DE1931564A1 - Photochromic masses - Google Patents

Description

American Gyanamid Company, Wayne, New Jersey, V.St.A.

Photochromic masses

The invention relates to photochromic compositions that an IR absorber, a photochromic material and a self-supporting material, and to a method to generate a real-time image with these masses. The invention also relates to articles that (1) a photochromic Material that is photochromically effective when exposed to UV light at about 200 to about 420 nm, (2) a IR absorber that absorbs IR energy from a source ranging from about 0.7 to about 20 microns. and (3) contain a self-supporting pad!, where the photochromic material is in intimate contact with the IR absorber and the self-supporting base.

The use of photochromic substances as coatings or additives to plastics is known. These known systems are generally used as devices for the presentation of data and similar purposes, wherein

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• the photochromic material is irradiated with UV light in order to color the system as a whole or through to the system limited exposure to UV light to "write". The message or caption is then "deleted" by irradiate the system with visible light or keep it in the dark for a long time.

One difficulty that has been encountered is that the "erase" process is generally slow and that therefore the system used is not available for a further "labeling" for a long time. It's another one "Problem that the" lettering "is always" colored-on-white " are, d. H. the message appears as colored lettering on a white background.

A system has now been found which overcomes these two difficulties. In other words, when using the new compounds according to the invention, the “inscription” can be “erased” in a significantly shorter time than with the known systems. Second, the "writing" of the message or data on the system is done by IR radiation rather than the UV light or visible light previously used. The result is a ) "message" that is "white-on-color", a system that is more advantageous for many technical applications than the conventional systems mentioned above.

With the new system according to the invention, contrasting representations of information, for example a white symbol on a dark background, can be generated, a result which cannot be achieved with existing systems. Thus, the production of real-time data presentation systems for data processing _f for optical storage, computer, photographic masks and the like possible.

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Thanks to the novel combination of an IR absorber and of a photochromic material, the new masses can work by first irradiating them with UV light to "color" the photochromic material. The IR absorber can then use an infrared source, for example a Laser beam or a focused heating lamp while maintaining the colored state. This has the consequence that the IR absorber takes the energy out adsorbed by the IR source, converting it into heat and thereby the photochromic material bleaches. Since the photochromic material only has UV light and the IR absorber only has IR energy absorbed, the two systems do not compete with each other. With the help of the IR absorber, therefore, the IR energy converted into thermal energy. Since photochromic substances are bleached by heat, but not colored, the IR absorber leads effective aur bleaching (labeling) of the photochromic Materials, a result that cannot be achieved with the photochromic material itself. This interaction between the IR absorber and the photochromic material was not previously known, although ^ every component was already used individually or in other arrangements for other purposes.

The first essential component of the new masses is a photochromic material. For the purposes of the invention can generally; any photochromic material can be used, that in solution, d. H. in liquid or solid solution, photochromic is effective. Such photochromic materials are known, for example from US Pat. No. 3,304,180, in US Pat suitable photochromic substances are described both by class and individually. In the new masses according to the invention can generally use photochromic substances such as indanone oxides, the metal bisdithia zones, chromones, the xanthenones, the dibenzofuran dicarbonitriles and xanthene dicarbonitriles be used.

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The photochromic substances used must be exposed to ultraviolet light with a wavelength of around 200 nm

1 pm

up to about 420 nm (nm means nanometer; 10 ") photochromic be effective. The concentration of the photochromic material in the mass or the shaped body should be about 0.01 to about 50.0% by weight, preferably about 0.2 to about 20.0% by weight, based on the weight of the matrix in which it is is embedded.

The second essential component of the new compositions according to the invention is an IR absorber. As with the photochromic In general, any known IR absorber can be used.

The IR absorbers are only required to emit IR energy from a source ranging from about 0.7 to about 50.0 microns, preferably from about 0.72 to about 20.0 microns, for example Ruby lasers, neodymium glass lasers, thulium lasers, helium-neon lasers or nitrogen lasers. Amounts from about 0.01 to about 50.0% by weight, preferably from about 0.2 to about 20.0% by weight, based on the weight of the matrix to which the IR absorber is added, can be used.

Suitable IR absorbers are, for example, 1,4,5,8-tetracyclohexylaminoanthraquinone; N, N, N ¹ , N'-tetrakis (p-dibutylaminophenyl) -p-benzoquinone-bis- (imonium hexafluoroantimonate); Trie (p-diethylaminophenyl) aminium hexafluoroantimanate; N, K, N ¹ , N'-tetrakis (p-diethylaminophenyl) -p-benzoquinone-bis (ammonium hexafluorantimonate) and bis (p-diethylaminophenyl) (N _f N-biB- (ρ- "diethylaminophenyl) -p-aminophenyl ) aminiumhexafluorantimonat · These and / or other suitable IR absorbers are from the US patents 2,971,921, 3,000,833, 3,099,630, 3,251,881, 728,675, 739,444 and 742,266 known.

