TW201803B - - Google Patents

Description

OibO ^ A6 B6 V. Description of the invention (1) (Please read the precautions on the back before filling this page) Various textiles, such as: woven fabrics caused by a blend of cellulose fibers or cellulose fibers and other fibers Miscellaneous fabrics, needle-woven fabrics, yarns and filaments, for example, when there is an existence test, for example, Na〇Η, NaCOa or sodium silicate, and when there is an electrolyte, for example: NaC $ or Na2S. 4. At an elevated temperature, for example, at 60 t :, use anionic dyes (especially fiber-reactive anionic dyes) for traditional dyeing. In addition, the continuous Burmese and semi-continuum entanglement methods are used, for example: padding steaming dyeing method or coil cold pile dyeing method. In the two methods of padding steaming and cold rolling, the textile is first paddled with an aqueous mother liquor containing (fiber reactive) dye, and later, in a separate impregnation step, the fixing alkali is applied to the textile on. The alkali used is preferably NaOH solution, KOH solution, Na2CO3 (aqueous solution) or an aqueous sodium silicate solution. Especially with regard to fiber reactive dyes, (it enters into covalent bonds with fibers), the fiber molybdenum material dyed in this way has a high brightness of dyeing and excellent general fastness properties such as wet fastness properties, friction resistance Fastness properties, cooking fastness properties and light fastness properties. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs because of the process of fixing the fiber reactive dye, in the aqueous solution, the strong alkaline dyeing solution may be accompanied by the hydrolysis reaction of the fiber reactive dye, or incomplete fixation on the fiber material , So in some examples, the dyeing process must be followed by extensive and timely washing and light washing processes, such as: repeated cold washing with hot and cold water, and intermediate neutralization treatment for self-dyeing materials In the process, excess alkali is removed, and, for example, a non-ionic detergent is used to ensure good fastness properties of the dye. 81.9.25,000 agricultural paper & Mao general siege standard (CNTS) A 4 specifications (210 X 297? 'A 3 _ L01bG3 A6 B6 V. Description of the invention (2) There is no lack of trial improvement of these post-processing Method to make them more economical and effective, and in addition, to improve the fastness properties of dyeing. For example, US-PS 4,806, 1 2 6 shows the use of fiber-reactive dyes to dye cellulose fiber lozenges without the use of alkali ; That is, before dyeing, the fiber material is anodized and sized by anodizing the fiber material by pretreatment with the reaction product of polyethylene (di) amine and a difunctional alkylating agent. Similarly, US -PS 4, 988, 365: Shown that pretreatment with the reaction product of epihalohydrin and an alkyl amine can improve helix fiber. Using fiber reactive dyes, it is possible to obtain good general fastness properties The dyeing is good on these fiber materials so pretreated; but these fastness properties, especially the light fastness properties, are not equivalent to the dyeing obtained by using the traditional method mentioned at the beginning Of quality. The Central Standard of the Ministry of Economy is beyond the expectation of the R5 Consumer Cooperative Print 5 clothing. It has been found that anionic dyes, especially fiber reactive dyes, can produce dyes with good general fastness properties. These properties are equivalent to a traditional Method, using a modified, anodized cellulosic fiber material obtained by dyeing, in this case, the N-containing, basic ethylenic monomer polymerization is directly carried out on the fibrous material, and These monomers are selected from the monomer groups specified below; using such modified cellulose fiber materials, low electrolyte and alkali-free mother liquor can be used for dyeing, which is why it is not necessary Any expensive post-treatment through light washing and boiling dyeing. Therefore, the present invention provides anionic dyes, especially the use of fiber-based paper. The standards are applicable to China National Standard (CNS) A 4 specifications (210 X 297 public loan) -4 -81: 9.25,000

LOibGS A6 B6 V. Description of the invention θ) Reactive dyes to dye cellulose fiber lozenges. This method includes: dyeing with low electrolyte and non-experimental dyeing solution, and using modified as described below The cellulose cellulose is used as the cellulose fiber material. According to the present invention, it can be used in the dyeing process. The modified cellulose fiber material is a cellulose fiber material to which a polymer has been grafted; this polymer contains the following formula (1), (1A), (2) and (2A) At least one polymerizable group selected from the group consisting of (2A), containing n, basic monomer as a forming system; (please read the precautions on the back before filling this page) -C H-

C- (CH2) n-C0-X- (C (1) Packing-(-) (+) (ΙΑ). Line. Printed by the Consumer Labor Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (2)

丨 -CH = C-CH R'-CH: s * (+) (2A) The size of clothing paper is applicable to the Zhongwei Family Standard (CNS) A 4 specifications (210 X 297 male yak) _ S — 8ι · 9.25, 000 LOlbCd A6 _B6 _ printed by the Central Standards Bureau of the Ministry of Economic Affairs, Mgong Consumer Cooperative V. Description of the invention (4) In this equation: RZ is hydrogen, an alkyl group containing 1 to 6 sulfonate atoms, and 5 to 7 percent Atomic ring radical or a hydroxyl radical (radical) alkyl of a radical atom nursery with 2 to 4 nitrile atoms; R2 has one of the various meanings mentioned in relation to R7 and may be the same as R7 or different from ; Or R1 and only 2 together with N atoms to form a saturated, unsaturated, or partially unsaturated 5-membered ring or 6-membered ring atom, which contains 1 to 3 hypoalkanes with 1 to 5 large atoms Group (wherein, optionally containing 1 or 2 hetero groups, these hetero groups are selected from the group consisting of: a 0-, a S-, -N = and a NH first group; R ^ Is hydrogen or methyl; R 4 is hydrogen or methyl; X is oxygen or is preferably a base of formula NH-; m is an integer from 1 to 6, preferably 2 or 3; η is from 1 An integer to 4 or preferably 0; it contains 1 to 6 masters The alkyl group of the child has a phenyl group or formula of aryl group containing 丨 to 々 sulfon atoms: a (CH2-CH2-〇) phenyl group-value atom group, where Ρ is from 1 to 4 An integer; R6 is hydrogen, an alkyl group containing 1 to 6 sulfonic atoms, a stack alkyl group with 5 to 7 large atoms, or a hydroxyalkyl group with an alkyl group of 2 to 4 sulfonic atoms; (please first Read the precautions on the back and then fill out this page) — Binding · Order ·-Line · The size of the table paper applies to China National Control Standard (CXS) A 4 specifications (210 X 297 public exchange · -6 81.9.25,000 A6

LOibGE __B6__ 5. Description of the invention (5) (please read the notes on the back before filling this page) R7 is hydrogen, an alkyl group containing 1 to 6 large atoms, a cycloalkyl group containing 5 to 7 large atoms, or Formula: —CH2—CH = CH2, -CH 2- C (C Η 3) = C Η 2, -CH2-CH = CH-CH3 or a CH2_C (CHj) = CH-CH3 atomic group; or R5 and R7 together N atom, forming a saturated, unsaturated and partially unsaturated 5- or 6-membered ring atom, which contains: 1 to 3 sub-alkyl radicals with 1 to 5 primary atoms (where Optionally contains 1 or 2 hetero groups, these hetero groups are selected from the group: ―0 —, one S-, — N = and one NH — and other groups; R β is hydrogen or methyl; R 9 is hydrogen or methyl; .Line. Is a single-charged anion, or the equivalent of a multi-charged anion. The Ministry of Economic Affairs, Central Bureau of Standards, Employee and Consumer Cooperatives prints a single charged anion, for example It is an inorganic acid, sulfonic acid or carboxylic acid with a single-charged atomic range, or a polyvalent inorganic acid, sulfonic acid or carboxylic acid equivalent. The single-charged anion, for example, is a nitrate , Hydrogen sulfate, benzene sulfonate, fluoride, chloride, bromide, iodide, acetate or propionate anion, or another aliphatic or aromatic carboxylic acid anion atoms. Multi-charged anions An equivalent, for example, is half of sulfate anion or 1/3 of phosphate anion. The paper iron ruler is suitable for a ® home standard (CNS) A 4 gauge ironing (210 X 297 conversion) — 7-81.9 .25,000 Printed L0ibC3 A6 ______B6_ by the employee consumer cooperative of the Central Standards Bureau of the Ministry of Manpower. 5. Description of the invention (6). Υί_; preferably a halogen anion, for example: Βγ · or I ·, especially C ί-. The alkyl atoms in the group are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, second.butyl, isobutyl, n-pentyl and n-hexyl. Cycloalkyl Atomic groups are, for example, cyclopentyl, cyclohexyl and cycloheptyl, of which cyclohexyl is preferred. Hydroxyalkyl radicals are, for example, 2-hydroxyethyl and 2-hydroxy-n-propane , 3-hydroxy-n-propyl, 2, 3 or 4-hydroxy-n-butyl and 2-methyl-3-hydroxy- • Propyl. On the one hand, if R /, R2, and on the other hand, R5 and R7, combined with n atoms associated with them to form 5 or 6 sections that may be interrupted by heteroatoms, Saturated or unsaturated radicals, then this radical is, for example, pyrrolidinyl, piperidinyl, pyrazolyl, pyridyl, piperazinyl, morpholinyl or thiomorpholinyl. Phenylalkyl Atom atom (wherein the alkyl atom atom may be linear or branched), for example, benzyl, phenethyl, 3-phenyl-n-propyl, 2-phenyl-n-propyl , 3-phenyl-n-propyl, 3-phenyl-n-butyl and 4-phenyl-n-butyl; among them, benzyl is preferred. An example of the formula _ (CH2—CH2— 〇) 〃-phenyl atom is, for example, A— (phenylamino) ethyl and an atomic ring, where P is 2 or 4. Particularly suitable and preferred olefinic, N-containing monomers are, for example, compounds of the following formula (3 a) to (3 m): (please read the precautions on the back before writing the clothing page) 丨 装 · Order. • The size of the line and clothing paper is applicable to the Zhongyuanyuanjia Standard (CNS) A 4 gauge (2 丨 0 X 297 public loan). 8-81.9.25,000

