TWI238812B - Pigmented vitreous material - Google Patents

Abstract

The present application relates to a process for the manufacture of pigmented vitreous materials, as well as to pigmented vitreous materials, characterized by the use of soluble pigment precursors and preferably the absence of significant amounts of dispersants. These pigmented vitreous materials can be used as coloured materials for any known purposes. Soluble pigment precursors comprising a partial structure are also claimed, wherein X1 is an aromatic or heteroaromatic ring, B is hydrogen or a group of the formula, but at least one group B is not hydrogen, and L is a solubilizing group.

Description

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1238812 The case of going to P is related to a method for manufacturing pigmented glass materials and its coloration, which is characterized by the production of soluble color cuts and preferably does not exist ",,,: Dispersant. Pigment-containing glass materials can be used as coloring materials for any known purpose. Uses such as thin layers on beverage bottles, TV screens and other broken items. As pigment-containing glass materials, it is important to understand that they contain polycondensation transition metal oxygen. Or hydroxide crosslinked matrix materials (references commonly known as "sol · spin gum") where the organic pigment particles are trapped inside the material. The matrix is mainly composed of metal-oxygen-metal bonds and also contains organic bonds between metal atoms. The substrate may also be an organic-inorganic hybrid system such as a metal substrate (ceramic) or a ceramic substrate (ceramer). All these materials are well known in the industry and are described, for example, in many patents and patent applications such as Ep 465 'EP 426 037' EP 504 926 and EP 590 740, as well as in monographs, reference books and technical encyclopedias. EP 648 770 and EP 648 817 disclose carbamic acid g functional group-soluble chromophoric groups which can be converted into corresponding pigments by heating to a relatively high temperature followed by removal of the carbamic acid group. These compounds are suitable for large-scale coloration of polymers and can be used for coloring resists and polymer coatings according to EP 654 711. Compounds of the same type but with improved properties are known, for example, from EP 742 556, WO 98/32802, WO 98/45757, WO 98/58027 and WO 99/01511. US 5,243,052 discloses carbonates of quinophthalone which have limited solubility and can be used in heat sensitive recording systems. White dye is embedded inside the polymer, preferably inside the polyoxazoline. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

(Please read the notes on the back before filling this page) 4 A7 B7

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

1238812 EP 504 926 discloses a coating solution composition for forming a glass gel film, a colored glass gel filter and a display device, wherein the coloring material particles are mixed with not less than 0.01% by weight dispersant, preferably relative to 1 The scratch weight ratio is 5 to 1000 parts by weight. The coloring material particles are dyes or pigments such as azo yellow and red, perylene, naphthone, stilbene, sulfur, isoindolinone, quinone g-one, quinacridone, cyanine or inorganic pigment. . The glass gel film is formed at a temperature of 100 to 300 ° C. Similar sol-gel methods and compositions further using organic pigment dispersions are disclosed in JP-A-07 / 207186, JP-A-08 / 175823, JP-A-09 / 239311 and jp-A-10 / 204296. Removing the dispersant can strengthen the gel film layer, so it can compensate for the negative effects caused by the colored particles. However, the sol-gel of the prior art still cannot satisfactorily meet today's high requirements regarding processability, strength, homogeneity, light weight, heat and moisture stability, transparency and color. The colorant is not completely sealed inside the inorganic gel, so it is exposed to oxygen and moisture and is partially extracted with chemicals used in the manufacture of gel-containing objects. High concentrations of colorants require high amounts of dispersants, resulting in further deterioration in quality. The key limitation is that different categories of organic pigments cannot be combined satisfactorily 'because they require different and often mutually dispersing dispersants. ... unexpectedly, the present invention obtains significantly improved properties by using a soluble pigment precursor which is thermally split into insoluble organic pigments. High Out = Unexpectedly ’pigment particles are strongly bonded without additional dispersion: suspicious. Nonetheless, surfactants can be added, for example to improve surface quality. 1 The advantage is selectivity and no need to adjust the adaptation pigment. Although the actual mechanism is still unknown * I. Ί; -Η ---- Μ ------- it --------- < Please read the notes on the back before filling in this page)

The size of this paper is applicable to the national standard $ (CNS) A4 size ⑵G χ Norwegian ^ 5 1238812 V. Description of the invention (3) White understanding, but it is believed that the solubilizing group of the pigment does interfere with the gel formation mechanism, so the gel is improved. The affinity of organic pigments is not the case with ordinary solution, and the system splits into dioxide. Thus, the present invention relates to a method for producing a pigment-containing glass material from a liquid or dissolved transition metal compound, wherein the liquid or dissolved transition metal compound reacts to form between the liquid or dissolved transition metal atoms of the pigment-containing glass material. Cross-linking, characterized in that the solution also contains a soluble compound of the formula / Α (Β) χ Χ where X is an integer of 1 to 8, Α is awake yah, anthracene, perylene, and blue ㈣_, Danshi left, isododelinone, isoteric turn, two ,, azo, phthalocyanine, two «Houkou each blend or 3_low methyl_2,3_dihydro m net series hair A chromophore, which is attached to X B groups through-or multiple heteroatoms selected from the group consisting of N and ow, and forms part of an eight group. , Here at least one 3-base non-ammonia is printed by the Shellfish Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

For 2 to 8 ', the B groups may be the same or different, and L is any suitable solubilizing group, and the glass material is heated to convert the compound of formula ⑴ into a pigment of formula A (H)', and its tx is defined as formula (1). " Transition metals are well known in the industry such as Ming, Zinc, Wrong, Titanium, Nickel and Nickel, which are extremely special for reading. Liquid or dissolved transition metal valences are also well known in the industry ’such as alkoxides or mixed oxides,

This paper size applies to Chinese National Standard (CNS) A4 Tibetan (2 $ 297mm) A7 B7

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1238812 ^ Compounds of formula (I) can be converted into formula A (H) X (II) pigments by heating and can be carried out simultaneously or separately with the cross-linking reaction of liquid or decomposed transition metals The final step. In addition to the excellent properties of the product, the method of the invention also has the advantage that it does not require a dispersing step and is therefore much faster than the prior art. In addition, the reaction can be performed at a cutting temperature and at a higher pigment content in the presence of substantially no dispersant without compromising transparency, hue or hue. The reaction is usually carried out by first mixing the ingredients to form a composition, and then applying and heating as needed to regenerate the pigment. The composition may also contain an effective amount of a catalyst such as an acid or a precursor that forms an acid when heated. The acid or precursor can be added during the preparation of the composition, or preferably, an effective amount of the catalyst is added just before the composition is applied, which is any number suitable for starting or accelerating the reaction. The catalyst and its proper amount are well known in the industry. For example, it includes inorganic acids such as hydrochloric acid or nitric acid, Lewis acids such as succinate, organic acids such as formic acid, acetic acid, or oxalic acid, etc., preferably having a pKa of 3 or less. In addition to catalysts or even alternative catalysts, it is well known to use a light source or heat the mixture to a mild temperature, for example, until the crosslinking reaction (gelation) begins. Prior to or during gelation, the composition can be processed into a predetermined form by conventional means, such as by spray coating or printing to form a coating, such as screen printing or inkjet printing. Similar resist technology (for example, disclosed in Ep 654 711), can make this paper size applicable to Chinese National Standard (CNS) A4 specification (21〇 X Nokia

• Install ---------- Order --------- (Please read the notes on the back before filling this page) 1238812

