Liquid crystalline substance mixtures

专利摘要:
The present invention A) a liquid crystal mixture containing at least one compound selected from the group consisting of compounds of formula (Ia) and compounds of formula (Ib), B) if desired, further additives selected from the group consisting of b1) photoinitiators, b2) reactive thinners, and b3) diluents, C) if necessary, c1) antifoaming and degassing agents, c2) lubricants and flow aids, c3) thermosetting or radiation curing aids, c4) base wetting aids, c5) wetting aids and dispersing aids, c6) hydrophobic agents, c7) A further additive selected from the group consisting of fixatives, and c8) anti-improving aids, D) if desired, further additives selected from the group consisting of d1) dyes and d2) pigments, and E) further additives selected from the group consisting of light stabilizers, heat stabilizers and / or oxidative stabilizers, if desired It relates to a liquid crystal composition comprising as a component: Formula Ia Z 1 -Y 1 -A 1 -Y 3 -M 1 -Y 4 -A 2 -Y 2 -Z 2 Formula Ib Z 3 -Y 5 -A 3 -Y 7 -M 2 -P In the above formula, P is hydrogen, a C 1 -C 15 alkyl or -Y 8 -A 4 -Y 6 -Z 4 group, Z 1 to Z 4 are polymerizable groups, Y 1 to Y 8 are each a linking group, A 1 to A 4 are spacers, M 1 and M 2 are mesogenic groups. The liquid crystal composition optionally further contains additives selected from photoinitiators, reactive thinners and diluents, adjuvants, pigments and stabilizers. The present invention also relates to the use of such liquid crystal compositions as printing inks, for printing or coating substrates, for use in electro-optical components, for anti-counterfeit marking of articles, and for producing films or coatings. It is about.
公开号:KR20010102025A
申请号:KR1020017010099
申请日:2000-02-05
公开日:2001-11-15
发明作者:마이어프랭크；이시다히로키；슈마커페터；노이만호르스트
申请人:요헨 카르크, 안드레아스 비베르바흐；바스프 악티엔게젤샤프트；
IPC主号:

专利说明:

