JPS62289687A - Color intensifying agent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a color deepening agent for textile products. For more details,
This invention relates to a color deepening agent that improves the color development of dyed products and improves the depth and clarity of colors.

[Conventional technology and problems]

Conventionally, a major drawback of synthetic fibers, particularly polyester fibers, is that the color depth and clarity of dyed products is inferior to that of natural fibers such as wool and silk. For this reason, research has been continued to improve the clarity and depth of color of dyed products, and several reports have been made.

For example, “Dye and Medicine J Vol. 15. No. 1
．． pp. 5-8 (1970) describes dyed cloth in water (refractive index 1.3).
Based on the fact that 3) looks darker and more vivid when wet, we experimentally and theoretically explain that if dyed cloth is treated with a resin finishing agent with a low refractive index, the same four-color ratio effect can be obtained when wet with water. The reason for this is said to be to reduce the surface reflectance. Also, [Textile Engineering J Vol, 26. N
O, 3.186 (1973), in a summary of the discussion entitled “Fiber Surfaces and Color Development,” found that color development of polyester fibers with disperse dyes reduces the reflection of the surface layer and increases the amount of light that enters the fiber. In order to increase the coloring effect, it is effective to create a layer with an appropriate refractive index on the fiber surface.
It has been shown that coating an ET filament with a trifluorochloroethylene low polymer (refractive index 1.4) produces a deep color.

Various proposals have been made based on these facts. JP-A-53-111192 discloses a fiber structure having a thin film formed from a polymer having a refractive index of 1.50 or less, and a method for producing the same includes a method for manufacturing the fiber structure using a polymer having a refractive index of 1.5 or less.
We have proposed a method in which the following monomers are placed together with fibers in a closed container and subjected to plasma polymerization or discharge graft polymerization to form a thin film. Furthermore, Japanese Patent Publication No. 58-51557 discloses that a compound having a low refractive index of 1.45 or less is adsorbed on the surface of a fiber structure in the form of a thin film of 0.3% to 10% and subjected to dry heat or warm heat treatment. Discloses a method for forming thin films, describes scales using fluororesins, acrylic ester resins, vinyl polymers, and silicone resins whose polymer refractive index is 1.45 or less as raw materials for thin film formation, and provides specific examples thereof. It discloses a method of forming a thin film on fibers using an emulsion and a solvent solution of a fluorine compound or acrylic acid ester, by infiltration and adsorption at high temperature, or by spray coating and then dry heat or heat treatment.

However, the method disclosed in JP-A-53-111192 is a batch production method that is inefficient and requires special equipment. During monomer polymerization, the polymerized polymer adheres to the container wall, resulting in large losses and cleaning. It has many drawbacks such as being troublesome, making it unsuitable for industrial production.

In addition, the method disclosed in Japanese Patent Publication No. 58-51557 requires immersion in a large bath, which requires a large amount of solution to be heated to a high temperature because uniform adsorption is impossible unless the temperature is high. However, it has the disadvantage of high cost.

Furthermore, Japanese Patent Publication No. 60-30796 discloses an aqueous resin composition obtained by polymerizing a jiii polymer having a polymerizable unsaturated bond in the presence of a polyurethane emulsion having thermosetting reactivity; The patent discloses a color deepening agent characterized in that the refractive index of the dry film of the composition is 1.50 or less, but this color ratio agent has an excellent color deepening effect that cannot be easily performed on an industrial scale. However, because it contains a polyurethane emulsion, it has the disadvantage that the processed fabric yellows when exposed to light, heat, etc.

[Means for solving problems]

The present inventors thoroughly researched the necessary functions for producing a deep color effect in order to find a color deepening agent that does not have the above-mentioned drawbacks, and came to the following conclusion.

The color deepening agent treatment process can be divided into (1) adsorption process and (2) film formation process.

■ Adsorption process This is the process in which the darkening agent adsorbs to the fibers, and mainly involves electrostatic interactions between the darkening agent and the fibers. Since fibers are generally negatively charged in water, a positive charge is essential for uniform adsorption of the color deepening agent to the fibers. However, if the positive charge is too strong, the stability in water will be too good, and adsorption will be suppressed.

In addition, in the case of a color deepening agent using a cationic emulsifying dispersant, only the emulsifying dispersant is adsorbed to the fibers, and the polymer of the color darkening agent remains in the liquid and aggregates, resulting in a four-color effect. This may not occur and the solution stability of the processing bath may deteriorate.

In such cases, if a cationic monomer is copolymerized with the polymer of the color deepening agent, rapid aggregation and deterioration of the bath stability of the processing bath will not occur even if the emulsifying dispersant is detached. A stable deep color effect can be produced.