V. Description of the invention (5 The Intellectual Property Bureau of the Ministry of Economy ’s Employees ’Cooperative Cooperative has printed the thermal element array and only cross-linked the specific area, so it forms an image. For example, the image can be washed off with an appropriate solvent. *; After the glue / spin is completed, the required materials are converted to the broken glass form by heating to a higher temperature, and the pigment will be regenerated at this time. The pigment-containing glass material is highly transparent and highly resistant to water, solvents and chemicals. Shear and scratch resistance is highly resistant, especially under severe conditions: also has very high thermal resistance. Due to the high pigment content, it can be applied to H with a transparent and low diffractive layer 'layer thickness It is ^ to 3 microns. The transition metal atom cross-linking, for example, consists of oxygen, alkylene, oxyalkylene, or oxyalkylene bridging, and may be unsubstituted or further-for example, substituted by drinking or gas. Polymer materials with appropriate substituents such as -OH can also be used for cross-linking. Preferred pigment-containing glass materials contain 2 to 10 organic pigments, preferably 2 to 5 organic pigments. Suitable solvents are: Water, or preferably any predetermined protonic or Aprotic solvents such as hydrocarbons, alcohols, amines, nitriles, nitro compounds, sulfur derivatives, N-heterocycles, ethers, ketones and esters. They can also be mono-unsaturated or poly-unsaturated. Or gasification: e.g. methanol, ethanol, isopropanol, n-butanol, isobutanol, 2-butanol, diethyl ether, acetone, methyl ethyl methane, methyl isobutyl ketone, 1,2-dimethoxy Ethane, it diethoxyethane, n-butoxyethanol, 2-methoxyethanol, 2-ethoxyethanol, ethyl acetate, tetrahydrofuran, dihumane, acetonitrile, benzamidine, nitrobenzene, N, N • Dimethylformamide, ν, ν · Dimethylacetamide, Dimethylarsine, Tetramethylenearidine, N · Methylpyrrolidone, 吼 ° 疋, Methyl. Ratio σ, 0 Kui Lin, Dichloroethane, Sanqi Yiyuan, A paper size is applicable to China National Standard (CNS) A4 (210 X 297 meals) I Ί ^ --- " -I ---- pack -------- 丨 Order --------- ^ _ wi (Please read the notes on the back before filling this page) I238812 A7 _B7 " -----— V. Description of the invention ( 6) Benzene, xylene, myrtle, and chlorobenzene. Other solvents are described in, for example, Tables and references. Instead of a single solvent, a mixture of two or more solvents can also be used. The transition metal compound that can perform the cross-linking reaction can also act as a solvent itself. The comparison of the transition metal compound to other solvents is preferably 25: 丨The range is from 2 to 5: 1. The concentration of the pigment precursor in water or solvent is usually from 0.01% by weight to about 99% by weight based on the weight of the solution. In some cases, supersaturated solutions can also be used without Causes the premature precipitation of solvates. For a variety of pigment precursors, the most ideal concentration is about 0 05_ 30% by weight of the solution, often about 01-15% by weight. The pigment precursor is converted into a pigment The form is carried out by heating sections, which can be performed simultaneously with gel formation or at a higher temperature as a subsequent treatment. As such, the segmentation temperature of the pigment precursor is usually in the same range as the gel formation, and is suitable from 50 to 400. 〇, preferably from 100 to 30 (rc and most preferably from 150 to about 25 ×:), as for the effective coloring amount means that when the pigment-containing glass material is compared with the pigment-free glass material manufactured in a similar manner at 10 degrees The angle viewing angle is compared with the standard lighting meter D65, which is sufficient to bring about the number of color differences. Here, it preferably accounts for 0.001 to about $ 0% by weight of the pigment-containing glass material, and more preferably 0.1 to 30% by weight. The best weight ratio is from 10 to 25/0. Usually it is more likely that the pigment / Chen degree can be used without jeopardizing the properties of the glass material. The suitable segmentable pigment precursors include a complete pigment wood structure in the structural formula. } -A heteroatom ^^, 0 or 8 pigments substituted with _ oxygen radicals (please read the precautions on the back before filling out this page) • Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

-9-1238812 A7

1238812 A7 V. Description of the invention (8) Compounds are, for example, EP 742 556, WO 98/32802, WO 98/45757, WO 98/58027, WO 99 / 〇1511, WO 00/17275 and the application PCT / EP -G_3 () 85's theme and quoted by it? Several other publications are known, the contents of which are incorporated herein by reference. Preferred compounds of formula (I) are the compounds best disclosed in WO 98/328 02 and WO 98/58027. Particularly noteworthy soluble formula chromophores can be prepared from the following ingredients: Color Index Pigment Yellow 13, Pigment Yellow, Pigment Yellow 74 'Pigment Yellow 83' Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow%, Pigment Yellow 109 ' Pigment Yellow 11〇'Pigment Yellow 12〇'Pigment Yellow 128, Pigment Yellow Cologne Consumption of the staff of the Customs Bureau Consumption Pigment Yellow 15 and Pigment Yellow 154, Pigment Yellow 175, Pigment Yellow 18〇 Factory Pigment Yellow 181 'Pigment Yellow 185, Pigment Yellow Yellow 194, Pigment tincture, Pigment dial 7, Pigment dial 73 'Pigment red 122, Pigment red 144, Pigment red 166, Pigment red 184, Pigment red 185, Pigment red 202' Pigment red 214, Pigment red 22, Pigment red 221 Pigment Red 222, Pigment Red 242, Pigment Red 248, Pigment Red W 'Pigment Red 255, Pigment Red 262, Pigment Red 264, Pigment Brown 23, Pigment Brown 4, Pigment Brown 42, Pigment Blue 25, Pigment Blue%, Pigment Blue, Pigment Blue 64, Pigment Violet 19, Pigment Violet 29, Pigment Violet 32, Pigment Violet 2 (4'-cyano-phenyl) -2,5-dihydro "Biloxi and Pyrex Xitong or 3-phenyl tert-butylbenzyl) _2,5_dihydro_para- [3,4exobilo_ 1,4-dione. Ketone pigment dial 71 It is a super good orange. Pigment violet 37 is a super good blue-red. Super good black is a cyanine derivative with pigment violet 37, pigment yellow% or pigment yellow%, and one or more selected from pigment red 222, & pigment red 254 and 3_phenyl ^ _ (4-second butyl-phenyl) _2,5-l each [3,4 yell m This paper size applies to China National Standard (CNS) A4 (210 X 297 Public love

I 1238812 A7 -------- B7__ 5. The red mixture of invention description (9). Particularly preferred is a 3-low methyl_2,3-dihydro-indole-2-vinyl-1 derivative (for example, disclosed in WO-00 / 24736, the center of which is fluorene, 2,5-dihydro-orbital pyrrole [3,4-c] Pyrrole-1,2-one derivatives carry a residue substituted with at least one amine group at the 3 and / or 6 position (for example, disclosed in EP-B-3 53 184 or EP- A-75 5933) and β-crystal modification of acid sigma-yam brewing I. WO-OO / 24736, EP-B-353 184 and EP-A-755933 are also described here for reference. Whether these pigments are single This kind or combination of other pigments is particularly suitable for obtaining purple or green colors. It also has unexpectedly improved properties in glass materials. When unsubstituted quinacridone is used, it is preferred that the glass material contains the pigment in β crystal modification. As mentioned above, the crystal modification is determined by the solubilizing group and regeneration conditions. Particularly preferred is the 3-hydroxymethyl-2,3-dihydro-indole-2-gig derivative of the following formula (please read the precautions on the back first) (Fill in this page) I · II — II ί I ^ 1111111. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

