleic acid, maleic anhydride, fumaric, itaconic, citracon-5, mesaconic and aconitic acids as well as halogenated ones Acids such as chloromaleic acid.

Some of the α, 3 -unsaturated dicarboxylic acids can thereby in a manner known per se by saturated dicarboxylic acids, for example o-, iso- and terephthalic acid, Tetra- and hexahydrophthalic acid, tetrachlorophthalic acid, hexachlorendomethylene-tetrahydrophthalic acid, endomethylene-tetrahydrophthalic acid, Adipic and sebacic acid as well as dimerized linseed oil and soybean oil fatty acid or their Anhydrides, to be exchanged. The α, 3-unsaturated dicarboxylic acids are from 100 "-MoI - /? To about 20 MoI-Ji, preferably 70 mol% to about 30 mol% based on the Sum of carboxylic acids used *

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Preferred polyhydric alcohols are dihydric alcohols, for example ethylene glycol, 1,2-propanediol, Butanediol ~ 1,3, 1,4-butanediol, diethylene glycol, Dipropylene glycol and its higher homologues, neopentyl glycol, 2,2,4-trimethylpentanediol-1,3 »pent glycol, oxalkylated bisphenols, hydrogenated bisphenol, dimethylolcyclohexane. However, trivalent and polyvalent Alcohols such as glycerol, trimethylolethane, trimethylolpropane and pentaerythritol are also used proportionally.

Cf. as mischpolymerisationsfähige vinyl compounds, individually or in a mixture in amounts of 20 to 50 parts by JS ₉ based on the mixture of unsaturated polyester resin and anpolymerisierbaren monomers are included (for example:. Bulletin IP 8, July 1961, Amoco Chemicals Corporation, with the title "The Effect of Resin Ingredients on the Properties of Isophthalic-Unsaturated Polyesters", pages 5 to 19), for example, are suitable: styrene, vinyl toluene, p-tert-butyl styrene, divinylbenzene, vinyl acetate, vinyl propionate, acrylic acid esters, methacrylic acid esters , Methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethylene glycol dimethacrylate and its higher homologues, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate. Examples of allyl compounds that can be used are: diallyl phthalate, diallyl maleate, diallyl fumarate, triallyl cyanurate.

The molding compositions can be obtained by adding conventional inhibitors, for example p-benzoquinone, 2,5-di-tert-butylbenzoquinone, hydroquinone, tert-butyl catechol, toluyl hydroquinone _s 1, ^ - naphthoquinone, triphenyl phosphite, and also copper compounds such as copper naphthenate,

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stabilized in the known amounts, as for example in the book Kirk-Othmer, Encyclopedia of Chemical Technology, Interscience Publisher, New York, 1969, second edition, Volume 20, pages 822 to 825.

Quaternary ammonium salts of the general formula can also be used as inhibitors

in which R ₁ , Rp, R, and R ₁ denote an alkyl, aryl or aralkyl radical and X is a halogen atom, can be used. Specific examples are trimethylbenzylammonium chloride, triethylbenzylammonium chloride or tris (isopropyl) benzylammonium chloride.

Naphthalene-1-sulfonyl chloride or Naphthalene-2-sulfony2; chloride in amounts from 0.05 to about 5 wt .- ^, preferably 0.5 to 2.5 wt .- J? used will. There are also mixtures of naphthalene-1-sulfonyl chloride and naphthalene-2-sulfonyl chloride are usable.

The tin compounds which can be used in amounts of 0.01 to about 1% by weight , preferably 0.03 to 0.3% by weight, individually or in a mixture together with naphthalene sulfonyl chloride of the types mentioned for example in question: tin (II) octoate, tin (II) oleate, tin (II) versatate, and tin (II) compounds of

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saturated or unsaturated aliphatic straight-chain or branched-chain or cyclic Cg - Cp ₀ fatty acids. This combination of at least one naphthalene sulfonyl chloride with the formula

as a sensitizer and tin (II) compounds as an accelerator in molding compositions curable by UV radiation is described in DOS 2,259,161.