■ Film Formation Process Until now, only a low refractive index has been considered a necessary function in the process of forming a film, in which color-enhancing agent particles adsorbed on fibers are fused as they dry. However, this study revealed that high Tg with low refractive index
It has been found that the substance forms micro-craters on the fiber surface after drying, resulting in an excellent darkening effect.

As mentioned above, as a result of intensive research, the present inventors found that the ζ-potential in the adsorption process, the refractive index and Tg in the film forming process are the functions required of a color deepening agent,
Furthermore, it has been found that by using a cationic or nonionic substance other than urethane as an emulsifying dispersant, it is possible to suppress yellowing of processed cloth due to light or heat. We also discovered that by copolymerizing a cationic monomer with the polymer of the coloring agent, bath stability does not deteriorate even if the emulsifying dispersant is detached, and stable darkening processing can be achieved at all times. , we have completed the present invention.

That is, the present invention relates to a polymer or a derivative thereof obtained by polymerizing a monomer having a polymerizable unsaturated bond in the presence of a cationic or nonionic emulsifying and dispersing agent, and which contains a cation in the molecule. The dry film of the aqueous resin emulsion has a glass transition point (Tg) of 20 to 110°C.
and has a refractive index of 1.50 or less,
and the ζ-potential of the aqueous resin emulsion is +5 to +8
0 mV (measurement conditions: ionic strength 10-3, pH 7).

The emulsifying dispersant used in the present invention may be a cationic or nonionic surfactant or a polymeric dispersant (
(protective colloid) can also be applied. However, urethane emulsions are excluded from the present invention because the processed fabric may yellow due to light or heat.

As the monomer having a polymerizable unsaturated bond used in the present invention, a radically polymerizable compound is used, such as pentadecafluorooctyl acrylate (no =
1.339), tetrafluoro-3-(pentafluoroethoxy)propyl acrylate (no = 1,
35), heptafluorobutyl acrylate (no =
1, 367), 2-(heptafluorobutoxy)ethyl acrylate (nn=1.39), trifluoroisopropyl methacrylate (nn=1.42), 2.2
．． Fluorinated acrylic or methacrylic esters such as 2-trifluoro-1-methylethyl methacrylate (nn = 1.42), vinyl isobutyl ether (n
n=1.45), vinyl ethyl ether (nn=1.4
54), vinyl butyl ether (nn=1°456)
Vinyl ether compounds such as butyl acrylate (nn
= 1.46), ethyl acrylate (nn = 1.47)
, 2-ethoxyethyl acrylate (no ” 1.4
71) , isoprobilmekkurire) (no = 1.
473), n-butyl methacrylate (no = 1
, 483), n-hexyl methacrylate (nn=1.
4813), methyl methacrylate (no=1.4
α, β-, β-compounds of vinyl ester compounds such as α, β-unsaturated carpon ster, vinyl acetate (no = 1, 4665), vinyl propionate (no = 1, 4665), etc. is mainly used.

One or more monomers selected from these groups are used.

Further, in addition to the above monomers, the aqueous resin composition emulsion obtained by polymerization with the addition of a jRffi compound having a polymerizable unsaturated bond and a crosslinking reactive group provides an even more excellent deep color effect.

Examples of monomers having a polymerizable unsaturated bond and a crosslinking reactive group include α, β-unsaturated carponsylamide, methacrylamide, etc., such as itaconic acid, acrylic acid, methacrylic acid, fumaric acid, and maleic acid. α, β-, β-carboxylic acid amides such as maleic acid amide and maleic acid imide, unsaturated carboxylic acid substituted amides such as methylol acrylamide, methylol methacrylamide, methoxymethyl acrylamide, N-isobutoxymethyl acrylamide, vinyl pyridine, Examples include heterocyclic vinyl compounds typified by vinylpyrrolidone, allyl compounds such as allyl alcohol and allyl acetate, and glycidyl methacrylate, which can be used as subcomponents for modification to impart reactivity. One or more selected monomers are used.

Ratio (molar ratio) of a monomer having a polymerizable unsaturated bond to a monomer having a polymerizable unsaturated bond and a crosslinking reactive group
is preferably 99.910.1 to 50150.

The cationic polymer compound containing a cationic group according to the present invention comprises a monomer having a polymerizable unsaturated bond as described above, and an unsaturated polymerizable polymerizable compound with a cationic group such as a tertiary amino group or a quaternary ammonium group. It can be obtained by copolymerizing with a monomer having a bond. When the cation group is a tertiary amino group, it can be quaternized if necessary after copolymerization. In addition, an ethylenically unsaturated monomer having a halogenated methyl group, an ethylenically unsaturated monomer having an epoxy group, or an ethylenically unsaturated monomer having a hydroxyl group may be substituted with the above-mentioned monomer having a polymerizable unsaturated bond. It can also be obtained by reacting the copolymerized product with a tertiary amine, a secondary amine (quaternized if necessary), or a quaternizing agent that reacts with a hydroxyl group (such as glycidyltrimethylammonium hydrochloride). It will be done.