This paper size applies to China National Standard (CNS) A4 specification (21 × 297 mm) 12 1238812

V. Description of the invention (i0), other 3_lowmethyl_2,3_dihydroringatos with other substituents are described in, for example, the aforementioned reference WO_00 / 24736. Include at least one \

Part of the compounds whose structural formula is novel also constitutes the object of the present invention. The special feature is a species of 2,5-monohydrogen-aqueous and [3,4 · c] σbilo-1,4-, which has the following formula:

Where Xt & X2 are respectively

〇 、 s 丨 ，;! 丨 ί 7 · -install -------- order --------- (Please read the precautions on the back before filling this page) Staff of the Intellectual Property Bureau of the Ministry of Economic Affairs The divalent aromatic group R5 R3 printed or best printed by the consumer cooperative is CN 'cor6' c〇2R6, con (r6) 2, no2, so2r6, SOR6, S02N (R6) 2 or p0 (0R7) 2 Groups, R4 and Rs are each hydrogen, gas, bromine, methyl, ethyl, methoxy or ethoxy, R7 is C ^ -C ^ alkyl or phenyl, 111'112'111''112 'And 1 ^ 6 are each hydrogen, 〇1 _ (: 18 alkyl or (:: 1_ (: This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) 13 1238812 A7 B7 V. Invention Explanation (η) Alkenyl is unsubstituted or substituted, or is substituted by alkynyl, succinyl, oxy, or c ”c6 sulphenyl” or phenyl. It is unsubstituted or substituted by chlorine, molybdenyl, alkyl, or alkyl. , Cl-C6, weixyl, CN, _ or ⑶ substituted or RARAm, together with the nitrogen atom to which it is attached, together form a 5- or 6 · ring group, which is unsubstituted or is composed of Or phenyl substituted, and is selected from the group consisting of molybdenum, hexabenzyl, hexabenzyl, " biblyl, triazole Base, t-sityl, sialyl, hexa-H-based, morphinyl, thiomorphinyl, carbazol-1-yl'indol-1-yl'indazole] -yl, benzimidazole small group, A group consisting of tetrahydrofluorin-1-yl and tetrahydroquinolin-2-yl, or wherein X3 and X4 are each hydrogen, gas, bromine, NO2, methyl, oxy or ethoxy, and xs and χό form a 5- or 6-membered heterocyclic ring linking A to produce benzimidazolone, dihydroquinazoline, quinolone, benzoxazolone, phenmorpholinone, quinazoline g Identical or phthaloimine or 丨 丨 丨 T # -Package I --- Γ 丨 Order --------- Awi C Please read the precautions on the back before filling this page)

If the heart or the heart ’is hydrogen, r2 & r2 is of formula A

Among them, the rule 1 is [1- (1! 6 alkyl or printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economics or X2-R3 can be N-O group, and E1 and E2 are both chlorine. Formula (Ilia) And the compound of the formula (Illb) where El is hydrogen and d is 6 groups, d is B group and E2 is hydrogen or E! &Amp; E2 is B group are novel, but its center is (Illb) compounds are excluded. The present invention also relates to these papers. The paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) 14 1238812 A7 B7 V. Description of the invention (π compound. Special acid acne Pyridones are unsubstituted quinacridone and dimethoxyquinacridone, monomethyl acridinone, or dichloroquinone, which are 2,9-, 3,10-, and 4,11-isomers. Compounds, especially unsubstituted quinacridones. Compounds of the formula VII are known or can be prepared in a similar manner as described for example in EP 648 770, EP 648 817 and EP 742 556. Preferably -L is the formula R2

• FU

I4 —C ~ CSC * R5

(Please read the Jiang Yi matters on the back before filling this page) 〇ρ) π

—Q-χ-U 'where Ri, 113, and 112 are each C "C6 alkyl, and R5 are each c" c6 alkyl, 0, s, or n (r12) 2-interrupted Crc6 alkyl, unsubstituted Or Ci_c6 alkyl-, c "c6 alkoxy-, halo-, alkyl or nitro-substituted benzyl or biphenyl, r6, and 7 and 118 are each hydrogen or c" c6 alkyl, R9 is IL 'C 「C6 burn-in or the following formula 0 · 丨 I 丨 丨 丨 Order ------- Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

II

: ―R 13

And " and 1 ^ () are each hydrogen, Crc6 alkyl, CVC6 alkoxy, halogen atom 'cyano, nitro, N (R12) 2, unsubstituted or halogen-, cyano-, nitro- . "(: 6 alkyl- or C" C6 alkoxy-substituted phenyl, Ri2 and R13 are Ci_C6 alkyl groups 'are nitrogen or Ci-C6 alkyl groups and are hydrogen, C "c6 alkyl' unsubstituted or crc6 alkyl Base-substituted phenyl, this paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 public love) 1238812 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of invention (u Q is p, q- C2_C6 alkynyl is unsubstituted or substituted by crC6 alkoxy, C "C6 alkylthio or c ^ -Ci2 dialkylamino substituted one or more times, 卩 and ^ are different numbered positions, X is selected from N A hetero atom of a group consisting of 〇 and S, where m is 0 if X is 0 or S, m is 1 if X is n, and 1 and 1 ^ are each unsubstituted or or--or Poly-(: 1-(: 12alkoxy_, -CVC12alkylthio _, _ c2-C24: alkylamino group, CfCu aryloxy group, -c6-c12 arylthio group, -c7-c24 Alkylarylaminodiarylamino-substituted C6C6alkyl or [-(p ,, q, -C2-C6alkylenealkyl, where η is a number from 1 to looo, p, & q is a different numbered position, each z is independently a hetero atom 0, s * Cl_Ci2 alkyl is taken, and The C2_c6 alkylene groups in the complex unit [-c ^ c: 6alkylene_z_] may be the same or different, and Li and La are saturated or mono- to ten-unsaturated, without interruption or at any predetermined point by 1 to 10 groups selected from the group consisting of _ (C = 〇) _ and _c6H4- are interrupted, and may have none or 丨 to 进一步 further selected from the group consisting of halogen atom, hydrogen group and nitro group Substituents. Of particular interest are compounds of the formula VII where L is Ci_c6 alkyl or special Q-i1imL2 'wherein 卩 is dynyl and L ^ L ^ [-C2-C12 alkylidene-zl -cvc ^ alkyl or (^ {is an alkyl group which is substituted by 〇1 {12 alkoxy, CrCu thio or dialkylamino group one or more times, and m and n are as defined before. Particularly amazing Those interested are the compounds of formula ⑴ where [is (: 4 _ (: 5 alkyl) (This paper size applies to China_tsuka standard (CNS) A4 specifications (21 () χ 297 meals) (Please read the precautions on the back before (Fill in this page) --Installation--Γ-- Order --------- P 16 1238812 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (Η) Special third butyl or Tripentyl) or special (lT1) m, where Q is C2 -—Qx-l2 C4 alkylene 'X is, and is C2_C12 alkylene_〇_] n_CrCn alkyl or Ci_Ci2 alkyl which is substituted by Ci_Ci2 alkoxy group one or more times, especially where -QX- It is a group of formula -C (CH3) 2-CH2-0-. Alkenyl or alkylene can be linear, branched, monocyclic or polycyclic. The Cl-Ci2 alkyl group is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, isobutyl, third butyl, cyclobutyl, n-pentyl, and pentyl. , 3-pentyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl 'n-hexyl' n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl , Nonyl, dimethylcyclohexyl, decyl, menthol, thuja, borneol '1-adamantyl, 2-adamantyl or dodecyl. If the C2-cualkyl group is mono- or polyunsaturated, it is an alkenyl group, an alkynyl group, an even alkylene group or an alkylpolyalkynyl group in which two or more double bonds can be separated or conjugated if appropriate, such as Vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, i, 3 · butadiene_2_yl, 2-cyclobutene · Imidyl, 2-penten-1-yl, 3-pentene_2_yl, 2-methyl_1_butene-3-yl, 2-fluorenyl-3-butene_2_yl, Hong Fluorenyl butenyl, pentadien-3-yl, 2-cyclopentenyl, 2-cyclohexene_yl_, 3-cyclohexene_1, 2,4-cyclohexanyl, 1 · Pentemen-8-yl, 4 (1〇) _Thullene-10-yl, 2-orbornenyl, 2, Hongyuan-bornyldienyl, 7,7-dimethyl-2,4-ortho Kaidien 3-yl or various isomers of hexenyl, octenyl, nonenyl, decenyl or dodecenyl. C ^ C: 4-alkylene is, for example, i, 2-ethyl, 2-, 2-propyl, 3-, 3- (Please read the notes on the back before filling this page) I -II—11 H 111111 n ^ wi.