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As mentioned briefly above, the new compositions must be produced in such a way that the IR absorber is in direct contact with your photochromic material and the self-supporting base is present. For this purpose, the IR absorber (A) can be embedded in its own matrix and between them as well photochromic material contained in its own matrix and the self-supporting base are arranged, (B) alone be introduced into the base, which is then coated with the photochromic material in a plastic matrix will, (C) be introduced into the base together with the photochromic material or (D) with the pbotochromen Material mixed in a matrix and applied as a layer to the base.

For the purposes of the invention, the base can consist of a Any self-supporting material, for example one of the polymeric materials listed below or made of glass, paper, metal or wood.

The total thickness of the novel articles of the invention should be about 0.0127 mm (0.5 mil) to about 6.35 mm (1/4 "), each individual component itself being from about 0.0025 mm (0.1 mil) to about 3.2 mm (1/8 ") in thickness, if separate layers can be used.

It has been shown that the new items that beer are particularly suitable for displaying information or data. A ray of light is containing information sent to a recording medium, to keep the information in the beam for those who need it to represent. Therefore, the information-containing photochromic system must be colored with UV light and transmitted through V / poor from the IR system on which the information was imprinted has been bleached, permeable to visible light be when to display the information on a receiving device, for example a screen, projection method

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can be applied. W _e nn other hand, the representation of information by reflection method is carried out, only a color contrast, for example, black and white, between the photochromic and the background system, that must be available to the IR system and / or the backing.

The finished mass or article can be made by layering with each component (photochromic material - IR absorber - base) generated, and these with or without the help of an adhesive to one Laminate united. They can also be produced by successively laying layers on the substrate from the photochromic. System and the IR absorber system applies or introducing both the photochromic material and the IR absorber into the substrate before or after this is generated, for example, before, during or after the polymerization, if the substrate is made of a plastic consists.

The mass or the object should be free of other additives, for example UV absorbers, dyes or pigments, be free that affect the activity of the photochromic material or the IR absorber. On the other hand, substances which do not interfere with these components, are added.

As a self-supporting base or as a matrix for the IR absorber "or for the photochromic material or for all any synthetic or naturally occurring polymeric material can be used. Examples for polymers suitable for the purposes of the invention are described in more detail below.

Resin-like substances that can be used to produce the compositions or articles according to the invention are various esters. of acrylic acid and methacrylic acid, for

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Example those of the formula

CHo = CCOR ¹ R

wherein R is a hydrogen atom or a methyl radical and R denotes an alkyl radical having 1 to 6 carbon atoms. Compounds which correspond to the formula I and therefore as Monomers for the preparation of the purposes according to the invention Suitable polymers can be used are, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-amyl acrylate, isoamyl acrylate, tert-amyl acrylate, Hexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, Isopropyl methacrylate, n-butyl methacrylate, isobutyl methaorylate, tert-butyl methacrylate, n-amyl methacrylate; Ieoamyl methacrylate, tert-amyl methacrylate and hexyl methacrylate.

Other suitable polymers are polymers _; obtained from styrene monomers, for example those of the formula

, 2

(ID

2
wherein R represents a hydrogen atom or a lower alkyl radical having 1 to 4 carbon atoms and R represents a hydrogen atom, a lower alkyl radical having T to 4 carbon atoms or a halogen atom. Suitable monomers of the formula II are, for example, styrene, ο-, m- or p-methyl -, - ethyl ^ or "propylstyrene,

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ο-, m- or ρ-butylstyrene, ο-, m- or p-chlorostyrene, o-, m- or p-bromostyrene, o-, m- or p-fluorostyrene, o-, m- or p-iodostyrene, oc-methylstyrene, a-ethylstyrene, a ~ butylstyrene, a-methyl-o-, -m- or -p-ethylstyrene, a-ethyl-o- ^ -in- or »p-chlorostyrene and a-propyl-o-, -m- or p-iodostyrene.

Other polymers used to produce the new compositions or articles of the invention are, for example, polymers of acrylonitrile, "polymers of acrylamide, polymers of vinyl halides, for example polyvinyl chloride, polymers of vinylidene halides, for example polyvinylidene chloride, Polymers of vinyl carbonate, vinyl alcohol, vinyl acetate and vinyl butyral and various aldehydes, for Example of oxymethylene polymers, polymers of acetaldehyde and orotonaldehyde, polymers of ethylene oxide and Cellulosic polymers such as cellulose acetate butyrate, cellulose triacetate, and cellulose acetate propionate.