Specifically, as a cationic polymer compound containing a cationic group, the following general formula (1) or [where R+, R
z and R1 are an alkyl group or a substituted alkyl group having 1 to 18 carbon atoms, or hydrogen, and the kings may be the same or different, or the kings of the three are connected together with the adjacent nitrogen atom to form a pyridyl group or an imidazoyl group. A heterocycle, cycloalkyl group, or heterocycloalkyl group may be formed, such as Y represents a halogen or an acid residue. ] Examples include cationic polymer compounds having a cationic group represented by the following.

The above cationic group can be introduced into the polymer by industrially easy copolymerization or chemical reaction of the polymer, for example, as follows: a) Vinylpyridine, 2-methyl-5-vinylpyridine, 2-methyl-5-vinylpyridine, Monovinylpyridines such as ethyl-5-vinylpyridine; N,N-dimethylaminostyrene, N,N
- Styrene having a dialkylamino group such as dimethylaminomethylstyrene [;N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-diethylaminoethyl acrylate] ), N,
N-dimethylaminopropyl methacrylate, N,N-
esters of acrylic acid or methacrylic acid having a dialkylamino group, such as dimethylaminopropyl acrylate, N,N-diethylaminopropyl methacrylate, and N,N-diethylaminopropyl acrylate; 2-
Vinyl ether i having a dialkylamino group such as dimethylaminoethyl vinyl ether; N-(N',
N”-dimethylaminoethyl) methacrylamide, N-
(N',N''-dimethylaminoethyl)acrylamide, N(N',N'-diethylaminoethyl)methacrylamide, N(No,No-diethylaminoethyl)acrylamide, N-(N').

No-dimethylaminopropyl)methacrylamide, N
- Acrylamides having a dialkylamino group such as (N', N'-dimethylaminopropyl)acrylamide, N-(N',N'-diethylaminopropyl)methacrylamide, and N-(N',N''-diethylaminopropyl)acrylamide. Alternatively, a polymer obtained by copolymerizing methacrylamide and the above-mentioned lipophilic ethylenically unsaturated monomer by a known method may be used with a halogenated alkyl group (the alkyl group has 1 to 18 carbon atoms, chlorine or bromine as the halogen). ,
iodine), benzyl halides such as benzyl chloride or bromide, alkyl esters (the alkyl group has 1 to 18 carbon atoms) of alkyl or arylsulfonic acids such as methanesulfonic acid, benzenesulfonic acid or toluenesulfonic acid, and sulfuric acid. Quaternization with a known quaternization agent such as dialkyl (alkyl group having 1 to 4 carbon atoms).

b) Chlormethylstyrene, 3-chloro-l-propene, 3-7'rom-1-propene, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, 2-bromoethyl acrylate, 2-bromoethyl methacrylate, 3- A halogenated methyl group (-CIl□X ) and the lipophilic ethylenically unsaturated monomers mentioned above, or copolymers of polystyrene or styrene and other lipophilic ethylenically unsaturated monomers. Polymers having a halogenated methyl group such as chloromethylated products of Reaction with tertiary amines or aromatic amines such as dimethylaniline, diethylaniline, tribenzylamine.

C) Ethylenically unsaturated monomers having epoxy groups, such as glycidyl (meth)acrylate, vinyl phenyl glycidyl ether, vinyl phenyl ethylene oxide,
A second polymer is obtained by copolymerizing allyl glycidyl ether and the above lipophilic ethylenically unsaturated monomer.
A tertiary amino group is introduced at the same time as the epoxy group is ring-opened by the action of an amine, and then quaternization is performed by the method described in a) above.

d) An ethylenically unsaturated monomer having a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, N-2-hydroxyethyl acrylamide and the above lipophilicity. A copolymer with an ethylenically unsaturated monomer, or a saponified copolymer of the above lipophilic ethylenically unsaturated monomer with a fatty acid ester of vinyl alcohol, and a polymer having a hydroxyl group, such as glycidyl trimethyl. Reaction with a cationizing agent such as ammonium hydrochloride or 3-chloro-2-hydroxypropyltrimethylammonium salt.

e) quaternizing the ethylenically unsaturated monomer having the 37th mino group as described in a) above using a quaternizing agent as described in a) above or as described in b) above; The ethylenically unsaturated monomer having a chloromethyl group such as b)
Copolymerization of an ethylenically unsaturated monomer having a cationic group obtained by reaction with an aliphatic tertiary amine or an aromatic amine as described in 1. and the above lipophilic ethylenically unsaturated monomer.