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 38819 A7 ~ —— R7_ IX. Description of the invention (15) Mouth, tert-butyl, I3-tert-butyl, 2,3-tert-butyl, ι, 4 -Butyl or 2-methyl-1,2-propyl. The caxenyl group is, for example, an isenyl group, a hexyl group, an octyl group, a decyl group, or a dodecyl group. C2Cl2oxy is 0- to 12-radical, preferably 0. Ci-C4 ^. C6_Cl2 square-oxy is O-C ^ Ci2-aryl, such as phenoxy or naphthyloxy, preferably phenoxy.

CrC ^ alkylthio is 8- 1-(: 12 alkyl, preferably 8-44 alkyl. C6 arylthio is s-C6_Ci2 aryl such as phenylthio or naphthylthio, preferably phenylthio C ^ c: 24-alkylamino is N (alkyl ^ (alkylj, where the sum of carbon atoms of alkyl 1 and alkyl 2 diyl is 2 to 24, preferably n (Ci_C4 alkyl Base) _Ci_C4 Burned base.

CrC24 alkylarylamino is N (alkylι) (aryl2), where the sum of carbon atoms of alkyl ^ and aryl2 diyl is 7 to 24, for example methylphenylamino, ethyl The cumylamino or butylphenanthramino group is preferably a methylphenylamino group or an ethylphenylamino group.

CfC: 24 diarylamino is n (aryl 0 (aryl 2), where the sum of carbon atoms of aryl a aryl 2 diyl is 12 to 24, such as diphenylamino or phenyl The naphthylamino group is preferably a diphenylamino group. The C6-C16 # group is, for example, a phenyl group, a naphthyl group, an anthryl group, a pernaphthyl group, or a naphthylnaphthyl group. A C 7-C24 aralkyl group contains at least An alkyl group and any group of an aryl moiety, such as benzyl, phenethyl, tolyl, dodecylphenyl, tetrahydrosulfenyl or fluorenyl. This paper size applies to China National Standard (CNS) A4 Specifications (210 X 297 mm) 18 丨 I; —17 ---- install ---------- order --------- (Please read the precautions on the back before filling this page ) 1238812 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 -------- B7______ V. Description of the invention (16) Tooth element is chlorine, molybdenum, fluorine or moth, preferably fluorine or chlorine, and most preferably The number of η branches is from 1 to 100, and the number from 2 to 12 is particularly good. The pigment precursors are particularly good in which the chromophore is the color index pigment scutellaria baicalensis, pigment yellow 73, pigment yellow 74, and pigment yellow 83. , Pigment Yellow ％, Pigment Bitter ％ Main Pigment Yellow 95, Pigment Yellow 1 〇9, Pigment Yellow 11, Pigment Yellow 12, Pigment Page 128, Pigment Yellow 139, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow M, Pigment Yellow 180, Pigment Yellow 181, Pigment Yellow ⑻, Pigment Yellow 194, Pigment Orange 31'Pigment Orange 71'Pigment Orange 73, Pigment Red 122, Pigment Red 144, Pigment Red 166, Pigment Red 184, Pigment Red Pigment, Pigment Red Transport, Pigment Red River, Pigment Red 220, Pigment Red 221'Pigment Red 222 , Pigment Red 242, Pigment Red 248, Pigment Red 254, Pigment Red 255, Pigment Red 262, Pigment Red Brown 23, Pigment Brown 41, Pigment Brown 42, Pigment Blue 25, Pigment Blue 26, Pigment Blue 60, Pigment Blue 64 , Pigment Violet 19, Pigment Violet 29, Pigment Violet 32 Pigment 37,3,6_bis (4'_cyano-benzyl) _2,5-dihydro · Horropyrrolo [3,4_c] each mouth] 4-dione or 3-phenyldong (4, -third butyl_phenyl) _2,5_diazepine_pyrolo [3,4-c] bipyr_1,4_dione , All B is the same formula group, and L of each of the aforementioned chromophores is a third butyl group, a third pentyl group, a 3-oxo-2-methyl! Propyl group, a 3- (2, · methoxy_ethoxy group ) _2_fluorenyl_2_propyl, 2-methyl-3-butyn-2-yl or 3-methyl_2_buten-1-yl. In a glass material, a matrix containing a crosslinked liquid or / dissociated transition metal atom and an effective pigment amount is selected from the group consisting of color index pigment yellow 13, pigment yellow 73, pigment yellow 74, pigment yellow 93, pigment vapor 94, Pigment 95, Pigment Yellow 10, Pigment Yellow 丨 20, Pigment Yellow 128 Pigment Page 139, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 175, Pigment This paper size applies Chinese National Standard (CNS) A4 specifications ⑽χ 297 Public. -------- -19-ΙΊ. ΊΤ ^ ------ *-^ --- (Please read the note on the back ^^ before filling out this page) f 1238812 Ministry of Economy Wisdom Printed by A7 B7 of the Consumer Cooperative of the Property Bureau V. Description of invention (Π) Scutellaria baicalensis, Pigment yellow 181, Pigment yellow 185, Pigment yellow 194, Pigment lamp 31, Pigment dial 7, Pigment dial 73, Pigment red 144, Pigment red 166 , Pigment Red Pigment, Pigment Red Pigment, Pigment Red 202, Pigment Red 214, Pigment Red 22, Pigment Red 221 'Pigment Red 222, Pigment Red Plus, Pigment Red 248, Pigment Red Condition, Pigment Red 262' Pigment Red 264, Pigment Brown 23, Pigment Brown 41, Pigment Brown 42 'Pigment Monitor 25' Pigment Blue 26 'Pigment Blue 60' Pigment Blue 64 Pigment violet 29 'Pigment violet 32, Pigment violet 37,3,6_bis (4, _cyano_phenyl) _2,5dichloro-pyrrolo [3,4-c] pyrrole-1,4-dione Or 3-phenyl tert-butyl-phenyl) -2,5-dihydro-pyrrolo [3,4-c] pyrrole. 4-dig is the same. In addition to pigments, glass materials also contain other compounds such as additives known in the industry. Improved material properties such as ultraviolet light absorption or transparency improvers can be heated by any predetermined heating means including irradiation such as processing in a hot oven or by electromagnetic radiation such as IR4NIR radiation. Or laser pulse or microwave irradiation treatment. There is no particular limitation on the heating time of the regenerated pigment, as long as it is long enough to complete the segmentation of the pigment precursor. A range typically from seconds to hours' is preferably from about 1 minute to about 30 minutes. The appropriate heating time for gel formation is determined according to the thermodynamic rule based on the temperature ', so it can be determined based solely on the predetermined temperature. However, the heating temperature must be carefully evaluated. It is generally suitable to use 150 to 300. (:: Especially about 180 to 250 ° C. The preferred temperature is 180 to 200 ° C. Together with the solubilizing group and solvent used for gel formation, the temperature affects the pigment crystals, .Typically, parallel experiments must be performed at 150 ° C and 200 ° C to check the final color. The paper size is in accordance with the Chinese National Standard (CNS) A4 specification (21 × x297 mm).