Furthermore, the monomers of the formula I and II _s which are suitable according to the above information for the production of homopolymers, either individually or multiply (2,3,4 or any desired number) ^ can be polymerized, multiple copolymerization is often appropriate to to improve the compatibility and the copolymerization behavior of mixtures of monomers of the same class, or be copolymerized with various other copolymerizable monomers in order to obtain copolymers with the properties which are desired for the respective application. Examples of such monomers as copolymers

S O 9 8 8 2/1 S 6 3

with the abovementioned monomers or even as homopolymers suitable for the purposes of the invention are the esters of unsaturated alcohols, especially the allyl, methallyl, 1-chloroallyl, 2-chloroallyl, Cinnamyl, vinyl, methvinyl and 1-phenylallyl esters of saturated aliphatic and aromatic, monobasic and polybasic acids, for Example of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oxalic acid, malonic acid, Succinic acid, glutaric acid, adipic acid, pimellic acid, suberic acid, azelaic acid, sebacic acid, benzoic acid, Phenylacetic acid, phthalic acid, terephthalic acid, benzoylphthalic acid and similar acids, also vinyl naphthalene, Vinylcyclohexane, vinylfuran, vinylpyridine, vinyldibenzofuran, vinylbenzene, trivinylbenzene, allylbenzene, Diallylbenzene, N-vinylcarbazole, unsaturated Ethers, e.g. ethyl vinyl ether, diallyl ether and ethyl methallyl ether, unsaturated amides, e.g. N-allylcaprolactan, W-substituted acrylamides, e.g. N-methylolacrylamide, H-methylacrylamide and N-phenylacrylamide, unsaturated Ketones, e.g. methyl vinyl ketone and methylally! Ketone, and methylene malonic esters, e.g., methylene methyl malonate.

Can be thermoplastic or thermosetting polyester can also be used for the purposes of the invention. These polyesters are well known and are produced by reacting polycarboxylic acids or their anhydrides with polyhydric alcohols Curable polyesters are obtained by a process in which at least one of the reactants is α, β-ethylenically unsaturated. According to these procedures resin-like, essentially linear solidification or condensation products are obtained which have a large number of ethylenically unsaturated bonds that are distributed along the length of the backbone of their polymer chains.

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The use of α, β-ethylenically unsaturated polycarboxylic acids provides a convenient means of introducing ethylenically unsaturated sites into the Polyester resins. Preferably, α, β-ethylenically unsaturated dicarboxylic acids, e.g. maleic acid, fumaric acid, Citraconic acid, γ, γ-diniethylcitraconic acid, mesaconic acid, Itaconic acid, a-methylitaconic acid, γ-metbylitaconic acid, or teraconic acid, as well as mixtures thereof, but smaller amounts of α, ß-ethylenic can also be used unsaturated polycarboxylic acids, "the three or contain more Carbomy! groups, e.g. Aconitic acid, together with the α, β-äthylenisc'h unsaturated dicarboxylic acids used in the individual case will.

The acids can be replaced entirely or in part by the anhydrides the abovementioned α, β-ethylenically unsaturated polycarboxylic acids are replaced when such anhydrides are available are.

Any polyhydric alcohols from the large class of these compounds commonly used in the preparation of reactive polyester resins can be used for the purposes of the present invention. Dihydric alcohols and particularly saturated aliphatic diols are preferred as co-reactants for the production of the polyester resins, but it is not absolutely necessary that the total amount of the polyols used consists of such alcohols, since small amounts of polyols with more than two hydroxyl groups, e.g. amounts, up to about 10 fo the total equivalent of hydroxyl groups in the esterification mixture amount can be usually used. The dihydric alcohols that can be used include saturated all- "phatic diols, for example ethylene glycol, propylene glycol,

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Butylene glycol, dietbylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, I-pentanediol, 4 ₉ pentanediol 1,5, hexanediol-1,2, hexanediol-1,3, hexane <3iol ™ 1 ₉ 4, hexanediol-1,5, hexanediol-1,6 and neopentyl glycol and mixtures thereof. The polyols with more than two hydroxyl groups, which can be used in small amounts together with the above-mentioned diols, include saturated aliphatic polyols, aB »glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, arabitol, xylitol, dulcitol, adonitol, sorbitol and mannitol and mixtures thereof.

To prepare the thermoplastic polyester resins used for the purposes of this invention, the above-mentioned alkynols with non-polymerizable polycarboxylic acids, do h _e are acids, which are saturated or only benzenoid unsaturation, such as oxalic acid, malonic acid, succinic acid, glutaric j adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid , Malic acid, tartaric acid, tricarballylic _{acid s} citric acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid and endomethylenetetrahyrophthalic acid or mixtures thereof.

These saturated acids can be used alone in the manufacture of thermoplastic resins or in combination with the above-mentioned unsaturated acids for the production of. curable haraen are used to make these many to give favorable properties. For example, one can use non-polymerizable polycarboxylic acids that only have two Contain carboxyl groups and no other reactive substituents to achieve an advantageous degree of flexibility, by using the α, β-ethylenically unsaturated Polycarboxylic acids cannot be used, their amount being at least about 20 #, however

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should not boxy more than about $ 80> of the total equivalent of Car "! groups in the esterification mixture account. Preferably, the total equivalent of carboxyl groups are used in the esterification mixture to about 75 i <> such non-polymerizable dicarboxylic acids in amounts of about 25.