Furthermore, acyloins ₃ acyloin esters or acyln ethers, such as benzoin and benzoins, benzoin esters or benzoin ethers substituted in the α-position by hydrocarbon radicals, of primary or secondary alcohols or benzoin ethers (Deutsche Qffenlegungsschriften 1 93 ¹ J 637, 1 571 08l and 1 621 820 ; German Auslegeschrift 1,297,269; French Patent 1,300,582 and 1,450,589 ₃ German Auslegeschrift

1 902 930; German Offenlegungsschrift 1 945 725; German Auslegeschrift 1,694,149; Austrian patent specification 286,642 'and U.S. Patents 2,448,828 and

2 722 512) in the photopolymerization of unsaturated monomeric compounds and unsaturated polyesters or Mixtures of unsaturated polyesters with copolymerizable ones Find monomers use. Polymerization is possible in a relatively short time.

Based on the mixture of unsaturated polyester and copolymerizable monomers, a content of 1 to 2 % by weight of sensitizer is necessary in order to achieve sufficient reactivity.

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Examples of suitable benzoin ethers are the benzoin ethers of the following alcohols:

Methanol, ethanol, propanol-1, propanol-2, butanol-2, pentanol-2, cyclohexanol, n-butanol, isobutanol, 2-methyl-t-pentanol, 2-methylpentanol-3 _} primary and sec. ~ Octanol, 2-ethylhexanol, n-nonanol, n-dodecanol, 6-dodecanol, lauryl, myristyl, stearyl alcohol, 2-chloro-1-propanol, 3-brora-1-propanol, 2,2-dichloro-1 -propanol, 1-chloro-2-propanol, abiethyl alcohol and tetrahydroabietyl alcohol. Of the ethereally bound monoalcohols, the compounds which have primary alcoholic hydroxyl groups are preferred. However, the monoalcohols with secondary and tertiary alcoholic hydroxyl groups are also useful. In addition to the saturated alcohols, the unsaturated alcohols are also suitable. The following may be mentioned by way of example: β, γ-unsaturated alcohols, such as allyl alcohol, methallyl alcohol, ethyl alcohol, chlorallyl alcohol, crotyl alcohol, phenyl allyl alcohol, methyl vinyl carbinol, and also unsaturated fatty alcohols obtained by selective hydrogenation of unsaturated fatty acids.

Benzoinary ethers are also of the formula

\ J

0 ο Ar

where Ar is an aromatic radical, are suitable.

Examples of benzoin ethers which can be used as sensitizers are the benzoin ethers of phenol, 2-cresol, 3-Kre sols, 4-cresol, 3,4-dimethylphenol, 2,6-diethylphenol, ^ -tert-butylphenols, 2-methoxyphenols, 4-methoxyphenols, 2-chlorophenols, ^ - 'chlorophenols, 2,6-dichlorophenols, 2,4,6

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Trichlorophenols, naphthols (1), naphthols (2) and des 2,2-bis (4-hydroxylphenyl) propane (bisphenol A).

A sensitizer described in DOS 2 104 958 or DOS 2 104 9 72 can also be used as a sensitizer for the present purpose Find photo initiator combination use. Here if an overall combination is used as the photo initiator, consisting of:

(a) 0.1 to 4 wt .- * benzoin ethers and

(b) a sub-combination of at least two different compounds of trivalent phosphorus , consisting of:.

(b \) 0, l to 20 wt -.% organic esters of phosphorous acid having the general formula

.0- R,

¹ I L

P .: Zi π ~ R (1)

where R ^, Hp and R-, can be the same or different and represent aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic radicals - "however, one of the radicals R ^, R ₂ or R, must always be an aromatic radical - and

(b ') 0.05 to 2 wt -.% organic derivatives of the phosphine having the general formula

₃
where R ₁ , Rp and R- can be the same or different and represent aliphatic, cycloaliphatis.che, aromatic, arali phatic or heterocyclic radicals - but one of the radicals R ₁ , Rp or R ^. always be an aromatic residue.