Equipment ------------ Order --- (Please read the precautions on the back before filling this page) Ρ 1238812 A7 B7 V. Description of the invention (18) Color difference. Unexpectedly found the use of a pigment precursor where L is (lP) m together with a structural formula Q-X-L,

Cri) m HOH — l, gel-forming solvent results in improved color. In particular, such a combination allows the quinacridone to obtain a predetermined β crystal phase at 2000 or even lower temperatures. The invention is thus also directed to the method as defined above, which additionally comprises adding a compound of the structural formula and then heating to a temperature of 150 to 300 ° C to form a glass material. The compound may be added at one time or in portions and added in any amount from the beginning to immediately before the heating step. It is preferred that the weight ratio of such a compound to the compound (I) is from 1: 4 to 100: 1. The preferred gel-forming solvent is 2-CVC 2 alkoxyethanol, 2_Ci_Ci 2 alkoxypropanol, 2,3-di- ^ heptaalkoxypropanol, diethylene glycol-{{[ηalkyl ether, Triethylene glycol · mono-Ci-Cu alkyl ether, dipropylene glycol-Ci2 alkyl ether, tripropylene glycol-mono-Ci-Ci2 alkyl ether, or diethylene glycol, triethylene glycol, dipropylene glycol or Tripropylene glycol is a single esterification of each carboxylic acid. When the catalyst is used in the form of a precursor, the catalyst precursor such as ί ί, ------- ^ w «Μ ----------- order- -------- up- (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs * |: 7 R? T? An · (IVa),

R 16 S--0-N7 ^ dvb) / ~ Vs 〇_yRa2 'i \ RkJ ^ fr ° ^ = ((ivo, 21 K19 OD ^ 23 where r16, heart and heart are respectively Ci_c24 courtyard base, c6_c24 aromatic Or c7-c24 aralkyl

1238812 V. Description of the invention (i9) Heart 9 is Ci-Cy alkyl, 'R2jR23 are each K24 alkyl, C & 4 aryl or C7-C24 aromatic alkyl, or R20 and Rh together or RMR23 together are extended Alkyl, C4-C24 arylene, 34 pentyl or NC "C24 alkynyl κ pentyl, An is PX6, AsX6, SbX6, BX4, r24_s〇3, R24_〇s〇3 or R25-P03R26, Wherein r24 ′ r25 and r26 are Ci_c24 alkyl, C6-C24 aryl or c7-c24 aralkyl, respectively. R25 and R26 are preferably Ci_c24 alkyl, most preferably C ″ C4 alkyl, particularly preferably methyl And X is a halogen atom. Further substituents may be present in compounds of formulae (IVa), (IVb) and (IVc) such as a halogen atom or a nitro or crc24 alkoxy group. Of course 'new 3-low methyl-2,3- Dihydro-indole-2-one and amine-substituted 2,5-dihydropyrrolo [3,4_cppyrrole-i, 4-dione colorants can also be used in other fields such as fluorescent colorants And as a latent pigment, it is described in, for example, US-5,484,943, EP-B-0 648 817, US-5,879,85 5, W098 / 45756, W098 / 45757, WO98 / 58027, WO00 / 27930, and EP petition 99980467.3. The following Examples are provided to illustrate the invention but not to Limit its scope. 1.— _! 「---- t- 装 --- (Please read the precautions on the back before filling this page) -MMmm l · — 1 ^ δ, τ I It ml 11 ϋ mMmm p Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives 22 This paper is sized for China National Standard (CNS) A4 (210 x 297 mm) 1238812 A7

(Please read the precautions on the reverse side before filling out this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 23 I Packing! ---- ^-Order --------- ^ wi 1238812 A7 B7 V. Description of the invention (21

This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 24 1238812 A7 B7 V. Description of the invention (22)

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 25 1238812 A7 _B7 V. Description of the invention (23)

cl

α 5); (A1 (Please read the notes on the back before filling out this page) I —Bi ^ 1 ϋ ϋ ϋ ϋ ϋ · ϋ · 1B1 ρ Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Employee Cooperatives This paper is applicable to China Standard (CNS) A4 specification (210 X 297 mm) 26 1238812 A7 B7 V. Description of invention (24) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

T ---- install · (Please read the precautions on the back before filling this page)

MB MB · ΜΒ I Μ ·· If f This paper size is applicable to Chinese National Standard (CNS) A4 (210 x 297 mm) 27 1238812 A7 B7 V. Description of the invention (25)