Halogenated unsaturated polycarboxylic acids can also be used to prepare the suitable for the present purposes * curable polyester, so get these various advantageous properties as f above in connection with the saturated sow were called reindeer. Examples of suitable halogenated acids are monochloro and monobromomaleic acid, monochloro and monobromofumaric acid, monochloro and monobromomalonic acid, dichloro and dibromomalonic acid, monochloro and mono bromosuccinic acid, α, β-dichloro and dibromosuccinic acid or hexachloroendomethylenetrophthalic acid and their hexachlorendomethylenetrophthalic acid. These halogenated acids can also be replaced in whole or in part by their anhydrides, if these are available.

Among the halogenated polyols _f used "may include 2,2'-Chlormethylpropandiol-I, 3» adducts of hexachlorocyclopentadiene with unsaturated polyols such as butenediols or Pentendiolen, and adducts of hexachlorocyclopentadiene with polyols having 3 or more hydroxyl groups, one of which is etherified with an unsaturated alcohol which is able to react with hexachlorocyclopentadiene. Examples of the last-mentioned adducts are 3- <Λ, 4,5, -6,7,7-hexachlorobicycle- (2.2.1) -5-hepten-2-yloxy / -1,2-propanediol, ie the adduct of hexachlorocyclopentadiene with vinyl glycerol ether, 3- ^ J, 4.5 »6» 7,7-hexachlorobicyclo- (2 _e 2.1) -5 ~ hepten-2-yl7-methoxy ~ 1,2-propanediol, ie the adduct of hexachlorocyclopentadiene with allyl glycerol ether and Adducts of hexachlorocyolopene

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tadiene with pentaerythritol vinyl and allyl ethers. Mixtures these halogenated polyols can also be used if necessary.

The esterification mixtures that make up both the thermoplastic as well as the curable polyester resins which are suitable for the purposes of the invention are generally formulated to have at least a stoichiometric equilibrium contain between carbonyl and hydroxyl groups. So if a diol and a dicarboxylic acid are used, they are usually reacted in a molar ratio of at least 1: 1. In practice it becomes common a small excess of polyol, usually from about 5 to about 15 # excess, is mainly used for economic reasons, d. H. to achieve a rapid rate of esterification.

Both types of polyester resins used for the purposes of the present invention are conventionally used generated. Thus, the polycarboxylic acid or the polycarboxylic acids and the polyol or are used in the individual case the polyols reacted at elevated temperatures and atmospheric pressure. As resin-forming participants in the heaps of this type tend to undesirable discoloration when they come into contact with air at higher temperatures, it is generally advisable to carry out the esterification reaction in an inert atmosphere, e.g. by introducing a Inert gases such as carbon dioxide or nitrogen in the esterification mixture, to carry out «The heating temperature is not critical. The implementation will therefore preferably carried out at a temperature usually just below the boiling point of the most volatile Component of the reaction mixture, generally the polyol, lies.

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The esterification mixture should be implemented to such an extent that finally a polyester resin has an acid number is obtained which is not significantly above 75 «Preferably polyester resins with acid values in the range from about 30 to about 50 or less is used.

Further details of the production of polyester resins as used for the purposes of the invention include U.S. Patents 2,255,313 and 2,443

to 2 443 741. .

The curable ones used for the purposes of the invention Polyester resins can be crosslinked by adding a suitable crosslinking agent.

The curable polyester resins are crosslinked by mixing with a monomeric compound which contains the polymerizable group OH ₂ = ^ C ^ to form a mass which can be cured to a stable thermoset state. One can apply about 10 parts by weight of the monomer to about 90 parts by weight of the polyester resin up to about 60 parts by weight of the monomer to about 40 parts by weight of the polyester resin. Preferably, however, about 25 to about 35 parts of the monomer are employed with about 75 to about 65 parts of the polyester resin.

The monomer that can be used for the purposes of the invention and which contains the polymerizable group GIL) = 0 ^ "has a boiling point of at least 60 ^° C. The polymerizable monomeric substances that can be used for the purposes of the invention include styrene in the side chain alkyl- and halogen-substituted styrenes, e.g. α-methyl styrene, cc-onlor styrene and α-ethyl- <styrene or in the ring alkyl- and halogen-substituted styrenes, e.g. o-, m- and p-alkylstyrenes, such as o-methylstyrene, p- itbylstyrene, m-propylstyrene, 2,4-dimethylstyrene,