However, it is not necessarily necessary to convert all of them into quaternized products or salts.

The copolymerization ratio of the cationic monomer may be any ratio, but it is 0.1 to 9 with respect to the total polymerizable jiiffi form.
It is preferable to copolymerize the cationic monomer in an amount of 5Xi, more preferably 1 to 80% by weight.

Examples of polymerization catalysts used in the radical emulsion polymerization of the above-mentioned monomers having polymerizable unsaturated bonds in the presence of a cationic or nonionic emulsifying dispersant include potassium persulfate, ammonium persulfate, and peroxide. Peroxides such as hydrogen, benzoyl peroxide, [-butyl hydroperoxide, succinic acid hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, di-tert-butyl peroxide, tert-butyl perbenzoic acid, etc. thing or 2゜2''-Azobis(2-
Preferred representative examples include azobis-based initiators such as (amidinopropane) hydrochloride and azobiscyclohexanecarbonitrile, and if necessary, ethylenediamine,
Water-soluble amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, monoethanolamine, jetanolamine, triethanolamine, propylenediamine, diethylamine, monoethylamine, pyrosulfite, sodium bisulfite, sodium formaldehyde Using sulfoxylate etc. as an activator in combination with a polymerization catalyst,
Further, organic halogen compounds, nitro compounds, alkyl mercaptans, diisopropyl xanthic acid, etc. can also be used as polymerization degree regulators.

In the emulsion polymerization reaction according to the present invention, the above-mentioned polymerizable monomer, catalyst,
The catalyst activator, the degree of polymerization regulator, etc. are suitably combined, and the process is carried out by a known method without any special devising.

Further, the mixing ratio of the cationic or nonionic emulsifying dispersant and the polymerizable monomer may be any ratio, but 9
It is preferable to use a cationic or nonionic emulsifying dispersant in an amount of 0.5 to 50% by weight based on a weight of 9.5 to 50% by weight of the polymerizable polymer, more preferably 98 to 7% by weight.
It is desirable to use 2 to 30 weight percent of the cationic or nonionic emulsifying dispersant based on 0 weight percent of the polymerizable monomer.

Among the aqueous resin compositions thus obtained, the Tg of the dry film is in the range of +20 to 110°C, the refractive index is 1.50 or less, and the ζ- Potential (measurement conditions: ionic strength 10-3,
The color deepening agent of the present invention has a pH of 7) in the range of +5 to +80 mv.

Although the method for adjusting these Tg, refractive index, and ζ-potential is not necessarily clear, Tg and refractive index can be estimated in advance from the polymer handbook. The Tg and refractive index of a copolymer of two or more monomers can generally be estimated according to the following formula.

In the case of a copolymer of monomers ^, B and C, (Tg)a,
(Tg)m, (Tg)c: Tg -1, wl, Wc of each homopolymer of A, B, and C: composition ratio of each of A, B, and C in the copolymer (ii) refractive index of the copolymer n” Wane + W!
, nB + W (ncn A + n B + n C
: A + B + C refractive index of each homopolymer, Wm, We : Composition ratio of each A, B, C in the copolymer The ζ-potential of the emulsion is the amount of cationic activator added, nonionic surfactant It can be controlled by adding agents, inorganic salts, etc.

By using the color darkening agent of the present invention, dyed fibers can be simply immersed or pad-treated in the color darkening agent aqueous solution at room temperature.
The resin can be uniformly adsorbed onto the fiber surface, and is further fixed by air drying or heat drying, making it possible to give depth and clarity to the color of the dyed fiber.

The color deepening agent of the present invention can be used not only for polyester fibers, but also for dyed fibers such as cationically dyeable polyester, polyamide, acrylic, triacetate, rayon, silk, and cotton, by adding depth to the color and increasing clarity. Can be done.

The color deepening agent of the present invention can be adsorbed under normal conditions after dyeing, and can also be applied at the same time as dyeing for cationic dyeable polyester and acrylic fibers, or can be adsorbed before dyeing. However, it is also possible to dye it afterwards.

〔Example〕

EXAMPLES The present invention will be specifically described below with reference to Examples, but it goes without saying that the present invention is not limited to these Examples.

In addition, all parts and percentages in the examples are based on weight unless otherwise specified.

