Claims
- 1. A shade enhancing agent comprising an aqueous resin composition obtained by radical emulsion polymerization of a polymerizable monomer component comprising a first polymerizable monomer ingredient selected from the group consisting of fluorinated acrylic esters, fluorinated methacrylic esters, vinyl ether, .alpha.,.beta.-ethylenically unsaturated carboxylic acid esters, vinyl esters and mixtures thereof, in the presence of a cationic protective colloid of dimer acid/diethylenetriamine polycondensate neutralized with phosphoric acid, a dry film of said composition having a glass transition temperature (Tg) in the range of from 20.degree. C. to 110.degree. C. and a refractive index of 1.50 or less, said aqueous resin composition having a zeta potential in the range of from +5 to +80 mV at an ion strength of 10.sup.-3 and a pH value of 7.
- 2. A shade enhancing agent as claimed in claim 1, in which said polymerizable monomer component is a mixture of said first polymerizable monomer ingredient and a second polymerizable monmomer ingredient selected from the group consisting of .alpha.,62 -ethylenically unsaturated carboxylic acids, .alpha.,.beta.-ethylenically unsaturated carboxamides, substituted unsaturated carboxylic acid amides, heterocyclic vinyl compounds, allyl compounds, glycidyl methacrylate and mixtures thereof, the weight ratio of said first polymerizable monomer ingredient/said second polymerizable monomer ingredient being from 99.9/0.1 to 50/50.
- 3. An agent as claimed in claim 1 in which, in said polymerizing step, the polymerization reaction mixture comprises 50 to 99.5 wt. % of said monomer component, 0.5 to 50 wt. % of said cationic protective colloid, and water.
- 4. An agent as claimed in claim 1 in which said emulsion composition has a resin solid content of 0.1 to 50 grams per 1 liter.
- 5. A shade enhancing agent as claimed in claim 1 in which said first monomer ingredient comprises one or a mixture of two or more monomers selected from the group consisting of fluorooctyl acrylate, tetrafluro-3-(pentafluoroethoxy)propyl acrylate, heptafluorobutyl acrylate, 2-(heptafluorobutoxy)ethyl acrylate, trifluoroisopropyl methacrylate, 2,2,2-trifluoro-1-methylethyl methacrylate, vinyl isobutyl ether, vinyl ethyl ether, vinyl butyl ether, butyl acrylate, ethyl acrylate, 2-ethoxyethyl acrylate, isopropyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, methyl methacrylate, vinyl acetate and vinyl propionate.
- 6. A shade enhancing agent as claimed in claim 2 in which said first polymerizable monomer ingredient is one or a mixture of two or more monomers selected from the group consisting of flurooctyl acrylate, tetrafluro-3-(pentafluoroethoxy)propyl acrylate, heptaflurobutyl acrylate, 2-(heptaflurobutoxy)ethyl acrylate, triflurooisopropyl methacrylate; 2,2,2-trifluoro-1-methylethyl methacrylate, vinyl isobutyl ether, vinyl ethyl ether, vinyl butyl ether, butyl acrylate, ethyl acrylate, 2-ethoxyethyl acrylate, isopropyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, methyl methacrylate, vinyl acetate and vinyl propionate;
- and said second polyerizable monomer ingredient is one or a mixture of two or more monomers selected from the group consisting of itaconic acid, acrylic acid, emthacrylic acid, fumaric acid, maleic acid, acrylamide, methacrylamide, maleamide, maleimide, methylolacrylamide, methylolmethacrylamide, methoxymethyl acrylamide, N-isobutoxymethylacrylamide, vinylpyridine, vinylpyrolidone, allyl alcohol, allyl acetate and glycidyl methacrylate.
- 7. A shade enhancing agent as claimed in claim 1 in which said first polymerizable monomer ingredient consists of n-butyl methacrylate.
- 8. A shade enhancing agent as claimed in claim 1 in which said first polymerizable monomer ingredient is selected from the group consisting of n-butyl methacrylate, isopropyl methacrylate, pentadecafluorooctyl acrylate, methyl methacrylate and trifluoroisopropyl methacrylate.
- 9. A shade enhancing agent as claimed in claim 2 in which said first polymerizable monomer ingredient consists of .alpha.,.beta.-ethylenically unsaturated carboxylic acid ester and said second polymerizable monomer ingredient of .alpha.-.beta.-ethylenically unsaturated carboxylic acid.
- 10. A shade enhancing agent as claimed in claim 2 in which said first polymerizable monomer ingredient consists of n-butyl methacrylate and said second polymerizable monomer ingredient consists of itaconic acid.
- 11. A shade enhancing agent as claimed in claim 2 in which said first polymerizable monomer ingredient is selected from the group consisting of n-butyl methacrylate, isopropyl methacrylate, pentadecafluorooctyl acrylate, methyl methacrylate and trifluoroisopropyl methacrylate, and said second polymerizable monomer ingredient is selected from the group consisting of itaconic acid and methacrylic acid.
