JP7079624B2 - Textile Material Printing or Dyeing Composition, Method for Producing Textile Material with Processing Layer for Printing or Dyeing, and Method for Producing Textile Material for Printing or Dyeing. - Google Patents

Description

The present invention relates to a composition for printing or dyeing a textile material, a method for producing a fiber material having a processing layer for printing or dyeing, and a method for producing a textile material to be printed or dyed.

The fiber material used for printing or dyeing may be treated with a treatment agent for the purpose of preventing bleeding of printing or dyeing. This treatment agent is removed by washing with water, steam treatment, or the like after printing or dyeing. Patent Document 1 describes a knitted fabric for inkjet printing, which is produced by preliminarily applying a treatment agent (pretreatment agent) that prevents bleeding and promotes dyeability to the yarn and knitting the yarn. There is. Further, in Patent Document 2, when at least a part or all of the fibers constituting the fabric are inkjet printed on the fabric made of synthetic fibers, the specific water-soluble polymer substances (A) and (B) are previously applied to the fabric. Described is an inkjet printing method characterized in that a treatment liquid to be contained is applied and dried.

Further, in Patent Document 3, after printing an inkjet ink for printing containing at least a water-soluble compound that can be polymerized by irradiation with a coloring material and an external energy ray on the cloth, the above-mentioned polymerizable water-soluble compound is described. A recording method on a cloth is described, which comprises irradiating an external energy ray to generate a polymer compound, and then performing a water washing treatment after a color development treatment to record an image.

For inks having a treatment agent for a fiber material to be printed or dyed and a polymerizable water-soluble compound, a material is required in which the treatment agent and the polymer compound of the water-soluble compound can be easily removed from the fiber material. There was room for improvement in these.

Japanese Unexamined Patent Publication No. 10-53973 Japanese Unexamined Patent Publication No. 2001-295186 Japanese Patent No. 4834979

Therefore, the subject of the present invention is a fiber material printing or dyeing composition used as a treatment agent for a fiber material to be used for printing or dyeing, or as a dye-containing composition such as an ink having a polymerizable water-soluble compound. It is an object of the present invention to provide a composition in which the water-soluble cured product after the polymerization treatment is easily removed from the fiber material.

As a result of diligent research to solve the above problems, the present inventors have found a composition for printing or dyeing a fiber material containing a water-soluble ethylenically unsaturated monomer containing an ionic group and a counter ion. The present invention has been completed by finding that it is easy to remove a cured product containing a structural unit derived from the above-mentioned monomer from the fiber material by applying it to the fiber material and washing it with water or the like after the polymerization treatment.

That is, the composition for printing or dyeing a fiber material of the present invention is a composition used at the time of printing or dyeing a fiber material, and is a water-soluble ethylenically unsaturated monomer containing an ionic group and a counterion. include.
The fiber material printing or dyeing composition preferably further contains a photopolymerization initiator.

Further, in the method for producing a fiber material having a treatment layer for printing or dyeing of the present invention, there is a treatment step of applying a treatment agent containing any of the above-mentioned textile material printing or dyeing compositions to the fiber material; Includes a polymerization step of curing the above-mentioned treatment agent applied to the fiber material with an electron beam to form a treatment layer.

Further, in the method for producing a textile material printed or dyed according to the present invention, there is a treatment step of applying a treatment agent containing any of the above-mentioned textile material printing or dyeing compositions to the fiber material; The applied treatment agent is cured with an electron beam to form a treatment layer containing a cured product having a structural unit derived from a water-soluble ethylenically unsaturated monomer containing the ionic group and a counter ion. A polymerization step for producing a fiber material having a treated layer; printing to obtain a textile material printed or dyed by further printing or dyeing the fiber material having the treated layer formed in the above polymerization step with a dye. Step: Remove the cured product having a structural unit derived from the water-soluble ethylenically unsaturated monomer containing the ionic group and the counterion from the printed or dyed fiber material obtained in the printing step. Includes removal steps and;