Synthesis Example 1 In a 300-inch turning flask equipped with a nitrogen introduction tube, a dropping funnel, etc., 3.2 parts (solid content) of Kotamiso 86P Conc (Nistearyltrimethylammonium chloride manufactured by Kao ■) was added, and 71.1 parts of ion-exchanged water was added. The temperature was raised to 45°C while purging the system with nitrogen, and then 2 parts of isobutyl methacrylate, 3 parts of 2-methyl-5-vinylpyridine, and 0.1 p-menthane hydroperoxide were added while stirring.
05 parts, radium formaldehyde sulfoxylate 1
Polymerization was started by adding 5 parts of % aqueous solution in that order. Further, 15 parts of isobutyl methacrylate was added dropwise over 30 minutes, and after the completion of the addition, the mixture was aged at 50°C for 2 hours, and finally quaternized with diethyl sulfuric acid to obtain an emulsion.

Synthesis Example 2 In the same manner as in Synthesis Example 1, 3.2 parts of Cortamiso 86P concrete (2 parts as solid content), 15 isobutyl methacrylate
5 parts of N,N-dimethylaminoethyl methacrylate were added dropwise to 0.0 parts of p-menthane hydroperoxide.
Emulsion polymerization was performed using 105 parts of radium formaldehyde sulfoxylate, 5 parts of a 1% aqueous solution of radium formaldehyde sulfoxylate, and 71.8 parts of ion-exchanged water to obtain a stable emulsion.

Synthesis Example 3 In the same manner as in Synthesis Example 1, 3.2 parts of Cortamiso 86P Conc (2 parts as solid content), 15 parts of propyl methacrylate, and 5 parts of 2-dimethylaminoethyl vinyl ether were added dropwise to p-menthane. Hydroperoxide 0.105
emulsion polymerization was carried out using 5 parts of a 1% aqueous solution (1% sodium formaldehyde sulfoxylate) and 71.8 parts of ion-exchanged water, and finally quaternized with benzyl chloride to obtain a stable emulsion.

Synthesis Example 4 5 parts of Emulgen 935 (manufactured by Kao: polyoxyethylene nonylphenyl ether type nonionic surfactant) was placed in a 500 m7 turning flask equipped with a nitrogen introduction pipe and a dropping funnel pipe, and 233 parts of ion-exchanged water was added. Next, the inside of the system was sufficiently purged with nitrogen, 10 parts of trifluoroisopropyl methacrylate and 20 parts of N-(N',N'-diethylaminoethyl)methacrylamide were added, and the temperature was raised to 60°C.
．． 0.105 parts of 2''-azobis(2-amidinopropane) hydrochloride was added, and after the start of polymerization, 70 parts of trifluoroisopropyl methacrylate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further aged at 60°C for 1 hour, and then dimethyl sulfuric acid was added. The mixture was quaternized to obtain a stable emulsion.

Synthesis Example 5 In the same manner as in Synthesis Example 4, 9355 parts of Emaldef, 80 parts of trifluoroisopropyl methacrylate, and reaction product 2 of 2-bromoethyl methacrylate and trimethylamine were prepared.
A stable emulsion was obtained by carrying out emulsion polymerization using 0.105 parts of 2,2''-azobis(2-amidinopropane) hydrochloride and 233 parts of ion-exchanged water by a sequential dropwise addition method.

Synthesis Example 6 In the same manner as in Synthesis Example 4, 2.2''-azobis(2 Emulsion polymerization was carried out using 0.105 parts of -amidinopropane) hydrochloride and 233 parts of ion-exchanged water, and after reaction with dimethylamine, the mixture was quaternized with diethyl sulfate to obtain a stable emulsion.

Synthesis Example 7 In the same manner as in Synthesis Example 4, 10 parts of JR-400, 70 parts of methyl methacrylate, and 20 parts of a reaction product of 2-hydroxyethyl acrylate and 3-chloro-2-hydroxypropyltrimethylammonium salt were added dropwise to 2.2 parts by sequential dropwise addition.゛-
Azobis(2-amidinopropane) hydrochloride 0
．． Emulsion polymerization was performed using 105 parts of ion-exchanged water and 233 parts of ion-exchanged water to obtain a stable emulsion. , Synthesis Example 8 In the same manner as Synthesis Example 4, Cortamino 86P Conc 11.9
(7.5 parts as solid content), 86 parts of isobutyl methacrylate, 3 parts of N-methylolacrylamide, 10 parts of a quaternized product of 2-methyl-5-vinylpyridine with benzyl chloride, and 1 part of itaconic acid were sequentially added dropwise. So, 2,2゛-
Azobis(2-amidinopropane) hydrochloride 0
．． Emulsion polymerization was performed using 15 parts of ion-exchanged water and 245.6 parts of ion-exchanged water to obtain a stable emulsion.