- 12. A shade enhancing agent comprising an aqueous resin composition obtained by radical emulsion polymerization of a polymerizable monomer component comprising a first plymerizable monomer ingredient of an .alpha.,.beta.-ethylenically unsaturated carboxylic acid ester, in the presence of a cationic protective colloid of dimer acid/diethylenetriamine polycondensate neutralized with phosphoric acid, a dry film of said composition having a glass transition temperature (Tg) in the range of from 20.degree. C. to 110.degree. C. and a refractive index of 1.50 or less, said aqueous resin composition having a zeta potential in the range of from +5 to +80 mV at an ion strength of 10.sup.-3 and a pH value of 7.
- 13. A shade enhancing agent as claimed in claim 12, in which said polymerizable monomer component is a mixture of said .alpha.,.beta.-ethylenically unsaturated carboxylic acid ester and an .alpha.,.beta.-ethylenically unsaturated carboxylic acid.
- 14. A shade enhancing agent as claimed in claim 12, in which said polymerizable monomer component is a mixture of n-butyl methacrylate and itaconic acid.
Priority Claims (3)
| Number |
Date |
Country |
Kind |
| 61-127451 |
Jun 1986 |
JPX |
|
| 61-127452 |
Jun 1986 |
JPX |
|
| 61-127453 |
Jun 1986 |
JPX |
|
PRIOR ART AND PROBLEMS
This application is a division of U.S. Ser. No. 07/053,177, filed May 21, 1987.
The invention relates to a shade enhancing agent or color deepening agent for fibrous products. In particular, the invention relates to a shade enhancing agent capable of improving the colorability of a substance to be dyed and also improving the deepness and vividness of the color.
A serious defect of synthetic fibers, particularly polyester fibers, is that their color deepness and vividness provided by dyeing are inferior to those of natural fibers such as wool and silk. Investigations were made, therefore, for the purpose of improving the deepness and vividness of the dyed fibers and several processes have been reported.
For example it is described in "Senryo to Yakuhin", 15, No. 1, pages 3 to 8 (1970) that when a dyed cloth is treated with a resin-finishing agent having a low refractive index, a color-deepening effect, similar to that provided when and cloth is wet with water having a refractive index of 1.33, can be provided. This is described therein theoretically and experimentally based on the fact that the deepness and vividness of the dyed cloth are increased when it is wet with water. It is also described therein that this phenomenon is caused by a reduction of the surface reflectance. In the summary of a discussion entitled "the fiber surface and colorability"described in "Sen'i Kogaku", 26, No. 3, 186 (1973), it is mentioned that the formation of a layer having a suitable refractive index on the polyester fiber surface is effective in reducing the reflectance on the surface layer and increasing the quantity of light coming into the fiber to improve the dyeability of polyester fibers with a disperse dye and that the color of dyed PET filaments can be deepened by coating them with a low polymer of trifluorochloroethylene (refractive index: 1.4).
Various processes developed on the basis of the above-mentioned facts have been proposed. A fiber structure having a thin film made of a polymer having a refractive index of 1.50 or less is disclosed in Japanese Patent Laid-Open No. 111192/1978 and a process for producing the structure is also disclosed therein which comprises placing a monomer capable of forming a polymer having a refractive index of 1.5 or less in a closed vessel together with the fibers and conducting plasma polymerization or discharge graft polymerization to form the thin film. Japanese Patent Publication No. 51557/1983 discloses a process wherein 0.3 to 10%, based on fibers, of a compound having a refractive index of as low as 1.45 or less is adsorbed on the surface of a fibrous structure to form a thin film and it is subjected to a dry or wet heat treatment. It is described therein that fluoro-resins, acrylic ester resins, vinyl polymers and silicon resins having a refractive index of 1.45 or less can be used as the starting material for the thin film. In examples given therein, the thin film is formed on the fiber surface by immersing the fibers in an emulsion or solution of a fluorine compound or acrylic ester at a high temperature to conduct the adsorption or by spraying the emulsion or solution on the fibers and subjecting the fibers to dry or wet heat treatment
The process disclosed in Japanese Patent Laid-Open No. 111192/1978 is unsuitable for the production on an industrial scale, since it has defects that it is of a batch system having a low efficiency, that it necessitates a special apparatus, and that the polymer adheres to the walls of the vessel in the course of the polymerization of the monomer to increase its loss and to make the washing of the vessel troublesome. The process disclosed in Japanese Patent Publication No. 51557/1983 in which a high bath ratio is necessitated in the immersion has also a defect that a large amount of the solution must be heated to a high temperature and, therefore, much energy is required to increase the cost, since homogeneous adsorption cannot be effected at a low temperature.