LOibCS A6 B6 5. Description of the invention (7) CH2-CH-C0-0-CH2-CH2-N (CHa) 2 (3a) CH2 = CH-C〇-〇-CH2-CH2-N (n-C4H9) 2 (3b) CH2-CH-C〇-〇-CH2-CH2-CH2-N (CH3) 2 (3c) CH2 = C-C0-0-CH2-CH2-N (CHj) 2 (3d)

CH CH2 = C-C0-0-CH2-CH2-N (n-C4H9) 2 (3e)

CH CH2 = C-C0NH- (CH2) 3-N (n-C4H9) 2 (3f)

CH (Please read the precautions on the back before writing this page.) )

CH This paper is also suitable for A Ψ S National Standard (CNS) A 4 specifications (210 X 297 S loan) -9-81.9.25.000 L0I8C3 A6 B6 Central Standard of the Ministry of Economic Affairs is printed by the employee consumer cooperative. V. Description of invention ( 8) CH2-C-CONH- (CH2) jN (CH3) 2 (3h) I CHj CH2-C-C0NH- (CH mountain-N (CH mountain (3j) I CHa CH2-C-C0NH- (CH2) 2 -N (n-C2H5) 2 (3k) I CH3 CH2-C-C0NH- (CH2) jN (C2H5) 2 (3m) I CHj The above monomers are all good, especially the pseudo-consistent with formula (1 A) It is in the form of a quaternary base compound, and the three alkyl radicals on the quaternary N atom are preferably the same. With regard to these compounds, special priority is given to those of formulas (4 a) to (4 c): Once again, the General Zhongyuan Family Standard (CWS) A 4 specifications do X 297 public loan) -10-81.9.25,000 (please read the precautions on the back before filling in Ben Luo). Pack. Order_. Line. L0ibG3 A6 B6 Five 3. Description of the invention (9 c H2 = c-C ON 'Η-(CH2) 3-N (nC, H9) 3

CH c H 2 = c-CONH- (CH2) 3 ——N (c HJ) 3 CHt CH 2 = c h-conh- (ch,) 3-n (ch3) (-) (-: (-: ( 4a: (4b) (4c) (Please read the precautions on the back before writing this page) 丨 Installed, which is printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, Y (~ has one of the above meanings, and it is preferably a Chloride anion. As for the compound of formula (2A), those compounds (wherein R7 is allyl, preferably dimethylallyl) are preferred. According to the present invention, it can be used to make cellulose fibers The modified monomer is, for example, a compound of formula (5):

Rn _c = CH-R (5) Among them, i paper is again suitable for medium-H garden home sample standard (C >: S) A 4 specifications (210 X 297 male yak) —11 — 81.9.25,000 order. Margin LOlbGo Afi A6 B6 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of invention (1 ()) R 〃 is hydrogen or methyl, R ii is a 5 or 6 section of the Achenchen atomic group, which contains at least one value Basic N atom, and it may have a fused benzene ring and / or may be substituted with one or more (preferably 1 or 2) substituents, and R i2 is hydrogen or methyl. The substituent in R〃 is, for example, an alkyl group containing 1 to 4 main atoms and a hydroxyalkyl atom containing 2 to 4 main atoms. R2 2 is preferably a hydrogen atom. In Section 5, the heterocyclic ring, saturated or unsaturated atom Rw, is, for example, imidazolyl, porazolinyl, pyrazolyl, pyrimidinyl, pyrrolidinyl or sacryl. The 5-section cyclic compound of formula (5) is, for example, N-vinylimidazole, 1-vinyl-2-pyrazoline, 2-vinyl-4-methylimidazoline, 2-vinyl-5 —Methylquinazoline, 1 monovinyl-2-monomethylquinazoline, 1-vinyl-4-(/ 3-hydroxyethyl) imidazole, N-vinylpyrazole, 2-isopropenyl-2 -Myrazoline and 1-vinyl-2,4-dimethylimidazole. Rw is a pseudo 6-membered heterocyclic ring, saturated or unsaturated radical, for example, pyridyl or quinolinyl. The 5-section heterocyclic compound of formula (5) is, for example, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 3-isopropenylpyridine, 2-vinylpyridine, 2 —Methyl-3-vinyl-8-hydroxyquinoline, 2-vinylquinoline, 2-methyl-3-vinylisoquinoline, 1-methyl-5-vinylisoquinoline and 2- Isopropenyl porphyrin. Among them, vinylpyridine and its derivatives are particularly preferred. (Please read the precautions on the back before filling in this shell) This paper scale is applicable to the China® National Standard (CNS) A 4 specifications (210 X 297 father Chu) -12-81.9.25,000 A6 B6

R 016G3 V. Description of the invention (11) The polymer grafted onto the cellulosic fiber material may be one or more of the above formulas (1), (1A), (2), (2A) and / or (5) The compound is formed by the monolithic forming system. It may additionally contain other polymerizable monomers. According to the present invention, the polymer to be grafted onto the cellulose fiber material contains, for example, 2 ° to 100%, preferably 40 to 100%, and particularly preferably 8 to 100%. ?% Of one or more compounds of the above formulas. The distribution of the above monomers can be freely selected. In general, the polymer grafted onto it contains only one of the compounds of the above formula; that is, a cellulose fiber material having a homopolymer grafted onto it is preferred. The copolymers that can be grafted onto the cellulose fiber material are those copolymers, except for the above monomers of formula (1), (1A), (2), (2A), and / or (5), it contains Consistent with the following formulas (6) and (7) as one or more comonomers: R2 (6) (Please read the precautions on the back before filling this page) Printed by the Employees Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs • Γ In this equation:

R1-N-CO- (CH2),-C-CHR

Rl 5-CH = C-C00R (7) Clothing paper ruler is applicable to China National Standard (CNS) A 4 regulation network (210 X 297 • Loan) 018C3 A6 B6 Printed by Employee Consumer Cooperative of Central Standards Bureau of Ministry of Economic Affairs Description of the invention (12) and Ruler 2 have one of the meanings mentioned above, or others, together with N atom, they can form the mentioned heterocyclic atom range; R 7 3 is hydrogen or methyl; R 24 is Hydrogen or methyl; R 7 5 is hydrogen or methyl; R 7 6 is hydrogen or methyl; Ri 7 is an alkyl group containing 1 to 6 carbon atoms; q is zero, 1, 2 or 3. The monomers of formula (6) are, for example, acrylamide and methacrylamide. The compound of formula (7) is, for example, (C, -C5) alkyl ester of acrylic acid and methacrylic acid, especially methyl ester and ethyl ester. When the homopolymer or copolymer is grafted on the cellulose compound, as in the presence or absence of one or more monomers of formula (6) and / or (7), the polymerization formula (1), (1A ), (2), (2A) and / or (5) one or more monomers. The polymerization / copolymerization pseudosequence on the following dimension occurs in an appropriate solvent. These are, in particular, water mixed with a water-miscible solvent, which is inert to various monomers. These solvents are, for example, low sulfanols, for example: phenols containing 1 to 5 sterol atoms, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol and tertiary · Butanol; various ethylene glycols and glycols, for example, ethylene glycol, propylene glycol and 1,3-propylene glycol, di and polyglycols, for example, diethylene glycol and triethylene glycol; various glycol ethers; For example, diethylene glycol monomethyl ether diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol (please read the precautions on the back before writing / booking / booking-line '' This paper scale is applicable to the Chinese National Standard (CM) A 4 specifications (210 χ 297 public rate) -14-81.9.25,000 Α6 Β6 Printed by the Xiaogong Consumer Cooperative Society of the Central Bureau of Standards of the Ministry of Economic Affairs *. 13) Mono-n-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether and ethylene glycol diethyl ether, and also ketones such as acetone and methyl, ethyl ketone. When present, homopolymerization and copolymerization can also be carried out in a mixture of different solvents containing water. If one or more components, When used in the form of an aqueous solution, generally speaking, it is not necessary to add additional water. Priority is given to water mixed with various alcohols, such as various alkanols, especially those containing 1 to 4 large atoms; Alcohol and / or ethylene glycol are mixed. During homopolymerization and copolymerization, it may be advantageous to add another organic solvent or solvent mixture at one time, or in particular, divided into portions and added several times. Before starting homopolymerization or copolymerization, it The advantage is: adjust the pH value to 3-1 1.5, preferably 3-8.5. Generally speaking, this adjustment should be done with an acid; it is preferably an organic acid, especially formic acid, Acetic acid, glycolic acid, and / or citric acid. Homopolymerized or copolymerized pseudo-cellulose fiber materials at room temperature (10 ° to 301C), or at higher temperatures of up to about 16 ° t It should be carried out at a time, but, generally speaking, it is at a temperature between 40 and 100, preferably between 60 ° and 901C, especially between 65 ° and 8 5 1C. Suitable polymerization initiators, for example , Free radical forming agents, are used in the traditional way for this purpose. Similar, In order to use the effect of high-energy radiation, for example: UV light, but also use microwaves and ultrasound to initiate polymerization. The initiators that form free radicals are, for example, benzoyl peroxide, tertiary butylated Hydrogen and oxygen, isophenylpropylated hydrogen, pervaporated laurel, (please read the precautions on the back before writing this book). Install. -Line-Clothing paper standard universal ® S home rubbing standard (CNS) A 4 Specifications (210 X 297 X redundant) ~ 15-81.9.25,000

