KR100993559B1 - Compositions for Making Insulating Coatings - Google Patents

Abstract

The present invention relates to a composition for making an insulating coating comprising at least one radiation-absorbing compound and at least one IR reflecting component. The invention also relates to a thermally insulative coating comprising the aforementioned oriented and cured composition and a method for producing the same.

Description

COMPOSITION FOR PRODUCING A THERMAL INSULATION COATINGS

The present invention relates to a composition for producing an insulating coating comprising at least one radiation-absorbing compound and at least one IR reflecting component, an insulating coating comprising such an oriented and cured composition and a method for producing the coating.

The problem of blocking against thermal radiation is an important issue in relation to residential, office or industrial buildings, especially in buildings with very wide windows, and also in connection with vehicles such as automobiles and public transport.

It is known to use materials which substantially reflect heat radiation for thermal insulation, in particular for blocking heat radiation in the wavelength range between 800 nm and 2000 nm. These materials can be, for example, cholesteric IR-reflective layers.

When a material exhibiting shape anisotropy is heated, it is possible for a liquid crystal phase, known as mesophase, to occur. Individual phases, on the other hand, differ in the spatial arrangement of the centers of molecular masses corresponding to the longitudinal axis (G.W. Gray, P.A. Winsor, Liquid Crystals and Plastic Crystals, Ellis Horwood Limited, Chich Ester, 1974).

The nematic liquid crystal phase has an orientation parallel to the vertical axis of the molecule (one-dimensionally ordered), provided that if the molecule forming the nematic phase is chiral, the result is that the longitudinal axis of the molecule is perpendicular to it. A chiral nematic (cholesteric) phase that forms a helical superlattice structure. The distance between two imaging layers with the same orientation of the longitudinal axis of the molecule is known as the pitch.

The chiral moiety can be present in the liquid crystal molecule itself or can be added to the nematic phase as a dopant, thus inducing a chiral nematic phase. This phenomenon was first studied on cholesterol derivatives (eg, B. H. Baessler, M. M. Labes, J. Chem. Phys. 52,631 (1970)). The wavelength range of the pitch and thus the radiation of the selectively reflected chiral nematic layer can be varied by varying the concentration of the chiral dopant.

Chiral nematic phases have special optical properties: significant circular dichroism and high optical rotation resulting from the selective reflection of circularly polarized light within the chiral nematic layer. This type of chiral nematic system has interesting possibilities for practical use.

Transparent thermal insulation coatings are known. EP-A-727306, for example, describes laminated glass consisting of two glass plates and an interlayer in which ultrafine particles are dispersed. Interlayers are used for thermal insulation and UV absorption.

JP-A-281403 / 92 describes a laminate consisting of a transparent plate, a coating that reflects IR radiation over a wide range of wavelengths, and a cholesteric liquid crystal wavelength filter that selectively reflects near infrared wavelengths and transmits significant amounts to visible light. Doing.                 

 DE-A-19817069 describes an IR-reflective coloring composition consisting of an IR-reflective cholesteric liquid crystal polymer and a light absorbing colorant. Colorants are defined as compounds having a maximum absorption in the 350 to 750 nm range. The use of IR-absorbing components is not mentioned.

WO-A-99 / 19267 describes thermal insulation coatings consisting of one or more cholesteric IR-reflective layers. The coating is transparent and colorless. However, efficient thermal insulation can be obtained by using a plurality of cholesteric layers.

It is an object of the present invention to provide an insulating coating which is as efficient, pale as possible and as thin as possible.

We have found that this object is achieved by a composition for producing an insulating coating comprising:

i) at least one radiation-absorbing tert-alkylphenoxy-substituted polycyclic compound A of general formula (I)

here                 

P is a conjugated polycyclic radical that is stable to base and nucleophile, optionally contains aryl substituents and any airway from the group consisting of -CO-NH-CO-, -COOH and -CO-O-CO- Does not contain;

R is C ₁ -C ₈ -alkyl and its carbon chain is selected from one or more groups selected from the group consisting of —O—, —S—, —NR ¹ —, —CO— and —S0 ₂ — A group consisting of C ₁ -C ₆ -alkoxy and 5- to 7-membered heterocyclic radicals which may be intermittent and linked via a nitrogen atom and may further contain hetero atoms and / or be aromatic May be mono-substituted or multi-substituted by the same or different radicals selected from; Or R is C ₅ -C ₈ -cycloalkyl and its carbon skeleton is one or more selected from the group consisting of -O-, -S-, -NR ^1- , -CO- and -S0 _2- May be interrupted by groups and may be mono- or multi-substituted by C ₁ -C ₆ -alkyl;

R ¹ is hydrogen or C ₁ -C ₆ -alkyl;

Hal is chlorine or bromine;

m is 0 to 15; And

n is 1 to 16, provided that the sum of m + n is ≤ 16

And                 

ii) at least one curable IR-reflective component B comprising

a) at least one achiral nematically polymerizable monomer and at least one chiral polymerizable monomer;

b) at least one cholesteric polymerizable monomer;

c) at least one cholesteric crosslinkable polymer: or

d) at least one cholesteric polymer in a diluent that can be polymerized.

The IR-reflective properties of component B, after the orientation and curing of component B, at least part of the oriented cholesteric polymer obtainable by polymerizing monomers a) or b) or at least of the oriented polymer c) or d) This is due in part to having a helical superlattice pitch that corresponds to wavelengths in the IR spectral range.

In the context of the present invention, cure means both polymerization of monomers and crosslinking of polymers.

The radiation-absorbing compound A has an infrared (IR) spectral range, ie, a wavelength having a wavelength of> 750 nm to about 1 mm, preferably 751 nm to about 2000 nm, and / or a visible light spectral range, ie 350 to 750 nm , Preferably those absorbing in the spectral range having a wavelength of 550 to 750 nm, and / or in the ultraviolet (UV) spectral range, ie in the spectral range having a wavelength of 10 to <350 nm, preferably 100 to 349 nm. do. Preferably, compound A absorbs an infrared spectral range, specifically 751 to 2000 nm, and / or a visible light spectral range, specifically 550 to 750 nm. Particularly preferably Compound A absorbs the infrared spectral range, in particular 751 to 2000 nm, and / or the visible light spectral range, specifically 550 to 750 nm.

Compound A can be used as a pure substance or as a mixture of positional isomers or as a mixture of pure substances.

Compound A of Formula I is described, for example, in PCT application PCT / EP 02/03279 and is based on conjugated polycyclic radicals P which are stable to base and nucleophiles under reaction conditions. Specifically, the radical P does not contain any airway from the group consisting of -CO-NH-CO-, -COOH and -CO-O-CO-.

P is an aryl substituent that resists base attack, such as unsubstituted or alkyl- and / or alkoxy-substituted aryl, in particular phenyl, or hetaryl such as 2-, 3- and 4-pyridyl and pyrimidyl ). These aryl substituents may be linked directly to the ring structure or, in the case of the polycyclic imides mentioned below, to imide nitrogen atoms.

Tert-alkylphenoxy radical (s), such as the aryl-substituted radical P, may also be substituted via an aryl substituent, such as diphenyldiketopyrrolopyrrole or N, N'-diphenylperylene-3,4: 9,10 In the case of -tetracarboxylic diimides it may be linked to P via the 4- or 3,5-position of the phenyl radical.