Japanese Patent Publication No. 30796/1985 discloses a color deepening agent comprising an aqueous resin composition prepared by polymerizing a polymerizable monomer having an unsaturated bond in the presence of a thermoplastic polyurethane emulsion, characterized in that a dry film of the aqueous resin composition has a refractive index of 1.50 or less. Though this color deepening agent is capable of deepening a color of a cloth easily on an industrial scale, it has a defect that the cloth thus treated is yellowed by light, heat, etc., since it contains the polyurethane emulsion.
After intensive investigations of the functions needed for providing the shade enhancing effects, made for the purpose of finding a shade enhancing agent free of the above-mentioned defects, the inventors have found the following facts:
The treatment with a shade enhancing agent comprises the following adsorption step (1) and film-forming step (2):
(1) Adsorption step:
A shade enhancing agent is adsorbed on the fibers mainly due to an electrostatic interaction between the shade enhancing agent and the fibers. Since the fibers have a negative charge in water, a positive charge is required from the shade enhancing agent for it to uniformly onto the fibers. However, when the positive charge is excessively strong, the stability in water becomes too high to conduct the suitable adsorption.
(2) Film-forming step:
The particles of the shade enhancing agent adsorbed on the fibers are fused during the drying to form a film. It has been considered that there is only one requisite in this step namely a low refractive index. However, after the investigations, the inventors have found that a substance having a low refractive index and a high glass transition temperature forms micro-craters on the fiber surface after the drying to exhibit an excellent color-deepening effect.
Thus, after intensive investigations, the inventors have found that the properties required of the shade enhancing agent ae zeta potential in the adsorption step and the refractive index and Tg in the film-forming step and that the yellowing of the treated cloth by light or heat can be inhibited by using a cationic surfactant as an emulsifier. The present invention has been completed on the basis of these findings.
A shade enhancing agent may comprise an aqueous resin emulsion composition obtained in an aqueous medium by:
(1) polymerizing a polymerizable monomer having a an unsaturated bond, in the presence of a cationic surfactant,
(2) polymerizing a polymerizable monomer having a an unsaturated bond, in the presence of a cationic protective colloid,
(3) polymerizing a polymerizable monomer having a an unsaturated bond, in the presence of an emulsifying dispersant and then adding a cationic protective colloid to the polymerization mixture or
(4) polymerizing a polymerizable monomer having a an unsaturated bond, in the presence of a cationic or nonionic emulsifying dispersant so as to have a cationic group in the molecule, a dry film of said composition having a glass transition temperature (Tg) in the range between 20.degree. C. and 110.degree. C. and a refractive index of 1.50 or less, said emulsion composition having a zeta potential in the range between +5 and +80 mV at an ion strength of 10.sup.-3 and a pH value of 7.
It is preferred that the component is a mixture of a first monomer with another monomer having a reactive group to effect a crosslinking reaction. In particular the monomer component comprises a mixture of a first unsaturated monomer and another unsaturated monomer having and a reactive group to effect a crosslinking reaction, at a weight ratio of 99.9/0.1 to 50/50.
It is preferable from the practical point of view, that the polymerization reaction mixture comprises (1) 50 to 99.5 wt. % of the monomer component, (2) 0.5 to 50 wt. % of the cationic surfactant, the cationic protective colloid or the cationic or nonionic emulsifying dispersant and (3) water. The resulting emulsion composition preferably has a solid content of 0.1 to 50 grams per 1 liter.
A preferable embodiment of the polymerization (4) comprises using a monomer having a cationic group or using a monomer having a reactive group to form a polymer having a cationic group and reacting the obtained polymer with a compound to introduce a cationic group thereinto.
The invention further provides a method for enhancing the shade of a fibrous material by treating the fibrous material with the shade enhancing agent as defined above before, after or during dyeing the fibrous material.
In a preferable embodiment of the method, the shade enhance agent having a solid content of 0.1 to 50 grams per liter is applied to the fibrous material so as to have 0.1 to 10 percent by weight, based liter on the weight of the fibrous material, preferably 0.3 to 5 percent by weight, of the solid component of the shade enhancing agent applied on the fibrous material. The treatment may be effected by padding, drying and curing or dipping, dehydrating and drying in air. The padding temperature, the drying temperature and the curing temperature are 5.degree. to 35.degree. C., 80.degree. to 120.degree. C. and 150.degree. to 200.degree. C., respectively. The dipping temperature and the air-drying temperature are 5.degree. to 70.degree. C. and room temperature, respectively.
The invention will be explained in detail in respect to the emulsion composition obtained by different polymrizations (1), (2), (3) and (4).
The emulsion obtained by the cationic surfactant polymerization, reference numeral (1) as earlier set forth is described below.