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2,5-diethylstyrene, bromostyrene, glorostyrene and dichlorostyrene. Allyl compounds can also be used, for example diallyl phthalate, tetrachlorodiallyl phthalate, allyl alcohol, metballyl alcohol, allyl acetate, allyl tfaacrylate, diallyl carbonate, allyl lactate, allyl-oc-hydroxyisobutyrate, allyl trichloro-allylate, allyl trichloro-allylate, allyl-allylate, allyl-allylate, diallyl-malally diallyl _f Diallylcitraconat, the Muconsäurediallylester, diallyl! taoonat, Diallylchlorphthalat, diallyldichlorosilane, the diallyl ester of endomethylenetetrahydrophthalic, the diallyl ester of Tetrachlorendomethylentetrahydrophthalsäureanhydrid silicate, triallyl, triallyl, triallyl, triallyl citrate, triallyl phosphate, Trimethallylphosphat, Tetrallylsilan, Tetrallylsilicat or Hexallyldisiloxan. This monomeiuu Verbindmigen can either be used singly or in combination rniteinanäer _o

Furthermore, according to the invention, cyanoethylated cellulose derivatives, such as those obtained, for example, from the cellulose of wood pulp or wood fibers, G-cellulose flakes, viscose, cotton linters, jute, ramie or linen in forms such as fibers, yarns, fabrics or raw material, can be used in the new compositions according to the invention, be used. In general, substances of this type have a nitrogen content as high as 13 % and a degree of substitution of up to about 3 after cyanoethylation with the aid of various known processes. A nitrogen content of at least 10 $ and a corresponding degree of substitution of about 2 _f 3 is generally considered to be an average. Processes for making such materials, as well as the products themselves, are known from U.S. Patents 2,375,847, 2,840,446, 2,786,736, 2,860,946 and 2,812,999.

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More examples of polymeric substances that are used to produce of the new compositions or articles which can be used according to the invention are the polyamide resins, i. hey those made from a dibasic acid and a polyamine. Polyamide resins of this type are known and are commonly called "NyIon" resins designated. These nylon resins, also called herein, are long chain synthetic polymers Amides, the repeating amide groups as integral Contain part of the main polymer chain and are able to form threads. Most of these nylons or polyamides are made by condensing a diamine with a Dicarboxylic acid or obtained by autocondensation of an amino acid. These polyamides have the structure

(III) (..NH (CH ₂ ) NHCO (CH ₂ ) CONH (CH ₂ ) _x ..)

where χ and y are greater than 1. Methods of making polyamides of this type are for example cited in the following U.S. patents: 2,191,556, 2,293,760, 2,293,761, 2,327,116, 2,359,877, 2,377,985 and 2,572,843.

Polymeric substances such as polyurethanes can also be used. For the purposes of the invention, any Polyurethane resins based on polyester or polyether suitable. The reactive organic polyfunctional polyols that are used for the production of a for the invention Purpose-suitable class of polyurethane resins by reaction with a suitable isocyanate compound are used include the polyalkylene ethers, thioether and »ether thioether glycols of the general formula

(IV) HO (R ¹⁵ X ¹ ) "" H

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1 '1
wherein K gloioho or voruohiodono alk-ylene radicals with up to about 10 carbon atoms, X is oxygen or sulfur and ζ is an integer with such a high value that the molecular weight of the polyalkylene ether, thioether or ether thioether glycol is at least about 500, for example about 500 to is about 10,000. Of the compounds that fall under this general formula, the polyalkylene ether glycols, for example polyethylene glycols, polypropylene glycols, polybutylene glycols, polytetramethylene glycols or polyhexamethylene glycols, for example acid-catalyzed condensation of the corresponding monomeric glyoxides or propylene oxide with one another, e.g. or with glycols such as ethylene glycol or propylene glycol are preferred.

Polyalkylene arylene ether, thioether and ether thioether glycols, which also have molecular weights from about 500 to about 10,000, but are different from those above

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. differentiate the described polyalkylene glycols by that they contain arylene radicals, e.g. phenylene, uaphthylene or anthrylene radicals, which are either unsubstituted or substituted may be, e.g., through alkyl or aryl groups, in place of some of the alkylene radicals of these polyalkylene glycols can also be used. Polyalkylenearylene glycols of the kind they are usually used for this purpose usually contain at least one alkylene ether radical with one Molecular weight of at least 500 per arylene radical.

' Virtually linear polyester, which is a variety of

Containing isocyanate-reactive hydroxyl groups form another class of reactive organic polyfunctional polyols which can be used for the preparation of polyurethane resins which are suitable for the purposes of the invention. The production of Ι polyesters which are suitable for this purpose is described in detail in the literature and does not form part of the invention, but for explanation it should be mentioned at this point that polyester of this type is produced by condensation of a polyhydric alcohol with a Polycarboxylic acid or an anhydride thereof can be prepared in the same manner as has been described above in the context of the explanation of polyester resins suitable for the purposes of the invention, it being possible in both cases to use the reactants mentioned above as examples. The substantially linear polyesters commonly used to make polyurethane resins preferably have a molecular weight of from about 750 to about 5,000. In addition, they generally have: relatively low acid numbers, for example not essential; lent acid numbers above 60 and preferably so

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low acid numbers, as can be achieved in practice, for example of 2 _% or less. Accordingly, they generally have relatively high hydroxyl numbers, for example from about 30 to about 700. In the manufacture of these polyesters, an "excess of polyol" over polycarboxylic acid is generally used so that the resulting essentially linear polyester chains contain a sufficient number of reactive hydroxyl groups.