Preferably, P is a base stable radical, naphthalene, anthracene, phenanthrene, tetracene, perylene, terylene, quaterylene, pentaryl and hexaylene, anthraquinone, indantron, N-substituted naphthalene-1,8 -Dicarboxylic monoimide (abbreviated herein as naphthalmo noimide), N, N'-disubstituted naphthalene-1,8: 4,5-tetracarboxylic diimide (abbreviated as naphthalimide) ), N-substituted perylene-3,4-dicarboxylic monoimide (abbreviated as peryl monoimide), N, N'-disubstituted perylene-3,4: 9,10-tetracarboxylic Diimide (abbreviated as perylimide), N, N'-disubstituted terylene-3,4: 11,12-tetracarboxylic diimide (abbreviated as terylimide), N, N'-disubstituted quaterylene -3,4: 13,14-tetracarboxylic diimide (abbreviated quaterylimide), acridine, carbazole, dibenzofuran, dinaphthofuran, benzimidazole, benzthiazole, Phenazine, dioxazine, quinacridone, metal phthalocyanine, metal naphthalocyanine, metal porphyrin, coumarin, dibenzofuranone, dinaphthofuranone, benzimidazolone, indigo compound, thioindigo compound, quinophthalone, naphthoqui Nophthalone and diketopyrrolopyrrole.

Particularly preferred in P are naphthalene, quinacridone, diketopyrrolopyrrole, dioxazine, indanthrone, metal phthalocyanine, metal naphthalocyanine, naphthalomonoimide, perylomonimide, perrylimide, terrylimide and quarteryl Very particular preference is given to the group consisting of meads, and metal phthalocyanines, metal naphthalocyanines, metal porphyrins, terrylimides and quaterylimides. From these, quateryl imide is especially preferable.

The tert-alkylphenoxy radicals characterized by compound I and also further any halogen atoms present may be directly or, as mentioned above, connected to the ring structure of the radical P via any aryl substituent. Two forms of linkage can occur in one and in the same compound I. Larger radicals P, such as perylmonimide, perylimide, terylimide and quaterylimide, preferably contain tert-alkylphenoxy radicals directly in the ring structure or arylene-linked tert-alkylphenoxy Have a tert-alkylphenoxy radical at least directly linked to the radical.

Depending on the size of the conjugated ring system, compound I contains at least 1 to 16 (n: 1 to 16), in particular 2 to 8 tert-alkylphenoxy radicals.

A generally suitable and preferred range for m + n will now be mentioned by way of example for the particularly preferred radical P. Naphthalene: 1-4, in particular 1-2; Quinacridone: 1-8, especially 2-4; Diketopyrrolopyrroles: 1-6, especially 2-4; Dioxazine: 1-8, especially 2-4; Indanthrone: 1-6, especially 2-4; Metal phthalocyanines: 1-16, especially 4-8; Metal naphthalocyanines: 1-16, in particular 8-16; Naphthalmonimide: 1-4, in particular 1-2; Perylmonimide: 1-6, in particular 1-3; Perylimides: 1-8, in particular 2-6; Terylimide: 1-12, in particular 2-8; Quinterimide: 1-14, especially 2-8.

When the radical P contains additional aryl substituents which are not used to connect with the tert-alkylphenoxy radicals, the maximum value for the m + n sum is thus reduced.

The tert-alkylphenoxy radicals and any Hal substituents are preferably distributed irregularly through the radical P.

Suitable examples of the radicals R and R ¹ and their substituents of formula I will now be listed:

C ₁ -C ₆ -alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl and 2-methylpentyl to be. In addition to these radicals, C ₁ -C ₈ -alkyl are, for example, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl and isooctyl.

C ₁ -C ₈ -alkyl may be interrupted by one or more —O— of its carbon chain, for example 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-iso Propoxyethyl, 2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and 3-propoxypropyl, 2- and 3-butoxypropyl, 2- and 4 -Methoxybutyl, 2- and 4-ethoxybutyl, 2- and 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanyl, 3,7 Dioxaoctyl, 3,7-dioxanyl, 4,7-dioxaoctyl, 4,7-dioxanyl, 2- and 4-butoxybutyl, 4,8-dioxadecyl, 3,6, 9-trioxadedecyl and 3,6,9-trioxoundecyl.

C ₁ -C ₈ -alkyl may be interrupted by one or more —S— of its carbon chain, for example 2-methylthioethyl, 2-ethylthioethyl, 2-propylthioethyl, 2-iso Propylthioethyl, 2-butylthioethyl, 2- and 3-methylthiopropyl, 2- and 3-ethylthiopropyl, 2- and 3-propylthiopropyl, 2- and 3-butylthiopropyl, 2- and 4 -Methylthiobutyl, 2- and 4-ethylthiobutyl, 2- and 4-propylthiobutyl, 3,6-dithiaheptyl, 3,6-dithiaoctyl, 4,8-dithianonyl, 3,7 -Dithiactyl, 3,7-dithianonyl, 4,7-dithiaoctyl, 4,7-dithianonyl, 2- and 4-butylthiobutyl, 4,8-dithiadecyl, 3,6, 9-trithiadecyl and 3,6,9-trithiaundecyl.

C ₁ -C ₈ -alkyl may be interrupted by one or more —NR ¹ — of its carbon chain, for example 2-monomethyl- and 2-monoethylaminoethyl, 2-dimethylaminoethyl, 2 And 3-dimethylaminopropyl, 3-monoisopropylaminopropyl, 2- and 4-monopropylaminobutyl, 2- and 4-monomethylaminobutyl, 6-methyl-3,6-diazaheptyl, 3, 6-dimethyl-3,6-diazaheptyl, 3,6-diazactyl, 3,6-dimethyl-3,6-diazactyl, 9-methyl-3,6,9-triazadecyl, 3, 6,9-trimethyl-3,6,9-triazadecyl, 3,6,9-triazadecyl and 3,6,9-trimethyl-3,6,9-triazadecyl

C ₁ -C ₈ -alkyl may be interrupted by one or more —CO— of its carbon chain, for example propan-2-one-1-yl, butan-3-one-1-yl, butane -3-one-2-yl and 2-ethylpentan-3-one-1-yl.

C ₁ -C ₈ -alkyl may be interrupted by one or more —SO ₂ — of its carbon chain, for example 2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2-propylsulfonylethyl , 2-isopropylsulfonylethyl, 2-butylsulfonylethyl, 2- and 3-methylsulfonylpropyl, 2- and 3-ethylsulfonylpropyl, 2- and 3-propylsulfonylpropyl, 2- and 3 -Butylsulfonylpropyl, 2- and 4-methylsulfonylbutyl, 2- and 4-ethylsulfonylbutyl, 2- and 4-propylsulfonylbutyl and 4-butylsulfonylbutyl.

C ₁ -C ₆ -alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, isopentoxy, neopentoxy , tert-pentoxy and hexoxy.

5- to 7-membered heterocyclic radicals may be linked via a nitrogen atom and may contain another hetero atom and / or be aromatic, for example pyrrole, pyrazole, imidazole, triazole, pyrroly Dean, pyrazoline, pyrazolidine, imidazoline, imidazolidine, pyridine, pyridazine, pyrimidine, pyrazine, triazine, piperidine, piperazine, oxazole, isoxazole, thiazole, isothia Sol, indole, quinoline, isoquinoline or quinaldine.

C ₅ -C ₈ -alkyl may be interrupted by one or more groups whose carbon skeleton is selected from the group consisting of —O—, —S—, NR ¹ —, —CO— and —SO ₂ — And mono- or polysubstituted by C ₁ -C ₆ -alkyl, for example cyclopentyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 3 And 4-propylcyclohexyl, 3- and 4-isopropylcyclohexyl, 3- and 4-butylcyclohexyl, 3- and 4-sec-butylcyclohexyl, 3- and 4-tert-butylcyclohexyl, cyclo Heptyl, 2-, 3- and 4-methylcycloheptyl, 2-, 3- and 4-ethylcycloheptyl, 3- and 4-propylcycloheptyl, 3- and 4-isopropylcycloheptyl, 3- and 4- Butylcycloheptyl, 3- and 4-sec-butylcycloheptyl, 3- and 4-tert-butylcycloheptyl, cyclooctyl, 2-, 3-, 4- and 5-methylcyclooctyl, 2-, 3-, 4- and 5-ethylcyclooctyl, 3-, 4- and 5-propylcyclooctyl, 2-dioxanyl, 4-mor Rinil, 2-and 3-tetrahydro-furyl, 1-, 2- and 3-pyrrolidinyl and 1-, 2-, 3- and 4-piperidyl.