Synthesis Example 9 Cortamino 86P Conc 11.9 was prepared in the same manner as in Synthesis Example 4.
part (7.5 parts as solid content), 76 parts of isobutyl methacrylate, 2-dimethylaminoethyl vinyl ether
0 parts of glycidyl methacrylate, and 2 parts of methacrylic acid were sequentially added dropwise, and emulsified using 0.105 parts of 2.2'-azobis(2-amidinopropane) hydrochloride and 245.6 parts of ion-exchanged water. Polymerization was performed to obtain a stable emulsion.

Synthesis Example 10 (Comparative product: Disclosed in Japanese Patent Publication No. 60-30796?
Agricultural coloring agent) Propylene oxide adduct of bisphenol A (hydroxyl value 3
15) was dehydrated under reduced pressure at 100°C, 115 parts of it was placed in a round bottom flask equipped with a thermometer and a stirrer, and 87.5 parts of
80 parts of methyl ethyl ketone, 2.4-tolylene diisocyanate and 2,6-tolylene diisocyanate:
112.5 parts of Mixture III of 20 was added and reacted at 70° C. for 4 hours to obtain a urethane prepolymer solution containing 8.36% of free isocyanate groups.

Meanwhile, put 487.4 parts of methyl ethyl ketone and 39.1 parts of diethylene triamine in another flask,
After mixing at ~40°C for 1 hour, 320 parts of the above urethane prepolymer solution was gradually added dropwise to this solution with stirring over 40 minutes, and then 162.5 parts of methyl ethyl ketone was added. In addition, the mixture was diluted and reacted at 50°C for 30 minutes. When an infrared absorption spectrum was measured using one drop of this reactant solution, no absorption of <2250c+w-' was observed based on free isocyanate groups.This reactant solution, 101.4 parts of water, and 18. Add 3 parts of epichlorohydrin and react at 50°C for 1 hour.
After adding 42.8 parts of a 70% aqueous glycolic acid solution and 707 parts of water, methyl ethyl ketone was distilled off at about 40°C under reduced pressure, and water was added to adjust the concentration, resulting in a uniform and stable resin with a resin content of 30%. A polyurethane emulsion was obtained.

Polyurethane emulsion 25 thus obtained
(7.5 parts as solid content), 100 parts of isobutyl methacrylate was added dropwise using 0.15 parts of 2.2''-azobis(2-amidinopropane) hydrochloride, and 245.6 parts of ion-exchanged water. Emulsion polymerization was performed to obtain an emulsion.

Synthesis Example 11 (Comparative product) Cortamino 86P Cough 25 part (
20 parts as solids), 7 parts of isobutyl methacrylate, and 3 parts of N,N-dimethylaminoethyl methacrylate.
0 parts of p-menthane hydroperoxide by sequential dropping method.
．． Emulsion polymerization was performed using 105 parts of radium formaldehyde sulfoxylate, 5 parts of a 1% aqueous solution of radium formaldehyde sulfoxylate, and 33 parts of ion-exchanged water to obtain an emulsion.

Synthesis Example 12 (comparative product) 23.2 parts of Cortamino 86P3 fume (solid content: 2 parts) was placed in a 300 m7 turning flask equipped with a nitrogen introduction tube, dropping funnel, etc., and 71.8 parts of ion-exchanged water was added. The temperature was raised to 45°C while purging the inside with nitrogen, and then, while stirring, 5 parts of isobutyl methacrylate, 0.105 parts of p-menthane hydroperoxide, and 5 parts of a 1% aqueous solution of radium formaldehyde sulfoxylate were added in that order to initiate polymerization. It started. Further, 15 parts of isobutyl methacrylate was added dropwise over 30 minutes, and after the monomer addition was completed, the mixture was aged at 50° C. for 2 hours to complete the polymerization.

Synthesis Example 13 (comparative product) Put 729,355 parts of emul into a 500-inch turning flask equipped with a nitrogen introduction pipe and a dropping funnel pipe, and add 233 parts of ion-exchanged water.
Next, the system was sufficiently purged with nitrogen, 10 parts of trifluoroisopropyl methacrylate was added, the temperature was raised to 60°C, and 0.105 parts of 2,2'-azobis(2-amidinopropane) hydrochloride was added. After the start of polymerization, 90 parts of trifluoroisopropyl methacrylate was added dropwise over 1 hour, and after the completion of the addition, the mixture was further aged at 60°C for 1 hour, cooled to room temperature, and filtered through a 100-mesh wire mesh to remove the precipitates produced during the polymerization. A stable emulsion free of unreacted monomer odor was obtained.