Liquid crystal substance mixture {LIQUID CRYSTALLINE SUBSTANCE MIXTURES}
[20] WO 96/02597 describes a method for printing or coating a substrate with a printing or coating composition comprising said liquid crystal polymerizable monomer. The coating or printing composition comprises a chiral liquid crystal monomer or an achiral liquid crystal monomer and a non-liquid crystal compound, and a polymer binder, and / or a monomer compound which can be converted into a polymer binder by polymerization.
[21] According to the examples presented herein, these printing or coating compositions can be applied on a variety of substrates by a variety of application methods, for example by spraying or offset printing, in which case these compositions are for example ultraviolet light. After curing by irradiation, a strong adhesive layer is formed which is resistant to external influences.
[22] However, layers obtained in this way usually do not exhibit the desired degree of brightness and brightness. In addition, the printing and coating compositions are particularly unsuitable for printing, in particular screen printing, flat printing and letterpress printing, since both have high viscosity.
[1] The present invention is a component,
[2] A) a liquid crystal mixture containing at least one compound selected from the group consisting of compounds of formula (Ia) and compounds of formula (Ib),
[3] B) additional additives selected from the group consisting of b1) photoinitiators, b2) reactive thinners, and b3) diluents, if desired,
[4] C) as needed, c1) antifoaming and degassing agents, c2) lubricants and flow aids, c3) thermosetting aids or radiation curing aids, c4) base wetting aids, c5) wetting and dispersing aids, c6) hydrophobing agents, c7 ) Additives selected from the group consisting of: fixatives, and c8) anti-improving aids,
[5] D) if desired, further additives selected from the group consisting of d1) dyes and d2) pigments, and
[6] E) If necessary, the present invention relates to a liquid crystal composition comprising an additional additive selected from the group consisting of a light stabilizer, a heat stabilizer and / or an oxidation stabilizer.
[7] Z ¹ -Y ¹ -A ¹ -Y ³ -M ¹ -Y ⁴ -A ² -Y ² -Z ²
[8] Z ³ -Y ⁵ -A ³ -Y ⁷ -M ² -P
[9] In the above formula,
[10] P is hydrogen, a C ₁ -C ₁₅ alkyl or -Y ⁸ -A ⁴ -Y ⁶ -Z ⁴ group,
[11] Z ¹ to Z ⁴ are polymerizable groups,
[12] Y ¹ to Y ⁴ are linking groups,
[13] A ¹ to A ⁴ are spacers,
[14] M ¹ to M ⁴ are mesogenic groups.
[15] Detailed definitions for the variables Z ¹ to Z ⁴ , Y ¹ to Y ⁴ , A ¹ to A ⁴ , P, M ¹ and M ² will be described below.
[16] In addition, the present invention relates to the manufacture of a film or coating as an ink for printing, in the electro-optical member, for the printing or coating of a substrate, for anti-counterfeit marking of an article, and for selectively reflecting light of wavelengths from 250 nm to 1300 nm It relates to the use of liquid crystal compositions of this type.
[17] The present invention furthermore relates to polymers or polymerized films obtained by polymerizing liquid crystal compositions according to the invention, and to optical films, spectrometers, decorations, anti-counterfeiting indicators, or radiation of wavelengths from 250 nm to 1300 nm of polymerized films of this type. And as a reflecting medium for selectively reflecting light.
[18] The invention also relates to a method of printing or coating a substrate using the liquid crystal composition according to the invention.
[19] The invention also relates to a substrate to which a liquid crystal composition according to the invention or a polymer or polymerized film according to the invention is applied, or a substrate printed or coated by the method according to the invention.
[23] An object of the present invention is a liquid crystal composition which can be used as a printing ink, in particular in a conventional printing method, can produce a print having high color fastness, brightness and whiteness, and can produce a homogeneous and smooth liquid crystal layer and film To provide.
[24] The inventors have found that this object is in addition to the optional components B) to E).
[25] A) was found to be achieved by the above liquid crystal composition containing as a component a liquid crystal mixture containing at least one compound selected from the group consisting of a compound of formula (Ia) and a compound of formula (Ib).
[26] Formula Ia
[27] Z ¹ -Y ¹ -A ¹ -Y ³ -M ¹ -Y ⁴ -A ² -Y ² -Z ²
[28] Formula Ib
[29] Z ³ -Y ⁵ -A ³ -Y ⁷ -M ² -P
[30] In the above formula,
[31] Z ¹ to Z ⁴ are polymerizable groups,
[32] Y ¹ to Y ⁸ are each a single chemical bond, oxygen, sulfur, -O-CO-, -CO-O-, -O-CO-O-, -CO-NR-, -NR-CO-, -O- CO-NR-, -NR-CO-O-, or -NR-CO-NR-,
[33] R is hydrogen or C ₁ -C ₄ alkyl,
[34] A ¹ to A ⁴ are spacers having 1 to 30 carbon atoms, wherein the carbon chain may be blocked by ether oxygen, thioether sulfur or nonadjacent imino or C ₁ -C ₄ alkylimino groups,
[35] P is hydrogen; Mono- or multi-substituted by methyl, fluorine, chlorine or bromine, wherein non-adjacent CH ₂ groups are oxygen, sulfur, -CO-, -O-CO-, -CO-O- or -O-CO-O C ₁ -C ₁₅ alkyl which may be substituted by; Or -Y ⁸ -A ⁴ -Y ⁶ -Z ⁴ groups,
[36] M ¹ is a mesogenic group of the general formula (Ic)
[37] M ² is a mesogenic group of the formula (Id) below.
[38] Formula Ic
[39] -T ¹ -Y ⁹ -T ^{1 '} -
[40] Chemical Formula Id
[41] (-T ² -Y ¹⁰ ) _r -T ^2-
[42] [In the formula,
[43] T ¹ , T ^{1 ′} and T ² are divalent saturated or unsaturated carbocyclic bicyclic radicals,
[44] Y ⁹ and Y ¹⁰ are crosslinking units as defined in Y ¹ to Y ⁸ , or —CH ₂ —O—, —O—CH ₂ —, —CH═N—, —N═CH— or —N = N -,
[45] r is a value of 0, 1, 2 or 3,
[46] When r is not 0, the radicals T ² and Y ¹⁰ may be the same or different.]
[47] Component A) of the novel liquid crystal composition encompasses both liquid crystal mixtures containing pure liquid crystal compounds of the formulas (Ia) and / or (Ib) and mixtures further containing non-liquid crystal mixture components, both of which have liquid crystal action. These non-liquid crystal mixture components are usually by-products formed during the synthesis of the liquid crystal compound or during the synthesis of the liquid crystal compound mixture.
[48] Component A) preferably comprises at least one chiral compound in addition to the liquid crystal compounds (and by-products) of the formulas (Ia) and / or (Ib), but the chiral compounds themselves do not necessarily have a liquid crystalline action. The presence of such chiral compounds leads to the formation of chiral-nematic (cholester) phases at least in certain temperature ranges, which phases usually have interesting optical properties.
[49] However, for the purposes of the present invention, the liquid crystal composition or liquid crystal mixture (component A)) does not necessarily need to include such a chiral compound.
[50] Suitable polymerizable groups Z ¹ to Z ⁴ together with the crosslinking units Y ¹ to Y ⁸ , for example, form the following.
[51]
[52] In the above formula,
[53] Y is as defined for crosslinking units Y ¹ to Y ⁸ , ie single chemical bond, oxygen, sulfur, -O-CO-, -CO-O-, -O-CO-O-, -CO-NR- , -NR-CO-, -O-CO-NR-, -NR-CO-O- or -NR-CO-NR-, R is hydrogen or C ₁ -C ₄ alkyl, ie methyl, ethyl, n- Propyl, i-propyl, n-butyl, i-butyl, secondary butyl or t-butyl, and Y 'is a single chemical bond (hereinafter polymerizable groups Z ¹ to Z ⁴ are crosslinking units Y ¹ to Y ⁸ Together as polymerizable units or ZY and / or Z-Y '.
[54] Of these polymerizable units, cyanates can be trimerized automatically to form cyanurates. The maleimido groups are particularly suitable for free radical copolymerization reactions with liquid crystal compounds of formula (Ia) and / or formula (Ib) containing styryl groups as polymerizable units.
[55] Epoxides, thiiranes, compounds of formula (Ia) and / or (Ib) containing aziridine, isocyanate and isothiocyanate groups, further require compounds containing complementary reaction units for the polymerization reaction. Thus, for example, the corresponding isocyanates can be polymerized with alcohols to form urethanes, and with amines to form urea derivatives. This applies equally to the corresponding thiiranes and aziridines.
[56] Complementary reaction units may be present in the liquid crystal compound, which may likewise be present in the compounds of formulas Ia and / or Ib in component A) of the liquid crystal composition. However, these compounds contain, for example, hydroxyl, mercapto or NHR groups instead of Z ¹ -Y ^1- , Z ² -Y ^2- , Z ³ -Y ⁵ -and / or Z ⁴ -Y ⁶ groups. In the latter case, R is hydrogen or, for example, C ₁ -C ₄ alkyl. In addition, complementary reaction units may be present in auxiliary compounds injected into the liquid crystal composition.
[57] Depending on whether component A) contains a liquid crystal compound of formula (Ib) containing one or two polymerizable units, if so, depending on the content of these compounds, and in particular liquid crystal compounds containing polymerizable units Depending on the mixing ratio between the liquid crystal compound containing the complementary unit and the liquid crystal compound containing the polymerizable unit and the auxiliary compound containing the complementary unit, a polymer product having a substantially different degree of crosslinking is obtained. In this way, this corresponds to a specific requirement.
[58] Spacers A ¹ and A ² usually contain 1 to 30 carbon atoms, preferably 1 to 12 carbon atoms, and consist mainly of straight-chain aliphatic groups. The carbon chain may also be monosubstituted or multisubstituted by methyl, fluorine, chlorine or bromine and / or blocked by ether oxygen, thioether sulfur or by non-adjacent imino or C ₁ -C ₄ alkylimino groups. have. C ₁ ~C ₄ C ₁ ~C ₄ alkyl radicals suitable alkyl imino group is methyl, ethyl, n- propyl, i- propyl, n- butyl, i- butyl, sec-butyl and t- butyl.
[59] Examples of representative spacers are as follows.
[60]
[61] In the above formula,
[62] p is an integer from 1 to 30, preferably 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, and m is an integer from 1 to 14, preferably 1, 2 Or three.
[63] Suitable C ₁ to C ₁₅ alkyl radicals for P include unbranched alkyl chains such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n -Nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl or n-pentadecyl.
[64] These C _{1 to} C ₁₅ alkyl radicals may be mono- or multi-substituted, typically up to triple, substituted by methyl, fluorine, chlorine or bromine. In that case, P is for example i-propyl ("1-methylethyl"), secondary butyl ("1-methylpropyl"), i-butyl ("2-methylpropyl"), t-butyl ("1 , 1-dimethylethyl "), 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2 -Methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3 , 3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl or mono-di- or tri-methyl substituted radical n-hexyl, n-heptyl, n-octyl, n-nonyl , n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl or n-pentadecyl and isomers thereof. When the methyl group in the abovementioned radicals is substituted, for example by fluorine, chlorine or bromine, the corresponding halogen substituted C ₁ to C ₁₅ alkyl radicals are provided.
[65] Non-adjacent CH ₂ groups in C ₁ -C ₁₅ alkyl may be substituted by oxygen, sulfur, —CO—, —O—CO—, —CO—O— or —O—CO—O—.
[66] In this case, the CH ₂ group in the C _{1 to} C ₁₅ alkyl is preferably replaced by oxygen or sulfur.
[67] In this case, it is preferable to CH ₂ groups in the C ₁ ~C ₁₅ alkyl which is substituted not more than four.
[68] Suitable C ₁ -C ₁₅ alkyl radicals for P, wherein the CH ₂ group in the carbon chain is substituted by ether oxygen, are, for example, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxy Ethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl, 4-methoxybutyl, 4-ethoxybutyl, 4-butoxybutyl, 3,6-dioxaheptyl, 3,6- Dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanyl, 4,7-dioxoctyl, 4,7-dioxanonyl, 4,8-dioxa Decyl, 3,6,8-trioxadedecyl, 3,6,9-trioxoundecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12-tetraoxatetradecyl and these Is the corresponding sulfur analogue.
[69] In addition, P may be a -Y ⁸ -A ⁴ -Y ⁶ -Z ⁴ group, where the variable is as described above.
[70] M ¹ corresponds to the mesogenic group of formula Ic, and M ² corresponds to the mesogenic group of formula Id.
[71] Formula Ic
[72] -T ¹ -Y ⁹ -T ^{1 '} -
[73] Chemical Formula Id
[74] (-T ² -Y ¹⁰ ) _r -T ^2-
[75] In Formulas Ic and Id,
[76] T ¹ , T ^{1 ′} and T ² are divalent saturated or unsaturated carbocyclic or bicyclic radicals,
[77] Y ⁹ and Y ¹⁰ are crosslinking units as defined in Y ¹ to Y ⁸ , or —CH ₂ —O—, —O—CH ₂ —, —CH═N—, —N═CH— or —N = N -,
[78] r is a value of 0, 1, 2 or 3.
[79] When r is 1, 2 or 3, the radicals T ² and Y ¹⁰ may be the same or different.
[80] It is preferable that r is 1 or 2.
[81] Thus, the mesogenic group M ¹ is "bicyclic" and the mesogenic group M ² is "monocyclic", "bicyclic", "tricyclic" or "tetracyclic" or "bicyclic" or "tricyclic" Units are preferred.
[82] The radicals T ¹ , T ^{1 ′} and T ² are preferably C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₂₀ alkoxycarbonyl, C ₁ -C ₂₀ monoalkylaminocarbonyl, C _1- Up to 3 same or different selected from the group consisting of C ₂₀ alkylcarbonyl, C ₁ -C ₂₀ alkylcarbonyloxy, C ₁ -C ₂₀ alkylcarbonylamino, formyl, halogen, cyano, hydroxy or nitro It may have a substituent. However, in the case of substituted radicals T ¹ and / or T ^{1 ′} and / or T ² a single substitution is preferred.
[83] Particularly suitable radicals T ¹ , T ^{1 ′} and T ² are as follows.
[84]
[85] Preferred mesogenic groups M ¹ are as follows, for example.
[86]
[87] Preferred mesogenic groups M ² are, for example, as follows.
[88]
[89] As mesogenic group M ¹ , the following chemical formula is particularly preferable,
[90]
[91] Roneun method gengi M ² is the following formula particularly preferred.
[92]
[93] In the above formula.
[94] Each ring Z is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₂₀ alkoxycarbonyl, C ₁ -C ₂₀ monoalkylaminocarbonyl, C ₁ -C ₂₀ alkylcarbonyl, C _1- C ₂₀ alkylcarbonyloxy, C ₁ -C ₂₀ alkylcarbonylamino, formyl, halogen, cyano, hydroxy or nitro may have up to 3 identical or different substituents.
[95] Preferred substituents of the aromatic ring Z are, in addition to fluorine, chlorine, bromine, cyano, formyl and hydroxyl, in particular short-chain aliphatic radicals such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i -Butyl, t-butyl and alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylcarbonyloxy, alkylcarbonylamino and monoalkylaminocarbonyl radicals containing said alkyl radicals.
[96] A particularly preferred group Z outer benzene rings in the benzene ring and Z, particularly preferred groups of M ¹ M ² is substituted or has the form of the following, or