OlbG ,: ί. Α6 Β6 Printed by WK Industrial and Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs. V. Description of the invention (14) Perbenzoic acid, tertiary butyl ester, dibutyl phthalate, diisocyanate Butyronitrile, 2, 2 diazobis (2, 4-dimethylpentanol), 2-phenylazo-2, 4-dimethyl-4-methylaminopentan, 2_ ambiyl one 2- Propyl azomethanamide, azobisisobutylamide, dimethyl valerate, diethyl or di-n-butyl *, azobismethyl ester, tert- neodecanoic acid, butyl ester, pergas Diisononamide, tertiary amyl pervalerate, diethyl 2-ethylhexyl pergasoate, dilaurin peroxide, diisotridecyl diperoxide, and hydrogen peroxide The third acid is butyl isopropyl peroxide. Preferred initiators are 2,2-_azobis (2-dipropane) dihydrochloride, 2,2 / azobis (2-diazolyl-2-ylpropane) dihydrochloride, 2 , 2 / -azobis (2-aminomethylpropane) dihydrate or 2,2 / azobis (2-methylaminocarbonylpropane). Based on the number of monomers, by weight, from 0.01 to 2% (preferably from 0.1 to 1%) initiator. The advantage is that oxygen is eliminated to carry out graft polymerization / copolymerization. This can be done in a manner known per se; that is, by flushing with an inert gas, for example: N2. Each monomer component is used in such an amount that the polymer grafted onto cellulose contains at least 20 moi%, preferably at least 40 moi%, and particularly preferably at least 80 m〇i% of the polymerized form One or more compounds of formula (1), (1A), (2), (2A) and / or (5). The grafting can be carried out according to the present invention by introducing the cellulosin fiber fiber material to be grafted into the polymerization vessel together with the solution of each monomer, and performing homopolymerization or copolymerization. Under these circumstances, in general, homopolymerization or copolymerization (please read the precautions on the back before writing the Ϊ) binding-binding. Thread. Clothing paper ruler / S applicable by a country (CNS) Specifications (210 X 297 public loan) ~ 16 ~ 81.9.25,000 L 0 18 u A6 B6 Ministry of Economic Affairs Central Standards Bureau Beigong consumer cooperation. Social printing and correction five, invention description (15) completed in about 0.5 to 4 hours, In many cases, it is completed after 0.5 to 2.5 hours. Then, the cellulosic fiber material is removed from the polymerization vessel so that it does not contain adherent liquid, for example, by squeezing; it is gently washed with water and dried. However, the grafting of cellulose fibers can also be carried out by applying a monomer solution to the cellulose woven material, that is, using: padding, pinch padding, dipping or spraying, and then at room temperature or high temperature, the Polymerization or copolymerization, advantageously through the action of high-energy radiation or ultrasound. Often, about 0.5 to 10 minutes is sufficient for irradiation or sonic methods. Then store the helix fiber material in the wet state for 2 to 36 hours, preferably 10 to 24 hours, and then, after possible light washing, dry it. Cellulose fiber materials suitable for modification in the manner of the present invention are, for example, cotton and viscose staple fibers, but also fibers such as flax, jute and ramie and regenerated cellulose fibers, preferably cotton . These modified cellulose fiber materials can also be present as a component of blended fabrics, for example, blended fabrics of these modified cellulose fibers and polyester fibers. The modification of the cellulose fiber according to the present invention can be carried out within the blended fabric itself and also in any state of treatment, such as yarn, fiber, neck roving, and H. A suitable substrate is cellulose fiber material (which has been modified in the aforementioned manner), that is, the polymer has been grafted onto it, and in particular, will be based on cellulose fibers, by weight, 〇. 5 to 4 0¾. (Preferably 2 to 25% by weight, particularly preferably 4 to 15% by weight of the polymer grafted on it). U.S. Patent Case 4, 464, 523 shows: Use N, N- (Please read the precautions on the back before writing the book? — Pack. Order. — Line. The size of the clothing paper is applicable to the S National Standard (CNS) A 4 specifications (LMO X 297 X loan) ~ 17 I 81.9.25,000 101BG3 A6 B6 DK Industrial and Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs Printing and Agriculture 5. Invention Description (16) Dipropylene-N, N-Secondary Base Saddle It is polymerized as a monomer to modify the cellulosin material. These modified cellulosin derivatives are used as auxiliary agents in shampoos and other hair care products. However, it has not been shown before: The cellulose fiber material modified in this way, such as cotton modified in this way, is used as a matrix for dyeing with anionic (especially fiber reactive) dyes. In particular, by using various polymers (including formula (1), 丨The modification resulting from the grafting of 1A), (2) and / or (2A) compounds is novel. Therefore, the present invention also provides: cellulose fiber materials modified in the manner according to the present invention; that is, through the polymerization of these compounds of formula (1) and / or (2), or their derivatives as quaternary emu Things to graft. The dyeing of cellulose fiber materials modified in the manner according to the present invention is pseudo similar to various well-known methods for dyeing cellulose fiber materials using anionic dyes, especially anionic fiber reactive dyes, using conventional temperature ranges and The quantity of conventional dyes is implemented; in addition to the new supply, the addition of basic compounds can be omitted in the dyeing baths and padding fluids of the dyeing process according to the present invention (for example, to fix the fiber reactive dyes, which are used by users), for example: Na2C 〇3, K ^ COa, NaOH, and sodium silicate; and, in addition, do not need to add electrolyte salts customarily, (the purpose is to enhance the migration of dyes on the fabric) or only need to add a small amount , That is: a dyeing bath or dyeing solution that does not exceed 10 g / i? Therefore, according to the dyeing process of the present invention, 傜 occurs in the pH range from 3 to 7.5, preferably from 4.5 to 7. According to the present invention, the dyeing process that can be used is, for example, each (please read the precautions on the back before writing this page)-Binding · Order _ This paper is ii?! Zhongwei family standard ( CNS) A 4 specifications (210 X 297 male wear) -18-81.9.25.000 & A6 Printed by the Central Standards Bureau of the Ministry of Economic Affairs KKK Consumer Cooperative Co., Ltd. 3. Description of the invention (17) Dip dyeing methods, such as: in a roll dyeing machine Dye on or on the gauze dyeing tank, or dye from a large bath ratio or a small bath ratio, dye in a jet dyeing machine, dye through the roll cold pile dyeing method, or dye through the padding steam dyeing method. Using conventional bath ratios from 3: 1 to 20: 1, the dyeing method is possible. The dyeing temperature may be between 3〇t: and 90t :, preferably lower than 60T :; like the above-mentioned use of self-rolling cold pile dyeing method, it is obvious that according to the present invention, dyeing is also at room temperature (10 ° to 30C) It is possible to succeed. The dyeing process according to the invention can also be carried out using various conventional auxiliary agents; for example: various interface activators (wetting agents), urea and levelling agents or aids that can improve the solubility of dyes in concentrated padding liquors Agents, for example: condensation products of formaldehyde and a certain sulfonic acid substituted by alkyl. For dyeing by the method according to the present invention, it is possible to use any anionic dye (in which, it has one or more sulfo and / or carboxyl groups), and if necessary, it may contain fiber-reactive groups. They may not only belong to this class of azo dyes, but also in these categories of copper-containing complex dyes, cobalt-containing complex dyes and chromium-containing complex azo dyes, copper and nickel phthalocyanine dyes, M copper quinones Dyes such as formaldehyde and triphenyldioxazine. These dyes have been described extensively in the literature and are completely familiar to those skilled in the art. According to the present invention, dyeing on modified cellulosin fiber material can be obtained, after being taken out from the dyeing bath, or after the dye is completely fixed on the substrate, no additional post-treatment is needed, especially without the cost of washing Post-processing process. In general, it is sufficient to wash the dyed substrate with cold or hot water one or more times in the usual way, and if necessary, it may contain a non-ionic wetting agent. It is not necessary to use it for boiling for the purpose of improving the fastness properties (please read the precautions on the back before buying the copy)-equipment ·. Thread · clothing paper standard universal 0 national standard (CNS) A 4 specifications ⑵ 0 X 297 public loan) -19-81.9.25,000 A6 B6 V. Description of the invention (18) Washing solution to finally process the dyed substrate. The present invention will be described further with reference to the examples. Unless stated otherwise, parts and percentages are by weight. Parts by weight have the same relationship as Kg to liter for parts by volume. Example 1 A cotton cloth with a weight of 2.8 g and a size of 8 x 30 cm was fixed in place inside a 5β three-necked flask equipped with a horseshoe stirrer, a nitrogen inlet tube, and a reflux condenser. Then the flask is filled with: 100mS of distilled water, 113.3g of sodium chloride, 573mg of ethylenediamine disodium methyl acetate and 2372. 5mg of dimethyldiallyl ammonium gas into 61% aqueous solution, It was evacuated and covered with N2 three times, and heated to 80t at 38◦ to 400mbar. At this temperature, with stirring, measure 64.5 g, 5.25% ammonium persulfate solution; followed by heating for one hour, then add another 5 4 g, 12.5% ammonium persulfate Solution and heat at 8 ◦ ° C for 1 hour. After adding another 1 Ig · g of aqueous persulfate saddle solution, the polymerization was carried out at 80 ° to 8 3 for 2 hours. This paper is again applicable to the standard 4 (210X2971: Loan) of the sibling home standard (CNS) -20-(Please read the precautions on the back before writing the book ¥. Installed, ordered. — Line · Central Standard of the Ministry of Economic Affairs Printed by the Bureau ’s Employee Consumer Cooperative 81.9.25,000 Printed by the Employee ’s Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