Synthesis Example 14 (Comparative Product) In the same manner as in Synthesis Example 4, 10 parts of JR-400 and 80 parts of methyl methacrylate were added dropwise to 0.105 parts of 2,2'-azobis(2-amidinopropane) hydrochloride.
Emulsion polymerization was performed using 233 parts of deionized water and 233 parts of ion-exchanged water to obtain a stable emulsion.

Synthesis Example 15 (comparative product) In the same manner as Synthesis Example 4, 10 parts of JR-400, 70 parts of benzyl methacrylate, and 20 parts of a reaction product of 2-hydroxyethyl acrylate and 3-chloro-2-hydroxypropyltrimethylammonium salt were sequentially added dropwise. Emulsion polymerization was carried out using 0.105 parts of 2,2'-azobis(2-amidinopropane) hydrochloride and 233 parts of ion-exchanged water to obtain a stable emulsion.

Synthesis Example 16 (comparative product) In the same manner as in Synthesis Example 1, 3.2 parts of Cortazine 86P concretion (2 parts as solid content), 17 parts of butyl acrylate, and N-(N',N'-diethylaminoethyl) methacrylate were added. 0.105 parts of p-menthane hydroperoxide, 5 parts of a 1% aqueous solution of radium formaldehyde sulfoxylate, and 71.8 parts of ion-exchanged water were added by sequential dropwise addition of 3 parts of amide.
Emulsion polymerization was carried out using a portion of the resulting product, and the emulsion was quaternized with diethyl sulfate to obtain an emulsion.

The compositions and physical property data of Synthesis Examples 1 to 16 are summarized in Table 1.

i-BuMA: Isobutyl methacrylate MVP:
2-Methyl-5-vinylpyridine DMAEM: N, N
-Dimethylaminoethyl methacrylate PMA: Propyl methacrylate DMAEVE: 2-dimethylaminoethyl vinyl ether TFIPM: ) Lifluoroisopropyl methacrylate DEAEMA: N-(N',N'-diethylaminoethyllylamide BEM: 2-bromoethyl methacrylate TMA
: ) Limethylamine MM: Methyl methacrylate MG: Glycidyl methacrylate 11EA: 2-hydroxyethyl acrylate CIIP
TMA: 3-chloro-2-hydroxypropyltrimethylammonium salt N-MAM: N-methylol acrylamide IA: itaconic acid MA: methacrylic acid BM: benzyl methacrylate BuA nibbutyl acrylate Example 1 (yellowing of darkening agent treated fabric) ) A black dyed polyester cloth was treated with the aqueous resin composition shown in Synthesis Example, and its darkening effect was investigated.

Furthermore, the fabric treated with the darkening agent (fabric treated with the puffed tri-cure method) was irradiated with light for 80 hours using a weather meter (manufactured by Suga Test Instruments, light source: carbon arc) to examine photoyellowing. The results are shown in Table 2.

Treatment conditions> l) Pad-dry-cure method Prepare a bath containing 6 g of the color deepening agent shown in Table 2 (in terms of solid content), keep it at room temperature to 30°C, pad it, and then squeeze it to 100%.
It was dried at 0°C for 3 minutes. It was further cured at 180°C for 1 minute.

2) Immersion - immersion in water and air drying method 0.5g/l of coloring agent shown in Table 2 (3t of solid fraction)
A bath was prepared, stirred at room temperature for 10 minutes at a bath ratio of 1:10 to ensure uniform adsorption, centrifugally dehydrated to 80% reduction, and then air-dried at room temperature.

Evaluation> 1) Deep color effect The dark color effect was measured using a color machine (manufactured by Suga Test Instruments 9m), and the L, a, and b values were determined. The smaller the L value, the lower the brightness (
, indicating that there are four colors.

2) Yellowing Photoyellowing was evaluated by determining the b value with a color machine before and after light irradiation, and by the difference Δb (b value after light irradiation - b value before light irradiation). That is, the larger Δb is, the more yellowing is.

Table 2 The color deepening agent of the present invention showed an excellent darkening effect in both the puff dry quenching method and the immersion air drying method, and hardly yellowed even after 80 hours of light irradiation. . On the other hand, the color deepening agent of Synthesis Example 10 using a urethane emulsion as a protective colloid showed an excellent flattening effect in the puff tri-cure method, but showed an insufficient four-color effect in the immersion air-drying method. In addition, it exhibited significant yellowing upon irradiation with light.

Example 2 (ζ-potential of emulsion and darkening effect) Polyester black dyed cloth and silk black dyed cloth were treated with the aqueous resin compositions shown in Table 3 by the puff tote tri-cure method, and the darkening effect thereof was investigated.