A color deepening agent can be prepared comprising an aqueous resin composition prepared by polymerizing a polymerizable monomer having an unsaturated bond, in the presence of a cationic surfactant, characterized in that a dry film of the aqueous resin composition has a glass transition temperature (Tg) in the range of 20.degree. to 110.degree. C. and a refractive index of 1.50 or less and an emulsion of the aqueous resin composition has a zeta potential in the range of +5 to +80 mV (determined under conditions comprising an ionic strength of 10.sup.-3 and a pH of 7).
The usable cationic surfactants include, for example, alkyl quaternary ammonium salts of the following formula (1), quaternary ammonium salts of the formula (2) in which part of the alkyl groups are replaced with a monovalent organic group having an ester bond and an amido bond, quaternary ammonium salts of the formula (3) in which part of the alkyl groups ar replaced with hydroxyethyl groups, alkylbenzyl quaternary ammonium salts of the formula (4), alkylpyridinium salts of the formula (5), alkylimidazolinium salts of the formula (6), alkylmorpholinium salts of the formula (7), alkylamine salts of the formulae (8), (9) and (10), and polymerizable cationic surfactants of the formulae (11) and (12) having an unsaturated bond: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 each represent an alkyl group having 1 to 22 carbon atoms, R.sub.5 represents an alkylene group having 1 to 22 carbon atoms and X represents a monovalent anionic group such as Cl, Br, I, CH.sub.3 SO.sub.4, C.sub.2 H.sub.5 SO.sub.4, NO.sub.3, ClO.sub.4 or HOCH.sub.2 COO.
The polymerizable monomers having an unsaturated soluble in the present invention are radicalpolymerizable compounds including fluorinated acrylic or methacrylic esters such as pentadecafluorooctyl acrylate (n.sub.D =1.339), tetrafluoro-3-(Pentafluoroethoxy)propyl acrylate (n.sub.D =1.35), heptafluorobutyl acrylate (n.sub.D =1.367), 2-(heptafluorobutoxy)ethyl acrylate (n.sub.D =1.39), trifluoroisopropyl methacrylate (n.sub.D =1.42) and 2,2,2-trifluoro-1-methylethyl methacrylate (n.sub.D =1.42); vinyl ethers such as vinyl isobutyl ether (n.sub.D =1.45), vinyl ethyl ether (n.sub.D =1.454) and vinyl butyl ether (n.sub.D =1.456); .alpha.,.beta.-unsaturated carboxylic esters such as butyl acrylate (n.sub.D =1.46), ethyl acrylate (n.sub.D =1.47), 2-ethoxyethyl acrylate (n.sub.D =1.471), isopropyl methacrylate (n.sub.D =1.473), n-butyl methacrylate (n.sub.D =1.483), n-hexyl methacrylate (n.sub.D =1.4813) and methyl methacrylate (n.sub.D =1.49); and vinyl esters such as vinyl acetate (n.sub.D =1.4665) and vinyl propionate (n.sub.D =1.4665), all of which are .alpha.,.beta.-unsaturated compounds. The monomers selected from the above-mentioned compounds can be used either singly or as a combination of two or more of them.
An emulsion of an aqueous resin composition which is produced by polymerizing a mixture of (1) a polymerizable monomer having both an unsaturated bond and a crosslinkable group and (2) a monomer having an unsaturated bond provides excellent color deepening effects.
The polymerizable monomers having both an unsaturated bond and a crosslinkable group include .alpha., .beta.-unsaturated carboxylic acids such as itaconic acid, acrylic acid, methacrylic acid, fumaric acid and maleic acid; .alpha., .beta.-unsaturated carboxamides such as acrylamide, methacrylamide, maleamide and maleimide; substituted unsaturated carboxylic acid amides such as methylolacrylamide, methylolmethacrylamide, methoxymethylacrylamide and N-isobutoxymethylacrylamide; heterocyclic vinyl compounds such as vinylpyridine and vinylpyrrolidone; allyl compounds such as allyl alcohol and allyl acetate; and glycidyl methacrylate They are usable as an additive component for improving the reactivity. The monomers selected from the abovementioned compounds can be used either singly or as a combination of two or more of them.
The molar ratio of (1) the polymerizable monomer having an unsaturated bond to (2) the polymerizable monomer having both an unsaturated bond and a crosslinkable linkable group is preferably in the range of 99.9/0.1 to 50/50.