Examples of preferred tert-alkylphenoxy radicals are p- (1,1-dimethylpropyl) phenoxy, p- (1,1-dimethylbutyl) phenoxy, p- (1,1-dimethylpentyl) phenoxy, p -(1,1,3,3-tetramethylbutyl) phenoxy, p- (2-cyclopentyl-1,1-dimethylethyl) phenoxy, p- (2-cyclohexyl-1,1-dimethylethyl) Phenoxy, p- (2-cycloheptyl-1,1-dimethyl-ethyl) phenoxy and p- (1,1-dimethyl-2- (4-morpholinyl) ethyl) phenoxy. Particular preference is given to p- (1,1,3,3-tetramethylbutyl) phenoxy.

Particularly preferred naphthalmonimide, perylmonimide, perylimide, terylimide and quaterylimide contain substituents R ² which are especially stable on bases such as the following on the imide nitrogen atom:

C ₁ -C ₃₀ -alkyl, its carbon chain may be interrupted by one or more groups selected from —O—, —S—, —NR—, —CO— and —SO ₂ —, and C ₁ − It may be mono-substituted or multiply substituted by the same or different radicals selected from C ₆ -alkoxy and 5- to 7-membered heterocyclic radicals linked via a nitrogen atom and may contain another hetero atom And / or may be aromatic;

C ₅ -C ₈ -cycloalkyl, its carbon skeleton can be interrupted by one or more groups selected from -O-, -S-, -NR-, -CO- and -SO _2- , C ₁ Optionally mono- or multi-substituted by -C ₆ -alkyl;

Aryl or hetaryl such as phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thianolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolyl , Quinolinyl, isoquinolinyl or quinaldinyl, wherein each of these radicals is C ₁ -C ₁₈ -alkyl, C ₁ -C ₆ -alkoxy, cyano, -CONH-R ¹ and / or -NH-COR ¹ Mono- or multi-substituted by

The following radicals may be mentioned in particular by way of example for these substituents in addition to the radicals already mentioned:

In addition to the aforementioned alkyl radicals, C ₁ -C ₃₀ -alkyl is, for example, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, hepta Decyl, octadecyl, nonadecyl and eicosyl (the names isononyl, isodecyl and isotridecyl as well as the aforementioned isooctyl are common names derived from alcohols obtained by the oxo method);

C ₁ -C ₃₀ -alkyl interrupted by —O— or —S—, such as 3,6,9-trioxadodecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9 , 12-tetraoxatetradecyl; 3,6,9-trithiadodecyl, 3,6,9,12-tetrathiatridecyl and 3,6,9,12-tetrathiatetradecyl;

Substituents -CO-NHR ¹ and -NH-COR ¹ are, for example, methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, butylaminocarbonyl, pentylaminocarbonyl, hexylaminocarbonyl, heptylaminocarbonyl , Octylaminocarbonyl, nonylaminocarbonyl and decylaminocarbonyl; Formylamino, acetylamino and propionylamino;

Aryl or hetaryl, which may be mono- or multiply substituted by C ₁ -C ₁₈ -alkyl, C ₁ -C ₆ -alkoxy, cyano, -CONH-R ¹ and / or -NH-COR ¹ , are, for example, , 2-, 3- and 4-methylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- and 4- Ethylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl, 2,4 -, 2,5-, 3,5- and 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-, 3- and 4-isopropylphenyl, 2,4-, 2,5 -, 3,5- and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4-, 2,5-, 3, 5- and 2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-, 3- and 4-isobutylphenyl, 2,4-, 2,5-, 3,5- and 2, 6-diisobutylphenyl, 2,4,6-triisobutylphenyl, 2-, 3- and 4-sec-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6- Di-sec-butylphenyl, 2,4,6-tri-sec-butylphenyl, 2-, 3- and 4-tert-butylphenyl, 2,4-, 2,5-, 3,5- and 2, 6-di-tert-butylfe And 2,4,6-tri -tert- butylphenyl; 2-, 3- and 4-methoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-, 3 And 4-ethoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-, 3- and 4- Propoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-dipropoxyphenyl, 2-, 3- and 4-isopropoxyphenyl, 2,4-, 2,5- , 3,5- and 2,6-diisopropoxyphenyl and 2-, 3- and 4-butoxyphenyl; 2-, 3- and 4-cyanophenyl; 3- and 4-carboxamidophenyl, 3- and 4-N- (methyl) carboxamidophenyl and 3- and 4-N- (ethyl) carboxamidophenyl; 3- and 4-acetylaminophenyl, 3- and 4-propionylaminophenyl and 3- and 4-butyrylaminophenyl.

Particularly preferred compound A is that quaterylene-3,4: 13,14-tetracarboxylic diimide of formula II, wherein P is N, N'-disubstituted                 

Wherein R ² is the same as the imido nitrogen atom substituent that is stable to the base described above.

In particularly preferred compound A of formula I, P is quaterylimide II,

R is preferably H, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopentyl, cyclohexyl, cycloheptyl, or morpholinyl, particularly preferably H, methyl, ethyl, butyl or tert -Butyl and especially tert-butyl;

R ² is preferably substituted phenyl, particularly preferably phenyl substituted by 1 to 3 C ₁ -C ₄ -alkyl and especially 2,6-diisopropylphenyl;

n is preferably 2 to 10, particularly preferably 4 to 8 and especially 6; And

m is preferably 0 to 4, particularly preferably 0 to 2 and in particular 0.

The n tert-alkylphenoxy substituent and the m Hal substituent are preferably irregularly dispersed across the quaterylene system. Particular preference is given to the same number of substituents present on both sides of the imaginary axis between the two imide nitrogen atoms.                 

Compounds of formula (I) may be prepared by a process comprising reacting a halide of general formula (III) with a tert-alkylphenol of general formula (IV) in an inert basic nitrogen containing solvent and in the presence of a base.

Useful inert basic nitrogen containing solvents are in particular polar solvents, in particular nitrogen containing heterocycles such as pyridine, pyrimidine, quinoline, isoquinoline, quinaldine and preferably N-methylpyrrolidone, also carboxamides, N, N -Dimethylformamide and N, N-dimethylacetamide.

The amount of solvent depends on the solubility of halide III and solvents in the range of 2 to 40 g, preferably 4 to 25 g per gram of halide III are common.

Useful bases are especially non-nucleophilic or only weak nucleophilic compounds. Examples of such bases are alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, alkali metal carbonates such as potassium carbonate and sodium carbonate, and alkali metal alkoxides of tertiary alcohols such as lithium tert-butoxide, sodium tert- Butoxide and potassium tert-butoxide, which are used in anhydrous form.

In general, a molar equivalent of 0.8 to 1.5, preferably 1.0 to 1.2, base is used per mole of halogenated atom to be substituted.

Halides III, used as starting materials, can be obtained according to known methods by reacting generally known or non-halogenated conjugated polycyclic compounds with halogenating agents, in particular halogen elements. Halides III containing halogen atoms linked to aryl substituents can generally be obtained by introducing halogenated aryl radicals into the polycyclic system.

The molar ratio of halide III to phenol IV depends on the number of halogen atoms substituted. Per mole of halogen atoms substituted in halide III, generally 1 to 2, preferably 1 to 1.3 moles of phenol IV are used.

