JPS63165588A - Non-aqueous darkening 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 [Industrial Field of Application] The present invention relates to a color deepening agent for textile products. For more details,
This invention relates to a non-aqueous 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 continued to improve the clarity and depth of dyed products, and several reports have been made.

For example, "Dye and Medicine J Vol. 15, Floor 1.3-8
Page (1970) found that when dyed fabric is wetted with water (refractive index 1.33), it looks dark and vivid, and if dyed fabric is treated with a resin finishing agent with a low refractive index, it will produce the same dark color when wetted with water. Experimentally and theoretically explain that the effect of
The reason for this is said to be to lower the surface reflectance. Also, “Textile Engineering J Vol. 26, 3.188 pages (
(1973), in a summary of the discussion entitled “Fiber Surface and Color Development,” found that the color development of polyester fibers by disperse dyes was
In order to reduce the reflection of the surface layer, increase the amount of light that enters the fiber, and increase color development efficiency, it is effective to create a layer with an appropriate refractive index on the fiber surface, and dyed PET filaments are coated with trifluoride. It has been shown that coating with a low ethylene polymer (refractive index 1.4) results in a dark color.

Various proposals have been made based on these facts. JP-A-53-111192 discloses a fibrous structure having a thin film formed from a polymer having a refractive index of 1.50 or less, and a method for manufacturing the same includes a method for producing the fiber structure in which the refractive index of the polymer is 1.50 or less.
The authors propose a method in which a 5- or less-sized hexamer is 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 Application Laid-open No. 55-26232 discloses that a compound having a low refractive index of 1.45 or less is adsorbed onto the surface of a fiber structure in the form of a thin film of 0.3% to 10%, and subjected to dry heat or hot heat treatment. Discloses a method for performing this, describes scales using fluororesin, acrylic ester resin, vinyl polymer, and silicone resin whose polymer refractive index is 1.45 or less as a raw material for forming a thin film, and as a specific example thereof,
It discloses a method of forming a thin film on fibers by using emulsions and solvent solutions of fluorine-containing compounds and acrylic esters, by soaking and adsorbing them at high temperatures, or by spray coating, followed by dry heat and heat treatment.

However, the method disclosed in Japanese Patent Application Laid-open No. 53-111192 is a batch production method that is inefficient, requires special equipment, and causes a lot of loss as polymerized polymer adheres to the wall of the container during monomer polymerization. It has many drawbacks such as troublesome cleaning, making it unsuitable for industrial production.

Furthermore, in the method disclosed in JP-A No. 55-26232, it is necessary to heat a large amount of solution to a high temperature because uniform adsorption is impossible unless the temperature is high for the method of immersion in a large bath ratio. Although it saves energy, it has the disadvantage of high cost.On the other hand, the spray coating method requires dangerous and complicated operations, and has the fatal disadvantage of uneven coating amount, resulting in a patchy and unfinished finish.

Furthermore, JP-A-57-176275 discloses a deep coloring agent consisting of a polymer in which a technical segment having a blocked polyfluoroalkyl group is bonded to a trunk segment, but the polymer and solvent are special. Therefore, it has little industrial utility value.

[Means for solving problems]

The present inventors can use inexpensive non-aqueous solvents such as tetrachloroethylene and trichloroethane as solvents,
In order to find a non-aqueous color deepening agent with great industrial value,
We thoroughly researched the functions necessary to create a deep color effect and obtained the following knowledge.

In other words, the deep coloring effect of synthetic fibers, especially polyester fibers, cannot be achieved simply by forming a film of a low refractive index polymer, but by roughening the polymer on the fiber surface, a remarkable darkening effect can be obtained. . Therefore, in order to adsorb a polymer onto synthetic fibers, especially polyester fibers, and roughen the surface, it is necessary for the polymer to be insoluble in a solvent and to be stably dispersed, that is, to form a non-aqueous emulsion. A graft copolymer obtained by graft polymerizing a solvent-soluble polymer to a solvent-insoluble base polymer is suitable. The present inventors completed the present invention based on the above knowledge.

That is, the present invention has a solubility parameter of 6.5.
A copolymer obtained by graft polymerizing a branch polymer that is soluble in a non-aqueous solvent to a trunk polymer that is substantially insoluble in a non-aqueous solvent having a molecular weight of 10 to 1090, The present invention provides a non-aqueous color deepening agent comprising a non-aqueous emulsion in which a copolymer having a weight ratio of 90/10 to 10/90 is diluted and dispersed in the non-aqueous solvent.

The backbone polymer in the present invention may be substantially insoluble in the solvent (eg, polybutadiene or a copolymer of butadiene and one or more monomers copolymerizable with butadiene). .

The branch polymer may be anything that is soluble in the solvent, and includes, for example, one type of vinyl monomer polymer or a copolymer of two or more types of vinyl monomers. More specifically, monomers copolymerizable with butadiene include acrylonitrile, acrylic esters, methacrylic esters, aromatic vinyl, and the like. In addition, examples of the vinyl monomer to be graft-polymerized to the backbone polymer include styrene, α-methylstyrene, α-ethylstyrene, or their nuclear substituted Pl, aromatic vinyl monomers such as vinyltoluene, isopropenyltoluene, chlorostyrene, and styrene. , methacrylic ester monomers such as methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, and n-butyl methacrylate; and acrylic ester monomers such as methyl acrylate, ethyl acrylate, and n-butyl acrylate.