According to the composition for printing or dyeing a fiber material of the present invention, it has a structural unit derived from a water-soluble ethylenically unsaturated monomer containing an ionic group and a counter ion after the application / polymerization treatment to the fiber material. The cured product can be easily removed by washing with water or the like.
Further, according to the method for producing a fiber material having a treatment layer for printing or dyeing of the present invention, a water-soluble ethylenically unsaturated monomer containing an ionic group and a counter ion after the application / polymerization treatment to the fiber material. It is possible to produce a fiber material having a treatment layer for printing or dyeing, which can easily remove a cured product having a constituent unit derived from a weight by washing with water or the like.
Further, according to the method for producing a textile material printed or dyed according to the present invention, it is derived from a water-soluble ethylenically unsaturated monomer containing an ionic group and a counter ion after the application / polymerization treatment to the fiber material. A printing or dyed fiber material can be produced in which the cured product having a structural unit is easily removed by washing with water or the like.

It is a photograph which a line was drawn with an oil-based pen on the cloth treated with the textile printing or dyeing composition of an Example. It is the photograph which the line was drawn with the oil-based pen on the cloth treated with the textile printing or dyeing composition of the comparative example.

[Composition used for printing or dyeing textile materials]
The composition used for printing or dyeing the fiber material according to the present invention (hereinafter, may be simply referred to as a composition for printing or dyeing) is a water-soluble ethylenically unsaturated single amount containing an ionic group and a counterion. Including the body. A composition for printing or dyeing containing a water-soluble ethylenically unsaturated monomer containing an ionic group and a counter ion is a water-soluble composition containing an ionic group and a counter ion after being applied to and polymerized on a fiber material. A cured product having a structural unit derived from an ethylenically unsaturated monomer can be easily removed by washing with water or the like. Further, preferably, since the viscosity is low as described later, it is easy to apply to the fiber material and also has excellent permeability to the fiber material. Further, preferably, since the treated layer is formed by polymerization and curing using an electron beam after being applied to the fiber material, bleeding during printing or dyeing can be suppressed.

Examples of the fiber material include yarn, woven fiber material, knitted fiber material, and non-woven fabric fiber material. The material is not particularly limited, and is a natural fiber material such as cotton, flax, wool, silk or cannabis, a synthetic fiber material such as viscose, polyester, nylon or cupra, rayon, a recycled fiber material, a mixture thereof, etc. Can be mentioned.

1. 1. Water-soluble ethylenically unsaturated monomer The water-soluble ethylenically unsaturated monomer contained in the textile printing or dyeing composition of the present invention is a monomer having one or more ethylenically unsaturated groups in the molecule. , It is a monomer with high water solubility by containing an ionic group and a counter ion.

The ethylenically unsaturated group includes an ethylene group, a propenyl group, a butenyl group, a vinylphenyl group, a (meth) acrylic group, an allyl ether group, a vinyl ether group, a maleyl group, a maleimide group, a (meth) acrylamide group, an acetylvinyl group and Examples include a vinylamide group. In the present specification, "(meth) acrylic" means both "acrylic" and "methacrylic", and "(meth) acrylate" means both "acrylate" and "methacrylate". means. Of these, a (meth) acrylic group, a vinyl ether group and a (meth) acrylamide group are preferable, and a (meth) acrylic group is more preferable.

Examples of the ionic group include carboxylic acid, phosphoric acid, sulfonic acid and the like. Of these, carboxylic acid is preferable.