The reaction temperature is generally in the range from 50 to 200 ° C, preferably 60 to 140 ° C.

It is preferred that the reaction is carried out under a protective gas such as nitrogen or argon.

The reaction time depends on the reactivity of halide III and is 2 to 48 hours.

Varying the reaction conditions—the amount of phenol IV and the base and the reaction temperature—provides advantageous control over halogen substitution, so there is no problem in preparing (m = 0) product I with all halogen atoms substituted, but product I Still contains halogen. If necessary, halogens can be removed sequentially from product I. Thus, if desired, one starting material III can be used to prepare various products I.

Component B, which is a preferred monomer from group a), is described in WO 99/19267 and German patent application P 10203938.0, the entire range of which is hereby incorporated by reference. The non-chiral nematic polymerizable monomer from group a) can preferably be polymerized bifunctionally and preferably corresponds to the general formula (V)

Z ^1- (Y ¹ -A ¹ ) _v -Y ² -MY ^3- (A ² -Y ⁴ ) _w -Z ²

here

Z ¹ and Z ² are the same or different reactive groups, or radicals containing such reactive groups, in which polymerization may occur, the reactive groups being C═C double bonds, C≡C triple bonds, or oxiranes, thiiranes, azides Is a cyanate, thiocyanate, isocyanate, carboxyl, hydroxyl or amino group, with C = C double bonds being particularly preferred;

Y ¹ , Y ² , Y ³ and Y ⁴ are each, independently of one another, a chemical bond, O, S, -CO-O-, -O-CO-, -O-CO-O-, -CO-S- , -S-CO-, -CO-N (R ³ )-, -N (R ³ ) -CO-, -N (R ³ ) -CO-O-, -O-CO-N (R ³ )- , -N (R ³ ) -CO-N (R ³ )-, -CH ₂ -O-, -O-CH _2- , preferably -CO-O-, -O-CO- or -O- CO-O-,

R ³ is hydrogen or C ₁ -C ₄ -alkyl;

A ¹ and A ² are the same or different spacers, for example linear C ₂ -C ₃₀ -alkylene groups, preferably C ₂ -C ₁₂ -alkylene groups, which can be interrupted by oxygen, sulfur Unsubstituted or monosubstituted with nitrogen, wherein the intervening groups may not be adjacent; Suitable amine substituents include C ₁ -C ₄ -alkyl groups, wherein the alkylene chain can be substituted by fluorine, chlorine, bromine, cyano, methyl or ethyl; And in this case particularly preferably A ¹ and A ² are — (CH ₂ ) _—n and n = 2 to 6;

v and w are 0 or 1;

M is preferably a mesogenic group of general formula VI:

(TY ⁵ ) _m -T

here

T is the same or different divalent isocyclo aliphatic, heterocyclo aliphatic, isoaromatic or heteroaromatic radicals, preferably 1,4-linked unsubstituted or mono- to multi-substituted, such as mono- to Represents a tetra substituted benzen ring,

here

R ⁴ is fluorine, chlorine, bromine, C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -alkoxy, C ₁ -C ₂₀ -alkylcarbonyl, C ₁ -C ₂₀ -alkylcarbonyloxy, hydroxy, nitro , CHO or CN, preferably chlorine, bromine or C ₁ -C ₄ -alkyl and especially methyl; And

n is an integer from 0 to 4, preferably 0 to 2 and in particular 0 or 1;

Y ⁵ is the same or different bridging member -CO-O-, -O-CO-, -CH ₂ -O-, -O-CH _2- , -CO-S-, -S-CO-, -CH ₂ -S-, -S-CH ₂ , -CH = N- or -N = CH- or a direct bond, preferably -CO-O- or -O-CO-, and

m is an integer of 0-3, Preferably it is 0, 1 or 2.

Mesogenic groups preferably contain substituted 1,4-dioxybenzene building blocks, especially methyl-substituted 1,4-dioxybenzene building blocks.

Particularly preferred mesogenic groups have the following structure VII:                 

here

R ⁴ is fluorine, chlorine, bromine, C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -alkoxy, C ₁ -C ₂₀ -alkylcarbonyl, C ₁ -C ₂₀ -alkylcarbonyloxy, hydroxy, nitro , CHO or CN, and

n is an integer of 0 to 4.

In the mesogenic group VII, particularly preferably R ⁴ is chlorine, bromine or C ₁ -C ₄ -alkyl, and in particular methyl, and n is 0 to 2, in particular 0 or 1, especially 1.

Very particularly preferred mesogenic groups have the structure VIII:

The polymerizable monomer of chiral from group a) is preferably of formula IX                 

((Z ¹ -Y ¹ ) _o -A ³ -Y ² -MY ³ ) _n X (Y ³ -MY ² -A ^4- (Y ¹ -Z1) _p ) _m (IX)

here

Z ¹ , Y ¹ , Y ² , Y ³ and M have been defined above,

o, p is 0 or 1, provided that both o and p may not be 0,

A ³ and A ⁴ are the same or different and

A ³ is defined for A ¹ if o = 1 or

Linear C ₂ -C ₃₀ -alkylene groups, preferably C ₂ -C ₁₂ -alkylene groups, which may be intermittent with oxygen, sulfur, unsubstituted or monosubstituted with nitrogen, wherein Groups may not be contiguous; Suitable amine substituents include C ₁ -C ₄ -alkyl groups which may be substituted by fluorine, chlorine, bromine, cyano, methyl or ethyl, in which case A ³ is particularly preferably CH _3- (CH ₂ ) _l group, and if o = 0 then l = 1-7;

A ⁴ is defined for A ¹ if p = 1 or

Linear C ₂ -C ₃₀ -alkyl groups, preferably C ₂ -C ₁₂ -alkyl groups, which can be interrupted by oxygen, sulfur, unsubstituted or monosubstituted with nitrogen, wherein the interrupting groups May not be contiguous; Suitable amine substituents include C ₁ -C ₄ -alkyl groups which may be substituted by fluorine, chlorine, bromine, cyano, methyl or ethyl, in which case A ³ is particularly preferably CH _3- (CH ₂ ) _l group, and if p = 0 then l = 1-7;

n and m are 0, 1 or 2, and the sum n + m is 1 or 2, and preferably 2; And

X is a chiral radical.

Particularly preferred chiral radicals X of the compounds of the general formula (IX) are given, not because of their easy availability, but those derived from sugars, dinaphthyl or diphenyl derivatives and optionally active glycols, alcohols or amino acids. In the case of sugars, special mention is made of pentose and hexose and their derivatives.

Examples of radicals X are the following structures, in which case the end line is denoted by free valence.

here

L ¹ is C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen, COOR ⁵ , OCOR ⁵ , NHCOR ⁵ and R ⁵ is C ₁ -C ₄ -alkyl or hydrogen.

Particularly preferred are as follows.

Also suitable are chiral groups having the structure:

In the above definition of A ¹ , A ² , A ³ , A ⁴ , R ³ , R ⁴ , R ⁵ and L ¹ groups, C ₁ -C ₂₀ -alkyl is specifically methyl, ethyl, n-propyl, isopropyl , n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octa Decyl, nonadecyl and eicosyl;

C ₁ -C ₄ -alkyl is specifically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl;

C ₁ -C ₂₀ -alkoxy is specifically alkoxy, the alkyl radical of which corresponds to the aforementioned C ₁ -C ₂₀ -alkyl group; And

C ₂ -C ₃₀ -alkylene is specifically alkylene corresponding to the divalent radical of the aforementioned C ₂ -C ₂₀ -alkyl group, or a linear C ₂₁ -C ₃₀ -homolog.

