JPS63211383A - Non-aqueous color 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.

Example Eva, “Dye and Medicine J Vol. 15, No. 1,
pp. 3-8 (1970) describes dyed cloth in water (refractive index 1.33).
), it is experimentally and theoretically explained that if the dyed cloth is treated with a resin finishing agent with a low refractive index, the same color deepening effect can be obtained as when it is wetted with water. The reason for this is said to be to lower the surface reflectance. Also, “Textile Engineering JVOI, 26, No. 3.
188 (1973), in a summary of the discussion entitled "Fiber Surfaces and Color Development," states 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, increasing color development efficiency. In order to increase the refractive index, it is effective to create a layer with an appropriate refractive index on the fiber surface.
It has been shown that by painting 4), the color becomes darker.

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.
They have proposed a method in which monomers of 5 or less 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 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 using an emulsion and a solvent solution of a fluorine-containing compound or acrylic ester, by immersion adsorption at high temperature, or by spray coating and dry heat or wet 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.

In addition, JP-A-57-176275 discloses a darkening agent made of a polymer in which a branch 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-insoluble branch polymer to a solvent-insoluble trunk polymer is suitable.

However, although a remarkable darkening effect can be obtained by adsorbing a polymer onto the fibers, the resulting fibers become hard and the original feel of the fibers is impaired.

To solve this problem, we need to maintain the original texture of the fiber without changing it drastically (and as an additive that can obtain a deep color effect, it can be dissolved arbitrarily in a non-aqueous solvent such as tetrachloroethylene or trichloroethane). However, additives that do not inhibit the roughening of the polymer on the fiber surface and the requirement for non-aqueous emulsion in the solvent are suitable.

The present inventors completed the present invention as a result of intensive research based on the above knowledge.

That is, the present invention provides (a) a trunk polymer that is substantially insoluble in a non-aqueous solvent with a solubility parameter in the range of 6.5 to 10.0, and a branch polymer that is soluble in the non-aqueous solvent. A copolymer obtained by graft polymerization, in which the weight ratio of trunk polymer/branch polymer is 90/10 to 10/9.
0 and (b) at least one or more of liquid paraffin and/or paraffin wax in a range of (a) copolymer/Q)) paraffin = 9515 to 20/80 (weight ratio). The present invention provides a non-aqueous color deepening agent characterized by the following.

The backbone polymer in the copolymer of the present invention may be substantially insoluble in the solvent, such as a copolymer of polybutadiene or one or more monomers copolymerizable with butadiene and butadiene. can be mentioned.

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, as the vinyl monomer to be graft-polymerized to the backbone polymer, aromatic vinyl monomers such as styrene, α-methylstyrene, α-ethylstyrene, or their nuclear-substituted derivatives, such as vinyltoluene, impropenyltoluene, chlorstyrene, and styrene are used. , methacrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate,
Examples include 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, the cane polymer alone is soluble in a solvent and forms a smooth film on the fiber surface, but does not roughen the surface, so that a sufficient deep color effect cannot be obtained. However, when a solvent-soluble branch polymer is graft copolymerized with a solvent-insoluble trunk 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, the backbone polymer to be graft-polymerized preferably forms latex, the average particle size of which 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.

The color deepening agent of the present invention can be added as a crosslinking agent during polymerization of the trunk polymer or graft polymerization of the branch polymer in order to improve ironing resistance.

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

The copolymer is preferably blended in the composition in an amount of 1 to 20% by weight.

As the liquid paraffin and paraffin wax in the present invention, those specified in Japanese Industrial Standards -2231 or -2235 can be used. Preferably, the liquid paraffin has a kinematic viscosity of 10 centistokes or more at 40°C, and the paraffin wax has a melting point of 60°C or less. If the melting point of paraffin wax is high, the low-temperature stability of the blended composition tends to deteriorate, so a lower melting point is desirable. These liquid paraffin and paraffin wax are preferably blended in the composition in an amount of 1 to 20% by weight.