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The percentages by weight mentioned relate to the total weight of unsaturated polyester resin and polymerizable resin Monomers.

When using the overall combination, consisting of (a) and (b) ((b ^f ) and (b ^{! T} )), surprisingly a synergistic effect occurs which causes extremely short polymerization times in the case of UV irradiation.

This use preparations referred benzoin ethers (a), individually or mixed together in amounts of from 0.1 h to about wt .- / ?, preferably 0.1 to about 1.5 wt .-% in combination with compounds of trivalent phosphorus ( b) ((b ¹ ) and (b ^tT )) included.

As an ester of phosphorous acid (b ·), the at least contain an aromatic radical are possible: triphenyl phosphite, tri-p-toluyl phosphite, trisnonylphenyl phosphite, Dodecylphenyl phosphite.

As organic derivatives of phosphine (b ^ff ), which contain at least one aromatic radical, for example: triphenylphosphine, tri-p-toluylphosphine, diphenylmethylphosphine, diphenylethylphosphine, diphenylpropylphosphine, dimethylphenylphosphine, Diethyl-phenyl-phosphine, dipropyl-phenyl-phosphine, divinyl-phenyl-phosphine, divinyl-p-methoxyphenyl-phosphine, divinyl-p-brom-phenyl-phosphine, divinyl-p-toluyl-phosphine, diallyl-phenyl-phosphine, diallyl-p-methoxyphenyl- phosphine, diallyl-p-bromophenyl-phosphine, dially1-p-toluy1-phosphine.

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The esters of phosphorous acid (b ') are in amounts of 0.1 to 20% by weight , based on the total weight of unsaturated polyester resin and polymerizable monomers, preferably 0.1 to 2% by weight , in a mixture with the above Contain benzoin ethers (a) and phosphines (b ^l? ).

The abovementioned phosphines (b ¹¹ ) are contained in amounts of 0.05 to 2% by weight , based on the total weight of unsaturated polyester resin and polymerizable monomers, in a mixture with the abovementioned benzoin ethers (a) and esters of phosphorous acid (b ') .

Finally, when using the sensitizer according to DOS 2 104 958, a special embodiment can also be used, which is described in DOS 2 332 820, whereby malic acid, lactic acid, ta-bronic acid, tartaric acid or citric acid are added to the preparations according to DOS 2 104 958 individually or in mixture, added as a stabilizer, generally 0.3 to about 2 wt -.% based of-mentioned organic carboxylic acids to the total weight of the unsaturated polyester resin and anpolymerisierbaren monomers used.

As fluorescent dyes and / or fluoro essence pigments on an organic basis, those are suitable for the present purpose which have the required UV resistance. This is the case with most of the relevant commercial products. The fluorescent dyes and / or fluorescent pigments on an organic basis can be used in amounts of 0.05 to about 2 % by weight, based on the weight of the preparations to be polymerized out.

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If in the method of the present invention, the fluorescent dyes and / or fluorescent pigments on an organic basis in amounts of 0.01 to 0.1% by weight used as an additive, plastic moldings of the type already mentioned are obtained after the light polymerization have transparent properties. With a corresponding increase in the content of fluorescent dyes and / or. These moldings can be produced in opaque form with organic-based fluorescent pigments.

In addition to the fluorescent dyes - apart from those already mentioned - other additives can be added to the polyester preparation. However, these other additives may only be used in such amounts that the photopolymerization is not significantly hindered or delayed. Thus, as other additives such as aluminum powder up to about 0.1 wt -.%, Lead carbonate, up to 4 wt -.% ₃ chalk in particular finely ground form up to 4 wt -.% Usable. Such additives make it possible to give the fluorescent plastic moldings cured by UV irradiation even more special effects in terms of appearance, for example a fish silver effect can be achieved by adding lead carbonate.