〇A20-A26 = A mixture containing the following ingredients (parts by weight): A20 (100) A2 (25) A5 (25) A7 (25) A12 (25) A21 (100) A2 (25) A5 (25) A9 (25) A12 (25) — A22 (100) A2 (121/2) A5 (25) A7 (25) A \ 0 (l2l / 2) A12 (25) A23 (100) Al (50) A6 (50 ) — One — A24 (100) A9 (8) A12 (77) A16 (15) One A25 (100) A12 (80) A16 (20) — One— A26 (100) A10 (50) A16 (50) One — — ---- V * · Packing --- (Please read the precautions on the back before filling this page) Printing example A4 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs: 5.3 grams of di-tert-butyl dicarbonate added Up to 5 g of 3,6-fluorene- (4-'monobenzylamino-phenyl) -2,5-digas-port ratio slightly 弁 [3,4-c] p ratio each -1,4- A solution of diS and 0.3 g of dimethylaminopyridine in 150 ml of tetrahydrofuran. After stirring overnight at room temperature, the reaction mixture was filtered through a small amount of kieselguhr. Hexane was added to the residue and then filtered to obtain 5.3 g of a purple compound having the above formula A4. Analysis: Calculated values: C 75.89%, Η 5.63%, N 6.81%, 〇 11.66%, measured values: C 74.96%, Η 5.79%, 6. 6.64%, 〇 11.88%. Mid-point decomposition temperature: 184.7 ° C; weight loss (calculated value) = 24.3%, weight loss (measured value) = 26.06%. This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 28 1238812 A7 B7 V. Description of the invention (26) Example of plug A6: 8.8 g of di- (2-methoxy-1,1) dicarbonate -Dimethyl-ethyl) vinegar was added to a suspension of 3 g of unsubstituted azetidinone and 0.4 g of dimethylaminopyridine in 100 ml of tetrahydrofuran. After stirring at room temperature overnight, 100 ml of tetrahydrofuran was added and the reaction mixture was filtered through a small amount of gel, and then filtered through a small amount of silica gel. The filtrate was evaporated and the residue was dissolved in dichloromethane, extracted three times with 3 parts of 100 ml of water, and then the organic phase was dehydrated with sodium sulfate and evaporated to dryness, to obtain 3.2 g of an orange compound having the above formula A6. Analysis: Calculated values: C 67.12%, Η 5.63%, Ν 4.89%, 〇 22.35%; found: C 67.39%, Η 5.65%, Ν 4.90%, 〇 22.31%. Midpoint decomposition temperature: 171.7 ° C; weight loss (calculated value) = 45.4%, weight loss (measured value) = 45.2%. Preparation Example A7: 255 grams of di- [2- (2 · methoxy-ethoxydimethyl_ethyl] dicarbonate was added dropwise to 5 5 grams of unsubstituted η-butanone and 5 _ 3 grams of dimethyl The aminopyridine σ was set at 750 ml of tetrahydrofuran suspension. After stirring overnight at room temperature, the reaction mixture was filtered through a small amount of gel, and the filtrate was evaporated. After adding n-hexane to the residue, it was filtered to obtain 4 0 g of the color-shifting compound has the above formula a 7 〇 Analytical calculation value C 65.44%, Η 6.10%, N 4.24%, 〇24.22% •, measured value C 65.25%, Η 6.48% 'NR 4.13%, 〇24.26%. Mid-point decomposition temperature: 164.3 C, weight loss (calculated value) = 52 · 7%, weight loss (measured value) = 52 · 9%. Preparation Example A9 · 8.8 g of distone inverse acid didipentane _ Added to 100 grams of 3,7-wu- (2-oxy-1,2-dihydro-indole-3-ylidene) -3,7-dihydro_benzo [i, 2-b; 4,5-b,] two mouthfuls of yanan-2,6-dione and 8.3 g of diamidoamino p bite in 1250 ml of dimethyl ether. This paper is applicable to Chinese National Standard (CNS) A4 size GW X 297. Chu) (Please read the precautions on the back before filling out this page) Loading -------- Order ----- 1 ---. Economy Printed by the Ministry of Intellectual Property Bureau's Consumer Cooperatives 29 A238812

V. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics Invention Description (27) Suspension of acetochlor. After stirring overnight at room temperature, the reaction mixture was filtered through a small amount of Sox and the filtrate was evaporated. Tetrahydrofuran and hexane were added to the residue, filtered and then dried to obtain 57.8 g (39% of theory) of a dark compound having the above formula A9. Midpoint decomposition temperature: 133.TC; weight loss (calculated value) = 33.7%, weight loss (measured value) = 28.6%. Example A18: Similar to US 2,351,119, tetraamine copper phthalocyanine was diazotized, and the diazonium compound thus obtained was coupled to acetoacetanilide. Eleven grams of this tetrazine product was fed to 120 ml of a suspension of dimethylacetamide in a suspension of 0.86 g of N, N-dimethylaminopyridine and 15.2 g of di-tert-butyl dicarbonate. After 18 hours, the reaction mixture was filtered through magnesium sulfate and the filtrate was concentrated by evaporation to about 30 liters. The crude product was precipitated with water, collected by filtration, washed with 200 l of hexane, dehydrated and dissolved in dichloromethane. After filtering through silica gel, the product was concentrated again and some hexane was added. The product was then filtered and dried to obtain 13.35 g (94% of theory) of a green powder. UV / VIS (tetrahydropyran): Xmax = 682 nm, ε == 60689. Elemental analysis [%]: Theoretical value: C 61.75 Η 4.73 Ν 15.66 Ο 14.31 Cu 3.55; C92H84N20O16Cu Real:? Regular value: C 61.06 Η 5.03 Ν 15.28 〇 14.55 Cu 3.60 〇TGA (heating rate 10 ° C / minute ): Breaking turning point = 171. (:; Mass loss of 25.6%. Example 1: 7 parts by weight of tetraethoxylate fired, 1.3 parts by weight of nitric acid in 1.5 parts by weight of water, 0.5 parts by weight of formula (A10) product in 89.89 parts by weight Water is mixed together to form a coating solution, which is spin-coated on a clean glass plate. After drying at 80 ° C for 20 minutes, the plate is heated to 200 ° C for 20 minutes to obtain a consistent purple coating. This paper scale is applicable to China Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) Installation------ Γ- Order · 30 1238812 A7 B7 V. Description of the invention (28) Ship: Treated as in Example 1, the difference is using the product of formula (A11). A similar uniform purple coating was obtained on the glass plate.)

Ml: As in Example 2, the difference is to use the formula, 0, .OEt (A24) homologous product instead of the formula ⑷υ product. The result is similar to Example 2. : It was performed as in Example 1, but the difference was that Erzhicha was used as a solvent instead of water. The results are similar to Example J. This was carried out as in Example 2 except that the dimorph was used as a solvent instead of water. The result is similar to Example 2. The fil was performed as in Example 3, except that dioxane was used as a solvent instead of water. The results were similar to Example 3. As in Example 4, the difference is to use the product of formula (i) instead of the product of formula (A. A homogeneous orange coating is obtained. As in Example 4, the difference is to use the product of formula (A14) to replace the (i)) product. A uniform blue-red coating was obtained. • As in Example 4, the difference is that the product of formula (A2) is used instead of the product of formula (Al0). A uniform red coating was obtained. ^ Once done as in Example 4, the difference is that the product of formula (A3) is used instead of the product of formula (A10). A uniform flame red coating was obtained. The scale of this button 1238812 A7 ---------- ----- V. Description of the invention (29)-One '

Mil: As in Example 4, the difference was that the product of formula (A5) was used instead of the product of formula (A10). A uniform blue-red coating was obtained. MI! ... It was performed as in Example 4 except that the product of formula (A12) was used instead of the product of formula (A10). A uniform yellow coating was obtained. Work ^: As in Example 4, the difference is that the product of formula (A13) is used instead of the product of formula (A10). A uniform yellow coating was obtained. -Beijie 4-It is carried out as in Example 4 except that the product of formula (A15) is used instead of the product of formula (A10). A uniform brown coating was obtained.肓 Example 15-It was performed as in Example 4 except that the product of formula (A16) was used instead of the product of formula (A10). A uniform blue coating was obtained. Example 16-It was performed as in Example 4 except that the product of formula (A17) was used instead of the product of formula (A10). A uniform blue coating was obtained. Reward Example 17-It was performed as in Example 4 except that the mixture (A20) was used instead of the product of the formula (A 10). Obtain a uniform black coating. -Example 18: It was carried out as in Example 4 except that the mixture (A21) was used instead of the product of the formula (A10). Obtain a uniform black coating. -Example 19: It was carried out as in Example 4 except that the mixture (A22) was used instead of the product of the formula (A 10). Obtain a uniform black coating. It should be carried out as in Example 4, but the difference is that the mixture (A23) is used instead of the product of formula (A10). A uniform brown coating is obtained but with a high transmission of blue, green and red light.-Example 21: 15 parts by weight of tetraethyl Oxysilane, 0.3 parts by weight of concentrated hydrochloric acid aqueous solution and 0.3 parts by weight of the product of the following formula The paper size is applicable to China National Standard (CNS) A4 (210 X 297 public love) (Please read the precautions on the back before filling this page ) i 装 i — *-I Γ | Sentence • Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 32 1238812 A7 B7 V. Description of the Invention (3G)