In certain embodiments, nematic non-chiral polymerizable monomers have the following structure:

In another specific embodiment, the polymerizable monomer of chiral has the formula XI or XII

And / or                 

The fraction of non-chiral nematic monomers to chiral monomers is chosen such that the polymers produced from these monomers, following orientation, have a helical superlattice pitch that corresponds to wavelengths in the IR spectral range. The fraction depends on the type of nematic and chiral monomer and must be determined for each individual case.

Alternatively, one or more cholesteric polymerizable monomers of group b) can be used as component B.

Preferred monomers of group b) are described in DE-A 19602848, the true text of which is hereby incorporated by reference. In particular, monomer b) comprises at least one cholesteric polymerizable monomer of formula XIII.

(Z ¹ -Y ¹ -A ¹ -Y ² -M ¹ -Y ³ ) _n X

The variables are as defined for the monomers of group a). Preferred embodiments apply correspondingly.

Alternatively, one or more cholesteric crosslinkable polymers of group c) can be used as component B.

Preferred monomers of group c) are cholesteric cellulose derivatives as described in DE-A-197 136 38, in particular

(1) with hydroxyalkyl ethers of cellulose

(2) saturated, aliphatic or aromatic carboxylic acids and

(3) unsaturated mono- or dicarboxylic acids

Mixed cholesteric esters.

Particularly preferably, the hydroxyalkyl radicals of component (1) linked via ether action are linear or branched chain C ₂ -C ₁₀ -hydroxyalkyl radicals, in particular hydroxypropyl- and / or hydroxyethyl radicals. Given mixed esters containing. Component (1) of the suitably mixed ester preferably has a molecular weight of about 500 to about 1 million. Preferably, the dehydrated lucose units of cellulose are etherified with hydroxyalkyl radicals with a substitution of an average molar degree of 2-4. The hydroxyalkyl groups in cellulose can be the same or different. Up to 50% of them may also be substituted by alkyl groups (especially C ₁ -C ₁₀ -alkyl groups). One example of such a compound is hydroxypropylmethylcellulose.

Compounds which can be used as component (2) of the appropriately mixed esters are straight chain aliphatic C ₁ -C ₁₀ -carboxylic acids, especially C ₂ -C ₆ -carboxylic acids, branched aliphatic C ₄ -C ₁₀ -carboxyl Acids, especially C ₄ -C ₆ -carboxylic acids or straight chain or branched halocarboxylic acids. Component (2) also includes aliphatic carboxylic acids containing benzoic acid or aromatic substituents, especially phenylacetic acid. Particularly preferably component (2) is selected from acetic acid, propionic acid, n-butyric acid, isobutyric acid or n-valeric acid, in particular from propionic acid, 3-chloropropionic acid, n-butyric acid or isobutyric acid.

Preferably component (3) is made from unsaturated C ₃ -C ₁₂ -mono- or monoesters of dicarboxylic or dicarboxylic acids, in particular α, β-ethylenically unsaturated C ₃ -C ₆ -mono- or Dicarboxylic acids or monoesters of dicarboxylic acids.

Particularly preferably, component (3) of the suitably mixed ester is selected from acrylic acid, methacrylic acid, crotonic acid, vinylacetic acid, maleic acid, fumaric acid or undecenoic acid, in particular acrylic acid or methacrylic acid.

Preferably component (1) is esterified with components (2) and (3) with an average molar degree of substituents of 1.5 to 3, especially 1.6 to 2.7, particularly preferably 2.3 to 2.6. Preferably about 0 to 30%, in particular 1 to 20% or 1 to 10%, particularly preferably about 5 to 7% of the 0H-group of component (1) is esterified with component (3).

The fraction of component (2) with respect to component (3) determines the reflection wavelength of the polymer.

Suitable polymers of group c) are propargyl-terminated cholesteric polyesters or polycarbonates described in DE-A-197 17 371.

Among these compounds, preferred are polyesters or polycarbonates having at least one terminal propargyl group of the formula R ⁶ C≡C-CH _2- , wherein R ⁶ is H, C ₁ -C ₄ -alkyl, aryl or Ar-C ₁ -C ₄ -alkyl (eg benzyl or phenethyl) and is directly linked to a polyester or polycarbonate or via a linker. The linker is preferably selected from the following;

(Propargyl group is connected to Z)

Wherein R ⁷ is H, C ₁ -C ₄ -alkyl or phenyl, Z is O, S or NR, and R ⁸ is H, C ₁ -C ₄ -alkyl or phenyl.

The terminal propargyl groups in the polyester are preferably linked via:

The polyester preferably comprises:

(4) one or more aromatic or aliphatic dicarboxylic acid units and / or one or more aromatic or aliphatic hydroxycarboxylic acid units and

(5) one or more diol units.                 

Preferred dicarboxylic acid units are of the formula

In particular, the chemical formula

Where each phenyl or naphthyl groups, C ₁ -C ₄ - alkyl, C ₁ -C ₄ - alkoxy group, may contain 1, 2 or 3 substituents selected independently of one another from the group consisting of halogen or phenyl, and wherein In the formula

W is NR, S, O, (CH ₂ ) _r O (CH ₂ ) _q , (CH ₂ ) _s or a single bond,

R ⁹ is alkyl or hydrogen,

s is an integer from 1 to 15, and

r and q are the integers 0-10 each independently of each other.

Preferred hydroxycarboxylic acid units are of the formula

Where each phenyl or naphthyl groups are C ₁ -C ₄ - alkyl, C ₁ -C ₄ - alkoxy, and may contain 1, 2 or 3 substituents each independently selected from the group consisting of halogen or phenyl.

Preferred diol units are of the formula

In particular, the formula

At this time, in the above formula

L is alkyl, alkoxy, halogen, COOR ¹¹ , OCOR ¹¹ , CONHR ¹¹ or NHCOR ¹¹ ,

X is S, O, N, CH ₂ or a single bond,

A is a single bond, (CH ₂ ) _n , O (CH ₂ ) _n , S (CH ₂ ) _n , NR ¹¹ (CH ₂ ) _n ,

이고,

ego,

R ¹¹ is alkyl or hydrogen,

R ¹⁰ is hydrogen, halogen, alkyl or phenyl, and

n is an integer from 1 to 15.

Preferred is a polyester comprising at least one dicarboxylic acid unit of the formula

And one or more diol units of the formula

Wherein R ¹⁰ is H, halogen, C ₁ -C ₄ -alkyl, in particular CH ₃ or C (CH ₃ ) ₃ , or phenyl.

More preferred compounds are diesters of the formula PYB-CO-OAO-CO-BYP, wherein P is a terminal propargyl group of the above formula, Y is O, S or NR ¹² and (R ¹² = C ₁ -C ₄ -Alkyl), B is

이고

ego

Wherein each group is phenyl or naphthyl, C ₁ -C ₄ - alkyl, C ₁ -C ₄ - alkoxy, and may contain 1, 2 or 3 substituents selected independently of one another from the group consisting of halogen or phenyl, and A (with adjacent oxygen atoms) is one of the diol units described above.

Particularly preferred diesters are of the formulas above, in which B is

And specifically formula

HC≡CCH ₂ OB-CO-OAO-CO-B-OCH ₂ -C≡CH diester, wherein

그리고(6) B is

And

A is

또는

or

그리고(7) B is

And

A is as defined in (6).

More preferred compounds are those described above, in particular

It is a polycarbonate containing at least one diol unit of.

Particularly preferred for such polycarbonates herein are those comprising one or more mesogenic units of the formula

그리고

And

Chiral units of one or more of the formulas

With or without a non-chiral unit of formula

Wherein R ¹⁰ is defined above and in particular H or CH ₃ .

Particularly preferred polycarbonates have terminal propargyl groups of the formula HC≡CCH ₂ OR ¹³ -CO, wherein R ¹³ is

이다.

to be.