The polyurethane resins which are suitable as a constituent of the new compositions or articles according to the invention can be prepared using numerous organic polyisocyanates, including aromatic diisocyanates, for example "m-phenylene diisocyanate, p-phenylene diisocyanate, 4-tert-butyl-m -pbenylene diisocyanate, 4-metboxy-m-phenylene diisocyanate, 4-phenoxy-m-phenylene diisocyanate, 4-chloro-m-phenylene diisocyanate, tolylene diisocyanate (either as isomer mixtures, see the commercially available mixture of $ 80> 2,4-tolylene diisocyanate and 20 generally 2,6-toluene diisocyanate or in the form of the individual isomers), m-xylylene diisocyanate, cumene-2,4-diisocyanate, durene diisocyanate, 1,4-liaphthylene diisocyanate, 1,5-naphthylene diisocyanate, 1,8-naphthylene diisocyanate, 2,6- Caphthylene diisocyanate, 1,5-tetrahydronaphthylene diisocyanate, p ^ '- diphenyl diisocyanate, diphenylmethane-4,4'-diisocyanate, 2,4-diphenylhexane-1,6-diisocyanate, "bitoluylene diisocyanate"(3,3' -dijnethyl-4,4 ' -biphenylendixsocyanat), "Dianisidindiisocya nat "(3,3'-dimethoxy-4,4 ^I -diphenylene diisocyanate) and polymethylene polyisocyanates of the general formula

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N = C = O

F = O = O

in which b is an integer between 0 and about 5, aliphatic ^ diisocyanates, e.g. methylene diisocyanate, ethylene diisocyanate, the tri-, tetra-7, penta-, hexa-, hepta-, octa-, nona- and decamethylene diisocyanates, 2-chlorotrimethylene diisocyanate and 2,3-Dimethyltetramethylene diisocyanate and triisocyanates and higher isocyanates, for example benzene-1,3,5-triisocyanate, tolylene-2,4,6-tx'iisocyanate, diphenyl-2,4,4'-triisocyanate and triphenylmethane-4,4 ¹ , 4 "triisocyanate. Mixtures of two or more of these organic polyisocyanates can also be used to produce the polyurethane resins by reaction with the ethers and esters described above by known processes, such as those described, for example, in U.S. Patents 2,729,618 and 3,016,364 are used.

Aminoplast resins are also suitable for the purposes of the invention. These substances are synthetic resins, by condensation of an amino compound (including Imino compounds) or amido compound (including imino compounds) with an aldehyde will. Resin condensates of this type and processes for their production have been described many times. Further details can be found, for example, in U.S. Patents 2,197,357, 2,310,004, 2,328,592 and

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. 2'26D 239. aminoplast resins, in .denen one or more Aminotriazines with at least two amide-forming groups, each of which has at least one aldebyd-reactive, amide-forming nitrogen atom bonded hydrogen atom e.g. melamine, with an aldehyde, e.g. formaldehyde, to form a curable resin condensate implemented, d. H. a product in which the condensation is carried out up to an intermediate level is, as a result of which it remains soluble or easily dispersible as a resinous substance in aqueous systems, but also the ability to convert into a practically insoluble and infusible form under suitable conditions for warmth and druok retains are preferred.

Melamine is the preferred aminotriazine for the preparation of the thermosetting or potentially thermosetting partially polymerize resinous aminotriazine-aldebyd reaction products which are suitable for the purposes of the invention, but other aminotriazines, for example mono-, di- and trisubstituted melamines, for example the Mono-, di- and trimethylmelamines, guanamines, for example formoguanamine, aoetoguanamine or benzoguanamine, and mixtures of such aminotriazines can be used as reactants. Also, formaldehyde, preferably in aqueous solution, the aldehyde is preferred as a reactant, it can ¹ but other aldehydes such as acetaldehyde, propionaldehyde, or butyraldehyde, or compounds releasing aldehyde are used, for example paraformaldehyde or hexamethylenetetramine. The properties required of the finished products and economic considerations are among the factors that determine the choice of aminotriazine and aldehyde used in each individual case.

Sf dtf ΙΪ2 / 15 6 3

The Mo! Ratio of aldehyde to aminotriazine in such resinous reaction products is not critical and can vary depending on the nature of the starting materials and the desired properties of the end product are on the order of about 1 ^ 5j1 to about 4 s 1, however, the molar ratio is preferably about 2-1 to about 5: 1.