/ Gu Jie at 1.2 wound ethanol slightly stirred for 5 minutes. A clear solution was obtained and left at 23 ° C for 12 hours. A gel was formed and heated to 150. (: 180 minutes. The printed material of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Industry and Economics was crushed in the research institute. The yellow fine particles obtained were composed of polysilicone in which the pigments were embedded with 99 3 particles. 20, the difference is the use of methyl tributoxysilane instead of tetraethoxyxan and the use of 0.6 parts by weight (A25) product of 0.3 parts by weight. The results are similar but the color saturation is much higher. 1 Example 23: 0.3 parts by weight of the product of formula (A25) was dissolved in 15 parts by weight of tetraisopropyl titanic acid g. A clear solution was obtained, in which parts by weight of water were added dropwise. Heating to 150 ° C formed a stable gel It is composed of titanium dioxide matrix with pigment yellow 93 particles behind. Example 24: A mixture of 2.0 g of tetraethoxysilane and 0.5 g of phenyl triethoxysilane is dissolved in a mixture of 12.5 g of ethanol and 3.75 g of 1 M hydrochloric acid. Hydrolysis After 2 to 4 hours, the reaction mixture was added dropwise to 0.40 g of the product of formula (A7) in 3.75 g of monomethylethyl & amine. Valley solution. After dilution with 20 g of isopropanol, the resulting The solution was microfiltered through a 0.45 micron filter membrane and then spin-coated on glass On the substrate (100 rpm for 10 seconds first, then 500 rpm for 30 seconds). The coated glass plate is dried at 100 ° C for 2 minutes and then heated at 200 ° C for 5 minutes. (Please read the precautions on the back first. (Fill in this page) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 33 1238812 V. Description of the invention (31) The color is changed from red orange to red purple. The difference is that the product of formula (A6) is used instead of the product of formula (A7). The color is changed from red orange to red purple. It is performed as in Example 24. The difference is that cyclohexanone is used instead of dimethylethyl S «amine and after coating after drying The glass plate was heated at 25CTC for 5 minutes. The color was changed from red orange to purple. The process was performed as in Example 24, the difference was that 2-ethoxyethanol was used instead of ethanol. The color was changed from red orange to purple. 2-n-butoxyethanol was used instead. The same result can be obtained with 2-ethoxyethanol. It is performed as in Example 27, but the difference is that the coated glass plate is heated at 18 ° C for 5 minutes. The color is changed from red orange to purple. It is shown that 2-ethoxyethanol is used instead of ethanol Unexpectedly, non-substitution can be obtained favorably at lower temperatures Cool purple acridinone is scheduled to be purple. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs: a mixture of 0.9 g of tetraethoxysilane and 0.01 g of phenyl triethoxysilane, dissolved in 2 g of isopropanol A mixture of 3 g of methoxy-propyl acetate and 1 g of 1% hydrochloric acid. After 2 to 4 hours of hydrolysis, the reaction mixture is added dropwise to 0.20 g of the product of formula (A7) in 5 g Dimethylacetamide solution. After diluting with 8 g of isopropanol, the resulting solution was micro-filtered through a 0.45-micron filter membrane, and then spin-coated on a glass substrate (the initial 5 seconds at 30 rpm, and then 20 At 500 rpm). The coated glass plate was dried at 100 ° C for 2 minutes, and then further heated at 25 ° C for 5 minutes, so the color changed from red orange to purple. The system was performed as in Example 26, but the difference was that the product of formula (A4) was used instead of the product of formula (A7). After drying, the coated glass substrate was heated at 2000 for 5 minutes. The color changed from orange to purple. 34 This paper size applies to China National Standard (CNS) A4 specification (210 X 297 public directors) 1238812 A7 B7 V. Description of the invention (32) (Please read the notes on the back before filling this page) J'J31 · For example 24, but the difference is that 0.5 g of the mixture of formula (A25) is used instead of the product of formula (A7). Changing the color to green closely matches the conventional green glass color, for example for wine or beer bottles. [Example 32] It was performed as in Example 31, but the difference was that 0.52 g of the product of formula (A24) was used instead of 0.5 g of the mixture of formula (A25). The color also turns green. -^, A mixture of J33 · 2.0 g of tetraethoxysilane and 0.5 g of phenyltriethoxysilane> glutamate is a mixture of 12.5 g of isopropanol and quinone M hydrochloric acid. After 2 to 4 gadolinium was hydrolyzed, the reaction mixture was added dropwise to a solution of 0.05 g of the formula (A25) in 3.75 g of dimethylacetamide. After dilution with 20 g of isopropanol, the resulting solution was microfiltered through a 0.45 micron filter membrane. Then a 25 ml glass bottle was immersed in the solution and slowly pulled out. After a short drain time, the glass was heated to 200 ° C. Get extremely transparent and attractive green coloring. Magic column 34 was performed as in Example 33, except that the product of formula (A12) was used instead of the mixture of formula (A25). Obtains extremely transparent green-yellow coloration. —, J35 · was carried out as in Example 33, except that the product of formula (A19) was used instead of the mixture of formula (A25). Obtains extremely transparent yellow coloring. The procedure was carried out as in Example 33, except that the product of formula (A10) was used instead of the mixture of formula (A25). Obtains extremely transparent purple coloring. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [Example 37 · It is performed as in Example 33, but the difference is that the product of formula (A8) is used instead of the mixture of formula (A25). Obtains extremely transparent red-violet coloring. -It was carried out as in Example 33, except that the product of formula (A2) was used instead of the mixture of formula (A25). Get extremely transparent red coloring. The procedure was carried out as in Example 33, except that the product of formula (A1) was used instead of the mixture of formula (A25). Obtained extremely transparent orange National Standard (CNS) A4 size (2 $ 297 mm) for paper towels 35 1238812 A7

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

The procedure was carried out as in Example 33, except that 0.4 g of the mixture of formula (A26) was used instead of 0.5 g of the mixture of formula (A25). Obtains extremely transparent dark blue tinting. Μϋ: It was carried out as in Example 1, except that the product of formula (A9) was used instead of the product of formula (A10). A uniform coating was obtained on the glass plate, and its absorption peak was about 760-765 nm. On the column "... 2.0 g of diphenyldiethoxysilane was dissolved in a mixture of 7.5 g of ethoxyethanol and 0.25 g of water. After hydrolysis to i hours, the reaction mixture was mixed with 0.18 g of the product of formula (A7) and 12 g of polyhydroxystyrene (MarUCaLyncor resin, molecular weight = 53〇〇, Maruzan Petrochemical Co., Ltd.) in A solution of 7.5 g of ethoxyethanol. The resulting solution was diluted with isopropanol and micro-filtered through a 0.45 micron filter membrane and then spin-coated on a glass substrate with a trowel for 5 seconds at pm, and then 15 seconds at the end). The coated glass plate was dried at 分钟 C for 2 minutes and then further heated at 2000 ×: 5 minutes, so that the color changed from red to purple. Hill: It was performed as in Example 42 but the difference was that it was diluted with 24 g of isopropanol and the glass plate was heated at 18 (rc instead of 200t for 5 minutes. The results were similar .: It was performed as in Example 42 but the difference was that 0.2 g was used D1Sperbyk 306 was diluted in a solution of 18 g of isopropanol. The results were similar, but the difference was an improvement in surface quality. ^ Li ^ was performed as in Example 44, but the difference was the use of Tipperby 306 instead of Tipperby 306. The results are similar. _... is performed as in Example 42, but the difference is to make it! The cretin axis is diluted with 31 g of two grams of isopropyl alcohol. The results are similar, and the difference is that the surface quality is improved and the color shirt is more purple. A high amount of better quinone acridone. (Please read the precautions on the back before filling out this page) --Installation ^ τ ·