More suitable polymers of group c) are cholesteric polycarbonates and also contain photoreactive groups at positions other than the terminal. Such polycarbonates are described in DE-A-196 31 658. They are preferably of formula XIV

Wherein the molar ratio w / x / y / z is about 1-20 / about 1-5 / about 0-10 / about 0-10. Especially preferably the molar ratio w / x / y / z is from about 1 to 5 / about 1 to 2 / about 0 to 5 / about 0 to 5.

In formula (XIV)

A is a mesogenic group of the formula

B is a chiral group of the formula

D is a photoreactive group of the formula

And

E is further a non-chiral group of the formula

At this time, in the above formula

L is alkyl, alkoxy, halogen, COOR ¹⁵ , OCOR ¹⁵ , CONHR ¹⁵ or NHCOR ¹⁵ ,

X is S, O, N, CH ₂ or a single bond,

R ¹⁵ is alkyl or hydrogen,

A is a single bond, (CH ₂ ) _n , O (CH ₂ ) _n , S (CH ₂ ) n, NR (CH ₂ ) _n ,

이고,

ego,

R ¹⁴ is hydrogen, halogen, alkyl or phenyl and

n is an integer from 1 to 15.

If R ¹⁴ is alkyl or halogen and A is a single bond or if R ¹⁴ is H or alkyl and A is

라면,

Ramen,

Those groups are groups that improve solubility. Examples of these are:

Preferred chiral components are isosorbide, isomannide and / or isoidide.

The fraction of chiral diol structural units depends on the desired reflecting tendency, and is in the range of 1 to 80 mol% of the total content of the diol structural units, particularly preferably in the range of 2 to 20 mol%.

Alternatively, the cholesteric polymer in the diluent that can be polymerized (group d)) can be used as component B.                 

Examples of preferred polymers of group d) are the crosslinkable cholesteric copolyisocyanates described in US-A-08 834 745, the entirety of which is incorporated herein by reference. Such copolyisocyanates have the following formula

And, if appropriate, having a repeating unit of the formula

At this time,

R ¹⁶ is a chiral aliphatic or aromatic radical,

R ¹⁷ is a radical which can be crosslinked, and

R ¹⁸ is a non-chiral radical.

Unless specified otherwise, “alkyl” (including the meaning of alkoxy, dialkyl, alkylthio, etc.) is branched and unbranched C ₁ -C ₁₂ -alkyl, preferably C ₃ -C ₁₂ -alkyl, particularly preferred Preferably C ₄ -C ₁₀ -alkyl, in particular C ₆ -C ₁₀ -alkyl.

Preferably R ¹⁶ is a (chiral) branched or unbranched alkyl-, alkoxyalkyl-, alkylthioalkyl-, cycloalkyl-, alkylphenyl- or C ₃ -C ₉ -epoxyalkyl radical or C ₁ -C ₆ Ester radicals of -fatty acids with C ₁ -C ₆ -alkanols or C ₃ -C ₉ -dialkylketones. The ester radical can be linked to nitrogen via a fatty acid component or via an alkanol radical. The radical R ¹⁶ is the same or different and is a 1, 2 or 3 substituent selected from the group consisting of an alkoxy group, a di-C ₁ -C ₄ -alkylamino group, a CN, a halogen atom or a C ₁ -C ₄ -alkylthio group It may contain.

Preferably R ¹⁶ is alkyl, alkoxyalkyl, C ₁ -C ₆ - fatty acids and C ₁ -C ₆ - alkynyl moiety of the ester of play, C ₃ -C ₉ - dialkyl ketones and epoxidized C ₃ -C Selected from a ₉ -epoxyalkyl radical, where R ¹⁶ is the same or different and can be substituted by one or two radicals selected from the group consisting of alkoxy, halogen, CN or CF ₃ . Preferred substituents of branched or unbranched alkyl- or alkoxy radicals are from the group consisting of alkoxy groups, halogen atoms or CN; C ₁ -C ₆ - fatty acids and C ₁ -C ₆ - alkanol ester of an alkoxy group, a halogen atom, from the group consisting of CN or CF _3, and C ₃ -C ₉ - dialkyl ketone is an alkoxy group, a halogen It is selected from the group consisting of an atom or CN.

In particular, the main chain of radicals R ¹⁶ has a length of 3 to 12, in particular 6 to 10, preferably 6 to 8 members (carbon, oxygen and / or sulfur atoms). Particularly preferably R ¹⁶ is selected from the group consisting of:

Very particularly preferably the component XV of the suitable copolyisocyanate is derived from 2,6-dimethylheptylisocyanate.

Radicals R ¹⁷ of suitable copolyisocyanates are preferably C ₃ -C ₁₁ -alkenyl radicals, C ₄ -C ₁₁ -vinylether radicals (= vinyl-C ₂ -C ₉ -alkyl ethers), ethylenically unsaturated C ₃ Is selected from the group consisting of -C ₁₁ -carboxylic acid radicals and esters of ethylenically unsaturated C ₃ -C ₆ -monocarboxylic acids with C ₂ -C ₆ -alkanols, wherein the bond to the nitrogen atom is ester Via alkanol radicals. Especially preferably, the radicals are methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl meth It is selected from the group consisting of acrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, in particular from the group consisting of ethyl acrylate or ethyl methacrylate.

The radical R18 is preferably as defined for R ¹⁶ . However, it is non-chiral, ie without the center of chiral or present in racemic mixtures.

Particularly preferably, the main chain of radicals R18 has 4 to 12, in particular 6 to 10, preferably 6 to 8 members (carbon, oxygen and / or sulfur atoms). More particularly preferably, component XVII of the copolyisocyanate of the invention is derived from n-hexyl isocyanate, n-heptyl isocyanate or n-octyl isocyanate.

The components XV, XVI and XVII preferably have a molar ratio XV: XVI: XVII of about 1-20: 1-20: 50-98, especially about 5-15: 5-15: 65-90, particularly preferably about 15 It exists at: 10: 75.

The units XV, XVI and XVII are preferably irregularly present in the appropriate copolyisocyanate.

Preferred component B of the composition of the present invention is a mixture of at least one non-chiral nematically polymerizable monomer and a chiral polymerizable monomer, ie group a).

The compound (s) A is preferably 0.01 to 20% by weight, particularly preferably 0.01 to 15% by weight, particularly preferably 0.01 to 10% by weight, especially 0.01 to 7% by weight and especially based on the total amount of component B It is present in an amount of 0.01 to 5% by weight.

The composition is preferably a solution or dispersion of components A and B in a suitable mixture of components A and B or a suitable diluent. The fraction of the diluent is preferably 5 to 95% by weight, particularly preferably 30 to 80% by weight and especially 40 to 70% by weight, based on the total amount of the composition.

Suitable diluents for the compounds of groups a) or b) are linear or branched esters, in particular acetic esters, cyclic ethers and esters, alcohols, lactones, aliphatic and aromatic hydrocarbons such as toluene, xylene and cyclohexane, and ketones , Amides, N-alkylpyrrolidones, in particular N-methylpyrrolidone, and in particular tetrahydrofuran (THF), dioxane and methylethyl ketone (MEK).