OibOii A6 _ _B6 _ V. Description of the invention (19) Then take the cotton cloth out of the reaction flask, squeeze it dry, wash it twice with 500 mi? Water each time, squeeze it dry between light wash, then at 100 t: Allow to dry for 5 minutes. The polymer addition rate is 5.3%. Example 2 A cotton cloth with a weight of 5.4 g and a size of 8 × 60 cm is fixed to one with a horseshoe stirrer, a gas inlet tube and a reflux condenser. Appropriate position inside the three-necked flask, and add: 9〇g, NaCi ™ that has been dissolved in 100 μm water, 130.9 g, dimethylaminopropyl methacrylamide, 3 1 9 5 g of ethanol and 40mg of disodium edetate. Using 231 g of glacial acetic acid, the pH was set at 8.5 to 9.0. Add 96〇8 of water and 206〇1118, 2,2'-azobis (2-fatty propane) dihydrochloride (as an initiator); then, the flask was evacuated and covered with N 2 three times, And heated to 7 9 _ 8 0. . 〇Once the internal temperature reaches 8 0 1C, immediately add ethanol in the following consecutive parts: 4 5. 8 g, (please read the precautions on the back before filling in this 1)-丨 install. Order. --Thread · Appropriate degree of clothing and paper is applicable to the Central Wai Nationality Standard (CNS) (4) branding (2〗 0 X 297 father seam) -21 81.9.25,000 Printed by the Central Bureau of Standards of the Ministry of Economic Affairs 8 Industrial and Consumer Cooperatives * 'Agricultural LOiBoS A6 _______B6_ V. Description of invention (2〇) 38.5g, 93g and finally, 322.5g. Between each addition, the mixture was stirred for 15 minutes, and at the end, it was polymerized to completion at 8010 for 2 hours. Then, the cotton cloth was taken out of the flask, washed with 200mJ2 of water each time, and washed lightly three times. In each time, it was squeezed to dryness, and then dried for 5 minutes. The polymer addition rate is 4.9%. The active substance concentration in the polymer is 25%. The K value of 1% aqueous solution is 112, 600. Example 3 Example 2 was repeated except that the cotton cloth was replaced with a viscose staple fiber cloth weighing 3.4 g and having a size of 8 × 47 cm. The polymer addition rate was 2.9 5 96 〇 Example 4 The cotton cloth was removed and replaced with a cloth of equal size, weighing 5.7 g and containing 65:35% polyester / cotton blended fabric, repeating Example 2. The polymer addition rate is 3.4%. Example 5 A solution containing the following compounds was added to one equipped with a horseshoe-shaped stirrer, a gas inlet pipe and a reflux condenser. A 4 gauge network (210 X 297 public loan) -22-81 · 9 · (please read the precautions on the back before writing this page) Installation · Order · 01BG3 A6 B6 5. Description of the invention (21) in a three-necked flask ： (Please read the notes on the back before filling this) 2 0 ◦ g, distilled water, 56.7 g, sodium vapor, 287mg, disodium ethylenediaminetetraacetate, 250g, ethanol and 1210g, Dimethyl diallyl ammonium chloride is a 61% aqueous solution. Subsequently, 9.5 g of glacial acetic acid was added to adjust the pH to 3.7 to 3.8, and diluted with 368.8 g of ethanol. The concentration of the active substance of the monomer is 34.7%. τ Introduce 827 g of this 34.7% monomer solution into a one-foot flask. A piece of cotton cloth weighing 11.6 g and having a size of 100 × 25 cm was immersed in the solution, and subjected to ultrasonic treatment for 30 minutes. Then squeeze the cotton cloth and store it in a wet state at room temperature for 24 hours. The polymer addition rate was 37%. Example 6 printed by Shengong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs. Using glacial acetic acid, adjust the pH value of the solution containing the following compounds to 8.5 to 9.0: 200 m of water, 18.1 g Of N a C β, clothing paper and Mao General Zhongzhong National Standard (CNS) Tian 4 specifications (210 X 297 father loan) ~ 23-81.9.25,000