The polymerizable monomer having an unsaturated bond or a mixture thereof with the polymerizable monomer having both an unsaturated bond and a crosslinkable group is subjected to a radical emulsion polymerization in the presence of a cationic surfactant. The polymerization catalysts used preferably in the polymerization include for example, peroxides such as potassium persulfate, ammonium persulfate, hydrogen peroxide, benzoyl peroxide, t-butyl hydroperoxide, succinic acid hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, di-tert-butyl peroxide and tert-butyl perbenzoate; and azobis initiators such as 2,2'-azobis(2-amidinopropane) hydrochloride and azobiscyclohexanecarbonitrile. The polymerization catalysts can be used, if necessary, in combination with activators such as water-soluble amines, e.g. ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, monoethanolamine, diethanolamine, triethanolamine, propylenediam:ine, diethylamine and monoethylamine; pyrosulfurous acid; sodium hyposulfite; and sodium formaldehyde sulfoxylate. Further, polymerization regulators such as organic halogen compounds, nitro compounds, alkylmercaptans and diisopropylxanthogenic acid can be used.
The emulsion polymerization reaction is conducted by suitably mixing the above-mentioned polymerizable monomer(s), catalyst, catalyst activator and polymerization regulator in the presence of the cationic surfactant according to a known process.
Although the mixing ratio of the cationic surfactant to the polymerizable monomer(s) is not particularly limited, it is preferred to use 0.5 to 50 wt. % of the cationic surfactant and 99.5 to 50 wt. % of the polymerizable monomer(s). More preferably, 2 to 30 wt. % of the former and 98 to 70 wt. % of the latter are used.
Described below are the emulsions obtained by the polymerization techniques numbered 2 and 3, respectively, polymerization in the presence of a cationic protective colloid and polymerization in the presence of an emulsifying dispersant with a cationic protective colloid are described below.
The present invention is directed to a color deepening agent comprising an aqueous resin composition prepared by polymerizing a polymerizable monomer, having an unsaturated bond, in the presence of a cationic protective colloid. A color deepening aqueous resin composition may also be prepared by polymerizing a polymerizable monomer having an unsaturated bond in the presence of an emulsifying dispersant and adding a cationic protective colloid to the product, wherein a dry film of the aqueous resin composition has a glass transition temperature (Tg) in the range of 20.degree. to 110.degree. C. and a refractive index of 1.50 or less and an emulsion of the aqueous resin composition has a zeta potential in the range of +5 to +80 mV (determined under conditions comprising an ionic strength of 10.sup.-3 and a pH of 7).
The cationic protective colloids usable in the present invention must have a basic nitrogen atom or a cationic nitrogen atom and further they may have a group of a carboxylic acid salt, sulfonic acid salt, amide or enter in the molecule. They include the following substances (a) to (i):
(a) homopolymers of salts of nitrogen-containing monomers or quaternary ammonium salts of the following general formulae (I) to (V) or copolymers of two or more of them: ##STR2## wherein A represents --O-- or --NH--, n represents an integer of 1 to 3, R.sub.1 represents H or CH.sub.3 and R.sub.2 and R.sub.3 each represent H, CH.sub.3 or C.sub.2 H.sub.5, ##STR3## wherein R.sub.1, R.sub.2, R.sub.3 and n.sub.1 are as defined above, ##STR4## wherein R.sub.1 is as defined above and the pyridine nucleus is bonded at position 2 or 4, ##STR5## wherein R.sub.1 and R.sub.2 are as defined above and the pyperidine nucleus is bonded at position 2 or 4, ##STR6## wherein R.sub.1, R.sub.2 and R.sub.3 are as defined above.
Examples of the monomers include dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, dimethylaminopropylacrylamide, diemthylaminopropylmethacrylamide and diethylaminopropylmethacrylamide of the formula (I); dimethylaminomethylethylene, diethylaminomethylethylene, dimethylaminomethylpropene and diethylaminomethylpropene of the formula (II); vinylpyridine of the formula (III), vinylpiperidine and vinyl-N-methylpiperidine of the formula (IV); and vinylbenzylamine and vinyl-N,N-dimethylbenzylamine of the formula (V).
The homopolymers and copolymers of these monomers usable in the present invention have an average molecular weight of 1,000 to 10,000,000.
(b) copolymers of (1) one or more of the nitrogen-containing monomers of the above general formulae (I) to (V) and their salts or quaternary ammonium salts with (2) one or more vinyl monomers selected from the group consisting of .alpha., .beta.-unsaturated carboxylic acids and their salts and derivatives, vinyl compounds having a sulfonic acid group and their salts, acrylonitrile, vinylpyrrolidone and aliphatic olefins having 2 to 20 carbon atoms.
Examples of the vinyl monomers include vinylpyrrolidone and acrylonitrile; acrylic acid, methacrylic acid, maleic acid and their alkali metal salts, ammonium salt, amide compounds and esters; and vinylsulfonic acid, methallylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, p-styrenesulfonic acid and their alkali metal salts and ammonium salts. Among the copolymers of the nitrogen-containing monomers, those having an average molecular weight of 1,000 to 10,000,000 are used.