The shaping of the unsaturated polyester resin composition in the process of the present invention can carried out in the usual way by centrifugal, die-casting and rod casting processes.

In order to achieve the hardness required for optimal mechanical processing, the molded polyester resin preparations are so long in the method of the present invention in a metered manner with UV light

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irradiated until the desired processing hardness (Shore A hardness of 20 to about 60) has been reached. The molded body blanks obtained are stored with exclusion of light if they are not immediately subjected to mechanical processing. The shaped body blanks are subjected to the necessary mechanical processing such as deburring, faceting, grinding, polishing and punching, depending on the requirements. In many cases, the irradiation time of the molded body to be hardened up to Shore A hardness of up to about 6Q _{1 is} sufficient for mechanical processing and the use of the finished molded body, so that industrial Mach irradiation with UV light is not always necessary. In many cases, it is sufficient if the finished moldings are exposed to daylight during use, as they can be hardened to the required hardness (Shore A hardness of 60 to 110) in a relatively short time by the UV-containing components of daylight. to be brought. If, however, very high requirements are placed on the finished shaped bodies of the type mentioned in terms of light stability, resistance to cooking and detergents and ironing resistance, it is advisable to subject the finished shaped bodies to subsequent irradiation with UV light up to the required hardness has been reached.

In general, it is in the method of the present invention Invention possible by irradiating the molded polyester resin preparations Shaped bodies of the type mentioned up to about 15 mm thick by irradiation with UV light polymerize out. This is either in the form

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a UV reflective film inserted, or the shape is sufficiently UV-permeable so that, if necessary, irradiation with UV light from all sides can be done.

For the curing of the unsaturated polyester resin preparations used in the process of the present Invention find use, depending on the type of photoinitiator used and the amounts of photoinitiator used generally times of 3 to 30 minutes are required. However, these times can be both be exceeded as well as undercut.

Expediently, high-pressure mercury vapor lamps are used as UV light irradiation sources are commercially available for photopolymerization purposes.

Embodiments of the invention are now illustrated by the the following examples. The abbreviation GT. means parts by weight.

example 1

100 GT. a polymerizable mixture consisting of 67 GT. Polyester resin (made from 2 moles of maleic anhydride, 3 moles of phthalic anhydride and 5.2 moles of 1,2-propanediol) and 33 GT. Styrene, with 0.014 parts by weight. Hydroquinone stabilized, a viscosity of approx. 1400 cP at 20 ⁰ C and an acid number of 28, are 0.8 parts by weight. Naphthalene (2) sulfonyl chloride and 0.1 GT. admixed red fluorescent dye. (The dye is known from the literature as Hostasol fluorescent dye RotB-K.)

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To produce a flat, punchable 4 mm thick plate with dimensions of 30 × 40 cm, the so Mixture produced between two glass plates held at a distance of 4 mm by a spacer frame were poured and with two high pressure mercury vapor lamps of the type Osram HQI-TS-400 W from both Pages irradiated at a distance of 25 cm for 6 minutes. Thereafter, the pre-hardened plate was made with a Shore A hardness 30 removed, punched into button washers, mechanically processed to a finished button and through ' an additional irradiation with the same high-pressure mercury vapor lamps in 4 minutes to the hardness of use (Shore A hardness 80 to 100).

Example 2

100 GT. a polymerizable mixture consisting of 67 GT. Polyester resin (made from 2 moles of maleic anhydride, 3 moles of phthalic anhydride and 5.2 moles of 1,2-propanediol) and 33 GT. Styrene, with 0.014 wt -.% Stabilized hydroquinone, a viscosity of about 1400 cP at 20 ⁰ C and an acid number of 28, 0.8 GT. Naphthalene (2) sulfonyl chloride, 0.04-0.07 wt. Tin-II-octoate and 0.1 GT. Orange fluorescent pigment dye RK mixed in. (The fluorescent pigment dye is known from the literature as hostas oil pigment Orange RK)

To produce a 60 χ 80 mm buckle, the mixture produced in this way was mixed with a commercially available Mold prepared from mold release agents with a thickness of 4 mm and poured with a high-pressure mercury lamp of the type Osram HQI-TS-400 W irradiated from above at a distance of 25 cm.