OibO A6 B6 Five'Invention Description 2) C Please read the notes on the back and fill in 4 206.18g, dimethylaminopropylmethacrylamide, 63.9g of ethanol, 81.4mg of ethylenedioxide Disodium edetate, $ 1, dyed on a cotton cloth and squeezed out. After squeezing out, the liquid absorption rate was 14.4%. The wet cloth was microwaved (at 90 watts for 30 seconds, then at 720 watts for 30 seconds). The wet cloth was then left at room temperature for 24 hours, after which it was dried at 10010 for 5 minutes. The polymer addition rate was 29.5%. Example 7 In the manner indicated in Example 6, the monomer solution specified in Example 6 was applied to a cotton cloth and squeezed dry. To initiate polymerization and grafting, the wet cloth is exposed to UV radiation. The post-processing of the cloth was carried out as shown in Example 6. The polymer addition rate was 30.8%. The Ministry of Economic Affairs, Central Standard, Consumer Engineering Co., Ltd. Printing and Burning Example 8 is equipped with a horseshoe-shaped stirrer, a gas inlet pipe and a reflux condenser with a 5P, three-necked flask, containing a piece of weight 5.7g, the size is 8 X 6 0 cm of 3: 7 ◦% cotton / polyester blend fabric. Add 800g of distilled water, put 127.5g of NaCJH in it, then add 1452g of dimethylaminopropylmethacrylamide, followed by the addition of 713.6g of ethanol and 573mg of ethylenediamine * Because of the specifications of CNS A4 (210 X 297) -24-81.9.25,000 01BG3 A6 B6 The Ministry of Economic Affairs Central Standards Bureau employee consumption cooperative printed the agricultural five, invention description (23) two sodium acetate. Use 246.4g of glacial acetic acid to set the pH at 8 to 9. Then, 2.9 g of 2, 2 / —azobis-2-—fatty propane dihydrogen compound and 290.5 g of water were added. Under 20 to 25t :, the monomer solution was searched and mixed for 1 hour. Squeeze the cloth dry and divide it into 2 half pieces. Each half was subjected to the following treatments: I. One of the halves of the cloth was microwaved at 90 watts for 30 seconds and at 720 watts for 2 minutes. Then dry it under 1◦◦ for 5 minutes. The polymer addition rate is 7.9% on the weight of the fiber. I. Expose the other half of the cloth to UV irradiation for 15 minutes, and then dry under the same condition for 1 minute for 5 minutes. The polymer addition rate is 9.11% on the weight of the fiber. Example 9 Equipped with a horseshoe shaped mixer, a gas inlet tube and a reflux condenser. One of the three-necked flasks holds a piece of cotton cloth weighing 5.7 g and 8 X 6 0 cm in size. Add 2 ◦ 〇m of distilled water, continuously add 127_ 5g of NaCi? (Dissolved into it), and then in the form of 61.2% aqueous solution of 1186. 3g of dimethyl biszylpropyl chloride, 1452g of Trimethylammonium propyl methacrylamide, 573mg of ethylenediamine tetraacetic acid bis-Na and 450g of ethanol. Use 1.0 g of glacial acetic acid to set the pH to 6.◦. With the addition of 76.9 g of ethanol, add 2. 9 g of 2, 2 / —azobis (please read the precautions on the back before writing the table; pack. Order · thread. Clothes paper does not apply & Mao + Far SI home rubbing standard (CNS) Jia 4 菌 珞 (210 297 熈) ^ .25,00 A6 018C3 _B6_ V. Description of the invention (24) (2-Fatty Propane) Hydrogenated Anode as initiator The mixture is heated to an internal temperature of 78 to 80 = under N2. Once this internal temperature is reached, the polymerization / grafting starts immediately, with the temperature increasing to 8410. After the polymerization is terminated, 64.5g, 54.2g, 118. 4g and 453g of ethanol are added in portions at intervals of 10 to 15 minutes. After adding the last portion, the mixture is stirred at 7 7 ° to 80T for 1 hour. Then, remove the cloth and proceed as in Example 1. After treatment, the polymer addition rate is 14.6%. Example 10 is equipped with a horseshoe-shaped stirrer, a gas inlet tube and a reflux condenser. It has a 55 three-necked flask, containing one piece, heavy 5. 6g, cotton cloth with a size of 8X60cm. Continuously added: 100g of distilled water, 127.5g of NaCi ?, 1452g of trimethylammonium propyl methyl propane Acetamide chloride (which forms a 50% aqueous solution), 726g of dimethylaminopropylmethacrylamide, 573mg of disodium ethylenediaminetetraacetate, 4 50 g of ethanol and 6 3 8 2 g Glacial acetic acid. Then add 2. 9g, 2,2-azobis (2-fatty propane) dihydrogenate as an initiator, and heat the mixture under N 2 to 8 0 10. Once the temperature reaches 8 0 C, the polymerization starts, and then the temperature continues to rise to 89 ° C. After that, it is divided into 64. 5g, 54.2 g, 1 18.4 g and 4 0 ◦ g and other parts are added with ethanol; each addition , Followed by 1 ◦ minutes of agitation, and the final addition was followed by heating at 7 8 to 8 ◦ t for 2 hours. The clothing and paper are also compliant with the Shiguo Instinct (CNS) A 4 specifications (210 X 297 public are all) -26 * ------------------------ installed 丨 -------. 玎 ------ ^ (please Read the precautions on the back first and then write.) 1. Industrial and Consumer Cooperation Du Yin, Central Bureau of Standards, Ministry of Economic Affairs 81.9.25,000 A6 B6 5. Description of the invention (25) The polymer solution obtained is 38% strength (in order to determine the polymer Content, heat the sample at 200 mbar to 12010 (2 hours). The solution Viscosity of 44.6 seconds is generated by the time the jet nozzle 6mm DIN cup. The cloth was removed and as in Example 1, to be after processing of the polymer added was 4.7%.

Example A The cotton cloth modified as in Example 1 was first treated with boiling water for 15 minutes and then dried. The fabric is then dyed by cold roll pile dyeing. For the purpose of this project, an aqueous dye solution (which is 10 parts by volume) contains: 28.5 parts of a 50% pure, well-known dye with the following formula, containing electrolyte (predominantly NaCin powder) : (Please read the notes on the back before writing this page)

Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, 100 parts of urea and 3 parts (in solution) of a commercial non-ionic wetting agent, applied to the fabric by a pad dyeing machine, Achieve 80% absorption rate of mother liquor based on the weight of fabric. Wrap the dyed fabric on a cloth roll, wrap it in a plastic sheet, and leave it for 16 hours at 2 01C. After that, wash it gently with cold and hot water and dry it. 81.9 .25,000 paper k-gauges_ Applicable to Zhongxuyuan Complete Standard Zhuo (CXS) A 4 gauge road (2) η X 297 hU)-27 —

Oibi A6 B6 Printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs * '* · V. Description of invention (26) The dyeing obtained has a strong, uniform orange color, and has good general fastness properties, especially good rub resistance and light resistance Fastness and other properties. Example B 1 ◦ part of cotton cloth was modified as in Example 1, and then boiled in water, post-treated for about 15 minutes and dried cotton cloth, introducing 2 ◦ 0 parts by volume of an aqueous dye solution (where Contains: 0.2 part of the dyeing powder described in Example A in solution). This dyeing bath is heated to 60 ° C for 30 minutes, and at this temperature, the dyeing process is followed for 60 minutes. Then, the fabric was taken out of the bath, gently washed with cold and hot water and dried. The result obtained, as in Example A, is an orange dyeing with good general fastness properties, for example, in particular, good rubbing resistance and light fastness properties. Example C The cotton fabric modified as in Example 1 was first treated in boiling water for 15 minutes, then dried and dyed by the cold rolled coil dyeing method. For the purpose of this project, at 20 ° C, an aqueous dye solution (in 1000 parts by volume, it contains: 28.6 parts of 50% pure with the following formula, containing electrolyte ( Predominantly NaC5) Powder dyes: (Please read the precautions on the back before writing this page) _Packing_ Apparel paper size is applicable to the Chinese Standard (CNS) ® 4 gauge (2 丨 0 X 297 Public Yak) One 28 — 81.9.25.000

) IBC A6 B6 V. Description of invention

ϋ iV Η-C Ο-C Η-S Ο, N The Ministry of Economic Affairs Central Standards Bureau employee consumption cooperation du printing i. (In the traditional way, the diazo and tin components shown in the formula can be prepared), 10 ◦Parts of urea and 3 parts of a commercial non-ionic wetting agent (in solution) are applied to the fabric by a pad-dyeing calender and have a mother liquor absorption rate of 80%, based on the weight of the fabric. Wrap the dyed fabric on a cloth roll, wrap it in a plastic sheet, and leave it under 16 ° for 16 hours. After that, wash it gently with cold and hot water and dry it. The obtained dyeing has a strong, bluish-red uniformity, and has good general fastness properties, especially good rubbing resistance, washing and light fastness properties. Example D The cotton fabric modified as in Example 1 was first treated with boiling water for 15 minutes and then dried. Then the fabric was pad dyed at 201C with an aqueous dye solution; this dye solution contained 1000 parts by volume: 28.5 parts of 50% pure with the following formula, containing electrolytes (dominant is N a C 5) The well-known dyes of powder: (Please read the precautions on the back before filling in this 1)-Pack · Order _ Can ·: Paper ruler in the use of a home standard (CNS) «Μ specification (210 X 297 W ~ 29 ~ 81.9.25,000 Ο 1 b ί ^ Α6 Β6 V. Description of invention ¢ 8): .. HO Hr,-CO— ^

(Please read the precautions on the back before filling in Benbei) 10 parts of urea and solution, 3 parts of a commercial non-ionic wetting agent; this pad dyeing custom is applied by a pad dyeing machine ; Has a mother liquor absorption rate of 8◦%, based on the weight of the fabric. Wrap the dyed fabric on a roll of cloth, wrap it in a plastic sheet, and leave it at 20 ° C for 16 hours. After that, wash it gently with cold and hot water and dry it. The dyeing obtained has a strong, uniform red color, and has good general fastness properties, in particular, good rubbing resistance and light fastness properties.