For the preparation of aminotriazine Aldenyd resins usual reaction conditions are used, ie, the aldehyde and the aminotriazine can under heat at temperatures of about 40 ⁰ G to Rückflußtemperatür, ie, about 100 ⁰ C, for a time of about 30 to 120 minutes at a pH in the range of about 7 »0 to 10, preferably in an aqueous medium. To control the pH, any substance can be used which gives acidic or alkaline aqueous solutions, for example alkalis such as alkali or alkaline earth oxides, for example sodium or potassium carbonate, mono-, di- or trialkylamines, for example ethanolamine, triethylamine or triethanolamine , and alkylene polyamines or polyalkylene polyamines, for example 3,3'-iminobispropylamine.

Furthermore, further amido or imido connections which contain at least two aldehyde-reactive hydrogen atoms bonded to amide-forming nitrogen atoms can be used in addition to the aminotriazines for the production of the aminoplast resins suitable for the purposes according to the invention. For example, one can use such urea and derivatives thereof, which are commonly used for the preparation of aminoplast resins, "for example, the alkylureas, for example, mono- and dimethyl or halogen urea.

903802/1563

Optionally, the properties of the thermosetting aminoplast resins can be improved by introducing various other substances in the aminotriazine-aldehyde resin can be further modified. Such substances include for example plasticizers such as the a-alkyl glucosides, for example cc-methyl-E-glucoside, which is described in the United States patent 2,773,848, methylol derivatives of the general formula

R ⁴ (VI) R ³ -XN-CH ₂ OH

where R ^{5 is} an alkyl radical, aryl radical or aralkyl radical, R ^{4 is} a hydrogen atom or an alkyl radical, alkylol radical, aryl radical or acyl radical and X is the group -SO ₂ - or -C-, for example N-methylol-p-toluenesulfonamide (which can be added by adding can be generated in situ from p-toluenesulfonamide to an amidogen-formaldehyde reaction mixture) or combinations of these glucosides and methylol derivatives, for example a mixture of oc-methyl-D-glucoside and p-toluenesulfonamide, as described in US Pat. No. 2,773 788 is described.

The invention is further illustrated by the following examples explained. Parts and percentages are based on weight, unless otherwise stated.

Example 1 Manufacture of IR film

79 parts of a solvent mixture of toluene and methyl ethyl ketone and ethyl alcohol (90: 5: 5) are placed in a mixing vessel that contains as much polyethylene methacrylate

909882/1563

contains that a solution with a P _e material content of 21 # is obtained. '1 # N, N, N ¹ , üf'-TetrakisCp-dibutylaminophenylJ-p-benzoquinone bis (iminonium hexafluoroantimonate) is then added to this solution. Then a Piim on a 3.2 mm is 0/8 ") thick sheet of Polyäthylenglycolterephthalat cast from the resulting solution. The film is 10 minutes at 60 ⁰ O to a thickness of about 0.013 mm dried mil) (0.5.

Manufacture of an object with an IR absorber and p_hoto-

chrome material ■ - '- "

80 parts of the same solvent mixture as above (80 ί 10:10) are placed in a mixing vessel which contains enough polyethylene methacrylate to achieve a pesticide content of 20 io . 7.0 $ 1 ', 3', 3'-trimethyl-ö-nitro-S-methoxyspiro (2H-1-benzopyran-2,2'-indoline) is added to the solution obtained. This solution then becomes a PiIm on the IR layer side of the Pormkörper produced above. poured and 10 minutes at 60 ⁰ O a 0.015 mm (0.6 mil) thick Piim dried.

909882/1563

The side with the second layer (photochromic side) of the molded body obtained is then irradiated with ultraviolet light. The shaped body changes from a colorless, water-white state to a deep blue state. Then the same side of the shaped body is irradiated with a 1.06 laser beam (neodynium source) in a certain pattern. The blue dye® bleaches out at the points that the laser beam hits as a result of the heat generated by the IR material in the middle layer of the molding ₉ . This fading has the consequence that the pattern becomes visible as a "message" white-on-blue. Projection through a lens onto a large screen gives a real time representation of information.

Following the procedure of Example 1, numerous objects or moldings with different ZR absorbers, photocbromic materials and polymeric matrices. The results are in the following. Tabel specified.

909Ö8271563

Tabel

example

IR absorber In
Matrix (Movie A)

Photochromic material in matrix (film B)

Film of 10 # piIm from 20 # (solid (Feetatofi content) solvent content) solution of polysation of cellulose styrene in methylene chloride acetate butyrate in methyl with 12% 2,3-diphenyl-1-ethylketoG- acetone (80:20) indenonoxid i on film A overall with 2 * bis (p-diethyl poured, aminophenyl \ $, N-bi s (ρ- diäthylaminophenylTaminiumhexafluorarsenat on
Cast base.

reinforcing
document

Polymethyl

methacry

lat

Results

"Write on" when exposed to UV radiation with a laser and projection onto a screen becomes excellent Get real-time image.