Examples of the counter ion include monovalent counter ions such as sodium ion, potassium ion and ammonium ion; and polyvalent metal ions such as zinc ion, magnesium ion, calcium ion, aluminum ion and neodium ion. Among them, monovalent counterion is preferable, sodium ion, potassium ion, or ammonium ion is more preferably used, and potassium ion is more preferably used. In addition to the monovalent counter ion, it is also preferable to use a polyvalent metal ion such as zinc ion, magnesium ion, calcium ion, aluminum ion or neodium ion.
Printing or dyeing when a water-soluble ethylenically unsaturated monomer containing a monovalent counterion and a water-soluble ethylenically unsaturated monomer containing a polyvalent metal ion are used in combination as a counterion. It is possible to further improve the bleeding inhibitory property of the dye in the treatment layer obtained by photocuring the composition for use. Further, in addition to these, it is a preferable form of the present invention to be used in combination with an organic acid and / or a salt thereof, which will be described later. The polyvalent metal ion is preferably zinc ion, magnesium ion, or calcium ion.

The content of the water-soluble ethylenically unsaturated monomer containing an ionic group and a counter ion contained in the textile printing or dyeing composition of the present invention is preferably 100% by mass of the above composition, as an upper limit. Is 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and the lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more. In this case, the balance between the viscosity of the printing or dyeing composition and the feathering after the polymerization treatment can be further improved.

The total content of the water-soluble ethylenically unsaturated monomer containing a monovalent counterion as a counterion and the water-soluble ethylenically unsaturated monomer containing a polyvalent metal ion as a counterion In 100% by mass of the composition for printing or dyeing, the upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more.
The content of the water-soluble ethylenically unsaturated monomer containing a monovalent metal ion as a counter ion is preferably 50% by mass or less, more preferably 50% by mass or less, in an upper limit of 100% by mass of the composition for printing or dyeing. It is 40% by mass or less, more preferably 30% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more.
The content of the water-soluble ethylenically unsaturated monomer containing a polyvalent metal ion as a counter ion is preferably 15% by mass or less, more preferably 10% by mass, with an upper limit of 100% by mass of the composition for printing or dyeing. It is mass% or less, and the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.
When the above is done, the solubility of the textile for printing or dyeing composition after the polymerization treatment can be further improved.

Examples of the water-soluble ethylenically unsaturated monomer containing a carboxylic acid as an ionic group and a counterion contained in the textile printing or dyeing composition according to the present invention include acrylic acid, methacrylic acid, maleic acid, and fumal. Acid, 2- (meth) acryloyloxy benzoic acid, 3- (meth) acryloyloxy benzoic acid, 4- (meth) acryloyloxy benzoic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) ) Acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2-vinyl benzoic acid, 3-vinyl benzoic acid, 4-vinyl benzoic acid, N- (meth) acryloyl aspartic acid, ω- (meth) ) Acroylalkane-1,1 dicarboxylic acids, alkali metal salts such as sodium salt and potassium salt, and monovalent salts such as ammonium salt; polyvalent salts such as zinc salt, magnesium salt, calcium salt, aluminum salt, or neodium salt. Examples include salt.
Among them, alkali metal salts such as sodium salt and potassium salt and monovalent salts such as ammonium salt are preferable, and sodium salt, potassium salt or ammonium salt are more preferable. More preferably, it is a potassium salt.
When a monovalent salt of a carboxylic acid and a polyvalent metal salt are used in combination, the dye bleeding suppressing function of the treatment layer obtained by photocuring the textile printing or dyeing composition can be further improved. Further, in addition to these, it is a preferable form of the present invention to be used in combination with an organic acid and / or a salt thereof, which will be described later. The carboxylic acid polyvalent metal salt is preferably a zinc salt, a magnesium salt, or a calcium salt.

The total content of the monovalent salt and the polyvalent metal salt of the carboxylic acid is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 40% by mass or less, based on 100% by mass of the composition for printing or dyeing. Is 30% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more.
The content of the monovalent metal salt of the carboxylic acid is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less in 100% by mass of the composition for printing or dyeing. be. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more.
The content of the polyvalent metal salt of the carboxylic acid is preferably 15% by mass or less, more preferably 10% by mass or less, and preferably 0.5% by mass as the lower limit in 100% by mass of the composition for printing or dyeing. % Or more, more preferably 1% by mass or more.
When the above is done, the solubility of the textile for printing or dyeing composition after the polymerization treatment can be further improved.