(c) salts and quaternary ammonium salts of ring-opening polymerization products of ethyleneimine:
They comprise repeating units of the following formula (VI) and have an average molecular weight of 1,000 to 10,000,000: ##STR7## wherein n.sub.2 represents an integer of 1 to 5 and n.sub.3 represents an integer of 0 to 5.
(d) salts and quaternary ammonium salts of polycondensates of an aliphatic dicarboxylic acid with a polyethylenepolyamine or dipolyoxyethylenealkylamine:
They include polycondensates of an aliphatic dicarboxylic acid with a polyethylenepolyamine comprising a recurring unit of the following general formula (VII) or with a dipolyoxyethylenealkylamine comprising a recurring unit of the following general formula (VIII) and having a molecular weight of 1,000 to 10,000,000:
wherein R is as defined above, R.sub.5 represents an alkyl group having 1 to 8 carbon atoms, R.sub.6 represents H or CH.sub.3, and n.sub.5 and n.sub.6 each represents an integer of 1 to 10.
The aliphatic dicarboxylic acids include, for example, dimer acids and adipic acid and the polyethylenepolyamines include, for example, diethylenetriamine and triethylenetetramine.
(e) dihaloalkane/polyalkylenepolyamine polycondensates:
The polycondensates are quaternary ammonium salts of (1) a dihaloalkane such as 1,2-dichloroethane, 1,2-dibromoethane or 1,3-dichloropropane with (2) a polyalkylenepolyamine having two or more tertiary amino groups in the molecule, which salts have an average molecular weight of 1,000 to 10,000,000.
Examples of the polyalkylenepolyamines include the following compounds: ##STR9##
(f) epihalohydrin/amine polycondensates:
Among the polymers (a) to (f), those having an average molecular weight of 10,000 to 1,000,000 are more preferred.
(g) chitosan salts and cation-modified starches and celluloses,
(h) cation-modified polyvinyl alcohols, and
(i) diallylamine polymers and salts thereof.
The cationic protective colloids of the present invention are not limited to the above-mentioned high molecular substances of types (a) to (i).
The emulsion polymerization reaction according to the present invention may be conducted by suitably mixing the above-mentioned polymerizable monomer(s), catalyst, catalyst activator and polymerization regulator in the presence of the emulsifying dispersant, characterized in that a dry film of the aqueous resin emulsion has a glass transition temperature (Tg) in the range of 20.degree. to 110.degree. C. and a refractive index of 1.50 or less and an emulsion of the aqueous resin composition has a zeta potential in the range of +5 to +80 mV (determined under conditions comprising an ionic strength of 10.sup.-3 and a pH of 7).
When a color deepening agent containing a cationic emulsifying dispersant is used, only the dispersant is adsorbed on the fibers, and a color deepening polymer left in the emulsion is coagulated and, therefore, no color deepening effect can be exhibited and the solution stability of the treating bath is deteriorated.
Such a defect can be prevented by copolymerizing the polymer constituting the color deepening agent with a cationic monomer. By this process, neither rapid coagulation nor deterioration of the stability of the treating bath occurs and the stable color deepening effect can be exhibited even when the emulsifying dispersant is liberated. colloid according to a known process. The emulsion polymerization reaction according to the present invention is conducted by suitably mixing the above-mentioned polymerizable monomer(s), catalyst, catalyst activator and polymerization regulator in the presence of the cationic protective.
The function of the cationic protective colloid can be exhibited not only when it is added in the emulsion polymerization step but also when it is added after completion of the emulsion polymerization conducted in the presence of another emulsifying dispersant.
Although the mixing ratio of the cationic protective colloid to the polymerizable monomer(s) is not particularly limited, it is preferred to use 0.5 to 50 wt. % of the cationic protective colloid and 99.5 to 50 wt. % of the polymerizable monomer(s). More preferably, 2 to 30 wt. % of the former and 98 to 70 wt. % of the latter are used.
Described below is polymerization technique earlier referred to as technique number 4, involving polymerizing a monomer in the presence of a cationic or nonionic emulsifying dispersant so as to have a cationic group in the molecule.
A color deepening agent may also be prepared comprising an aqueous resin emulsion of a cationic high molecular compound having a cationic group in the molecule which compound is a polymer or its derivative prepared by polymerizing a polymerizable monomer having an unsaturated bond, in the presence of a cationic or nonionic emulsifying dispersant, characterized in that a dry film of the aqueous resin emulsion has a glass transition point (Tg) in the range of 20.degree. to 110.degree. C. and a refractive index of 1.50 or less and an emulsion of the aqueous resin composition has a zeta potential in the range of 30 5 to +80 mV (determined under conditions comprising an ionic strength of 10.sup.-3 and a pH of 7).
The emulsifying dispersants that can be used in the polymerization techniques include cationic and nonionic surfactants and cationic and nonionic high-molecular dispersants. Urethane emulsions are excluded since a cloth treated with a urethane emulsion might yellow by exposure to light or heat.