The ζ-potential of the sample aqueous resin composition emulsion was measured using a zetameter.

(Measurement conditions) Aqueous resin composition emulsion 1 g/l (solid content equivalent) Ionic strength 1O-3 pH 7 The results are shown in Table 3.

Table 3 Although all of the synthetic examples in the above table showed similar refractive index and Tg, only the product of the present invention had excellent dark color effect.

Synthesis Example 11 has a significantly high ζ-potential of 98 rsV and exists very stably in water, which is thought to have prevented adsorption onto fibers. Since Synthesis Example 13 exhibits the same negative potential as the fiber surface, it is thought that adsorption to the fibers was suppressed by electrostatic repulsion.

Example 3 (Refractive index and deep color effect) Acrylic black dyed cloth was treated with the aqueous resin composition shown in Table 4 by dipping and air drying, and the four color effects were investigated.

After drying the test aqueous resin composition to form a film, its refractive index was measured using a refractometer.

The results are shown in Table 4.

Table 4: Is the product of the present invention superior? ; However, Synthesis Example 15, which had a high refractive index, did not show any color effect.

Example 4 (Tg and deep color effect) Black dyed cotton and wool fabrics were treated with the aqueous resin composition shown in Table 5 by a pad-dry-cure method, and the dark color effect was investigated. Isopropyl alcohol was added to the bath at 4% as a penetrant only during wool treatment.

The sample aqueous resin composition was dried and its Tg was measured by DSC method. The results are shown in Table 5.

Table 5 Both products of the present invention exhibited excellent four-color effects.

On the other hand, in Synthesis Example 16, the Tg was too low, so the dawn effect was not exhibited.

From Examples 2 to 4, it has become clear that an excellent deep coloring effect can be obtained only when the optimum values of ζ-potential, refractive index, and Tg are all satisfied.

Example 5 (Crosslinking reactive group and deep color effect) A black dyed polyester cloth and a red dyed polyester cloth were treated with the aqueous resin composition shown in Table 6 by a pad-dry-cure method, and the dark color effect was investigated.

In the case of red dyed cloth, the evaluation was performed based on the measured values a and b in terms of ~p-, that is, chroma. The larger the value of $, the darker and more vivid the color becomes. The results are shown in Table 6.

Table 6 All of the products of the present invention exhibit excellent deep color effects, but Synthesis Examples 8 and 9 in which monomers having crosslinking reactive groups are copolymerized
exhibited a particularly excellent darkening effect.

Example 6 (Addition of cationic monomer and mechanical force stability) An aqueous dispersion of 6 g/l (in terms of solid content) of the aqueous resin composition shown in Table 7 was prepared, and mixed with a homomixer at 8000 rpm for 1
The mixture was stirred for 0 minutes, filtered through black filter paper, and mechanical stability was evaluated.

The results are shown in Table 7. The product of the present invention copolymerized with a cationic monomer has a self-dispersing function even if some of the dispersant is detached, so it is resistant to strong mechanical stirring. No aggregates were generated. The results of this test suggest that the bath stability during on-site processing is also excellent.

On the other hand, in the comparative product, the emulsion particles received shear due to mechanical stirring, some of the dispersant was detached, and aggregates were formed.

Claims (1)

[Scope of Claims] 1 A polymer or a derivative thereof obtained by polymerizing a monomer having a polymerizable unsaturated bond in the presence of a cationic or nonionic emulsifying dispersant, which It consists of an aqueous resin emulsion of a cationic polymer compound containing a cationic group, and the glass transition point (Tg) of the dry film of the aqueous resin emulsion is in the range of 20 to 110°C, and the refractive index is 1.50. A color deepening agent which is as follows, and the ζ-potential of the aqueous resin emulsion is in the range of +5 to +80 mV (measurement conditions: ionic strength 10^-^3, pH 7). 2. The color deepening agent according to claim 1, wherein the cationic group is a tertiary amino group or a quaternary ammonium group. 3. A patent claim that is a polymer obtained by polymerizing a cationic polymer compound having a cationic group with a monomer having a polymerizable unsaturated bond and a tertiary amino group as an essential monomer, or a quaternized product thereof. A darkening agent according to Range 1 or 2. 4. A cationic polymer compound having a cationic group is a polymer obtained by polymerizing a monomer having a polymerizable unsaturated bond and a quaternary ammonium group as essential monomers, or 2. Darkening agent according to item 2. 5. Claims 1, 2, 3, or 5, wherein a part of the monomer having a polymerizable unsaturated bond is a monomer having a polymerizable unsaturated bond and a crosslinking reactive group. The color deepening agent according to item 4.