[97]
[98] It is preferred to be substituted similarly by F, Br, CH ₃ , OCH ₃ , CHO, COCH ₃ , OCOCH ₃ or CN instead of Cl, in which a mixture of substituents may also be present. The following is mentioned as a structure.
[99]
[100] In the above formula,
[101] s is an integer from 2 to 20, preferably 8, 9, 10, 11, 12, 13, 14 or 15.
[102] Preferred substitution forms of the central benzene ring Z in the particularly preferred group M ² are as follows.
[103]
[104] In the compounds of formula (la) and (lb), Y ¹ to Y ⁵ , Y ⁷ , Y ⁹ and Y ¹⁰ , and when present, Y ⁶ and Y ⁸ are oxygen, —O—CO—, —CO—O— or —O, respectively. Preference is given to -CO-O-.
[105] Preferred liquid crystal compositions comprise as component A) a liquid crystal mixture comprising at least one compound of formula (Ia) and at least one compound of formula (Ib).
[106] The liquid crystal composition and preferred embodiments thereof preferably comprise a compound of formula (Ia) and / or formula (Ib), wherein the polymerizable units Z ¹ -Y ^1- , Z ² -Y ^2- , Z ³ -Y ⁵ -and Z ⁴ -Y ^6- , when present, is selected from the group consisting of methacryloyloxy, acryloyloxy and vinyloxy.
[107] Particular preference is given to liquid crystal compositions according to the invention having a viscosity at 20 ° C. of from 0.5 to 10.0 Pa · s and preferred embodiments thereof.
[108] The viscosity value here means the flow viscosity value measured by the cone-plate geometry method.
[109] Viscosity can be measured using a current dynamic spectrometer, for example.
[110] Further liquid crystal compounds which may conform to formulas Ia and Ib and which may be present in component A) which contain a liquid crystal mixture are described in the specifications of WO 97/00600 and WO 98/47979, and in the prior German patent application 197 35 829.3. .
[111] It is preferable that the liquid crystal composition and component A) of the preferred embodiment thereof contain 40% to 99.5% by weight of the compound of formula (Ia) and / or formula (Ib) based on the total amount of component A).
[112] When chiral compounds are present in the liquid crystal mixture (component A)), they preferably conform to the formulas Ie, If, Ig and Ih.
[113] (Z ⁵ -Y ¹¹ ) _n X
[114] (Z ⁵ -Y ¹¹ -A ⁵ -Y ¹² ) _n X
[115] (Z ⁵ -Y ¹¹ ) _n X
[116] (Z ¹¹ -Y ¹¹ -A ⁵ -Y ¹² -MY ¹³ ) _n X
[117] In the above formula,
[118] Variable Z ⁵ is a polymerizable group,
[119] Y ¹¹ to Y ¹³ are crosslinking units,
[120] A ⁵ is a spacer,
[121] M is a mesogenic group, all of which are Z ¹ to Z ⁴ , Y ¹ to Y ⁸ , A ¹ to A ⁴ , and M ¹ and M ² (and M in formulas Ic and Id) for formulas Ia and Ib; Has the same meaning. n is 1, 2, 3, 4, 5 or 6 and X is an n-valent chiral radical. Here, the n groups bonded to the chiral radical X may be the same or different.
[122] The corresponding radical X is for example as follows.
[123]
[124]
[125]
[126] In the above formula,
[127] L is R, RO, COOR, OCOR, CONHR or NHCOR, halogen, in particular fluorine, chlorine or bromine, R is C ₁ -C ₄ alkyl, for example methyl, ethyl, n-propyl, i-propyl, n- Butyl, i-butyl or t-butyl.
[128] Particularly preferred ones are as follows.
[129]
[130] Chiral compounds containing such chiral radicals and other suitable chiral radicals are described, for example, in WO 95/16007, DE-A 1 95 20 660, DE-A 1 95 20 704 and previous German patent application 198 43 724.2. It is.
[131] The liquid crystal composition according to the present invention may further contain the additives listed in components B) to E).
[132] In addition to component A) and its corresponding preferred embodiments, preferred compositions of the present invention include one or more photoinitiators (b1)), one or more reactive stone diluents (b2)) containing photopolymerizable groups, and diluents (b3), if necessary). And a further additive selected from the group consisting of components C), D) and E), if necessary.
[133] In addition to component A) and its corresponding preferred embodiments, another preferred composition according to the invention contains component C) and further additives selected from the group consisting of components B), D) and E) as required.
[134] In addition to component A) and its corresponding preferred embodiments, another preferred composition according to the invention comprises one or more photoinitiators (b1)), one or more reactive thinners (b2) containing photopolymerizable groups), and diluents (if necessary) component B) containing b3)) and further additives selected from the group consisting of components C) and, optionally, components D) and E).
[135] Examples of suitable photoinitiators (b1)) are the materials sold under the trade names Lucirin®, Irgacure® and Darocure®. Preferred initiators include Lucirin® TPO, Irgacure® 184, Irgacure® 369, Irgacure® 907, and Darocure® 1173.
[136] Photoinitiators are usually used in amounts of 0.5% to 5.0% by weight based on the total weight of the liquid crystal composition.
[137] The reactive thinner (b2) used is not only the substance referred to as the actual reactive thinner (group b2.1), but also the aforementioned auxiliary compounds (group b2.2) comprising at least one complementary reaction unit, for example a hydroxy group or an amino group. ), The reaction with the polymerizable unit of the liquid crystal compound may be made through the complementary reaction unit.
[138] Substances in group b2.1) that are usually photopolymerizable include, for example, monofunctional, difunctional and multifunctional compounds containing one or more olefinic double bonds. Examples include vinyl esters of carboxylic acids such as lauric acid, myristic acid, palmitic acid and stearic acid, and vinyl esters of dicarboxylic acids such as succinic acid and adipic acid, monofunctional alcohols such as For example allyl and vinyl ethers of lauryl, myristyl, palmityl and stearyl alcohols and methacrylic acid and acrylic acid esters, and difunctional alcohols such as diallyl and divinyl ethers of ethylene glycol and 1,4-butanediol have.
[139] Also suitable are compounds containing no further functional groups or at most ether groups, in addition to methacrylic acid and acrylic acid esters of polyfunctional alcohols, especially hydroxy groups. Examples of such alcohols are difunctional alcohols such as ethylene glycol, propylene glycol and their more highly condensed representative compounds such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and the like, butanediol, pentane Diols, hexanediol, neopentyl glycol, alkoxylated phenolic compounds such as ethoxylated and propoxylated bisphenols, cyclohexanedimethanol, trifunctional and polyfunctional alcohols such as glycerol, trimethylolpropane, butanetriol, Trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, and corresponding alkoxylated, especially ethoxylated and propoxylated alcohols.
[140] Another suitable reactive thinner selected from group b2.1) is polyester (meth) acrylate, which is the (meth) acrylic ester of polyesterol.
[141] Examples of suitable polyesterols are those which can be prepared by esterifying polycarboxylic acids, preferably dicarboxylic acids, using polyols, preferably diols. Starting materials for such hydroxy containing polyesters are known to those skilled in the art. Dicarboxylic acids that can be used include succinic acid, glutaric acid, adipic acid, sebacic acid, o-phthalic acid and its isomers and hydrogenation products, and esterifiable and ester convertible derivatives of such acids, for example anhydrides and di Alkyl esters. Suitable polyols are the aforementioned alcohols, preferably ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, and ethylene glycol And polyglycols of the propylene glycol type.
[142] b2.1) Suitable reactive thinners selected from the group are also 1,4-divinylbenzene, triallyl cyanurate, acrylic esters of tricyclodekenylalcohols having the formula: this is dihydrodicyclopentadienyl acrylate Also known) and allyl esters of acrylic acid, methacrylic acid and cyanoacrylic acid.
[143]
[144] Particularly in light of the above-mentioned preferred compositions, for example, among reactive thinners selected from the group b2.1) mentioned, those containing polymerizable groups are used.
[145] b2.2) group, for example dihydric and polyhydric alcohols such as ethylene glycol, propylene glycol and their more highly condensed representative materials such as diethylene glycol, triethylene glycol, dipropylene glycol, Butanediol, pentanediol, hexanediol, neopentyl glycol, cyclohexanedimethanol, glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, Sorbitol, mannitol and the corresponding alkoxylated, especially ethoxylated and propoxylated alcohols.
[146] Groups b2.2) also include, for example, alkoxylated phenolic compounds such as ethoxylated and propoxylated bisphenols.
[147] These reactive thinners may also be, for example, epoxides or urethane (meth) acrylates.
[148] Epoxide (meth) acrylates can be obtained, for example, by reacting poly- or diglycidyl ethers such as bisphenol A diglycidyl ether or epoxidized olefins with (meth) acrylic acid via reactions known to those skilled in the art. That can be.
[149] Urethane (meth) acrylates are products obtained by reacting hydroxyalkyl (meth) acrylates with poly- or diisocyanates, in particular through reactions known to those skilled in the art.
[150] Such epoxides and urethane (meth) acrylates are included among the compounds listed as "mixed forms" in the groups b2.1) and b2.2).
[151] When reactive thinners are used, their amounts and properties must be met to each condition so as to achieve a satisfactory desired effect, for example the desired color of the composition according to the invention, while not overly impairing the phase performance of the liquid crystal composition. do. Low-crosslinking (high-crosslinking) liquid crystal compositions can be produced using, for example, corresponding reactive thinners having a relatively small (large) number of reaction units per molecule.
[152] Reactive thinners are usually used in amounts of about 0.5% to 20.0% by weight, based on the total weight of the liquid crystal composition.
[153] Liquid crystal mixtures (component A) having a relatively high (low) content of a compound of formula (Ib) containing radicals P, which are not polymerizable, are also (or alternatively) suitable for the preparation of low-crosslinking (high-crosslinking) liquid crystal compositions. Of course, it can be used.
[154] As the diluent of group b3), for example, C ₁ -C ₄ alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, secondary butanol, in particular C ₅ -C ₁₂ alcohol, n- Pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol and n-dodecanol, and isomers thereof,
[155] Glycols such as 1,2-ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 2,3- and 1,4-butylene glycol, di- and triethylene glycol and di -And tripropylene glycol,
[156] Ethers such as methyl t-butyl ether, 1,2-ethylene glycol mono- and dimethyl ether, 1,2-ethylene glycol mono- and diethyl ether, 3-methoxypropanol, 3-isopropoxypropanol, tetra Hydrofuran and dioxane,
[157] Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone),
[158] C ₁ -C ₅ alkyl esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and amyl acetate,
[159] Aliphatic and aromatic hydrocarbons such as pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene, white spirit, Shellsol® and Solvesso® brand)
[160] Mineral oils such as gasoline, kerosene, diesel oil and heated oil, and
[161] Natural oils such as olive oil, soybean oil, rapeseed oil, cottonseed oil and sunflower oil.
[162] Of course, mixtures of these diluents can also be used in the compositions according to the invention.
[163] As long as at least partially miscible, these diluents can also be mixed with water. Examples of suitable diluents here include C ₁ -C ₄ alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol and secondary butanol, glycols such as 1,2-ethylene glycol, 1, 2- and 1,3-propylene glycol, 1,2-, 2,3- and 1,4-butylene glycol, di- and triethylene glycol, and di- and tripropylene glycol, ethers such as tetrahydro Furan and dioxane, ketones such as acetone, methyl ethyl ketone and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), and C ₁ -C ₄ alkyl esters such as methyl, ethyl , Propyl and butyl acetate.
[164] This type of water-containing mixture often exhibits limited miscibility with nonpolar diluents, such as the aliphatic and aromatic hydrocarbons, mineral oils and natural oils described above, which may contain water, at least It means that it can be prepared and used with partially water miscible diluents and non-water miscible diluents.
[165] Diluents are usually used in amounts of about 0.5% to 10.0% by weight, preferably about 1.0% to 5.0% by weight, based on the total weight of the liquid crystal composition.
[166] Antifoaming and degassing agents (c1)), lubricants and flow aids (c2)), thermosetting or radiation curing aids (c3)), base wetting aids (c4), listed under component C), wetting and dispersing aids (c5) ), Hydrophobing agents (c6)), fixatives (c7)), and anti-improving aids (c8)) are usually not strictly limited in their function. For example, lubricants and flow aids may act as antifoams and / or degassing agents and / or anti-improving aids. Radiation curing aids may also act as lubricants and flow aids and / or degassing agents and / or substrate wetting aids. In each case, some of these adjuvants may satisfy the function of the fixer (c8)).
[167] Thus, certain additives can be classified into groups c1) to c8) below.
[168] Defoamers of group c1) include silicon-free polymers and silicon-containing polymers. Silicon-containing polymers are, for example, unmodified or modified polydialkylsiloxanes or branched chain copolymers, combs or block copolymers comprising polydialkylsiloxanes and polyether units, wherein the polyether units Can be obtained from ethylene oxide or propylene oxide.
[169] Examples of degassing agents in group c1) are organic polymers such as polyethers and polyacrylates, dialkylpolysiloxanes, in particular dimethylpolysiloxanes, organic modified polysiloxanes such as arylalkyl modified polysiloxanes, and fluorosilicones .
[170] The action of the antifoaming agent is mainly to destroy bubbles already formed or to prevent the formation of bubbles. Defoamers mainly act to promote the coalescence of finely divided gases or bubbles to form larger bubbles in the medium to be degassed, for example the composition according to the invention, thereby promoting the escape of gas (air). Defoamers can be frequently used as degassing agents, and degassing agents can also be used as defoamers, so these additives are included together in group c1).