This paper size applies to China H ^ ?? CNS) A4 (2ΐΓχ 297)

Claims (1)

123 & 812, Β8 C8 D8 VI. Application for Patent Scope No. 89120555 Application for Amendment of Patent Application Amendment to this Amendment Date: April 1994 1. A kind of pigment-containing glass material made of liquid or dissolved transition metal compounds A method in which a liquid or dissolved transition metal compound reacts to form a crosslink between a liquid or dissolved transition metal atom of a pigmented glass material, and is characterized in that the solution also contains a dissolved compound of the formula A (B) X (I) where X is an integer from 1 to 8, A is quinacridone, onion quinone, perylene, indigo, quinophthalone, indantansone, isoindolinone, isoindolin, dioxin, even Nitrogen, phthalocyanine, diketopyrrolo, bipyrrole or 3-lowerino-2,3_dihydro ^ indolone chromophores, which pass through one or more selected from N, O & s. The heteroatoms of the group are attached to X B groups and constitute part of the 尨 A group, B is hydrogen or a group of formula ，, where at least one B group is not hydrogen and f I 70 * «Read Note 1 on the back side of the matter 丨 · Item I Page 1 II If X is 2 to 8, then the B groups may be the same or different, and L is any suitable solubilizing group, The Ministry of Economic Affairs and Intellectual Property Bureau of the Consumer Cooperative Press and glass materials are heated to transform the compound of formula 成为 into a pigment of formula A (Η) χ (Π), where χ is defined as formula (1). 2. The method according to item 1 of the patent application, wherein 丄 is the following formula The size of this paper is in line with China's national standard (2i0 >: 297 male S> 37 1238812 C3 D8 __ VI. Patent application scope-qH2 'where R]' R3 and R2 are each CKC6 base R4 and R5 are each cvc6 alkyl, 0, s or N (R12) 2-interrupted < ^-(: 6 alkyl, unsubstituted or Cl_c6 alkyl ... Cl_c6 alkoxy ... halo-, cyano- or nitro-substituted phenyl Or biphenyl, R6, R7 & r8 are each hydrogen or chloro-alkyl, R9 is hydrogen, (VC6 alkyl or the following formula (Please read the notes on the back first (On this page) and R1 () are hydrogen, Cl-C6 alkyl, cvc6 alkoxy 'dent atom' cyano, nitro, N (R12) 2, unsubstituted or halogen-, cyano-, nitro ... cKc6 alkyl · or cKc6 alkoxy-substituted phenyl, R] 2 and R] 3 are c] -c6 alkyl, r], 4 is hydrogen or (^ -〇: 6alkyl and R] 5 is Hydrogen, cKC6 alkyl, unsubstituted or Cl-C6 alkyl-substituted phenyl, PQ is p, q-CrC6 alkylene which is unsubstituted or by Cl_c6 alkoxy 'C] -C6 thiol or (: 2-(: 12 dialkylamine group substituted one or more times, p and q are different numbered positions, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, X is a heteroatom selected from the group consisting of N, 0 and S Here, if X is 0 or S then m is 0, if X is N then m is 1 and L] AL2 are each unsubstituted or or mono- or poly-Ckc] 2alkoxy-, alkylthio —, Dialkylamino-,-C6-Ci2aryloxy-,-CVC] 2arylthio-,-c7-c24alkylarylamino- or -C12-C24diarylamino-substituted (^ (^ Alkyl or text paper is suitable for China) " ^ «UMCNS) / ^ present (2. [0 29Ϊ 公 S) k 1238812 BS C8 D3 6. Apply for a patent (Please read the phonetic notes on the back. Alkyl Z-] nC] -C6 alkyl, where η is a number from 1 to 1000, p, and q are different numbered positions, and each Z is independently a heteroatom. 〇, S or C ^ C] 2 alkyl substituted N, and the C2-C6 # alkyl group in the repeating unit [-C2-C6 alkylene-Z-] may be the same or different, and 1 ^ and 1 ^ 2 is saturated or one-to-ten-unsaturated, without interruption or at any predetermined point is interrupted by a group of 1 to 10 groups selected from-(C = 0)-and -C6H4- 1 to 10 substituents further selected from the group consisting of a halogen atom, a hydrogen group, and a nitro group. 3. The method according to item 1 of the scope of the patent application, wherein the pigment of formula A (Η) × (Π) is a color index pigment Yellow 13, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 83, Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 109, Pigment Yellow U0, Pigment Yellow 120, Pigment Yellow 128, Pigment Yellow 139, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 175, Pigment Yellow 18, Pigment Yellow 181, Pigment Steam 185, Pigment Yellow 194, Pigment Orange 34, Pigment Orange 71, Pigment Orange 73 'Pigment Red 122, Pigment Red 144, Pigment Red 166, Pigment Red 184 Pigment, I85, Pigment Red 202, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 222, Pigment Red 242, Pigment Red 248, Pigment Red 254 ..... 255 Pigment Red 262, Pigment Red 264, Sesame Brown 23, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ¾ Plain brown, one pigment blue 25, pigment blue 26 = 37 colors: f64, pigment violet 19, pigment violet, pigment violet 32, pigment violet (cyano 'stupid Radical) · 2,5-dihydro ^ pyrrolo [3,4-c] t7pyrrole_, Dongdi S or 3-phenyl, 6_ (4, · Second v Le monobutyl-benzyl ) -2,5-Dihydro-Earth mouths are opened two mouths each. 4. If the method is applied by a patentee, the liquid or dissolved transition is required. Specification (2iQ >: 2Q7 39 Scope of patent application The metal compound is shaped to be coated into the newly-formed parent-coupling and _ 5 · such as the patent application rn- pigmented glass material film. The method of item 1 additionally includes adding a compound having a structural formula HOH-12 and then heating to 150 to ·. c. Temperature to form a glass material. 6. The method according to item 5 of the scope of patent application, in which the Luy group, —Q-x-l2 and the pigment of formula A (Η) χ (π) are β crystal phase quinone acridine 酉 As stated in the patent supplement! The method of the item includes 2 to 10 kinds of organic pigments. 8. A composition for the manufacture of a glass material, comprising a crosslinkable liquid or 'dissolved transition metal compound' and a dissolved formula A (Β) × (Ι) as defined in the scope of the patent application] Compounds. 9.-A glass material obtained by the method of applying for the third item in the scope of patent application, the pigment of "Effective Pigment ®" is contained in a matrix of crosslinked liquid or dissolved transition metal atoms. Consumption by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative seal M 10. If the glass material in the scope of patent application No. 9 is applied, it is in the form of a thin film with a thickness of 0-1 to 3 microns. 11. If the glass material in scope of patent application No. 9 or 10 is applied, it is coated On a glass item. 12. If the glass material of the nth item in the scope of patent application, the glass item is a bottle or a display screen. 40 This paper size applies to the national standard (CNS) A '丨 specifications (210 X 297g>