The cationic high-molecular compounds having a suitable cationic group can be prepared by copolymerizing (1) the above-mentioned polymerizable monomer having an unsaturated bond with (2) A polymerizable monomer having an unsaturated and having a cationic group such as a tertiary amino group or a quaternary ammonium group. When the cationic group is a tertiary amino group, the copolymer obtained can be quaternized, if necessary. They can be obtained also by copolymerizing an ethylenically unsaturated monomer having a halogenated methyl group, epoxy group or hydroxyl group with the above-mentioned polymerizable monomer having an unsaturated bond and reacting the obtained copolymer with a tertiary amine, secondary amine (quaternized, if necessary) or quaternizing agent (such as glycidyltrimethylammonium hydrochloride) capable of reacting with the hydroxyl group, respectively.
Examples of the cationic high-molecular compounds having a cationic group include those having a cationic group of the following general formulas (1) or (2): ##STR11## wherein R.sub.1, R.sub.2 and R.sub.3 may be the same or different and each represent a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms or a hydrogen atom or two of the three groups may be connected together to form a heterocyclic ring such as a pyridyl or imidazolyl group with the adjacent nitrogen atom or two of the three groups may form together a cycloalkyl or heterocycloalkyl group and Y represents a halogen atom or an acid residue.
The above-mentioned cationic group can be introduced easily in the polymer according to the following copolymerization or chemical reaction with the polymer on an industrial scale:
a) quaternization of a polymer prepared by copolymerizing a monomer-selected from the group consisting of monovinylpyridines such as vinylpyridine, 2-methyl-5-vinylpyridine and 2-ethyl-5-vinylpyridine; styrenes having a dialkylamino group, such as N,N-dimethylaminostyrene and N,N-dimethylaminomethylstyrene; acrylates and methacrylates having a dialkylamino group, such as N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-diethylaminoethyl acrylate, N,N-dimethylaminopropyl methacrylate, N,N-dimethylaminopropyl acrylate, N,N-diethylaminopropyl methacrylate and N,N-diethylaminopropyl acrylate; vinyl ethers having a dialkylamino group, such as 2-dimethylaminoethyl vinyl ether; acrylamides and methacrylamides having a dialkylamino group, such as N-(N',N'-dimethylaminoethyl)methacrylamide, N-(N',N'-dimethylaminoethyl)acrylamide, N-(N',N'-diethylaminoethyl)methacrylamide, N-(N',N'-diethylaminoethyl)acrylamide, N-(N',N'-dimethylaminopropyl) methacrylamide, N-(N',N'-dimethylaminopropyl)acrylamide, N-(N',N'-diethylaminopropyl)methacrylamide and N-(N',N'-diethylaminopropyl)acrylamide, with the abovementioned oleophilic ethylenically unsaturated monomer by a known process with a known quaternizing agent such as an alkyl halide (wherein the alkyl group has 1 to 18 carbon atoms and the halogen is chlorine, bromine or iodine), a benzyl halide, e.g. benzyl bromide, an alkyl ester (wherein the alkyl group has 1 to 18 carbon atoms) of an alkyl- or arylsulfonic acid, e.g. methanesulfonic acid, benzenesulfonic acid or toluenesulfonic acid or a dialkyl sulfate (wherein the alkyl group has 1 to 4 carbon atoms),
b) a reaction of (1) a polymer having a halogenated methyl group (--CH.sub.2 X), such as a copolymer of an ethylenically unsaturated monomer (e.g. chloromethylstyrene, 3-chloro-1-propane, 3-bromo-1-propene, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, 2-bromoethyl acrylate, 2-bromoethyl methacrylate, 3-chloropropyl acrylate, 3-chloropropyl methacrylate, 3-bromopropyl acrylate, 3-bromopropyl methacrylate, 4-chloropropyl acrylate, 4-chloropropyl methacrylate or 2-chloroethyl vinyl ether) with the above-mentioned oleophilic ethylenically unsaturated monomer, chloromethylated polystyrene or a chloromethylated copolymer of styrene with another oleophilic ethylenically unsaturated monomer with (2) an aliphatic tertiary amine such as trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, n-octyldimethylamine, n-dodecyldimethylamine or n-tetradecyl-dimethylamine or an aromatic amine such as dimethylaniline, diethylaniline or tribenzylamine,
c) reaction of a polymer, obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group, such as glycidyl (meth)acrylate, vinyl phenylglycidyl ether, vinylphenylethylene oxide or allyl glycidyl ether with the above-mentioned oleophilic ethylenically unsaturated monomer, with a secondary amine to open the epoxy ring and also to introduce the tertiary amino group thereinto followed by quaternization conducted in the same manner as in the above process a),
d) reaction of (1) a polymer having a hydroxyl group, such as a copolymer of an ethylenically unsaturated monomer having a hydroxyl group (such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate or N-(2-hydroxyethyl)acrylamide) with the above-mentioned oleophilic, ethylenically unsaturated monomer or a saponified copolymer of the above-mentioned oleophilic ethylenically unsaturated monomer with a vinyl alcohol/fatty acid ester with (2) a cationizing agent such as glycidyltrimethylammonium hydrochloride or 3-chloro-2-hydroxypropyltrimethylammonium salt, and
e) copolymerization of (1) an ethylenically unsaturated monomer having a cationic group prepared by quaternizing an ethylenically unsaturated monomer having a tertiary amino group as mentioned in the above process a) with a quaternizing agent mentioned in the above process a) or by reacting an ethylenically unsaturated monomer having a chloromethyl group as used in the above process b) with an aliphatic tertiary amine or aromatic amine as used in the above process b) with (2) the above-mentioned oleophilic, ethylenically unsaturated monomer.