Film from 15 $ (solids content) solution of
Cellulose acetate propionate
in ü) oluene-lthanol (80: 5)
with 5 $> 5 »$ - 3is (dimethylamino) -9-phenylfluoren-9-olecnlorozincate poured onto a base.

Film of 30 $ strength (solid content) painted solution of polyvinyl chloride in methyl ethyl ketone with 8 $> Quecksilberbisdithiazon on film A.

Polyethylene

glycoltereph-

thalat

Film of 10% (solids content) solution of Po ^
Iyvinyl chloride in methyl ethyl ketone isopropyl alcohol '' (90:10) with 1 % mangano
complex of 5 * dimethylamino-2.-nitrosophenj3l poured onto a base.

Film made of hardened, dry polyester free of residual acid (maleic anhydride-phthalic anhydride-propylene glycol t5.1 / 46.2 / 38.7) and styrene crosslinker with 15 fo tetrahydro-anaphthylaminocamphor on film A.

CO CO

cn

Table (continued)

Example: IR absorber in play matrix (film A) Photochromic material
in matrix (film B)

stiffening pad

Results

O CO OO CD

Mixture of 1 fi ferro-1 ^ -naphthoquinone2-oximate and 8 $> pararosaniline cyanide to 10 $ (solid content) solution of commercially available clear polycarbonate and methylene chloride and poured onto a base (mixture of IR absorber and photochromic ^ material in one Movie). Glass

When irradiated with UV light, "label" with a laser and projection on a screen, an excellent real-time image is obtained.

Molding made of pigmented (T102) melamine-formaldehyde resin (molar ratio of melamine to formaldehyde 1: 2) with 4 1 ° absorber according to Example 1 and a base bonded with adhesive. $ 28 polymethyl film

(Solids content) solder methacrylate

solution of polymethyl meth-

crylate in benzene with

10 io hexamethyltris (p-

aminophenyl) carbinol

cast on film A. Projection on screen by reflection method .

Hardened film made of polyurethane resin based on polyester (NCO content 3.4 #) and 3 5 »absorber according to Example 2 on a base.

like example 3 white paper

like example 2

as in Example 2, but with cellulose acetate butyrate. Polyethylene glycol terephthalate

like example

Table (continued)

to ο α »co α»

IR absorber in matrix (film A)

as in example 4; 3.2 mm (1/8 ") thick layer of photochromic material stiffening in matrix (film B) backing

like example 4, however
3.2 mm (1/8 ") thick
Layer of polyvinyl chloride

Results

no

When irradiated with UV light, "labeling" with a laser and projection on a screen becomes excellent real-time image. obtain.

10

as in example 3 as in example 3, however

Cellulose acetate

pioneer

no

11th

as in example 5, but 3.2 mm (1/8 ") thick cast layer as in example 5

no

Claims (1)

Claims \ 1./Photochromic masses or moldings, characterized by (1) a photochromic material that is photochromically effective when exposed to UV light from about 200 to about 420 nm is, (2) an IR absorber, the IR energy from a Absorbs source emitting in the range of about 0.7 to about 20 microns, and (3) a self-supporting one. Underlay, the photochromic material being in intimate contact with the IR absorber and the self-supporting Pad is located. 2. mass or shaped body according to claim 1, characterized in that the IR absorber is embedded in a matrix ' is that as a layer between the self-supporting base and a layer of a matrix with photoobroaem Material is arranged. 3. mass or shaped body according to claim 1, characterized in that both the IR absorber and the photochromic material dispersed in the base (3) are. 4. mass or molded body according to claim 1, characterized in that that it contains a benzospiropyran as a photochromic material. ι 5. mass or molding according to claim 1, characterized in that that the self-supporting base made of polyethylene glycol terrephthalate consists. 6. mass or molded body according to claim 2, characterized in that that any matrix made of polyethylene methacrylate consists. - ORIGINAL INSPECTED 908882 / 1S63 • 7. Composition or molding according to claim 1, characterized in that the IR absorber consists of Ν, Ν, Ν ¹ , IT ^I -Tetrakis- "(dialkylaminopbenyl) -p-benzoquinone-bis (iπlmoniumhexahalogenantimonat"). 8. A method for generating a real-time image, characterized in that one (A) irradiates the mass or the object according to claim 1 with ultraviolet light, (B) by irradiating the mass or the object with an information-containing light beam from a source in the Emitted in the region of about 0.7 to about 50.0 microns, the information is imprinted on the component (1) according to claim 1 and (C) the information thus transmitted is transmitted to an information receiving and imaging device. 9. The method according to Anipruoh 8, daduroh characterized in that the transmission durob projection takes place. 10. The method according to claim S _9, characterized in that the transmission takes place duroh reflection. ORJQtNAL INSPECTED 8O90S2 / 1583. !