As the water-soluble ethylenically unsaturated monomer containing a carboxylic acid as an ionic group and a counter ion, a sodium salt, a potassium salt, a zinc salt, and a calcium salt having 3 to 15 carbon atoms are preferable, and the calcium salt has a carbon number of 3 to 15. 3-12 sodium salts, potassium salts, zinc salts, and calcium salts are more preferred. As the number of carbon atoms, 3 to 9 carbon atoms are more preferable, and 3 to 6 carbon atoms are particularly preferable. Of these, potassium (meth) acrylate, sodium (meth) acrylate, zinc (meth) zinc acrylate, and calcium (meth) acrylate are the most preferable. By using a monomer having a small number of carbon atoms, the hydrophobic portion in the molecule can be reduced, and the water solubility of the water-soluble ethylenically unsaturated monomer after the polymerization treatment can be further enhanced.

Examples of the water-soluble ethylenically unsaturated monomer containing a phosphoric acid as an ionic group and a counterion contained in the textile printing or dyeing composition according to the present invention include mono (2-acryloyloxyethyl). Acid phosphate, mono (2-methacryloyloxyethyl) acid phosphate, diphenyl (2-acryloyloxyethyl) phosphate, diphenyl (2-methacryloyloxyethyl) phosphate, phenyl (2-acryloyloxyethyl) phosphate, acidphosphooxyethyl methacrylate, Metachlorooxyethyl acid phosphate, phosphooxypolyoxyethylene glycol monomethacrylate, acid phosphooxypolyoxypropylene glycol methacrylate, (meth) acryloyloxyethyl acid phosphate, (meth) acryloyloxypropyl acid phosphate, (meth) acryloyloxy- Molecules such as 2-hydroxypropyl acid phosphate, (meth) acryloyloxy-3-hydroxypropyl acid phosphate, (meth) acryloyloxy-3-chloro-2-hydroxypropyl acid phosphate, and vinyl phosphate, p-vinylbenzene phosphate, etc. Examples thereof include sodium salt, potassium salt, and ammonium salt of the compound having a phosphono group within.

Examples of the water-soluble ethylenically unsaturated monomer containing sulfonic acid as an ionic group and counterion contained in the textile printing or dyeing composition according to the present invention include allyl sulfonic acid and isoprene sulfonic acid. 2- (meth) acrylamide ethyl sulfonic acid, 3- (meth) acrylamide propyl sulfonic acid, 4- (meth) acrylamide butyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, p-vinylbenzene sulfonic acid , And compounds such as vinyl sulfonic acid, sodium salts, potassium salts, and ammonium salts.
The water-soluble ethylenically unsaturated monomer containing the above-exemplified ionic group and counterion may be used alone or in combination of two or more.

As the water-soluble ethylenically unsaturated monomer containing an ionic group and a counterion contained in the textile printing or dyeing composition of the present invention, an acrylate is preferable, and an alkali metal such as lithium, sodium and potassium is preferable. A monovalent salt of acrylic acid such as a salt, an ammonium salt or an amine salt is more preferable, and an alkali metal salt or an ammonium salt is more preferable, and a sodium salt, a potassium salt or an ammonium salt is particularly preferable. Most preferably, it is a potassium salt.
In addition to the above, the water-soluble ethylenically unsaturated monomer containing an ionic group and a counterion contained in the textile printing or dyeing composition of the present invention includes zinc salt, magnesium salt, calcium salt and aluminum. It may contain a salt or an acrylic acid polyvalent metal salt such as a neodium salt. The acrylic acid polyvalent metal salt is preferably a zinc salt, a magnesium salt, or a calcium salt.
When a monovalent salt of acrylic acid and a polyvalent metal salt are used in combination, the dye bleeding suppressing function of the treatment layer obtained by photocuring the textile printing or dyeing composition can be further improved. As a combination of a monovalent salt of acrylic acid and a polyvalent metal salt in combination, a combination of potassium acrylate and zinc acrylate is preferable. By using zinc acrylate in combination, the curability is improved, and a treated layer having a higher dye bleeding suppressing function can be obtained.