[171] Such adjuvants are, for example, TEGO® Foamex 800, TEGO® Foamex 805, TEGO® Foamex 810, TEGO® Foamex 815, TEGO® Foamex 825, TEGO® Foamex 835, TEGO (R) Foamex 840, TEGO (R) Foamex 842, TEGO (R) Foamex 1435, TEGO (R) Foamex 1488, TEGO (R) Foamex 1495, TEGO (R) Foamex 3062, TEGO (R) Foamex 7447, TEGO (R) Foamex 8020, TEGO (R) Foamex N, TEGO (R) Foamex K3, TEGO (R) Antifoam 2-18, TEGO (R) Antifoam 2-57, TEGO (registered trademark) Antifoam 2-80, TEGO (registered trademark) Antifoam 2-82, TEGO (registered trademark) Antifoam 2-89, TEGO (registered trademark) Antifoam 2-92, TEGO (registered trademark) Antifoam 14, TEGO (registered trademark) Antifoam 28, TEGO (registered trademark) Antifoam 81, TEGO (registered trademark) Antifoam D 90, TEGO (registered trademark) Antifoam 93, TEGO (registered trademark) Antifoam 200, TEGO (registered trademark) Antifoam 201, TEGO® Antifoam 202, TEGO® Antifoam 793, TEGO® Antifoam 1488, TEGO® Antifoam 3062, TEGOPREN® 5803, TEGOPREN® 5852, TEGOPREN® 5863, TEGOPREN® 7008, TEGO (registered trademark) Antifoam 1-60, TEGO (registered trademark) Antifoam 1-62, TEGO (registered trademark) Antifoam 1-85, TEGO (registered trademark) Antifoam 2-67, TEGO (registered trademark) Antifoam WM 20 , TEGO® Antifoam 50, TEGO® Antifoam 105, TEGO® Antifoam 730, TEGO® Antifoam MR 1015, TEGO® Antifoam MR 1016, TEGO® Antifoam 1435 TEGO (registered trademark) Antifoam N, TEGO (registered trademark) Antifoam KS 6, TEGO (registered trademark) Antifoam KS 10, TEGO (registered trademark) Antifoam KS 53, TEGO (registered trademark) Antifoam KS 95, TEGO (registered trademark) Antifoam KS 100, TEGO (registered trademark) Antifoam KE 600, TEGO (registered trademark) Antifoam KS 911, TEGO (registered trademark) MR 1000, TEGOTEGO (registered trademark) Antifoam KS 1100, TEGO (registered trademark) Airex 900, TEGO (registered trademark) ) Airex 910 TEGO® Airex 931, TEGO® Airex 935, TEGO® Airex 960, TEGO® Airex 970, TEGO® Airex 980 and TEGO® TEEX Airex 985 What is marketed by (Tego) and BYK (registered trademark) -011, BYK (registered trademark) -019, BYK (registered trademark) -020, BYK (registered trademark) -021, BYK (registered trademark) -022, BYK (Registered trademark) -023, BYK (registered trademark) -024, BYK (registered trademark) -025, BYK (registered trademark) -027, BYK (registered trademark) -031, BYK (registered trademark) -032, BYK (registered trademark) Trademark) -033, BYK (registered trademark) -034, BYK (registered trademark) -035, BYK (registered trademark) -036, BYK (registered trademark) -037, BYK (registered trademark) -045, BYK (registered trademark) -051, BYK (registered trademark) -052, BYK (registered trademark) -053, BYK (registered trademark) -055, BYK (registered trademark) -057, BYK (registered trademark) -065, BYK (registered trademark) -066 , BYK®-070, BYK®-080, BYK®-088, BYK®-141 and BYK®-A 530 have.
[172] Adjuvants in group c1) are usually used in amounts of about 0.05% to 3.0% by weight, preferably about 0.5% to 2.0% by weight, based on the total weight of the liquid crystal composition.
[173] Within the c2) group, lubricants and flow aids are usually silicon-free polymers and silicon-containing polymers such as polyacrylates or modified compounds, low molecular weight polydialkylsiloxanes. The modified product is one in which part of the alkyl group is substituted with various organic radicals. These organic radicals are, for example, polyethers, polyesters or considerable long chain alkyl radicals, of which polyether is most often used.
[174] Polyether radicals in the correspondingly modified polysiloxanes are formed of ethylene oxide and / or propylene oxide units. Usually, the greater the amount of these alkylene oxide units in the modified polysiloxane, the greater the hydrophilicity of the product.
[175] Such adjuvants are, for example, TEGO® Glide 100, TEGO® Glide ZG 400, TEGO® Glide 406, TEGO® Glide 410, TEGO® Glide 411, TEGO ( Glide 415, TEGO® Glide 420, TEGO® Glide 435, TEGO® Glide 440, TEGO® Glide 450, TEGO® Glide A 115, TEGO® Trademark) Glide B 1484 (which can also be used as an antifoam and degassing agent), TEGO® Flow ATF, TEGO® Flow 300, TEGO® Flow 460, TEGO® Flow 425 and TEGO Flow ZFS 460, available from Tego. Suitable radiation curable lubricants and flow aids that may also be used to improve scratch resistance include TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600 And TEGO® Rad 2700, which are commercially available from Tego.
[176] Such adjuvants are, for example, BYK (registered trademark) -300, BYK (registered trademark) -306, BYK (registered trademark) -307, BYK (registered trademark) -310, BYK (registered trademark) -320, BYK (registered) Trademark) -333, BYK (R) -341, BYK (R) -354 and BYK (R) -361, are commercially available from BYK.
[177] Adjuvants in group c2) are usually used in amounts of about 0.05% to 3.0% by weight, preferably about 0.5% to 2.0% by weight, based on the total weight of the liquid crystal composition.
[178] Within the group c3), radiation curing aids are in particular polysiloxanes having terminal double bonds which are components of acrylate groups. Such adjuvants may be crosslinked by actinic rays or, for example, electron beams. These adjuvants usually combine a number of properties together. In the non-crosslinked state they may also act as defoamers, degassing agents, lubricants and flow aids and / or substrate wetting aids, while in the crosslinked state they may be prepared in particular using the compositions according to the invention, for example. Improve the scratch resistance of the coating or film. For example, the improvement of the gloss properties of a coating or film is considered to be the result of these auxiliaries acting primarily as antifoams, degassing agents and / or lubricants and flow aids (in a noncrosslinked state).
[179] Examples of suitable radiation curing aids include TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600 and TEGO® Rad 2700 available from Tego. And BYK (registered trademark) -371 sold by BYK.
[180] c3) The thermosetting aids in the group contain, for example, primary OH groups which can react with the isocyanate groups of the binder.
[181] Examples of thermosetting aids that can be used are the products BYK (R) -370, BYK (R) -373 and BYK (R) -375 available from BIC.
[182] Adjuvants in group c3) are usually used in amounts of about 0.1% to 5.0% by weight, preferably about 0.1% to 3.0% by weight, based on the total weight of the liquid crystal composition.
[183] Substrate wetting aids within the group c4) serve to improve the wettability of substrates to be printed or coated, for example using printing inks or coating compositions, for example compositions according to the invention. Improvements that are typically made in the lubrication and flow action of such printing inks or coating compositions affect the appearance of the finished (eg crosslinked) printing or coating.
[184] A variety of such supplements are available from TEGO under TEGO® Wet KL 245, TEGO® Wet 250, TEGO® Wet 260 and TEGO® Wet ZFS 453, and BYK®. ) -306, BYK (registered trademark) -307, BYK (registered trademark) -310, BYK (registered trademark) -333, BYK (registered trademark) -344, BYK (registered trademark) -345, BYK (registered trademark)- 346 and BYK®-348 are commercially available from BIC.
[185] Adjuvants in group c4) are usually used in amounts of about 0.05% to 3.0% by weight, preferably about 0.1% to 1.5% by weight, based on the total weight of the liquid crystal composition.
[186] The wetting and dispersing aids in the c5) group in particular serve to prevent the flooding, flotation and precipitation of the pigments and are therefore suitable for the pigment compositions according to the invention as necessary.
[187] These adjuvants stabilize the pigment dispersion primarily through electrostatic repulsion and / or steric hindrance of the pigment particles containing these additives, in the latter case mainly the reaction of the adjuvant with the surrounding medium (eg binder).
[188] Such wetting and dispersing aids are those commonly used in the technical field of printing inks and paints, for example, and when using them, the selection of suitable aids of this type is not difficult for the skilled person.
[189] Such wetting and dispersing aids include, for example, TEGO® Dispers 610, TEGO® Dispers 610 S, TEGO® Dispers 630, TEGO® Dispers 700, TEGO® Dispers 705 , TEGO® Dispers 710, TEGO® Dispers 720 W, TEGO® Dispers 725 W, TEGO® Dispers 730 W, TEGO® Dispers 735 W and TEGO® Disperbyk (registered trademark) -107, Disperbyk (registered trademark) -108, Disperbyk (registered trademark) -110, Disperbyk (registered trademark) -111 Disperbyk (registered trademark) -115, Disperbyk (registered trademark) -130, Disperbyk (registered trademark) -160, Disperbyk (registered trademark) -161, Disperbyk (registered trademark) -162, Disperbyk (registered trademark) -163, Disperbyk (Registered trademark) -164, Disperbyk (registered trademark) -165, Disperbyk (registered trademark) -166, Disperbyk (registered trademark) -167, Disperbyk (registered trademark) -170, Disperbyk (registered trademark) -174, Disperbyk (registered trademark) Brand) -180, Disper byk (registered trademark) -181, Disperbyk (registered trademark) -182, Disperbyk (registered trademark) -183, Disperbyk (registered trademark) -184, Disperbyk (registered trademark) -185, Disperbyk (registered trademark) -190, Anti- Terra (registered trademark) -U, Anti-Terra (registered trademark) -U 80, Anti-Terra (registered trademark) -P, Anti-Terra (registered trademark) -203, Anti-Terra (registered trademark) -204, Anti -Terra (registered trademark) -206, BYK (registered trademark) -151, BYK (registered trademark) -154, BYK (registered trademark) -155, BYK (registered trademark) -P 104 S, BYK (registered trademark) -P 105, Lactimon (R), Lactimon (R) -WS and Bykumen (R).
[190] c5) The amount of adjuvant in the group mainly depends on the pigment surface area to be coated and the average molecular weight of the adjuvant.
[191] For organic pigments and low molecular weight adjuvants, the amount of low molecular weight adjuvants is expected to be from about 0.5% to 2.0% by weight based on the total weight of this aid and the pigment. In the case of high molecular weight aids, the amount increases from about 1.0% to 30% by weight.
[192] For organic pigments and low molecular weight adjuvant, the amount of low molecular weight adjuvant is from about 1.0% to 5.0% by weight based on the total weight of this adjuvant and the pigment. For high molecular weight aids, this amount can be from about 10.0% to 90% by weight.
[193] In any case, it is desirable to carry out a preliminary experiment, which can be easily carried out by those skilled in the art.
[194] c6) hydrophobizing agents in the group can be used, for example, to provide water repellency to printed materials or coatings prepared using the compositions according to the invention. This prevents or at least significantly inhibits swelling due to absorption, and hence changes in the optical properties of such prints or coatings. In addition, when the composition is used, for example as an ink for printing of offset printing, it can be prevented or at least significantly reduced.
[195] Such hydrophobizing agents are, for example, Tego® Phobe WF, Tego® Phobe 1000, Tego® Phobe 1000S, Tego® Phobe 1010, Tego® Phobe 1030, Tego® Phobe 1010, Tego (TM) Phobe 1010, Tego (TM) Phobe 1030, Tego (TM) Phobe 1040, Tego (TM) Phobe 1050, Tego (TM) Phobe 1200, Tego (TM) Phobe 1300, Tego (TM) Phobe 1310 And Tego ™ Phobe 1400.
[196] Adjuvants in group c6) are usually used in amounts of about 0.05% to 0.5% by weight, preferably about 0.1% to 3.0% by weight, based on the total weight of the liquid crystal composition.
[197] c7) The fixer in the group serves to improve the adhesion of the two interfaces in contact. This directly demonstrates that it is effective to have only part of the fixer at one or the other or both interfaces. This means that, for example, when applying printing ink, coating composition or paint in liquid or paste form to a solid substrate, the fixing agent must be added directly to the substrate or the substrate must be treated with the fixing agent in advance (also by priming). Known), that is to say, to provide modified chemical and / or physical surface properties to this substrate.
[198] When the substrate has been primed in advance by a primer, this means that one side of the interface to contact is the primer side, and the other side is the printing ink or coating composition or the paint side. In this case, not only the adhesion properties between the substrate and the primer, but also the adhesion properties between the substrate and the printing ink or coating composition or paint act on the adhesion of the entire multilayer structure on the substrate.
[199] Broader meaning fixatives that may be mentioned are also the base wetting aids listed in group c4), but they do not usually have the same fixation capacity.
[200] For example, it is surprising that the fixing system is diverse in view of the variety of physical and chemical properties of substrates for printing or coating and printing inks, coating compositions and paints.
[201] The silane fixing agent is, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane and vinyltrimethoxysilane. These and other silanes are commercially available from Huls for example under DYNASILAN®.
[202] Fixing agents based on titanate / zirconate and titanium zirconium bisacetylacetonate conform to the following formula, for example.
[203]
[204] In the above formula,
[205] M is titanium or zirconium,
[206] R, R ¹ and R ² are C ₁ -C ₄ alkyl, for example i-propyl or n-butyl. Examples of such compounds are tetra-i-propyl titanate, tetra-n-butyl titanate, titanium bis (acetylacetonate) diisopropoxide, titanium bis (acetylacetonate) dibutoxide, titanium bis (acetylaceto Nate) monobutoxide monoisopropoxide and titanium bis (acetylacetonate) monoethoxide monoisopropoxide.
[207] Other titanium and zirconium compounds that can be used as fixatives include n-butyl polytitanate, isopropyl triisostearoyl titanate, isopropyl tris (N-ethylaminoethylamino) titanate and zirconium bis (diethyl citrate) Diisopropoxide.
[208] These and other titanium and zirconium compounds are for example TYZOR® (Dupont), Ken-React® (Kenrich Petrochemicals Incorporated) and Tilcom® (Tyoxide Chemicals) Is sold.
[209] For example, a zirconium aluminate sold under Manchem® Ron Pollen may act as a fixative.
[210] Other compounds suitable for example as fixing agents in printing inks or paints are chlorinated polyolefins (e.g. from Eastman Chemical and Toyo Kasei), polyesters (e.g. Wheels Age, Basf Age, Gebrahart Bochers Age, Fruce) Commercially available from starwoofer, hulst and bolé), sucrose-based compounds such as sucrose benzoate and sucrose acetoisobutyrate (the latter latter being commercially available from Eastman Chemical for example), phosphate esters ( Eg, compound colophonium esters suitable as fixatives in the Lubrizol Company and Chast AG, and Polyethylenimine (eg BASF AG), and in printing inks for curved, planar and packaging printing ( Yes, commercially available from Robert Cramer GmbH.