Example E Printed by the Workers and Consumers Cooperative of the Central Bureau of Standards of the Ministry of Economy and Economics * 1 The farmer will modify 10 parts of the cotton fabric as in Example 1, and then post-treat it with boiling water for 15 minutes and dry it; introduce it 200 parts by volume of an aqueous dye solution (this solution contains 0.2 parts of the dye powder described in Example D in the solution). The dyeing bath is heated to 60 T within 3 ◦ minutes, and at this temperature, the dyeing process is continued for 60 minutes. The fabric is then removed from the bath, washed gently with cold and hot water, and dried. The results obtained, as in Example D, are orange dyeings with good general fastness properties, for example, in particular, good rubbing resistance and light fastness properties. Clothing and paper are also suitable for China Home Furnishing Standard (CNS) A 4 specifications (210 X 297 wear) 1 30-81.9.25.000

OlbGB A6 B6 V. Description of invention ¢ 9)

Example F The cotton fabric modified as in Example 1 was first treated in boiling water for 15 minutes, then dried, and dyed by cold rolled pile dyeing. For this project, under 2 Ot :, an aqueous dye solution, (which by volume, contains 1,000 parts of 28.6 parts of 50% pure with the following formula, containing electrolyte (dominated by NaCi? ) Powder dye: (Please read the notes on the back before filling this page)

Binding · Ordering_ (In the traditional way, the diazo and coupling components shown in the formula can be prepared), 1 ◦ 〇 parts of urea and 3 parts of a commercial non-ionic wetting agent (in solution) ， Apply a pad dyeing machine to the fabric, with a mother liquor absorption rate of 8 ◦%, based on the weight of the fabric. Wrap the dyed fabric on a roll of cloth, wrap it in a plastic sheet, and leave it at 20 ° C for 16 hours. After that, wash it gently with cold and hot water and dry it. The dyeing obtained has a strong, uniform orange-red color, and has good general fastness properties, especially good abrasion resistance, washing and light fastness properties. The paper is suitable for 11 standards (CNS) A 4 specifications (LM0 X 297 Yuan loan) -31. Quan. Central Bureau of Standards of the Ministry of Economy ®: Industrial and Consumer Cooperatives printed by Deputy Agriculture 81.9.25,000 .0ibG3 Central Bureau of Standards of the Ministry of Economy printed A6 B6 by the Consumer Cooperative V. Description of invention)

Example G 1 parts of cotton cloth was modified in the same way as Example 1, and then post-treated in boiling water for 15 minutes, and dried; it was introduced into 20 parts by volume of an aqueous dye Dye in the solution (this solution contains 0.2 parts, 50% pure with the following formula, containing electrolyte (predominantly N a C j?) Powder:

N Η-C 0-N Η 2 (In the traditional way, the diazo and coupling components shown in the formula can be prepared). Heat the dyeing bath to 60C within 30 minutes, and continue the dyeing process at this temperature for 6◦ minutes. The fabric is then removed from the bath, washed gently with cold or hot water and dried. The result obtained is a yellow dyeing with good general fastness properties, especially good rubbing resistance, washing and light fastness properties. Example Η 10 parts of cotton cloth was modified as in Example 1, and then post-treated in boiling water for 15 minutes, and dried; it was introduced into 2 parts by volume In the dye solution (this solution contains 0.2 parts, is 50% pure with the following formula, and contains electrolyte (dominated by

Dye of NaCin powder:-_____ · > * Applicable to clothing paper ruler / S, due to a home kneading (CXS) A 4 specification (210 X 297 ‘s) * 32 ~ 81.9.25,000 (please read the back Matters needing attention in writing λ) • Install · 丨 line.

, 0ibC Α6 Β6 V. Description of the invention (31)

(In the traditional way, the diazo and coupling components shown in the formula can be prepared). The dyeing bath is heated to 6010 within 30 minutes, and at this temperature, the dyeing process is continued for 50 minutes. Then, the fabric was taken out of the bath, gently washed with cold and hot water, and dried. The result obtained is a yellow dyeing with good general fastness properties, especially good rubbing resistance, washing and light fastness properties. Example J 10 parts of cotton cloth were modified as in Example 1, and then post-treated in boiling water for 15 minutes, and dried; it was introduced into an aqueous dye solution containing 20 parts by volume Medium (this solution contains: 0. 2 parts of 50% pure with the following formula, containing electrolyte (dominantly NaCiH powder dye: (please read the precautions on the back before writing I)) 丨 Package · Order · 丨 Line · Ministry of Economy, Central Bureau of Standards, Gougong Consumer Cooperation, Thorium Printing and Burning

(Can be prepared with instructions similar to the German patent case specification No. 1 2 2, 0 9 4). The dyeing bath was heated to 60 ° C within 30 minutes, and the paper was combined with the universal Chinese standard 0 (CNS) «4 specifications Uio X 297 public conversion) -33-δΐ.9.25, 〇〇〇Α6 Β6 ; Oib〇 V. Description of the invention (32) (Please read the precautions on the back before writing this page) At this temperature, continue the dyeing process for 60 minutes. Then, the debris was taken out of the bath, gently washed with cold and hot water, and dried. The result obtained is a red dyeing with good general fastness properties, especially good rubbing resistance, washing and light fastness properties.

Example K The cotton cloth modified as in Example 1 was first treated in boiling water for 15 minutes, then dried and then pad-dyed using the following aqueous dye solution at 20 ° C; by volume, 1 0 〇0 parts of this dye solution, containing: 28.5 parts of the dye powder described in Example G, 100 parts of urea and 3 parts, a commercial non-ionic wetting agent in the solution, with 80 % Mother liquor absorption rate (based on the weight of the fabric). Wrap the dyed objects on a roll of cloth, wrap it in a plastic sheet, and leave it at 20 ° C for 16 hours; after that, wash it gently with cold and hot water and give it dry. The obtained dye has a strong, uniform yellow color, and has good general fastness properties, especially good rubbing resistance, washing and light fastness properties. Printed by the consumer cooperation of the Central Bureau of Standards of the Ministry of Economy

Example L The cotton cloth modified as in Example 9 was first treated with boiling water for 15 minutes and then dried. The fabric is then dyed by cold-rolled pile dyeing. For this project, an aqueous dye solution was added at 2 ° C; in a volume of 100 parts of this dye solution, it contained: 28.5 parts of the dye powder described in Example A, 10 ◦ The original paper ruler is applicable to the Zhongyuan II Standard (CNS) φ 4 specification (210 X 297 Gongchu) 1 34-81.9.25,000

I A6 B6 V. Description of the invention (33) (Please read the precautions on the back before writing this page) Urea and 3 parts, a commercial non-ionic wetting agent in the solution, borrow a pad dyeing rolling liquid The machine is applied to the fabric to achieve a mother liquor absorption rate of 80% (based on the weight of the fabric). Wrap the dyed fabric on a cloth roll, wrap it in a plastic sheet, and leave it at 20 for 16 hours; after that, wash it gently with cold and hot water and dry it. The dye obtained has a strong, uniform orange color, and has good general fastness properties, especially good properties such as rubbing resistance and light fastness. Example Μ 10 parts of cotton cloth was modified as in Example 9 and then post-treated in boiling water for 15 minutes and dried; it was introduced into 200 parts by volume of an aqueous dye solution (This solution contains 0.2 parts (of the solution) of the dye powder described in Example A). Heat the dyeing bath to 60Ό within 30 minutes, and at this temperature, continue the dyeing process for 6◦ minutes. Then, the fabric was taken out of the bath, washed gently with cold and hot water and dried. The results obtained by Yin Zenong, the War Industry and Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, as in Example A, are an orange dyeing with good general fastness properties, especially good rubbing and light fastness properties. Example N: The cotton fabric modified as in Example 9 was first treated in boiling water for 15 minutes, then dried, and dyed by cold rolled coil dyeing. For the purpose of this project, an aqueous dye solution at a paper temperature of 20 ° C is used in the general standard siege (CNS) A4 regulation (210 X 297 conversion) _ 35 — 81.9.25,000, 0160 A6 B6 V. Description of the invention (34), by volume, 1 000 parts of this dye liquor contains 28.6 parts of the dye powder described in Example C, 100 parts of urea and 3 parts, A commercially available non-ionic wetting agent in the solution, applied to the fabric by a mess dyeing press to achieve a mother liquor absorption rate of 80% (based on the weight of the fabric). Roll the dyed fabric Wrap it around a roll of cloth, wrap it in a plastic sheet, and leave it under 20¾ for 16 hours; after that, it is gently washed with cold and hot water and dried. The dye obtained is strong and evenly blue. Red, and has good general fastness properties, especially resistance to rubbing, washing and light fastness (please read the precautions on the back before writing this page) 丨 Install.