The total content of the monovalent salt and the polyvalent metal salt of acrylic acid is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 40% by mass or less, based on 100% by mass of the composition for printing or dyeing. Is 30% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more.
Above all, the total content of potassium acrylate and zinc acrylate is preferably 10 to 30% by mass in 100% by mass of the composition for printing or dyeing. By doing so, the viscosity of the composition can be lowered.
The content of the monovalent salt of acrylic acid is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less in 100% by mass of the composition for printing or dyeing. Is. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more.
The content of the polyvalent metal salt of acrylic acid is preferably 15% by mass or less, more preferably 10% by mass or less, and preferably 0.5% by mass as the lower limit in 100% by mass of the composition for printing or dyeing. % Or more, more preferably 1% by mass or more.
In the above case, in addition to the solubility after the polymerization treatment of the printing or dyeing composition, the bleeding suppressing function of the dye can be further improved.

2. 2. Other Unsaturated Monomer The printing or dyeing composition of the present invention contains an unsaturated monomer other than the water-soluble ethylenically unsaturated monomer containing the above-mentioned ionic group and counterion. You may. Examples of the other unsaturated monomer include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Pentyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (Meta) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, n-stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl ( Meta) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, methoxy Ethoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, t-butyl Cyclohexyl (meth) acrylate, 2-ethylhexyl-diglycol (meth) acrylate, 4-hydroxybutyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, 2- (2-ethoxyethoxy) (Meta) acrylates such as ethyl (meth) acrylates, 2-cyanoethyl (meth) acrylates, methyl = 2- (hydroxymethyl) acrylates, and 2-ethylhexylcarbitol (meth) acrylates; phenylallyl ethers, o-, m- , P-cresol monoallyl ether, biphenyl-2-all monoallyl ether, biphenyl-4-all monoallyl ether, butyl allyl ether, cyclohexyl allyl ether, and allyl ethers such as cyclohexanemethanol monoallyl ether; butyl vinyl ether, butyl propenyl ether, Vinyl ethers such as butyl butenyl ethers, hexyl vinyl ethers, ethyl hexyl vinyl ethers, phenyl vinyl ethers, benzyl vinyl ethers, ethyl ethoxyvinyl ethers, acetyl ethoxyethoxy vinyl ethers, cyclohexyl vinyl ethers, and adamantyl vinyl ethers; maleimides such as phenylmaleimide, cyclohexylmaleimide, and n-hexylmaleimide. Benzyl acrylate, phenoxyethyl acrylate, phenoxyethoxyethyl acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, bisphenol A diacrylate, EO adduct bis (meth) of bisphenol A ) Acrylate, PO adduct bis (meth) acrylate of bisphenol A, EO adduct bis (meth) acrylate of hydrogenated bisphenol A, etc. Polyoxyalkylene di (meth) acrylates such as meta) acrylates and polyoxypropylene di (meth) acrylates; achloroylmorpholin; N-vinylpyrrolidone; hydroxyalkyl (meth) acrylates; (meth) acrylamides, N, N-dimethylacrylamides. , N-hydroxyethyl acrylamide and the like, acrylamide and the like.
These may be used alone by 1 type, or may be used in combination of 2 or more types.
The content of the other unsaturated monomer is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, based on 100% by mass of the composition. It is also preferable that the content of the other unsaturated monomer is less than 2% by mass in 100% by mass of the above composition. In this case, the odor of the printing or dyeing composition can be further suppressed.