[211] Conventional methods are, for example, appropriate pretreatment of the substrate to be printed or coated, that is to say that such additives are used as primers.
[212] The corresponding technical information obtained from the manufacturer of such additives is usually required or one of ordinary skill in the art can obtain this information in a simple manner through the corresponding preliminary experiments.
[213] However, when these additives are intended to be added to the composition according to the invention as an adjuvant of group c7), their amounts are usually from about 0.05% to 5.0% by weight based on the total weight of the liquid crystal composition. Since the amount and type of additives are determined on a case-by-case basis depending on the nature of the substrate and the nature of the printing / coating composition, these concentration data are used only as a guide. In such cases, the technical information can be obtained from the manufacturer of such additives or can be determined by a person skilled in the art in a simple manner through the corresponding preliminary experiments.
[214] c8) Adjuvants that improve the resistance to scratches in the group include, for example, TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600, and the like in Tego. There is a product available under TEGO® Rad 2700.
[215] For these adjuvants, the amount data presented for group c3) are appropriate, in other words, these additives are from about 0.1% to 5% by weight, preferably from about 0.1% to 3.0, based on the total weight of the liquid crystal composition Used in amounts of weight percent.
[216] As the dye in the group d1), for example, monoazo dyes, isoindolin derivatives, derivatives of naphthalene- or perylenetetracarboxylic acid, thioindigo derivatives, azomethine derivatives, quinacridone, dioxazine, pyrazoloquina Zolone and basic dyes such as triarylmethane dyes and salts thereof.
[217] In particular, photochromic, thermochromic or luminescent dye (s) having a combination of these properties may also be added to the solvent according to the invention. In addition to the usual fluorescent dyes, the term fluorescent dyes means an optical brightener.
[218] Optical brighteners, for example, belong to the class of bisstyrylbenzene, in particular cyanostyryl compounds, and have the formula:
[219]
[220] Another suitable optical brightener of the stilbenzene class has, for example, the formula:
[221]
[222] In the above formula,
[223] Q ¹ is C ₁ -C ₄ alkoxycarbonyl or cyano, respectively, Q ² is benzoxazol-2-yl, which may be single or disubstituted by C ₁ -C ₄ alkyl, in particular methyl, and Q ³ is C ₁ -C ₄ alkoxycarbonyl or 3- (C ₁ -C ₄ alkyl) -1,2,4-oxadiazol-3-yl.
[224] Another suitable optical brightener of the benzoxazole class has, for example, the formula
[225]
[226] In the above formula,
[227] Q ⁴ is each C ₁ -C ₄ alkyl, especially methyl, and L is
[228] Is a radical, and n is an integer of 0 to 2.
[229] Suitable optical brighteners of the coumarin class have, for example, the formula:
[230]
[231] In the above formula,
[232] Q ⁵ is C ₁ -C ₄ alkyl, respectively.
[233] Q ⁶ is phenyl or 3-halopyrazol-1-yl, in particular 3-chloropyrazol-1-yl.
[234] Another suitable optical brightener of the pyrene class has, for example, the formula:
[235]
[236] In the above formula,
[237] Q ⁷ is C ₁ -C ₄ alkoxy, especially methoxy.
[238] The aforementioned brighteners can be used alone or in mixtures.
[239] The aforementioned optical brighteners are commonly known and commercially available products. These are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A18, pages 156-161, or may be obtained through the methods presented herein.
[240] In particular, where this is required, one or more of the optical brighteners of the bisstyrylbenzene class, in particular of the cyanostyrylbenzene class, are used.
[241] Cyanostyrylbenzene can be used as an individual compound, but can also be used as a mixture of isomeric compounds.
[242] Isomers have the following formula.
[243]
[244] Optical brighteners are commercially available from BASF, for example, Ultraphor® SF 004, Ultra® SF MO, Ultraphor® SF MP and Ultra® SF PO.
[245] Suitable fluorescent dyes are for example DE-A 32 35 526, DE-A 34 00 991, DE-A 34 34 059 and DE-A 35 45 004, European Patent Application 0 033 079 and European Patent 0 055 It is a perylene derivative of 363.
[246] Fluorescent dyes are, for example, Lumogen® Yellow 083, Lumogen® Orange 240, Lumogen® Red 300, Lumogen® Violet 570 and Thermoplast® from BASF. F Yellow 084.
[247] Pigments in group d2) include inorganic pigments and organic pigments. An overview of inorganic colored pigments that can be used in the compositions according to the invention is described in H. Endless, "Aktuelle anorganische Bunt-Pigmente" (Editor U. Zorll, Curt-R, -Vincentz-Verlag Hannover (1997)). It is. Further pigments not listed in this document are Pigment Black 6 and Pigment Black 8 (Carbon Black), Pigment Black 11 (Iron Oxide Black, Fe ₃ O ₄ ), Pigment White 4 (Zinc Oxide, ZnO). Pigment white 5 (Lithopone, ZnS / BaSO ₄ ), pigment white 6 (titanium oxide, TiO ₂ ) and pigment white 7 (zinc sulfide, ZnS).
[248] An overview of organic pigments that can be added to the compositions according to the invention is described in W. Herbst and K. Hunger, "Industrielle Organische Pigmente-Herstellung, Eigenschaften, Anwendung" (VCH-Verlag Weinheim, New York, Basle, Cambridge, Tokyo, Second edition (1995).
[249] It is also possible to add magnetic, electrically conductive, photochromic, thermochromic or luminescent pigment (s) having a combination of these properties to the composition according to the invention.
[250] In addition to some organic pigments, for example Lumogen® Yellow 0790 (Basf AG), suitable pigments with luminescent properties are also alkaline earth metal oxides, alkaline earth metal transition metal oxides, alkaline earth metal / aluminum oxides, alkaline earth metal / silicon oxides or Alkaline earth metal / phosphorus oxide, alkaline earth metal halide, Zn / silicon oxide, Zn / alkaline earth metal halide, rare earth metal oxide, rare earth metal / transition metal oxide, rare earth metal aluminum oxide, rare earth metal / silicon oxide or rare earth metal As organic dope or undoped compound based on phosphorus oxide, rare earth metal oxide sulfide or oxide halide, zinc oxide, sulfide or selenide, cadmium oxide, sulfide or selenide or zinc / cadmium oxide, sulfide or selenide, The cadmium-containing compound is toxicological and In ecological terms it is lower than in importance.
[251] Dopants used in these compounds are usually aluminum, tin, antimony, rare earth metals (eg cerium, europium or terbium), transition metals (eg manganese, copper, silver or zinc), or combinations of these elements.
[252] The following luminescent pigments are given by way of example, and the indication of “compound: element (s)” is to inform those skilled in the art that the compound is doped with the element (s). In addition, the indication "(P, V)", for example, shows that the lattice position in the solid structure of the pigment is irregularly occupied by phosphorus and vanadium.
[253] Examples of such compounds capable of luminescence include MgWO ₄ , CaWO ₄ , Sr ₄ Al ₁₄ O ₂₅ : Eu, BaMg ₂ Al ₁₀ O ₂₇ : Eu, MgAl ₁₁ O ₁₉ : Ce, Tb, MgSiO ₃ : Mn, Ca ₁₀ (PO ₄ ) ₆ (F, Cl): Sb, Mn, (SrMg) ₂ P ₂ O ₇ : Eu, SrMg ₂ P ₂ O ₇ : Sn, BaFCl: Eu, Zn ₂ SiO ₄ : Mn, (Zn, Mg) F ₂ : Mn, Y ₂ O ₃ : Eu, YVO ₄ : Eu, Y (P, V) O ₄ : Eu, Y ₂ SiO ₅ : Ce, Tb, Y ₂ O ₂ S: Eu, Y ₂ O ₂ S: Tb, La ₂ O ₂ S: Tb, Gd ₂ O ₂ S: Tb, LaOBr: Tb, ZnO: Zn, ZnS: Mn, ZnS: Ag, ZnS / CdS: Ag, ZnS: Cu, Al, ZnSe: Mn, ZnSe: Ag and ZnSe: Cu.
[254] Examples that may be referred to as light stabilizers, heat stabilizers and / or oxidative stabilizers as component E) include
[255] Alkylated monophenols such as 2,6-di-t-butyl-4-methylphenol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-ethylphenol , 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- ( α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-diodedecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-t-butyl-4- Methoxymethylphenol, nonyl phenols with straight or branched chains, for example 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundec-1'-yl) Phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) phenol and these compounds Mixture of
[256] Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-t-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethyl Phenol and 2,6-didodecylthiomethyl-4-nonylphenol,
[257] Hydroquinones and alkylated hydroquinones such as 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2,6 -Diphenyl-4-octadecyloxyphenol, 2,6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanizol, 3,5-di-t-butyl-4 -Hydroxyanisole, 3,5-di-t-butyl-4-hydroxyphenyl stearate and bis (3,5-di-t-butyl-4-hydroxyphenyl) adipate,
[258] Tocopherols such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures of these compounds, and tocopherol derivatives such as tocopheryl acetate, succinate, nicotinate and polyoxyethylene succinate ( "Tocopherate"),
[259] Hydroxylated diphenyl thioethers such as 2,2'-thiobis (6-t-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4 ' -Thiobis (6-t-butyl-3-methylphenol), 4,4'-thiobis (6-t-butyl-2-methylphenol), 4,4'-thiobis (3,6-di- Secondary amylphenol) and 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide,
[260] Alkylidenebisphenols such as 2,2'-methylenebis (6-t-butyl-4-methylphenol), 2,2'-methylenebis (6-t-butyl-4-ethylphenol), 2,2 '-Methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6- Nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-t-butylphenol), 2,2'-ethylidenebis (4,6-di-t-butylphenol), 2 , 2'-ethylidenebis (6-t-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylene Bis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-methylenebis (6-t -Butyl-2-methylphenol), 1,1-bis (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-t-butyl-5-methyl-2- Hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-t-butyl-4-hydrate Roxy-2-methylphenyl) -3-n-dodecyl-mercaptobutane, ethylene glycol bis [3,3-bis (3'-t- Butyl-4'-hydroxyphenyl) butyrate], bis (3-t-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-t-butyl-2'-hydroxy Hydroxy-5'-methylbenzyl) -6-t-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2'-bis (3 , 5-di-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-t-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecyl mercaptobutane and 1 , 1,5,5-tetrakis (5-t-butyl-4-hydroxy-2-methylphenyl) pentane,
[261] 3,5,3 ', 5'-tetra-t-butyl-4,4'-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl 4-hydrate Hydroxy-3,5-di-t-butylbenzylmercaptoacetate, tris (3,5-di-t-butyl-4-hydroxybenzyl) amine, bis (4-t-butyl-3-hydroxy-2 , 6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide and isooctyl-3,5-di-t-butyl-4-hydroxybenzylmer O-, N- and S-benzyl compounds such as captoacetate,
[262] 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-t-butyl- Aromatic hydroxybenzyl, such as 4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene and 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) phenol compound,
[263] 2,4-bis (octylmercapto) -6- (3,5-di-t-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6 -Bis (3,5-di-t-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-t- Butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-t-butyl-4-hydroxyphenoxy) -1,2,3 -Triazine, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-t-butyl-3-hydroxy Hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-t-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1 , 3,5-tris- (3,5-di-t-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5-tris (3,5- Triazine compounds such as dicyclohexyl-4-hydroxybenzyl) isocyanurate and 1,3,5-tris (2-hydroxyethyl) isocyanurate,
[264] Dimethyl 2,5-di-t-butyl-4-hydroxybenzyl phosphonate, diethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di- benzylphosphonates, such as t-butyl-4-hydroxybenzylphosphonate and dioctadecyl 5-t-butyl-4-hydroxy-3-methylbenzylphosphonate,
[265] Acylaminophenols such as 4-hydroxylauroylanilide, 4-hydroxystearoylanilide and octyl N- (3,5-di-t-butyl-4-hydroxyphenyl) carbamate,
[266] Monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalate Mead, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2]- Propionic acid and acetic acid ester of octane,
[267] N, N'-bis (3,5-di-t-butyl-4-hydroxyphenylpropionyl) hexamethylene diamine, N, N'-bis (3,5-di-t-butyl-4-hydroxy Amine derivative propionamides such as phenylpropionyl) trimethylenediamine and N, N'-bis (3,5-di-t-butyl-4-hydroxyphenylpropionyl) hydrazine;
[268] Ascorbic acid (vitamin C) and ascorbic acid derivatives such as ascorbyl palmitate, laurate and stearate, and ascorbyl sulfate and phosphate,
[269] N, N'-diisopropyl-p-phenylenediamine, N, N'-di-secondary butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenyl Rendiamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'- Dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N ' -Phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine , N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl-N, N'-di-secondary butyl-p- Phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-t-octylphenyl) -1-naphthylamine , Octyl substituted diphenylamines such as N-phenyl-2-naphthylamine, p, p'-di-t-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4- Nanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6-di-t-butyl-4-dimethylaminomethylphenol, 2, 4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis [( 2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, t-octyl substituted N-phenyl-1-naphthylamine, mixture of mono- and dialkylated t-butyl / t-octyldiphenylamine, mixture of mono- and dialkylated nonyldiphenylamine, mono- and dialkylated dodecyldi Mixture of phenylamine, mixture of mono- and dialkylated isopropyl / isohexyldiphenylamine, mixture of mono- and dialkylated t-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl- 4H-1,4-benzothiazine, phenothiazine, mono- and dialkylated t-butyl / t-octylpheno Mixtures of azine, mixtures of mono- and dialkylated t-octylphenothiazines, N-allylphenothiazines, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene , N, N-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine, bis (2,2,6,6-tetramethylpiperidin-4-yl) seva Amine compound-based antioxidants such as Kate, 2,2,6,6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethylpiperidin-4-ol,