The weight ratio of trunk polymer/branch polymer is 90/10 to 10/
90, preferably in the range of 80/20 to 20/80. The backbone polymer alone is insoluble in the solvent, and furthermore, it is not possible to uniformly disperse and stabilize the secondary aggregated polymer in the solvent during polymer purification, making it unsuitable as a color deepening agent. On the other hand, a polymer polymer alone is soluble in a solvent and forms a smooth film on the fiber surface, but does not roughen the surface, so a sufficient deep color effect cannot be obtained. However, when a solvent-soluble technical polymer is graft-copolymerized with a solvent-insoluble backbone polymer according to the present invention, the copolymer is insoluble in a non-aqueous solvent but stably dispersed in the solvent. It forms a non-aqueous emulsion, which forms a rough surface with fine particles of 0.2 μm or less on the fiber surface, so it exhibits an excellent color-deepening effect as a non-aqueous color-deepening agent.

When the backbone polymer of the present invention is a copolymer of butadiene and another monomer, the content of butadiene is preferably 30% by weight or more, particularly preferably 50% by weight or more. When the butadiene content is less than 30% by weight, the color deepening agent obtained by graft polymerization is difficult to form a stable non-aqueous emulsion in a solvent, and the particle size increases due to secondary aggregation, resulting in poor color deepening effect.

In the present invention, it is preferable that the backbone polymer to be graft-polymerized forms latex, and the average particle size of the latex is 0.2.
μ or less, preferably 0.15 μ or less. If the average particle size exceeds 0.2μ, the stability of the resulting non-aqueous emulsion is poor and the darkening effect is small.

A crosslinking agent may be added to the color deepening agent of the present invention during polymerization of the backbone polymer or graft polymerization of the technical polymer in order to improve iron resistance.

Examples of crosslinking agents include divinylbenzene and difunctional monomers such as dimethacrylates, such as mono-, di-, tri- or tetraethylene dimethacrylate, and 1,3-butylene gelicol dimethacrylate.

The solvent used to form the non-aqueous emulsion of the present invention is a non-aqueous solvent with a solubility parameter in the range of 6.5 to 10.0, such as tetrachlorethylene,
Synthetic solvents such as trichlorethylene, trichloroethane, trichlorotrifluoroethane, etc., and petroleum solvents with a high content of naphthenes and paraffins can be used. If necessary, the polarity of the solvent may be changed to the above range by adding an alcohol solvent such as methanol, ethanol, isobutanol, or normal butanol, a ketone solvent such as methyl ethyl ketone or acetone, tetrahydrofuran, dioxane, or the like.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but 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.

Example-1 A non-aqueous darkening agent was synthesized by the following method.

A) Polymerization of backbone polymer 1,3-butadiene 75 parts styrene
25 Lauryl sulfate ester soda 3.0 Potassium persulfate 0.25 Dodecyl mercaptan 0.15 Water
150 The above formulation was polymerized at 60°C for 24 hours. The polymerization rate reached 92% or more. Thereafter, the mixture was degassed in a vacuum to obtain a stable latex. The average particle size of the latex was 0.084μ. This material is used as the trunk polymer,
Graft polymerization was carried out using isobutyl methacrylate as a technical polymer with the following formulation.

B) Graft polymerization of branch polymers Trunk polymer -
1.0 Ferrous sulfate 0.01
Water 16070℃,
The latex obtained by polymerization for 6 hours was poured into methanol to coagulate and precipitate the graft copolymer, and after filtration, the filtration residue was
Washed twice with methanol and dried.

The obtained sample was dissolved in tetrachlorethylene at 0.6%.
A black polyester taffeta was immersed in the solution for 1 minute and then air-dried.

The dark color effect can be measured using a colorimetric colorimeter (manufactured by Nippon Heavy Industries, NO-10).
The contrast index value was determined using the 0IDP type). The smaller the L value, the darker the color. The results are shown in Table-1.

$1ΔL = L value of untreated product - L value of treated product Book 2: Good dispersibility *3: Poor dispersibility The color deepening agent of the present invention forms a non-aqueous emulsion in tetrachlorethylene, has good dilution and dispersibility, and has a deep color. The effect is excellent.

Example 2 A sample was obtained by polymerization and purification under the same conditions as in Example 1, changing the ratio of 1,3 butadiene and styrene as the backbone polymer, and using inbutyl methacrylate as a technical polymer component. This sample was dissolved and dispersed in tetrachlorethylene at a concentration of 0.6%, and black polyester taffeta was treated and measured under the same conditions as in Example-1. The results are shown in Table-2.

Table 2 *L value of untreated product - L value of treated product The color deepening agent of the present invention forms a non-aqueous emulsion in tetrachlorethylene and is excellent in dilution and dispersibility and dark color effect.

Claims (1)

[Scope of Claims] 1 A trunk polymer which is substantially insoluble in a non-aqueous solvent and has a solubility parameter in the range of 6.5 to 10.0 is graft-polymerized with a branch polymer that is soluble in the non-aqueous solvent. A non-aqueous emulsion obtained by diluting and dispersing a copolymer having a trunk polymer/branch polymer weight ratio of 90/10 to 10/90 in the non-aqueous solvent. A non-aqueous darkening agent. 2 The trunk polymer is polybutadiene or a copolymer of butadiene and one or more monomers copolymerizable with butadiene, and the branch polymer is a polymer of one type of vinyl monomer or a polymer of two or more types of vinyl monomers. The non-aqueous darkening agent according to claim 1, which is a copolymer. 3. The non-aqueous color deepening agent according to claim 2, wherein the butadiene content of the backbone polymer is 30% by weight or more. 4. The non-aqueous darkening agent according to any one of claims 1 to 3, wherein the average particle diameter of the backbone polymer particles is 0.2 μ or less.