It is not always necessary to convert the polymer into its quaternary derivative or salt.
Although the proportion of the cationic monomer to other comonomer(s) is not limited, the amount of the cationic monomer is preferably 0.1 to 95 wt. %, more particularly 1 to 80 wt. %, based on the total polymerizable monomers.
The first unsaturated monomer, having a reactive group to effect a crosslinking reaction and the polymerization catalyst can be used in the same way as described with reference to polymerization technique number 1, which involves polymerization in the presence of a cationic surfactant.
The emulsion polymerization reaction according to the present invention is conducted by suitably mixing the above-mentioned polymerizable monomer(s), catalyst, catalyst activator and polymerization regulator in the presence of the cationic or nonionic emulsifying dispersant according to a known process.
Although the mixing ratio of the cationic or nonionic emulsifying dispersant to the polymerizable monomer(s) is not particularly limited, it is preferred to use 0.5 to 50 wt. % of the cationic or nonionic emulsifying dispersant and 99.5 to 50 wt. % of the polymerizable monomer(s). More preferably, 2 to 30 wt. % of the former and 98 to 70 wt. % of the latter are used.
Among the aqueous resin compositions prepared as describdd above, those constituting the color deepening agent of the present invention are characterized in that dry films prepared from them has a Tg in the range of 20.degree. to 110.degree. C. and a refractive index of 1.50 or less and that an emulsion of the aqueous resin composition has a zeta potential in the range of +5 to +80 mV (determined under conditions comprising an ionic strength of 10.sup.-3 and a pH of 7).
Methods of regulating the Tg, refractive index and zeta potential have not been completely established. The Tg and refractive index can be estimated according to Polymer Handbook. The Tg and Refractive index of a copolymer produced from two or more monomers can be estimated generally according to the following formulae:
a copolymer produced from monomers A, B and C: ##EQU1## wherein (Tg).sub.A, (Tg).sub.B and (Tg).sub.C represent the Tg's of homopolymers of A, B and C, respectively and W.sub.A, W.sub.B and W.sub.C represent the relative amounts of A, B and C, respectively, in the copolymer.
(ii) refractive index of the copolymer n=W.sub.A n.sub.A +W.sub.B n.sub.B +W.sub.C n.sub.C
The zeta potential of the emulsion can be controlled by changing the amounts of a cationic surfactant, a nonionic substance such as a nonionic surfactant, an inorganic salt and a cationic protective colloid.
By merely immersing the dyed fibers in an aqueous solution of the color deepening agent of the present invention at ambient temperature or by padding the fibers with the latter, the resin can be adsorbed uniformly on the fiber surface By subsequent air drying or heat drying, the resin is fixed on the fibers to improve the deepness and vividness of the color of the dyed fibers.
With the color deepening agent of the present invention, the deepness and vividness of not only the dyed polyester fibers but also dyed fibers of cation-dyeable polyester, polyamide, acrylic, triacetate, rayon, silk, and cotton fibers can be increased.
The color deepening agent of the present invention can be applied to the fibers by the adsorption treatment under ordinary conditions after the dyeing. Further, in case cation-dyeable polyester or acrylic fibers are to be treated, the treatment can be conducted simultaneously with the dyeing. In addition, the adsorption treatment can be conducted before the dyeing.
US Referenced Citations (13)
Foreign Referenced Citations (6)
| Number |
Date |
Country |
| 1377670 |
Sep 1964 |
FRX |
| 50-98990 |
Aug 1975 |
JPX |
| 57-61784 |
Apr 1982 |
JPX |
| 57-112480 |
Jul 1982 |
JPX |
| 59-100776 |
Nov 1984 |
JPX |
| 2081724 |
Feb 1982 |
GBX |
Divisions (1)
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Number |
Date |
Country |
| Parent |
53177 |
May 1987 |
|
Patent Grant
5126392