Examples of suitable diluents for the polymers of group c) are ethers and cyclic ethers such as tetrahydrofuran or dioxane, chlorinated hydrocarbons such as dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, 1,1,2,2- Tetrachloroethane, 1-chloronaphthalene, chlorobenzene or 1,2-dichlorobenzene. These diluents are particularly suitable for polyesters and polycarbonates. Examples of suitable suitable diluents for cellulose derivatives are ethers such as dioxane, or ketones such as acetone. When copolyisocyanates are used as polymers of group d), preference is given to using polymerizable diluents described in US-A-08 834 745. Such polymerizable diluents are as follows:

α, β-unsaturated mono- or dicarboxylic acids, in particular C3-C6-mono- or dicarboxylic acids and C ₁ -C ₁₂ -alkanols, C ₂ -C ₁₂ -alkanediols or their C ₁ -C ₆ Esters with -alkyl ethers and phenyl ethers such as acrylates and methacrylates, hydroxyethyl- or hydroxypropyl acrylates or -methacrylates and 2-ethoxyethyl acrylates or -methacrylates;

Vinyl-C ₁ -C ₁₂ -alkylethers such as vinylethyl-, vinylhexyl- or vinyloctyl ether;

Vinyl esters of C ₁ -C ₁₂ -carboxylic acids, such as vinyl acetate, vinyl propionate, vinyl laurate;

C ₃ -C ₉ -epoxides such as 1,2-butylene oxide, styrene oxide;

N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide;

Vinylaromatic compounds such as styrene, α-methylstyrene, chlorine styrene, and

Compounds having two or more crosslinkable groups such as diols (including polyethylene glycol) and diesters of acryl- or methacrylic acid or divinylbenzene.

Examples of preferred polymerizable diluents are 2-ethoxyethylacrylate, diethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene Glycol monomethyl ether acrylate, phenoxyethyl acrylate and tetraethylene glycol dimethacrylate. Particularly preferred polymerizable diluents are styrene.

The mixture of groups a), b) or c) may also contain small amounts of diluents which can be polymerized. Preferred polymerizable solvents which may be added to a), b) or c) are acrylates, in particular relatively high functional acrylates such as bis, tri- or tetraacrylates, particularly preferably high Boiling oligoacrylates. The preferred amount added is about 5% by weight based on the total weight of the mixture.

To adjust the viscosity and leveling tendency, the compositions of the present invention can be mixed with additional ingredients.

For example, it is possible to use polymeric binders and / or monomeric compounds which can be converted into polymeric binders by polymerization. Examples of such compounds are organic solvent-soluble polyesters, cellulose esters, polyurethanes, silicones and polyether- or polyester modified silicones. Particular preference is given to using cellulose esters such as cellulose acetobutyrate.

The addition of small amounts of appropriate leveling reagents may also be advantageous. It is possible to use about 0.005 to 1% by weight, in particular 0.01 to 0.5% by weight, based on the amount of cholester used. Examples of suitable leveling reagents are glycols, silicone oils and especially acrylate polymers such as acrylate copolymers Byk 361 or Byk 358 (obtained from Byk-Chemie) and modified, silicone-free acrylate polymers Tego flow ZFS 460 (obtained from Tego) )to be.                 

The composition may also contain UV- and weathering stabilizers. Examples of such additives are derivatives of 2,4-dihydroxybenzophenone, derivatives of 2-cyano-3,3-diphenylacrylate, derivatives of 2,2 ', 4,4'-tetrahydroxybenzophenone , Ortho-hydroxyphenylbenzotriazole derivatives, salicylic esters, ortho-hydroxyphenyl-s-triazines or sterically hindered amines. These components may be used alone or preferably as a mixture.

If the compositions of the invention are to be subjected to photochemical polymerization, they may also contain commercial photoinitiators. In the case of curing with an electron beam, such an initiator is not necessary. Examples of suitable photoinitiators are isobutyl-benzoin ether, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 1-hydroxycyclohexyl-phenyl ketone, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -furan-1-one, a mixture of benzophenone and 1-hydroxycyclohexyl-phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, perfluorinated diphenyl titanocene, 2- Methyl-1- (4- [methylthio] phenyl) -2- (4-morpholinyl) -1-propanone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4- ( 2-hydroxyethoxy) phenyl-2-hydroxy-2-propylketone, 2,2-diethoxyacetophenone, 4-benzoyl-4'-methyldiphenyl-sulfide, ethyl-4- (dimethylamino) Benzoate, a mixture of 2-isopropylthioxanthone and 4-isopropyl-thioxanthone, 2- (dimethylamino) ethylbenzoate, d, l-camphorquinone, ethyl-d, l-camphorquinone, benzofe ketones 4-methyl benzophenone mixture, benzophenone, 4,4'-dimethyl-amine-benzophenone, (η ^{5-cyclopropyl} Other dienyl) (η ^{5-isopropyl-phenyl)} iron (II) hexafluorophosphate, triphenyl sulfonium-mixture of phosphate or triphenyl sulfonium salt hexafluoropropane, and butanediol diacrylate, dipropylene glycol Diacrylate, hexadioxyl diacrylate, 4- (1,1-dimethylethyl) cyclohexylacrylate, trimethylolpropane triacrylate and tripropylene glycol diacrylate.

The present invention provides the use of the above-described composition for preparing an insulating coating.

The present invention further provides an insulating coating comprising at least one oriented and cured layer of the composition of the present invention.

The thermal insulation coating of the present invention preferably contains a cholesteric polymer that reflects and cures at least one IR, which has a helical superlattice structure corresponding to the wavelength in the IR-spectrum range.

A cholesteric polymer can be obtained by orienting and curing component B from groups a), b), c) or d).

When the thermal insulation coating comprises two or more layers, the IR-reflecting polymers in the different layers each have a different helical superlattice pitch, preferably corresponding to a wavelength in the IR spectral range, and / or opposite chirality (handeness). ) In thermally insulating coatings comprising two or more layers, the helical superlattice pitches of the two layers, preferably adjacent, are the same in each case, but their chirality is different. In insulating coatings comprising two or more layers, it is preferred that the media present between the layers have the same helical superlattice pitch and the same chiral properties, the medium having the direction of rotation of the transmitted circularly polarized light, in particular λ Inverted as known as / 2-film or -plate.

The thermal insulation coating preferably comprises 1 to 10 layers, particularly preferably 1 to 4 layers and in particular 2 layers. The two layers are preferably different in helical superlattice pitch or chiral properties. Particular preference is given to two layers having the same helical superlattice pitch but of opposite chiral properties.

The present invention provides a method of making the thermal insulation coating of the present invention, the method comprising applying the composition of the present invention to a substrate and, if necessary, orienting the composition and curing the composition. Curing is preferably carried out by polymerizing a monomer of group a) or b) or a solvent of group d) or by crosslinking a polymer of group c).

Additional layers are prepared by repeating the application, orientation and curing process, preferably using a composition of the present invention different from the first composition, to pitch other helical superlattices and / or with the first layer. In different layers with opposite chiral properties, the oriented cholesteric polymers can be obtained by polymerizing monomers of groups a) or b) or oriented cholesteric polymers of groups c) or d). Alternatively or additionally, it is possible to introduce a medium between two layers having the same helical superlattice pitch and the same chiral properties, especially as known as λ / 2-film or -plate.

Thermal insulation coatings are thus applied to those described above in connection with the preferred compositions.

The substrate is preferably transparent. The transparent substrate can be, for example, glass bricks, glazing, automotive glass or a film bonded with an adhesive to the glass for thermal insulation purposes.

The cholesteric IR-reflective layer can be applied to the substrate by common techniques, for example floating knife coatings, bar coatings, air-knife coatings, squeeze Coating, Impregnating, Reverse Roll Coating, Transfer Roll Coating, Gravure Coating, Kiss Coating, Casting, Spraying, Spin spin coating or printing techniques such as letter printing, flexography, intaglio, pffset or screen printing.

Prior to applying the composition of the present invention to the substrate, it may be diluted with any suitable diluent. Suitable diluents are those described above.

The IR-reflective layer (s) may be cured thermally, photochemically or by electron beam.

Curing must be performed in the cholesteric phase and during the retention of the cholesteric phase.