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The buckle was exposed to UV radiation for 12 minutes. After demolding it became a Shore A hardness found out of 60, which allows deburring and polishing of the buckle without difficulty. Post-curing by additional irradiation can be dispensed with if this is not dark, but is stored or used in daylight, as the UV-containing part of the light causes post-curing occurs until the hardness is reached.

Example 5

100 GT. a polymerizable mixture consisting of 67 GT. Polyester resin (made from 2 moles of maleic anhydride, 3 moles of phthalic anhydride and 5.2 moles of 1,2-propanediol) and 33 GT. Styrene, with 0.014 wt -% stabilized hydroquinone, a viscosity of about 1400 cP at 20 ⁰ C and an acid number of 2 #.

become 0.5 GT. Benzoin ethyl ether and 0.1 GT. greener Fluorescent dye mixed in. (The fluorescent dye used is known from the literature as Hostasol Green B-K ).

The mixture prepared in this way is put into a centrifugal drum for making button plates with a diameter from 245 mm at a speed of 250 to 300 At / min. entered in a layer thickness of 3 to 4 mm and with a high pressure mercury lamp from Type Osram HQI - TS - 400 W at a distance of 50 mm irradiated. After 15 minutes, the cured button plate with a Shore A hardness of 40 was centrifuged removed, punched into roundels and mechanically processed into the finished button. The after plate removed from the centrifuge after removal

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with a Shore A ~ hardness of 40, can through an immediate Storage can be maintained in the dark, which makes it possible to use the at any time to be able to carry out further mechanical processing to the finished button and by additional irradiation to bring it to the hardness for hardening.

Example 4

100 GT. a polymerizable mixture consisting of 67 GT. Polyester resin (made from 2 moles of maleic anhydride, 3 moles of phthalic anhydride and 5.2 moles of 1,2-propanediol) and 33 GT. Styrene, stabilized with 0.014 wt .-% of hydroquinone, a viscosity of about l4ö0 cP at 20 ⁰ C and an acid number of 28> 0.1 GT. Triphenyl phosphite, 0.5 wt. Benzoin ethyl ether 0.07 GT. Triphenylphosphine and 0.1 GT. yellow fluorescent pigment dye (known from the literature as Hostasol 8 GK fluorescent pigment dye) and 1 part by weight. Lead carbonate (fish silver pigment) mixed in as is customary in the trade.

The mixture prepared in this way is placed in a centrifugal drum for the production of button plates with a diameter of 245 mm at a speed of 250 to 300 rpm. entered in a layer thickness of 3 to 4 mm and with a high pressure mercury vapor lamp of the Osram type HQI-TS-4Ö0 W irradiated at a distance of 50 mm. After 15 minutes the hardened slab of the Schleuda? - machine with a Shore A hardness of 30 taken to form button washers punched and then mechanically processed to the finished button. As it is with the addition lead carbonate is a flaky pigment that is produced by the orientation of the individual scales on the Surface counteracts the UV radiation, it was all the more astonishing that curing without difficulty could be carried out.

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In the above examples 1-3, those cured products are obtained which are transparent and already fluoresce in daylight. The cured products produced according to Example 4 are not transparent and show a yellowish fluorescence with a fish silver effect.

In a special embodiment of the invention Procedure it is also possible now buttons, button plates. To provide buckles and jewelry items that already show fluorescence in daylight and have an opaque structure exhibit. It is essential in this special embodiment that the molded bodies obtained are on their surface have a completely uniform coloration and structure.