[270] Triphenylphosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2, 4-di-t-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t- Butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxy pentaerythritol diphosphite, bis (2,4-di-t-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4 , 6-tris (t-butylphenyl)) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylenediphosphonite , 6-isooctyloxy-2,4,8,10-tetra-t-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphosine, 6-fluoro-2,4 ,8 , 10-tetra-t-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxaphosphosine, bis (2,4-di-t-butyl-6-methylphenyl) methyl force Phosphites and phosphonites, such as fighters and bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite,
[271] 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'- t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '-(1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-di-t-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-t-butyl-2'-hydroxy-5'-methylphenyl) -5- Chlorobenzotriazole, 2 '-(3'-tert.butyl-5'-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) Benzotriazole, 2- (3 ', 5'-di-t-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3', 5'-bis- (α, α-dimethylbenzyl)- 2'-hydroxyphenyl) benzotriazole, and 2- (3'-t-butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-t-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'- t-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5- Chlorobenzotriazole, 2- (3'-t-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-t-butyl-2 '-Hydroxy-5'-(2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-t-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl ] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (3'-t-butyl-2'- A mixture of hydroxy-5 '-(2-isooctyloxycarbonylethyl) phenyl benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzo Triazol-2-ylphenol]; 2- [3'-t-butyl-5 '-(2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole and polyethylene glycol 300 Fully esterified product of: [R—CH ₂ CH ₂ —COO (CH ₂ ) ₃ ] _{2 wherein} R is 3′-t-butyl-4′-hydroxy-5′-2H-benzotriazole- 2- (2'-hydroxyphenyl) benzotriazole, such as 2-ylphenyl],
[272] Esters of 3,3'-thiodipropionic acid, for example lauryl, stearyl, myristyl and tridecyl esters, mercaptobenzimidazole, and 2-mercaptobenzimidazole, dibutylzinc dithiocarbamate Sulfur-containing peroxide scavengers and sulfur-containing antioxidants such as zinc salts of dioctadecyl disulfide and pentaerythritol tetrakis (β-dodecylmercapto) propionate,
[273] 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'-hydroxy- 2-hydroxybenzophenone, such as a 4,4'- dimethoxy derivative,
[274] 4-t-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-t-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di -t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, octadecyl-3,5-di unsubstituted and substituted, such as -t-butyl-4-hydroxybenzoate and 2-methyl-4,6-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate Esters of benzoic acid,
[275] Ethyl α-cyano-β, β-diphenylacrylate, isooctyl-α-cyano-β, β-diphenylacrylate, methyl α-methoxycarbonylcinnamate, methyl α-cyano-β- Acrylates such as methyl-p-methoxycinnamate, butyl-α-cyano-β-methyl-p-methoxycinnamate and methyl-α-methoxycarbonyl-p-methoxycinnamate,
[276] Bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis (1, 2,2,6,6-pentamethylpiperidin-4-yl) sevacate, bis) 1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidin-4-yl) -n-butyl-3,5-di-t-butyl-4-hydroxybenzylmalonate, 1- (2-hydroxy Oxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid condensation product, N, N'-bis (2,2,6,6-tetramethylpiperidine-4 Condensation product of -yl) hexamethylenediamine with 4-t-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethylpiperidine-4- 1) nitrilotriacetate, tetrakis (2,2,6,6-tetramethylpiperidin-4-yl) -1,2,3,4-butanetetracarboxylate, 1,1 '-(1, 2-ethylene) bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6 , 6-frame Lamethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidin-4-yl), 2-n-butyl-2- (2-hydroxy-3,5-di-t -Butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy -2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine with 4-morpholino-2,6-dichloro-1,3,5-triazine Condensation product, 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidin-4-yl) -1,3,5-triazine and 1,2 Condensation product of bis (3-aminopropylamino) ethane, 2-chloro-4,6-di (4-n-butylamino-1,2,2,6,6-pentamethylpiperidin-4-yl ) -1,3,5-triazine and condensation product of 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3 , 8-triazaspiro [4.5] decane-2,4-dione, 3- Dodecyl-1- (2,2,6,6-tetramethylpiperidin-4-yl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6, 6-pentamethylpiperidin-4-yl) pyrrolidine-2,5-dione, 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine Mixture, N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-tri Condensation product of azine, condensation product of 1,2-bis (3-aminopropylamino) ethane with 2,4,6-trichloro-1,3,5-triazine, 4-butylamino-2,2,6 , 6-tetramethylpiperidine, N- (2,2,6,6-tetramethylpiperidin-4-yl) -n-dodecylsuccinimide, N- (1,2,2,6, 6-pentamethylpiperidin-4-yl) -n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4- Oxo-spiro [4.5] -decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospyro [4.5] decane and epichlorohydrin Condensation product of 4-amino-2,2,6,6-te Condensation products of lamethylpiperidine and tetramethylolacetylenediurea, and poly (methoxypropyl-3-oxy)-[4- (2,2,6,6-tetramethyl) piperidinyl] siloxane Sterically hindered amines,
[277] 4,4'-dioctyloxyoxanide, 2,2'-diethoxyoxanide, 2,2'-dioctyloxy-5,5'-di-t-butoxanilide, 2,2'- Didodecyloxy-5,5'-di-t-butoxanilide, 2-ethoxy-2'-ethyloxanide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2- Ethoxy-5-t-butyl-2'-ethoxanilide, a mixture of this with 2-ethoxy-2'-ethyl-5,4'-di-t-butoxanilide, ortho and para-methoxy Oxalamides such as mixtures of disubstituted oxanilides, and mixtures of ortho- and para-ethoxy disubstituted oxanilides, and
[278] 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis ( 2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5- Triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4 -Octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2, 4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5 -Triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-tri Azine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5- Triazine 2 -[2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6- Diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-tri 2- (2-hydroxyphenyl) -1,3, such as azine and 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine 5-triazine can be mentioned.
[279] In the present specification, preferred embodiments of the liquid crystal composition according to the present invention and the ink for printing are claimed. Preferred methods are screen printing, flat printing and letterpress printing.
[280] Among the screen printing methods, in particular, silk screen printing, frame printing, film printing and textile screen printing, flat printing, and letterpress printing methods can be mentioned, and the flat printing method specifically includes offset printing and letterpress printing. As a method, a curved surface printing method and a book printing method are mentioned.
[281] The invention also relates to the use of the liquid crystal composition according to the invention and to its preferred embodiments for printing or coating a substrate.
[282] Substrates are products of various fields, such as automotive and auto parts, leisure, sports and games, cosmetics, textiles, leather and jewelry, decorations, gifts, writing utensils, milk powder, packaging, structures and household goods. Articles in the field of application, printing product field and medical field.
[283] Examples of such substrates / articles in the present invention include cardboard boxes, packaging materials, textile and plastic bags, paper, covers, plastic films, vehicles of all types, for example children's cars, bicycles, motorcycles, cars and trucks, Passenger and cargo planes and corresponding vehicles / airplanes and vehicles / aircraft parts, electrical and data processing facilities for sale, in particular casings of such devices, roller skates, indoor skates, skis, (wind) surfboards, hang glider, medical facilities And spectacle frames.
[284] In the present specification, preferred embodiments of the liquid crystal composition according to the present invention and the electro-optical components are claimed. In this case, for example, the low-crosslinked or low-crosslinked portion according to the present invention can serve as a liquid crystal matrix in the liquid crystal screen and the screen, for example. The composition according to the invention is also suitable as an alignment film in such screens and screens.
[285] In the present specification, there is claimed a preferred embodiment for the use of the liquid crystal composition according to the present invention and for anti-counterfeiting display of articles.
[286] These items are, for example, banknotes, bonds and other gratuities, check or credit cards, identification cards or expensive food and tobacco, badges, certificates and luxury packaging, or such luxury goods themselves. The key word associated with high-end products is the prevention or at least a hindrance to trademark piracy.
[287] Claimed herein are the preferred embodiments for the use of the liquid crystal compositions according to the invention and for the production of films or coatings which selectively reflect light in the wavelength range of 250 nm to 1300 nm. In addition to (selective) reflections in the visible spectral region, mention may also be made of reflections of infrared and ultraviolet rays. This may serve, for example, to protect a substrate with such a film or coating from heat or ultraviolet radiation.
[288] The present invention further relates to polymers or polymerized films obtained by the polymerization of liquid crystal compositions according to the invention and embodiments thereof.
[289] Furthermore, these polymerized films obtained in this way, as optical filters, in particular as spectral color filters and notch filters, ie as narrow interference filters, as spectrometers, in particular as liquid crystal screens and screens, especially as decorations for lamination applications, in particular checks, As anti-counterfeiting indications of cards and identification cards and as reflective media for selectively reflecting radiation in the wavelength range of 250 nm to 1300 nm.
[290] In addition, the present invention
[291] i) applying a liquid crystal composition according to the present invention and a preferred embodiment thereof on a substrate and, if appropriate, aligning the liquid crystal composition on the substrate,
[292] ii) if necessary, applying one or more other non-liquid crystal prints or one or more other non-liquid crystal layers
[293] iii) optionally applying one or more absorbent and / or protective layers and / or any thermally activatable adhesive layer, and
[294] iv) curing the i) and, if performed, the ignition and / or layer prepared in steps ii) and / or iii), wherein the curing is performed in step i) and, if performed, in steps ii) and / or iii). Steps that can be performed directly or after applying each individual print or each individual layer in
[295] It relates to a method of printing or coating a substrate, including, step i) and ii) may be performed in the reverse order.
[296] The invention also relates to a method similar to that described above for printing or coating a substrate which is at least partially transparent in the wavelength range from 250 nm to 1300 nm.
[297] For the sake of simplicity, such printed or coated substrates produced through this method will be referred to as multilayer structures hereinafter. In addition, in the process according to the invention, the printing and layers may be applied to the substrate in any desired order and number, or alternately, in addition to the application of only the printing or layers in all steps i) and, if used, in step ii).
[298] The first stated method relates to the manufacture of a multilayer structure in which the properties are clearly visible when viewed from the top, and the last specified method is a multilayer structure in which the properties are clearly known when viewed from the top or through perspective, ie Corresponding substrates relate to the production of at least partially transparent structures in the wavelength range of 250 nm to 1300 nm.
[299] As described above, the substrate may first be applied with a corresponding liquid crystal composition, and then, if desired, one or more other non-liquid crystal prints or one or more other non-liquid crystal layers, or first, one or more other non-liquid crystal prints. Or one or more other non-liquid crystal layers may be applied onto the substrate and then coated or printed with the liquid crystal composition (s).
[300] For example, when the multilayer structure manufactured according to the present invention is to be used as a laminated film, since the (at least partially light transmissive) substrate itself having the multilayer structure forms the outermost layer of the laminated product, application of the protective layer ( Step iii)) is not necessary.
[301] However, the multilayer structure may have a design in which a release layer is applied between the substrate and the liquid crystal composition that is at least partially transparent in the wavelength range of 250 nm to 1300 nm. This release layer makes it possible to separate the first substrate (outer substrate) after applying the multilayer structure to the further substrate via the side facing the substrate. This can be achieved, for example, by hot embossing treatment.
[302] Application of the release layer may be unnecessary if the adhesion characteristics of the liquid crystal composition to the (first) substrate are appropriately adjusted. In this case, (1st) base material can be removed immediately after apply | coating to a further base material.
[303] If the multilayer structure comprises colored liquid crystal compositions, an absorbing layer may be applied to enhance or control the color tone. When using this multilayer structure, for example as a lamination means for dark articles, the application of not only the protective layer but also the corresponding absorbent layer (step iii)) is unnecessary.
[304] Curing may be carried out immediately after each application as described in step i) and, if used, in steps ii) and / or iii), or with varying miscibility and / or viscosity of the printing ink / coating composition or partially / completely drying. If it is possible to prevent the mixing of the prints / layers via, alternatively it can be carried out simultaneously, ie in the curing step (step iii)).
[305] The substrate to be printed or coated may be precoated with one or more pigments.
[306] In addition, the adhesive and / or wettability and / or alignment properties of the substrate can be improved through suitable pretreatment as needed.