Example P The cotton fabric modified as in Example 9 was first treated with boiling water for 15 minutes and then dried, and then the fabric was placed under 20¾ using an aqueous dye solution with a pad dyeing calender Pad dyeing; in volume, 100 ◦ parts of this dye liquor contains: 28.5 parts of the dye powder described in Example D, 1 ◦ parts of urea and 3 parts, one of the commercially Ionic wetting agent; has a mother liquor absorption rate of 80% (based on the weight of the fabric). Wrap the dyed fabric on a cloth mark, wrap it in a plastic sheet, and leave it under 20¾ for 16 hours; after that, wash it gently with cold and hot water and dry it. The dye obtained has a strong, uniform red color, and has good general fastness properties, especially good properties such as abrasion resistance and light fastness. This paper scale is applicable to China National Standards (CNS) Grade A 4 (210 X 297 public conversion) -36 ~. Quan-Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Mr. Industrial and Consumer Cooperatives 81.9.25,000 Employee Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Printed A6 B6 Five 'Invention Description (35)

Example Q 10 parts of cotton fabric were modified as in Example 9 and then post-treated with boiling water for 15 minutes and dried; it was introduced into 200 parts by volume of an aqueous dye In the solution (this solution contains 0.2 parts (in the solution) of the dye powder described in Example D). The dyeing bath was heated to 601C within 30 minutes, and at this temperature, the dyeing process continued for 6◦ minutes. Then, the fabric was taken out of the bath, washed gently with cold and hot water and dried. The results obtained, as in Example D, are an orange dyeing with good general fastness properties, especially good properties such as rubbing resistance and light fastness.

Example R The cotton cloth modified as in Example 9 was first treated in boiling water for 15 minutes, then dried, and dyed by cold rolled coil dyeing. For this project, under 2 Ot :, an aqueous dye solution, by volume, in 100 ◦ part of the dye liquor, contains: 28.6 parts of the dye powder described in Example F, 100 parts A commercial non-ionic wetting agent in urea and 3 parts of the solution is applied to the fabric by a pad-dyeing calender, and the mother liquor absorption rate of 80% (based on the weight of the fabric) is achieved. Wrap the dyed fabric on a cloth roll, wrap it in a plastic sheet, and leave it under 20 ° C for 16 hours; after that, wash it gently with cold and hot water and dry it. The obtained dye has a strong, uniform orange-red color, and has one of good __ _ * · This paper ruler is applicable to China National Standard (CNS) ® 4 gauge _ grid (210 X 297 X loan) -37-81.9.25,000 (Please read the precautions on the back before writing the staff) 丨 Installation and ordering. LΌ1 b 0 3 A6 B6 Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Industry and Consumer Cooperatives, Co., Ltd. * 'Agriculture V. Description of invention (36) General fastness properties, especially It is resistant to rubbing, washing and light fastness. Example S 1 part of cotton cloth modified as in Example 9 and then post-treated in boiling water for 15 minutes and dried, introduced into 200 parts of an aqueous dye solution by volume; (this The solution contains 2 parts (in solution) of the dye powder described in Example G). This dye bath was heated to 60Ό within 30 minutes, and at this temperature, the dyeing process was continued for 6◦ minutes. The fabric is then removed from the bath, washed gently with cold and hot water and dried. The result obtained is a yellow dyeing with good general fastness properties, especially good rubbing resistance, washing and light fastness properties. Example Τ One part of cotton cloth modified as in Example 9 was then post-treated in boiling water for 15 minutes and dried. It was introduced into 200 parts by volume of an aqueous dye solution (this solution contains 〇 . 2 parts (in solution) of the dye powder described in Example H). The dyeing bath was heated to 60 ° C within 30 minutes, and at this temperature, the dyeing process was followed for 60 minutes. The fabric is then taken out of the bath, washed gently with cold and hot water and dried. The result obtained is a yellow dyeing with good general fastness properties, especially good rubbing resistance, washing and light fastness properties. ------------------------- installed ------------- β (please read the notes on the back before filling this page) This paper is fully applicable to the Chinese National Standard (CNS) A4 specifications (210 X 297 public loan) -38-81.9.25,000 A6 B6 V. Description of the invention (37)

Example U A piece of cotton cloth modified as in Example 9 was first treated in boiling water for 15 minutes, then dried, and then pad-dyed using an aqueous dye solution at 20¾; its volume was 1%. 〇〇 part of the dye liquor, containing: 28.5 parts of the dye powder described in Example G, 1 ◦ ◦ part of urea and 3 parts (in solution) of a commercial non-ionic wetting agent; has 80 The% mother liquor absorption rate is based on the weight of the fabric. Wrap the dyed fabric on a cloth roll, wrap it in a plastic sheet, and leave it for 16 hours at 20 ° C; after that, wash it gently with cold and hot water and give it dry. The dyeing obtained has a strong, uniform yellow color, and has good general fastness properties, especially good properties of rubbing resistance, washing and light fastness. (Please read the precautions on the back before writing this book) The Ministry of Economic Affairs Central Standards Bureau Staff Consumer Cooperative Prints $ Yiyi Paper Ruler Applicable to China National Standard (CNS) Grade 4 Specification (210 X 297, Red) -39- 81.9.25,000

Claims (1)