In the previous processes for the production of the same moldings from unsaturated polyester resin preparations, din were cured by means of peroxides and accelerators, it was previously not possible to produce such molded bodies of the type described produce, which in the opaque state the fluorescent color:? e or fluorescent pigment on an organic basis light-resistant contain.

These opaque moldings are obtained if the organic-based unsaturated polyester preparations containing the fluorescent dye and / or fluorescent pigment are added 10 to 30% by weight, based on the total weight of the preparation, chalk flour with a microstructure, the finest aluminum hydroxide or aluminum oxide or 0.1 to 1% by weight , 0 Ge \ j .-% aluminum, copper or other metal powder added.

Example 5

100 GT. a polymerizable mixture consisting of 67 GT. Polyester resin (made from 2 moles of maleic anhydride, 3 moles of phthalic anhydride and 5.2 moles of 1,2-propanediol) and 33 GT. Styrene with 0.014 parts by weight. Hydroquinone stabilized, a viscosity of about 1400 cP at 20 ⁰ C and an acid number of 28 are 0.2 parts by weight. Naphthalene (2) sulfonyl chloride, 0.07 wt. Tin (II) octoate _s 0.1 pbw. yellow fluorescent dye

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BATH ORIGINAL

(the fluorescent dye used is known from the literature as Hostasol yellow B-K) and 30 GT. Chalk (calcium carbonate) with Micro structure suggests.

The mixture prepared in this way is in a centrifugal drum for button plate production with a diameter of 245 mm at a speed of 250 to 300 Um./Min. entered in a layer thickness of 3 to 4 mm and irradiated with a mercury vapor high pressure lamp of the type Osram HQI-TS-400 W at a distance of 50 mm. After 10 minutes, the cured knob plate having a Shore A hardness 40 of the extractor was discharged _s punched into washers and to the finished button further processed mechanically. The plate with a Shore A hardness of 40, which was taken out of the centrifugal machine, can be kept in the dark by immediate storage, which makes it possible to carry out further mechanical processing to the finished button at any point in time can and can be brought to the hardness for use by additional irradiation for hardening. The plate obtained already fluoresces in daylight, looks yellow and has an opaque structure.

Example 6

Example 5 above is repeated using the same approach but only 15 GT. micronized chalk added. This shortens the exposure time to 8 minutes. It will also received a yellow plate fluorescing in daylight with an opaque structure; however, the opacity is lower.

Example 7

The procedure is as in Example 5, but no chalk is added. Be in place of the chalk now 1 GT. Aluminum bronze powder and 0.1 GT. yellow fluorescent dye used (the fluorescent dye used is known from the literature as Hostasol yellow B-K). The plate obtained already fluoresces in daylight, shows an approximately lime green color with a clear metallic effect and has an opaque structure. The curing time was 10 mins.

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Example 8

The procedure is as in Example 5, but the addition of chalk is omitted. Instead of the chalk there will now be a Share of 1 GT. Copper powder and 0.1 GT. yellow fluorescent dye mixed in (the fluorescent dye used is known from the literature as Hostasol yellow B-K). The plate obtained already fluoresces in daylight, shows a gold-colored metallic effect and has an opaque structure. The curing time was 11 minutes.

609815/0613

Claims (9)