When two or more layers are applied, in each case they are applied independently, oriented, dried, and cured as necessary. However, two or more or all of the layers are applied in one wet-in-wet application process to the article to be coated, drying of the cavity is performed as necessary and then It is possible that curing is carried out. However, the requirement for the simultaneous application of cholesteric layers is that there is no interdiffusion between the different layers with different reflection tendencies.

Casting techniques, in particular knife or bar casting techniques, cast-film extrusion or stripper casting techniques, and cascade casting methods are particularly suitable for the simultaneous application of cholesteric layers. These casting techniques are described, for example, in DE-A-19 504 930, EP-A-431 630, DE-A-3 733 031 and EP-A-452 959, which are incorporated herein by reference.

The compositions of the invention are particularly suitable for producing printed insulated windows or insulating transparent building materials or for insulating residential, office or industrial buildings against thermal radiation. In addition, the compositions of the invention are also particularly suitable for use in the automotive sector, in particular for the production of thermally printed glass windows. Accordingly, the present invention also provides an article having the thermal insulation coating of the present invention.

Due to the presence of compound A, the thermal insulation coatings of the invention have tints, preferably blue or green tints. In addition, Compound A advantageously absorbs IR radiation, thereby absorbing and not passing unreflected IR radiation, thereby improving the thermal insulation properties of the coating.

The thermal insulation coatings of the invention, measured in accordance with ISO 9050, exhibit light transmittance of at least 70%, preferably at least 72%, at wavelengths in the range from 350 to 750 nm.

The following examples illustrate the invention without limiting it.

Compounds of formula (X) were used as monomers capable of nematic non-chiral polymerization.                 

Compounds of formula (XI) were used as monomers capable of chiral polymerization.

Compound A, used as a compound of formula I in P, is a quaterylimide of formula II, which is symmetrically substituted with 6 tert-alkylphenoxy-radicals in the quaterylene backbone (n = 6) and halogen substituents Does not contain (m = 0) and where R ² is alkyl-substituted phenyl. This compound is then referred to as Ia.

The solvent used is tetrahydrofuran (THF).

The concentrations of mixtures of compounds X, XI and Ia, leveling reagent Byk 361 (10% strength; Byk Chemie) and photoinitiator Irgacure 184 (Ciba) are listed in Table 1 and 10 g THF was applied to the PET-film with a doctor blade and wetted. The thicknesses of the films are listed in Table 1. As the solvent evaporated at about 85 ° C., a layer of uniform, transparent and green tint was formed. This layer was cured by means of a UV-lamp.

Example X [g] XI [g] Ia [g] Byk 361 [g] Irgacure [g] A 1.5 - 0.15 0.5 0.2 B 4.5 - 0.45 0.5 0.2 C 4.5 0.245 0.45 0.5 0.2

The results for the visual evaluation are shown in Table 2.                 

Example Layer thickness [㎛] Visual evaluation
A 4.0 Transparency 5.5 Transparency 7.0 Slightly cloudy
B 3.8 blur 5.8 Increase blur 7.1 Increase blur
C 3.5 Transparency 5.3 Transparency 6.6 Transparency

In experiments B and C the visual evaluation was demonstrated by transmission measurements consistent with ISO 9050. The results are shown in Table 3 below.

Example Layer thickness [μm] Tvis (%) Tsol (%) B 3.8 59.2 51.6 C 3.5 72.8 38.8

Tvis = transmittance in the 350 to 750 nm field range

Tsol = transmittance in the wavelength range from 350 to 2500 nm

Preferred values consistent with ISO 9050 are:

Tvis ＞ 70%

Tsol <40%

Claims (14)

i) at least one radiation-absorbing tert-alkylphenoxy-substituted polycyclic compound A of formula (I); And ii) at least one curable IR-reflective component B comprising a) at least one achiral nematic polymerizable monomer and at least one chiral polymerizable monomer; b) at least one cholesteric polymerizable monomer; c) at least one cholesteric crosslinkable polymer: or d) at least one cholesteric polymer in diluents that can be polymerized Composition comprising: [Formula I]

here P is a conjugated polycyclic radical that is stable to base and nucleophile, optionally contains aryl substituents and any airway from the group consisting of -CO-NH-CO-, -COOH and -CO-O-CO- Does not contain; R is C ₁ -C ₈ -alkyl and the carbon chain of said C ₁ -C ₈ -alkyl is selected from the group consisting of —O—, —S—, —NR ¹ —, —CO— and —S0 ₂ — Which may be intermittent by one or more groups, wherein said C ₁ -C ₈ -alkyl is singled by the same or different radicals selected from the group consisting of 5 to 7 membered heterocyclic radicals and C ₁ -C ₆ -alkoxy May be substituted or multiply substituted, wherein the 5 to 7 membered heterocyclic radical is linked via a nitrogen atom and further contains a hetero atom, or is aromatic, or may be aromatic while further containing a hetero atom; Or R is C ₅ -C ₈ -cycloalkyl and its carbon skeleton is one or more selected from the group consisting of -O-, -S-, -NR ^1- , -CO- and -S0 _2- May be interrupted by groups and may be mono- or multi-substituted by C ₁ -C ₆ -alkyl; R ¹ is hydrogen or C ₁ -C ₆ -alkyl; Hal is independently selected from the group consisting of chlorine and bromine; m is 0 to 15; And n is 1-16, and it is provided that m + n sum is ≤16. The compound of formula (I) according to claim 1, wherein P is a radical which is stable to base and nucleophiles, naphthalene, anthracene, phenanthrene, tetracene, perylene, terylene, quaterylene, pentariylene, hexaylene, anthraquinone, Indanthrone, N-substituted naphthalene-1,8-dicarboxylic monoimide, N, N'-disubstituted naphthalene-1,8: 4,5-tetracarboxylic diimide, N-substituted perylene -3,4-dicarboxylic monoimide, N, N'-disubstituted perylene-3,4: 9,10-tetracarboxylic diimide, N, N'-disubstituted terylene-3,4: 11,12-tetracarboxylic diimide, N, N'-disubstituted quaterylene-3,4: 13,14-tetracarboxylic diimide, acridine, carbazole, dibenzofuran, dinaphthofuran , Benzimidazole, benzothiazole, phenazine, dioxazine, quinacridone, metal phthalocyanine, metal naphthalocyanine, metal porphyrin, coumarin, dibenzofuranone, dinaphthofuranone, benzimi Isothiazolone, indigo compounds, thioindigo compounds, quinophthalone, naphthoquinone Smirnoff etalon and diketopyrrolo a is selected from the group pyrrolo configuration composition. The composition according to claim 1 or 2, which contains 0.01 to 20% by weight of compound A, based on the total amount of compound B. The composition of claim 1 or 2, wherein component B contains at least one non-chiral nematically polymerizable monomer and at least one chiral polymerizable monomer. The composition of claim 1 or 2, further comprising at least one additive selected from the group consisting of photoinitiators, binders, leveling agents and UV and weathering stabilizers. A method of making an insulating coating using the composition of claim 1. The thermal insulation coating of claim 1, wherein the composition of claim 1 comprises at least one layer oriented and cured. 8. The thermal insulation coating of claim 7, comprising at least one oriented oriented and reflecting IR cured cholesteric polymer having a helical superstructures pitch corresponding to a wavelength in the IR spectral range. The thermal insulation coating of claim 8, comprising at least two layers, wherein the IR reflecting polymers in the other layers each have a different helical superlattice pitch corresponding to a wavelength in the IR spectral range, and / or opposite chiral properties. A method of making the thermal insulation coating of claim 7 comprising applying the composition of claim 1 to a substrate. An article having the thermal insulation coating of claim 7. The method of claim 10, further comprising orienting the composition. The method of claim 10, further comprising curing the composition. The method of claim 13, wherein the curing is carried out by polymerizing a monomer of group a) or b) or a diluent of group d) or crosslinking a polymer of group c).