In the present invention, the weight ratio of copolymer/paraffin is 9515 to 20/80, preferably 9515 to 30/
If it is used within the range of 70, clothing can be finished without disturbing the deep color effect and the original feel of Ia fiber. Outside this range, both the deep color effect and texture cannot be satisfied.

The non-aqueous color deepening agent of the present invention is prepared as a composition in which both components (a) and (b) are diluted and dispersed in a solvent, but the solvent used is not particularly limited. For example, the synthetic solvent described below,
Petroleum solvents, alcohol solvents, ketone solvents, tetrahydrofuran, dioxane, etc. are used. Water can also be added as long as it can be solubilized.

The total content of components (a) and (b) in the composition is 5 to 30
Weight percent is preferred.

The non-aqueous color deepening agent of the present invention may optionally include a cationic surfactant for the purpose of increasing the adsorption amount, an anionic or nonionic surfactant or a hydrotropic agent for the purpose of improving system stability, and an iron. For the purpose of improving slipperiness, oil agents such as silicone, fragrances, dyes, pigments, fluorescent dyes, antibacterial agents, preservatives, etc. can be added.

The non-aqueous darkening agent of the present invention is diluted and dispersed in a non-aqueous solvent in an amount of 0.05 to 5% by weight, preferably 0.3 to 2% by weight. Examples of the solvent for dilution and dispersion include nonaqueous solvents with a solubility parameter in the range of 6.5 to 10.0, such as synthetic solvents such as tetrachlorethylene, trichlorethylene, trichloroethane, trichlorotrifluoroethane, naphthene, etc. , petroleum solvents with high paraffin content can be used. If necessary, alcoholic solvents such as methanol, ethanol, isobutanol, and n-butanol, ketone solvents such as methyl ethyl ketone and acetone, tetrahydrofuran, dioxane, and the like can be added.

〔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 graft copolymer 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 a trunk polymer,
Graft polymerization was carried out using isobutyl methacrylate as the branch polymer with the following formulation.

B) Graft polymerization of branch polymers Trunk polymer -
1.0 Ferrous sulfate 0.0
1 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 three times with methanol and dried.

Using the obtained copolymer, the compositions shown in Table 1 were prepared, and the deep color effect and texture were examined as follows.

The obtained sample was dissolved in tetrachlorethylene at 1.0%.
A black polyester taffeta was immersed in the diluted and dispersed solution for 1 minute and then air-dried.

The dark color effect was measured using a colorimetric colorimeter (manufactured by Nippon Denshoku Kogyo@, No. 10).
The contrast index value was determined using the 0IDP type). The smaller the L value, the darker the color.

To measure the texture, the treated clothing was left in a constant temperature room at 25° C. and 65% RH for a day and night, and then cut into the desired size, and the tension and hardness was measured using a paper bending tester manufactured by Kato Iron Works. The larger the bending stiffness value, the harder the cloth is finished.

The color deepening agent of the present invention forms a non-aqueous emulsion in tetrachlorethylene, has good dilution and dispersibility, and has an excellent dark color effect.
It also has a good texture.

Example-2 Copolymer core polymer (X) shown in Example-1.

The weight ratio of inbutyl methacrylate (Y) is 50150
Processing and measurement were carried out under the same conditions as in Example 1, using a copolymer of , varying the blending ratio with liquid paraffin, and using various paraffin waxes. The results are shown in Table-2.

The product of the present invention becomes a non-aqueous emulsion in tetrachlorethylene, has good dispersibility, has an excellent deep coloring effect, does not drastically change the original texture of the fiber, and is excellent in both the dark color effect and texture.

Claims (1)

[Claims] 1(a) Solubility parameter is 6.5 to 10.
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 in the range of 0, wherein the weight of the trunk polymer/branch polymer is A copolymer with a ratio of 90/10 to 10/90, and (b) liquid paraffin and/or paraffin wax with a weight ratio of (a)/(b) of 95/5 to 20/
80. 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. Component 5(b) is a liquid paraffin having a kinematic viscosity of 10 centistokes or more at 40°C or a paraffin wax having a melting point of 40°C or more. Water-based darkening agent.