^ 0180 A7 B7 C7 D7 VI. Patent application 1. A method for dyeing cellulose woven material with an anionic dye containing a fiber-reactive group. This method uses an aqueous dyeing solution or padding solution, in which the dye It is in solution, this method includes using a cellulose fiber material as the matrix (on this matrix there is already a polymer grafted onto it by polymerizing at least one N-containing basic monomer) and without a base It is dyed in the presence or absence or only a small amount of an electrolyte, where the substrate used is a cellulosic fiber material with a polymer grafted onto it, this polymer contains at least one of the following compounds as N-containing alkali Sexual monomer: at least one compound corresponding to at least one formula of the following formulas (1), (1A), (2), (2A) and (5): s 1-cc-(C,),- C Ο-X-(C Κ,) Κ (1) (Please read the precautions on the back and then fill in the soft I) 丨 Installation · Order 'Link-Printed by R Industry and Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs] ί C- ( CH;) n-CO-X- (CH2) r > -KS η 2 ?. 4 R ι S5-C;-: = C-CH, -N < TT This paper scale is applicable to China National Standard (CNS) A 4 specifications (210 X 297 male cage) -40-81.9.10,000 / 1 ) 1803 A7 B7 C7 D7 R VI. Patent application R (5) R7 7-C-CH-R7 2 Among which: is hydrogen, an alkyl group containing 1 to 6 large atoms, and 5 to 7 V carbon atoms Cycloalkyl or a hydroxyalkyl group surrounding an alkyl atom with 2 to 4 large atoms; R2 has one of the various meanings described for R7 and may be the same as ruler 7 or different from R2; or R2 together with N atoms , Forming a saturated, unsaturated, or partially unsaturated 5-membered ring or 6-membered ring atom, which contains 1 to 3 secondary alkyl groups with 1 to 5 ring atoms (where, and can be selected The sex contains 1 or 2 mixed bases, and these other bases (please read the precautions on the back side before writing K) 丨 Package_ Order. The surrounding pseudo is selected from the formula: —◦ First-class bases; R 3 is hydrogen Or methyl; R 4 is hydrogen or methyl; S —,-N = and a NH-丨 margin. The Central Standard of the Ministry of Economic Affairs of the S industrial and consumer cooperatives printed «X is oxygen or is preferably a type NH- one of the base Circumference; m is an integer from 1 to 6, It is preferably 2 or 3; η is an integer ranging from 1 to 4, or preferably 0; R3 is a hospital group containing 1 to 6 carbon atoms, and a benzene having an alkyl group containing 1 to 4 carbon atoms Alkyl group or formula— (CH2—CHs—〇) A radical group of the base group. The paper size is applicable to the Chinese National Standard (CNS > A4 specification (210 X 297 male pyrene) -41-81 * 9.10,000 B7 C7 D7 01bG3 π 'patent application park, where ρ is an integer from 1 to 4; is hydrogen, an alkyl group containing 1 to 6 atomic atoms, a cycloalkyl group having 5 to 7 atomic atoms, or having 2 to 4 A hydroxyalkyl group of an alkyl group with a large number of atoms; R7 is hydrogen, an alkyl group containing 1 to 6 V atoms, a cycloalkyl group containing 5 to 7 sulfonic atoms, or the formula _CH2-CH = CH2, -CH2 -C (CHj) = ch2, -CH2-CH = CH-CH3 or a CH2-C (CH3) = CH-CH / atomic group; or R5 and R7 together with the N atom to form a value saturated, unsaturated or part Partially unsaturated 5 or 6 ring atoms, it contains: 1 to 3 subalkyl groups with 1 to 5 sulfon atoms (which can optionally contain 1 or 2 hetero groups, etc. Miscellaneous base nursery is selected from formula one 0 —, one S —, N = and _ N Η-those in the base garden; R 8 is hydrogen or methyl; R 3 is printed by R and Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economy. R 3 is hydrogen or methyl; it is a single charged anion, or The equivalent of a multi-charged anion; R; 0 is hydrogen or methyl, R 11 is a 5- or 6-membered heterocyclic atom, it contains at least one basic N atom, and it may have a fused The Benzene ring paper size GM China National Standards (CNS) A 4 specifications (210 X 297 public loan) -42-81.9.10,000 01803 A7 B7 C7 D7 VI. Patent application group and / or may be Or a polysulfide (preferably 1 or 2) substituent is substituted, and R i2 is hydrogen or methyl. 2. The method as claimed in item 1 of the patent scope, in which the substrate used is a grafted cellulosic fiber material; with weight, 0.5 to 40%, preferably 2 to 25% by weight It is appropriate to graft from 4 to 15% by weight of the polymer. 3. The method as claimed in item 1 or 2 of the patent application, wherein the matrix used is a grafted cellulose fiber material; a copolymer has been grafted onto it; in this copolymer, except In addition to one or more monomers of each formula (1), (1A), (2), (2A) and (5) described in patent application scope 1, it also contains: one or more other polymerizable monomers , In particular, one or more compounds that are consistent with the following formula (6) and (7): R2 R (6) (please read the precautions on the back and then fill out this page) Printed by the Central Bureau of Standards of the Ministry of Industry and Consumer Cooperatives, R'-N-CO- (CH2), -C-CHR R (7) R CH-C-COOR table paper scale applies China National Standard (CNS) A 4 specifications ( 210 X 297 mm) ~ 43-81.9.10,000 A7 0ibG3 B7 C7 D7 6. Application for patents: (Please read the precautions on the back and then fill in this page) and 2 only have the meaning mentioned above One, or others, together with N atom, can form the heterocyclic radical mentioned; R u is hydrogen or methyl; R 〃 is hydrogen or methyl; R is Or methyl; R i6 is hydrogen or methyl; to Ri7 is alkyl having 1 to 6 Zhi Master atoms; Q is zero, 1, 2 or 3. 4. The method as claimed in item 1 or 2 of the patent application, wherein the matrix used is a cellulose strand material having a copolymer grafted on it, which contains at least 2 Omo 5%, preferably at least 40 m. i%, especially preferably at least 8〇rn〇i% of the various types of the patent application described in the third: (1>, (1 A) n (2), (2A) and / or (5) One or more kinds of single skeletons. 5. The method as claimed in item 1 or 2 of the patent application, in which the dyeing of the substrate is usually carried out at a temperature between 10 ° and 30 ° C. The Ministry of Economic Affairs Central Standard Printed by Consumer Cooperatives 6. As for the method of applying for patent scope item 1 or 2, wherein the dyeing is carried out at a temperature of 30 to 60 1 C. 7. As for the method of applying for patent scope item 1 or 2, , The matrix used is a cellulose fiber material, the polymer grafted onto it contains: a compound of formula (1) and / or (1A); wherein, χ is a group of formula -ΝΗ- and / Or a compound of formula (2), and (2 Α) where R7 is a selective methyl-substituted allyl group. This paper is suitable for China National Standard (CNS) A 4 specifications (210 X 297 Gongchu) -44-81.9.! 0, 〇〇〇0i8G3 A7 B7 C7 D7 Six, apply for a patent fan base. 8. If applying for the patent scope item 1 Method, in which the matrix used is a fiber; a plain fiber material; a homopolymer has been grafted onto it. 9. A method as claimed in item 1 or 2 of the patent application, wherein the grafted fiber The fibroin fiber material is used in the form of fiber, especially in the form of grafted flax, jute or ramie fiber, or in the form of grafted, regenerated cellulose, especially the pseudo-grafted cotton fiber. 10 -A cellulose fiber material, which uses at least one N-containing basic single skeleton that is consistent with at least one of the following formulas (1), (1A), (2), (2A), and (5) If the polymer is grafted for modification: (1) (please read the precautions on the back before filling in this page) —installed_ordered. Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives (1A) This paper is applicable China National Standards (CNS) A 4 specifications (210 X 297 public conversion) -45 ~ 81.9.10,000 OibGS A7 B7 C7 D7 Benefits range: CH: R R11-C = CH-R (*) (5) (2A) (Please read the notes on the back before filling this page) RRR Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy Among them: is hydrogen , An alkyl group containing 1 to 6 nitrile atoms, a cycloalkyl group containing 5 to 7 stone atoms or a hydroxyalkyl group with one to two primary atoms, and a hydroxyalkyl group with a nucleus atom; One of the various meanings mentioned and may be the same as or different from 1 ^; or with R2 together with the N atom to form a saturated, unsaturated, or partially unsaturated 5-membered ring or 6-membered ring atom, it Containing 1 to 3 secondary alkyl groups with 1 to 5 primary atoms (wherein, optionally containing 1 or 2 hetero groups, these hetero groups are selected from the formula 101, a S- , One N = and one NH — in the base range; R 3 is hydrogen or methyl; R 4 is hydrogen or methyl; X is gas or should be a formula: a NH—a base range; this paper size applies to China National Standards (CNS) A4 specifications (21〇 < 297 Gongchu) -46 " 81.9.10,000 Α7 Β7 C7 D7 ^ 01603 VI. Patent application Fan Garden m is an integer from 1 to 6 The number is preferably 2 or 3; η is an integer from 1 to 4, or preferably 0; R5 is a hospital group containing 1 to 6-value carbon atoms, and has an alkyl group containing 1 to 4-value carbon atoms Phenylalkyl group or an atomic range of the formula one (CH2 — CH2 — phenyl group, where P is an integer from 1 to 4; Rs is hydrogen, an alkyl group containing 1 to 6 large atoms, 5 to 7 A sulfonic atom cycloalkyl group, or a hydroxyalkyl group having an alkyl group of 2 to 4 large atoms; R7 is hydrogen, an alkyl group containing 1 to 6 large atoms, a cycloalkane containing 5 to 7 large atoms Radical, or the formula —CH2— CH = CH2, —CHs— C (CHa) = CH2, -CH2-CH = CH — CH3 or a CH2 — C (CHa) = CH — CH3 atomic range; or and R7 together with N Atoms, forming a saturated, unsaturated or partially unsaturated 5 or 6-membered ring of atoms, it contains: 1 to 3 secondary alkyl atoms with 1 to 5 carbon atoms (of which, you can choose It contains 1 or 2 heterocyclic groups, and these heterogroups are selected from the group consisting of formula 101, S—, _N =, and —N Η—; R 8 is hydrogen or methyl; R 3 It is hydrogen or methyl; this paper is again applicable to the Chinese national standard CNS) A4 specifications (210 X 297 male cage) -47-81.9.10,000 (please read the notes on the back before writing this page) 丨 installed. Order R Α7 Β7 printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs C7 D7 6. The patent application is a single-charged anion, or the equivalent of a multi-charged anion; R / 〇 is hydrogen or methyl, R ”is a 5 or 6 heterocycle Atomium, which contains at least one basic N atom, and it may have a fused benzene ring and / or may be substituted by one or more (preferably 1 or 2) substituents, and R i2 is hydrogen or methyl base. 11. For example, the modified fibroin fiber material of item 10 of the patent scope, in which the polymer is a homopolymer. 12. The modified cellulose fiber material as claimed in item 10 of the patent scope, wherein the polymer includes: a copolymer of at least one monomer equivalent to the compounds of the following formulas (6) and (7): R2 (6) Please read the precautions on the back first and then fill out this-page < Printed by Beigong Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs: Ri-N-C0- (CH2) < 7-C = CHR R '^ CH-C-COOR' This paper scale is in accordance with the Chinese National Standard (CNS) A 4 specifications (210 X 297 mm) -48-(7) 81.9.10,000 A7 B7 C7 D7 VI. Patent application scope (please read first (Notes on the back and then fill in this page) mR2 has one of the meanings mentioned above, or others, together with N atom, they can form the mentioned heterocyclic atom ring; R 2 3 is hydrogen or methyl; R i4 is hydrogen or methyl; R; 5 is hydrogen or methyl; R 〃 is hydrogen or methyl; Ri7 is an alkyl group containing 1 to 6 sulfonic atoms; q is zero, 1, 2, or 3. 13. The modified cellulose iL dimension material as claimed in item 10 or 12 of the patent application, wherein the copolymer grafted on it contains: at least 20%, preferably at least 40π10%, In particular, one or more monomers of one of the formulas (1), (1A), (2), (2A), and (5) described in item i of the patent application scope of at least 80mo. Printed by the Central Standards Bureau of the Ministry of Economic Affairs of the People ’s Republic of China Co., Ltd. 14. If the modified cellulosic fiber material of patent application item 10 or 11 contains 0.5 to 40% by weight, it is preferably 2 To 25%, especially preferably 4 to 15% by weight of polymer graft. 15. A method for modifying cellulose fiber materials, which includes: the presence or absence of a comonomer (consistent with the formulas (6) and / or (7) mentioned above and applying for a patent (As defined in item 12 of the scope), when it exists, the formulas described in and defined in item 11 of the patent scope: (η, (1 A), (2), (2 A) And (5) at least one N-containing basic monomer is polymerized on the cellulose fiber material.- This paper is also applicable to the Chinese National Standard (CNS) A 4 specifications (210 X 297 male cage) -49 ~ 81.9. 10,000