P at e nt to the test (lj process for the production of buttons, button plates, Buckles and jewelry items made from stabilized polymerizable unsaturated polyester resin preparations, which contain polymerisable unsaturated monomers and coloring additives by shaping and polymerizing the molded body to a Shore A hardness of 20 to about 60, processing the molded body blank to the finished molded body by mechanical processing., characterized in that the preparation at least one lightfast from the unsaturated polyester resin and the polymerizable unsaturated monomer Fluorescent dye and / or lightfast fluorescent pigments on an organic basis and a photoinitiator contains and the preparation after shaping by metered irradiation with UV light up to the desired Processing hardness is cured and the resulting fluorescent shaped body blank to the finished shaped body is completed by mechanical processing and then, if necessary, through again Irradiation with UV light is brought to the required hardness. 2. The method according to claim 1, characterized in that naphthalenesulfonyl chloride is used as the photoinitiator will. 3. Process according to Claim 2, characterized in that the naphthalene-1-sulfonyl chloride or naphthalene-2-sulfonyl chloride in amounts of 0.05 to 5 wt .- ^, preferably from 0.5 to 2.5 wt .- ^, is used. 809815/0613 4. The method according to claim 2 or 3, characterized in that 0.01 to 1 wt. %, Preferably 0.03 to 0.3 wt. % Tin (II) compounds are used. 5. The method according to claim 1, characterized in that the sensitizer AcyIoine, AcyIoinester or Acyloin ether can be used. 6. The method according to claim 5, characterized in that an overall combination is used as the sensitizer will consist of: (a) 0.1 to 4 wt -.% benzoin ethers and (b) a sub-combination of at least two different compounds of trivalent phosphorus, consisting of: (b ') 0, l to 20 wt -.% organic esters of phosphorous acid having the general formula ¹ I. -0 -R, Pf—— 0 R ₂ (I) where R ^ ₅ R ₂ and R, can be the same or different and represent aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic radicals, however, one of the radicals R ^, R ^ or R ^ must always be an aromatic radical - and (b ') 0.05 to 2 wt -.% organic derivatives of the phosphine having the general formula -R ₂ (II) 609815/0613 where R ₁ , Rp and R- can be the same or different and represent aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic radicals - however, one of the radicals R., Rp or R- must always be an aromatic radical. 7. The method according to claim 6, characterized in that Malic acid, lactic acid, tartronic acid, or tartaric acid Citric acid, individually or in a mixture, is used as a stabilizer. 8. Means for performing the method according to one of claims 1 to 3, characterized in that this the end .. I) 99.95 to 93.00 Gevt .-% of a stabilized unsaturated polyester resin composition consisting of 50 to 80 wt -% of unsaturated polyester and 50 to 20 wt -% consists partially polymerized unsaturated monomers; II) 0.05 to 2 wt -% lightfast Pluoreszenzfarbstoff and / or light-fast Pluoreszenzpigmenten on an organic basis, wherein the percentages by weight on the total weight of components I, II and Illbeziehen. and .% Of naphthalene-1-sulfonyl chloride and / or naphthalene-2-sulfonyl chloride, where the percentages by weight on the total weight of components I, II and III relate - III) 0.05 to 5 percent; is composed. 9. A composition according to claim 8, characterized in that it additionally a component IV, in amounts of from 0.01 to about 1 wt -.% Of tin (II) compounds, wherein the wt% based on the total weight of components I, II, III and IV refer. 609815/0613 1Φ. Means for carrying out the method according to claim 6, characterized in that this consists of I) 99.85 to 94.00 wt. a stabilized unsaturated polyester resin preparation consisting of 50 to Weight? unsaturated polyester and 50 to 20 wt. polymerizable monomers; II) 0.05 to 2 wt. lightfast fluorescent dye and / or lightfast fluorescent pigments on organic Basis, the percentages by weight being based on the total weight of components I, II and III; and III) (a) 0.1 to 4 wt. Benzoin ether and (b) a sub-combination of at least two different compounds of the three-bond Phosphorus, consisting of: (b ¹ ) 0.1 to 20 wt. organic esters of phosphorous acid with the general Formula JS - ■ -R ₁ ■ 0 - R ₂ (I) ', U 'Π-7 where R ₁ , R _? and R, can be the same or different and represent aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic radicals - however, one of the radicals R ₁ , R ₂ or R must always be an aromatic radical - and (b ") 0.05 to 2 Organic phosphine derivatives with the general formula (ID where R ₁ , R ₂ and R, can be identical or different and are aliphatic, cycloaliphatic, aromatic, araliphatic or 609815/0613 represent heterocyclic radicals - however, one of the radicals R., R ₂ or R must always be an aromatic residue, is composed. ■ / - 609815/0613