[307] Adhesion properties can be improved (via priming treatment of the substrate) using, for example, fixatives exemplified in the additives of group c7).
[308] Wetting properties can be improved, for example, using substrate wetting aids, which can be suitably pretreated with the substrates, which are illustrated in the additives of group c4).
[309] In addition, the adhesion and wetting properties of the substrate can be improved through any type of physical / chemical activation. In this regard, mention may be made specifically of the activation of the substrate surface by various gas plasmas.
[310] Improvements in the alignment properties of the substrates (first step i) according to the liquid crystal composition according to the invention and the preferred embodiments thereof are, for example, physical or chemical modification of the surface of the substrate, for example stretching, gloss, This can be achieved by partial decomposition, etching or plasma treatment.
[311] Such methods of modifying the surface properties of the substrate are usually known to those skilled in the art.
[312] The method according to the invention can also be used to print or coat a substrate which is magnetic, electrically conductive, photochromic, thermochromic or luminescent, or has a combination of these properties.
[313] In this case, the substrate itself may have the above properties (bulk properties). However, these properties may be achieved by mixing (e.g., doping) the material (e.g., magnetic, electrically conductive, photochromic, thermochromic or luminescent pigments or photochromic, thermochromic or luminescent dyes), and also printing ink, coating composition or It may also be imparted by coating, printing or depositing using the deposition composition.
[314] In addition, for example, a combination method in which fluorescent thermoplastic films (eg, films dyed in bulk through fluorescent dyes or pigments) can be printed using magnetic or electrically conductive printing inks or pastes, or can be deposited coated with a metal layer. Also suitable.
[315] The substrate is pre-coated with one or more pigments and its adhesion and / or wettability and / or alignment properties have been improved by suitable pretreatment, or magnetic, electrical conductivity, photochromic, If thermochromic and / or luminescent are given, these preliminary treatments are considered part of the substrate and not as step ii) (which is carried out before step i)).
[316] If necessary, the application of the print or layer carried out in step ii) is carried out using a printing ink or coating composition by a suitable method. These printing inks or coating compositions are based on common binders and solvents and usually contain (effective) dyes and / or pigments, for example materials of the aforementioned groups d1) and d2).
[317] According to step iii), an absorbent layer and / or a protective layer may also be applied as necessary. This is also done using the corresponding coating composition by a suitable method. These coating compositions are also based on conventional binders and solvents and are usually additives to absorbent dyes and / or pigments and to provide, for example, improved scratch resistance to these absorbent and / or protective layers (e.g. c8 described above). ), Or additives (eg, additives of component E described above) which prevent degradation by light, heat and / or oxidation of these layers.
[318] For example, a multi-layer structure which is particularly advantageous in connection with the provision of anti-counterfeiting indications is based on the colored and photochemically polymerizable liquid crystal composition according to the invention in step i) (e.g., plastic film made of polyethylene terephthalate). And the composition is polymerized by ultraviolet light, and then in step ii) further phosphates or layers containing, for example, IR or UV absorbing or fluorescent dyes or pigments, and (if necessary, these ignitions or layers) After curing), the final absorbent layer can be applied to produce.
[319] The printing method that can be used for the liquid crystal composition and other non-liquid crystal layers is a full color printing method such as a curved surface printing method, a screen printing method or an offset printing method in addition to the usual coating method.
[320] During the day, when viewed from the film side, such multilayer films show only monochrome impressions depending on the viewing angle. Only when using an IR or UV lamp and any suitable viewing device (eg an IR camera) can additionally see additional dog tags hidden within the multilayer structure.
[321] The present invention also relates to a liquid crystal composition according to the present invention and a preferred embodiment thereof, or a substrate coated with a polymer or a polymer film prepared therefrom, or a substrate coated by the method of the present invention.
[322] As starting materials for component A) of the liquid crystal composition according to the present invention, chiral compounds were prepared as liquid crystal mixtures and dopants.
[323] Mixture 1 (M1):
[324] The following irregular mixture, in which four possible compounds were mixed in an irregular distribution, was prepared according to Example 48 of WO 97/00600 with 1,4-bis [4'-hydroxybenzoyloxy] -2-methylbenzene 4-acryloyl jade. Prepared by reaction with a mixture of sibutoxy chloroformate and butoxy chloroformate (molar ratio 1: 1).
[325]
[326] In the above formula,
[327] R is a radical to be.
[328] Mixture 2 (M2):
[329] The following irregular mixture, in which four possible compounds were mixed in an irregular distribution, was prepared according to Example 28 of WO 98/47979 with 1,4-bis [4'-hydroxybenzoyloxy] -2-methylbenzene 4-acryloyl jade. Prepared by reaction with a mixture of sibutoxy chloride and butyl chloride (molar ratio 1: 1).
[330]
[331] In the above formula,
[332] R is a radical to be.
[333] Mixture 3 (M3):
[334] From 37.5% by weight of the following compound and 62.5% by weight of the mixture M1 prepared by reacting 4- (4'-hydroxybenzoyloxy) phenol with 4-acryloyloxybutyl chloroformate according to example 18 of WO 97/00600 A mixture was prepared.
[335]
[336] Compound 1 (C1):
[337] The following compounds were prepared by reacting 1,4-bis [4'-hydroxybenzoyloxy] -2-methylbenzene with 4-acryloyloxybutyl chloroformate according to Example 6 of WO 97/00600.
[338]
[339] In the above formula,
[340] R is a radical to be.
[341] Chiral Compound 1 (CC1):
[342] Bis [4'-hydroxybenzoyl] -1,4: 3,6-dianhydrosorbitol is reacted with 4-acryloyloxybutoxycarbonyloxybenzoyl chloride according to example 1 of the preceding German patent application 198 43 724.2 The following chiral compounds were prepared.
[343]
[344] In the above formula,
[345] R is a radical to be.
[346] The liquid crystal composition (abbreviated as LCC in the table) was prepared from component A), component B) if necessary, and component C) as needed. In the tables below, percentages are by weight and percentages are by weight.
[347] Component B):
[348] The photoinitiator used (b1) is Irgacure® 184, 369 or 907, and the reactive reactive thinner (b2) used is hexanediol diacrylate (Laromer® HDDA, manufactured by BASF AG) or ethoxyethoxyethyl Acrylate, and the diluent used (b3)) was Solvesso® 100 / L33 or xylene.
[349] Component C):
[350] The antifoaming agent / degassing agent (c1) used was BYK® 57 or TEGO® Airex 900, and the lubricant and flow aid (c2) used were BYK® 361.
[351] LCCComponent A)Component B)Component C)ViscosityM1--29.9 Pas OneM1 85%15% Laromer® HDDA-Not measured 2M1: CC1 (97: 3) 84%15% Laromer® HDDA1% TEGO® Airex 900~ 3 Pas 3M1: CC1 (97: 3) 96%3% Irgacure® 9071% TEGO® Airex 900~ 39 Pas 4M1: CC1 (97: 3) 81%15% Laromer® HDDA, 3% Irgacure® 9071% TEGO® Airex 9004 Pas 5M1: CC1 (97: 3) 76%20% Laromer® HDDA, 3% Irgacure® 9071% TEGO® Airex 900~ 2 Pas 6M1: CC1 (97: 3) 83.8%15% Laromer® HDDA1.2% BYK (registered trademark) 361~ 3 Pas 7M1: CC1 (97: 3) 95.8%3% Irgacure® 9071.2% BYK (registered trademark) 361~ 39 Pas 8M1: CC1 (97: 3) 80.8%15% Laromer® HDDA, 3% Irgacure® 9071.2% BYK (registered trademark) 3614 Pas 9M1: CC1 (97: 3) 75.8%20% Laromer® HDDA, 3% Irgacure® 9071.2% BYK (registered trademark) 361~ 2 Pas
[352] Compositions 1,2,4,6,8, and in particular compositions 5 and 9, did not cause any problems when screen printing.
[353] LCCComponent A)Component B)Component C)ViscosityM2--9.6 Pas 10M2: CC1 (97: 3)--To 9 Pas 11M2: CC1 (97: 3) 84%15% Laromer® HDDA1% TEGO® Airex 900~ 2 Pas 12M2: CC1 (97: 3) 81%15% Laromer® HDDA, 3% Irgacure® 9071% TEGO® Airex 900~ 2 Pas 13M2: CC1 (97: 3) 83.8%15% Laromer® HDDA1.2% BYK (registered trademark) 361~ 2 Pas 14M2: CC1 (97: 3) 80.8%15% Laromer® HDDA, 3% Irgacure® 9071.2% BYK (registered trademark) 361~ 2 Pas
[354] Compositions 10, 11, 13, and in particular compositions 12 and 14, caused no problem at all in screen printing.
[355] LCCComponent A)Component B)Component C)Viscosity 15V1: CC1 (97: 3)--Not measured 16SG 15 96.95%3% Irgacure® 9070.05% BYK (registered trademark) 361Not measured
[356] Composition 16 caused no problem at all in screen printing.
[357] LCCComponent A)Component B)Component C)Viscosity 17M3: CC1 (96.5: 3.5) 90%9% Laromer® HDDA1% TEGO® Airex 9004.1 Pas 18M3: CC1 (96.5: 3.5) 96%3% Irgacure® 3691% TEGO® Airex 90011.5 Pas 19M3: CC1 (96.5: 3.5) 87%9% Laromer® HDDA, 3% Irgacure® 3691% TEGO® Airex 9004.4 Pas 20M3: CC1 (95: 5) 87%9% Laromer® HDDA, 3% Irgacure® 1841% TEGO® Airex 9003.8 Pas 21M3: CC1 (95: 5) 87%9% Laromer® HDDA, 3% Irgacure® 3691% TEGO® Airex 9004.5 Pas 22M3: CC1 (95: 5) 87%9% ethoxyethoxyethyl acrylate, 3% Irgacure® 3691% BYK (registered trademark) 574.3 Pas 23M3: CC1 (96: 4) 85.5%10% Laromer® HDDA, 3% Irgacure® 3691.5% Tego® Airex 9002.8 Pas 24M3: CC1 (97: 3) 85.5%10% Laromer® HDDA, 3% Irgacure® 3691.5% Tego® Airex 9002.5 Pas 25M3: CC1 (97: 3) 84%9% Laromer® HDDA, 3% Irgacure® 369, 3% Xylene1% Tego® Airex 9001.8 Pas 26M3: CC1 (97: 3) 83.5%9% Laromer® HDDA, 3% Irgacure® 369, 3% Solvesso® 199 / L331.5% Tego® Airex 9002.0 Pas 27M3: CC1 (96: 4) 83.5%9% Laromer® HDDA, 3% Irgacure® 369, 4% Xylene1.5% Tego® Airex 9001.5 Pas
[358] Compositions 17 and 19 to 27 caused no problem at all in screen printing and the liquid crystal composition was well aligned. Film formation by printing was also good and the color change was very remarkable.
[359] Printing / Coating Example:
[360] In all the examples below, the substrate used is a polyethylene terephthalate film coated with the composition 16 according to the invention as shown in Table 3 according to the method described in the preceding German patent application 197 38 369.6 using tetrahydrofuran as the diluent. (12 μm thick, manufactured by Teijin).
[361] Preparation of Base Mixture 1 (BM 1):
[362] 35 weight percent methoxypropyl acetate, 35 weight percent butyl glycol, 20 weight percent white spirit and 10 weight percent Laroflex® MP45 (PVC-based wetting agent, manufactured by BASF AG) were mixed.
[363] Preparation of Basic Mixture 2 (BM 2):
[364] 55 weight percent butyl glycol, 25 weight percent Laroflex® MP45 (product of BASF AG), 15 weight percent n-hexyl diglycol and 5 weight percent methoxypropyl acetate were mixed and based on this mixture 0.2% by weight of Uvinul 3039 (light / oxidation stabilizer, manufactured by BASF AG) was added.
[365] Example 1
[366] A mixture of 20% by weight Ultraphor® SF MO (ultraviolet excitation optical brightener) and 80% by weight of BM1 was added as a whole until the content of Ultraphor® SF MO in the mixture was 0.5% by weight. Diluted by BM 2 by weight. Using the resulting printing ink, a picture was printed by a flat screen printing method using a fine screen 180T on a plastic film surface coated with a liquid crystal composition. After drying, a larger full-screen screen print of black was printed on this figure using a larger screen mesh (120 T).
[367] The black printing ink used for this purpose was prepared by dispersing 20% by weight of carbon black (CK3, manufactured by Degussa) in 80% by weight of BM1 and then mixing the mixture so that the carbon black content in the mixture was 10% by weight as a whole. Prepared by dilution with BM2 at a weight ratio of 1.
[368] The coloring properties of the liquid crystal (cholesteric) layer are emphasized by coating with black printing ink. The observer cannot see the picture hidden in the multilayer structure under incident light or transmitted light. However, under ultraviolet light (Camag, 366 nm wavelength radiation), the picture is visible.
[369] Example 2
[370] A dispersion consisting of 20 wt% carbon black (CK3, Degussa) and 80 wt% BM1 was diluted by BM2 in a weight ratio of 1: 9 such that the carbon black content in the mixture as a whole was 2 wt%. Using this printing ink, a picture was printed on the plastic film surface coated with the liquid crystal composition by a flat screen printing method using a fine screen 180T. After drying, a larger full-screen screen print of black was printed on this figure using a larger screen mesh (120 T).
[371] The black printing inks used for this purpose were prepared by dispersing 20% by weight of pallagen black L 0086 (product of BASF AG) in 80% by weight of BM1 and then totally containing 10% by weight of pallagen black L 0086 in the mixture. This mixture was prepared by diluting with BM2 at a weight ratio of 1: 1.
[372] An observer can only observe the coloring effect of the liquid crystal (cholester) layer and the black full tint print. When using IR photography (EMO Electronics GmbH), only the picture is visible and no black full color prints are reflected.
[373] Example 3
[374] A dispersion consisting of 7.5% by weight Ultraphor® SF MO, 7.5% by weight carbon black (CK3) and 85% by weight BM1, as a whole, the Ultraphor® SF MO content and carbon black (CK3) content in the mixture Diluted with BM 2 in a weight ratio of 1: 9 until they were 0.75% by weight, respectively. Using this printing ink, a picture was printed on the plastic film surface coated with the liquid crystal composition by a flat screen printing method using a fine screen 180T. After drying, a larger full-screen screen print of black was printed on this figure using a larger screen mesh (120 T).
[375] Black printing inks used for this purpose were prepared as described in Example 2.
[376] The coloring property of the liquid crystal (cholester) layer is emphasized by coating with black printing ink. The observer cannot see the picture hidden in the multilayer structure under incident light or transmitted light. However, the picture can be seen under UV illumination (Camag, wavelength emission of 366 nm) and by IR photography.
[377] It is of course possible to apply different (eg auxiliary) ultraviolet and IR pictures to separate prints / layers.

权利要求:
Claims (18)
[1" claim-type="Currently amended] A) a liquid crystal mixture containing at least one compound selected from the group consisting of compounds of formula (Ia) and compounds of formula (Ib),
B) further additives selected from the group consisting of b1) photoinitiators, b2) reactive thinners, and b3) diluents, if desired,
C) if necessary, c1) antifoaming and degassing agents, c2) lubricants and flow control agents, c3) thermosetting aids or radiation curing aids, c4) base wetting aids, c5) wetting and dispersing aids, c6) hydrophobizing agents, c7) additional additives selected from the group consisting of fixatives, and c8) anti-improving aids,
D) if desired, further additives selected from the group consisting of d1) dyes and d2) pigments, and
E) further additives selected from the group consisting of light stabilizers, heat stabilizers and / or oxidative stabilizers, if desired
A liquid crystal composition containing as a component:
Formula Ia
Z ¹ -Y ¹ -A ¹ -Y ³ -M ¹ -Y ⁴ -A ² -Y ² -Z ²
Formula Ib
Z ³ -Y ⁵ -A ³ -Y ⁷ -M ² -P
In the above formula,
P is hydrogen; Mono- or multi-substituted by methyl, fluorine, chlorine or bromine, non-adjacent CH ₂ groups are oxygen, sulfur, -CO-, -O-CO-, -CO-O- or -O-CO-O- C ₁ -C ₁₅ alkyl which may be substituted by; Or -Y ⁸ -A ⁴ -Y ⁶ -Z ⁴ groups,
Z ¹ to Z ⁴ are polymerizable groups,
Y ¹ to Y ⁸ are each a single chemical bond, oxygen, sulfur, -O-CO-, -CO-O-, -O-CO-O-, -CO-NR-, -NR-CO-, -O- CO-NR-, -NR-CO-O- or -NR-CO-NR-,
R is hydrogen or C ₁ -C ₄ alkyl,
A ¹ to A ⁴ are spacers having 1 to 30 carbon atoms, wherein the carbon chain may be mono- or polysubstituted by methyl, fluorine, chlorine or bromine and / or ether oxygen, thioether sulfur or non-adjacent imino Or may be blocked by a C _{1 to} C ₄ alkylimino group,
M ¹ is a mesogenic group of the general formula (Ic)
M ² is a mesogenic group of the formula (Id) below.
Formula Ic
-T ¹ -Y ⁹ -T ^{1 '} -
Chemical Formula Id
(-T ² -Y ¹⁰ ) _r -T ^2-
(Wherein T ¹ , T ^{1 ′} and T ² are divalent saturated or unsaturated carbocyclic or bicyclic radicals,
Y ⁹ and Y ¹⁰ are crosslinking units as defined in Y ¹ to Y ⁸ , or —CH ₂ —O—, —O—CH ₂ —, —CH═N—, —N═CH— or —N = N -,
r is a value of 0, 1, 2 or 3,
If r is not 0, the radicals T ² and Y ¹⁰ may be the same or different)
[2" claim-type="Currently amended] The liquid crystal composition according to claim 1, comprising as component A) a liquid crystal mixture containing at least one compound of formula (Ia) and at least one compound of formula (Ib):
Formula Ia
Z ¹ -Y ¹ -A ¹ -Y ³ -M ¹ -Y ⁴ -A ² -Y ² -Z ²
Formula Ib
Z ³ -Y ⁵ -A ³ -Y ⁷ -M ² -P
Wherein the variable is as defined in claim 1.
[3" claim-type="Currently amended] The method according to claim 1 or 2, wherein as an additional additive in component B),
b1) one or more photoinitiators,
b2) at least one reactive stone thinner containing a photopolymerizable group, and as required
b3) diluent, and
If necessary, a liquid crystal composition containing a further additive selected from the group consisting of components C), D) and E).
[4" claim-type="Currently amended] The liquid crystal composition according to claim 1 or 2, further comprising component C) and further additives selected from the group consisting of components B), D) and E) as required.
[5" claim-type="Currently amended] The method according to claim 1 or 2, wherein as component B),
b1) one or more photoinitiators,
b2) one or more reactive thinners containing photopolymerizable groups, and as required
b3) diluent
Containing,
A liquid crystal composition containing component C) and further additives selected from the group consisting of components D) and E) as necessary.
[6" claim-type="Currently amended] The liquid crystal composition according to any one of claims 1 to 5, wherein the amount of the compound of formula (Ia) and / or formula (Ib) in component A) is 40% to 99.5% by weight based on the total amount of component A). .
[7" claim-type="Currently amended] The compound of claim 1, wherein Z ¹ -Y ^1- , Z ² -Y ^2- , Z ³ -Y ^5- , and Z ⁴ -Y ^6-, if present, are methacrylic. Liquid crystal composition selected from the group consisting of iloxy, acryloyloxy and vinyloxy.
[8" claim-type="Currently amended] The liquid crystal composition according to any one of claims 1 to 7, wherein the viscosity at 20 ° C. is 0.5 Pa · s to 10.0 Pa · s,
[9" claim-type="Currently amended] Use as a printing ink of the liquid crystal composition of any one of Claims 1-8.
[10" claim-type="Currently amended] Use of the liquid crystal composition according to any one of claims 1 to 8 for printing or coating a substrate.
[11" claim-type="Currently amended] Use of the liquid crystal composition as described in any one of Claims 1-8 in an electro-optical member.
[12" claim-type="Currently amended] Use of the liquid crystal composition according to any one of claims 1 to 8 for anti-counterfeiting indication of an article.
[13" claim-type="Currently amended] Use of the liquid crystal composition according to any one of claims 1 to 8 for the production of a film or coating which selectively reflects light in the wavelength range of 250 nm to 1300 nm.
[14" claim-type="Currently amended] The polymer or polymerized film obtained by superposing | polymerizing the liquid crystal composition of any one of Claims 1-8.
[15" claim-type="Currently amended] Use of the polymerized film of claim 14 as an optical filter, spectroscope, ornament, anti-counterfeit indication, or reflective medium for selectively reflecting radiation in the wavelength range of 250 nm to 1300 nm.
[16" claim-type="Currently amended] i) applying the liquid crystal composition according to any one of claims 1 to 8 to the substrate, if appropriate, aligning the liquid crystal composition on the substrate,
ii) optionally, applying one or more other non-liquid crystal phosphates or one or more other non-liquid crystalline layers,
iii) optionally applying one or more absorbent and / or protective layers and / or any thermally activatable adhesive layer, and
iv) curing the ignition and / or layer prepared in step i) and, if performed, in steps ii) and / or iii).
Including,
The steps i) and ii) can also be carried out in the reverse order, the curing step being carried out immediately after the application of each individual print or each individual layer in step i) and, if performed, in steps ii) and / or iii). A method of printing or coating a substrate, which may be carried out at the same time or at the same time.
[17" claim-type="Currently amended] i) applying the liquid crystal composition according to any one of claims 1 to 8 to the substrate, if appropriate, aligning the liquid crystal composition on the substrate,
ii) optionally applying at least one other non-liquid crystal phosphate or at least one other non-liquid crystal layer
iii) optionally applying one or more absorbent and / or protective layers and / or any thermally activatable adhesive layer, and
iv) curing the ignition and / or layer prepared in step i) and, if performed, in steps ii) and / or iii).
Including,
The steps i) and ii) can also be carried out in the reverse order, the curing step being carried out immediately after the application of each individual print or each individual layer in step i) and, if performed, in steps ii) and / or iii). A method of printing or coating a substrate that is at least partially transparent in the wavelength range of 250 nm to 1300 nm, which may be performed at the same time or simultaneously.
[18" claim-type="Currently amended] A substrate, to which the liquid crystal composition according to any one of claims 1 to 8 or the polymer or polymerized film according to claim 14 is applied, or printed or coated by the method according to claim 16 or 17.

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WO2000047694A1|2000-08-17|

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AU2670200A|2000-08-29|

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ES2220401T3|2004-12-16|

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AT267861T|2004-06-15|

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US20040140451A1|2004-07-22|

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JP2002536529A|2002-10-29|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
1999-02-10|Priority to DE19905394.4

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1999-02-10|Priority to DE19905394A

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2000-02-05|Application filed by 요헨 카르크, 안드레아스 비베르바흐, 바스프 악티엔게젤샤프트

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2000-02-05|Priority to PCT/EP2000/000915

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2001-11-15|Publication of KR20010102025A

优先权:

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申请号 | 申请日 | 专利标题

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DE19905394.4|1999-02-10|

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DE19905394A|DE19905394A1|1999-02-10|1999-02-10|Liquid crystalline mixture|

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PCT/EP2000/000915|WO2000047694A1|1999-02-10|2000-02-05|Liquid crystalline substance mixtures|