3. 3. Organic Acids and / or Salts thereof The textile printing or dyeing composition of the present invention may contain organic acids and / or salts thereof. The organic acid and / or a salt thereof is a compound other than the above-mentioned water-soluble ethylenically unsaturated monomer and the above-mentioned other unsaturated monomer.
Examples of the organic acid include an organic sulfonic acid such as p-toluene sulfonic acid, an organic phosphoric acid such as phenylphosphonic acid, an organic carboxylic acid, and a phosphoric acid ester. Of these, organic carboxylic acids are preferable. Examples of the organic carboxylic acid include an aliphatic carboxylic acid and an aromatic carboxylic acid. Examples of the aliphatic carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanic acid, octanoic acid, octyl acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid and stearic acid. , Bechenic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid, benzoic acid, glycine, polyacrylic acid, polylactic acid And so on. Examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, salicylic acid and the like. Of these, aliphatic carboxylic acids are more preferable, and lactic acid, propionic acid, and polyacrylic acid are even more preferable.
Examples of the salt of the organic acid include a metal carboxylate. Examples of the metal of the metal carboxylate include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as magnesium, calcium, strontium and barium; zinc; zirconium and the like. Of these, alkali metals such as potassium are preferable. As the salt of the organic acid, potassium lactate and potassium propanoate are preferable.
The textile printing or dyeing composition of the present invention further improves storage stability when it contains an organic acid and / or a salt thereof.
The content of the organic acid and / or a salt thereof is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, and the lower limit in 100% by mass of the composition for printing or dyeing. It is preferably 5% by mass or more, more preferably 15% by mass or more, and further preferably 25% by mass or more. In such a case, the storage stability of the composition for printing or dyeing can be further improved.

4. Solvent The textile printing or dyeing composition of the present invention may contain a solvent. Examples of the solvent include water; monohydric alcohols such as methanol, ethanol and propanol; alkylene oxide adducts containing oxypropylene groups such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerol and polyoxypropylene glycol. Glycol such as. Only one kind of the above solvent may be used, or two or more kinds may be used in combination.

The content of the solvent in 100% by mass of the composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 90% by mass as the upper limit. % Or less, more preferably 85% by mass or less, still more preferably 80% by mass or less.

5. Photopolymerization Initiator The textile printing or dyeing composition of the present invention preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone and 2,2-diethoxy-. 2-Phenylacetphenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) Phenyl] -acetophenone compounds such as -2-morpholinopropane-1-one; anthraquinone compounds such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; 2,4-diethylthioxanthone, 2 -Thioxanthone compounds such as isopropylthioxanthone, 2-chlorothioxanthone, [3- (3,4-dimethyl-9-oxothioxanthen-2-yl) oxy-2-hydroxypropyl] -trimethylazanium chloride; acetophenone dimethylketal, Ketal compounds such as benzyldimethyl ketal; benzophenone compounds such as benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 4,4'-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- ( Examples thereof include phosphine oxides such as 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; and mixtures thereof.
These may be used alone by 1 type, or may be used in combination of 2 or more types.
The content of the photopolymerization initiator is preferably 0.05 to 10.0% by mass, more preferably 0.1 to 7.0% by mass, and further preferably 0.3 in 100% by mass of the composition. ~ 5.0% by mass.

6. Dyes / Pigments Dyes and / or pigments may be added to the printing or dyeing compositions of the present invention. Dyes include toluidine red, permanent carmine FB, fast yellow G, disazo yellow AAA, disazo orange PMP, soluble azo pigment, condensed azo pigment, chelate azo pigment, phthalocyanine blue, indantron blue, quinacridone red, dioxazine violet, basic. Examples thereof include dyes, acidic dyes, aniline blacks, daylight fluorescent pigments, nitroso pigments, nitro pigments, natural pigments, metal oxides as inorganic pigments, carbon black and the like.

When a dye, a pigment, or both are added to the printing or dyeing composition of the present invention, the printing or dyeing composition of the present invention can function as an ink containing a glue material. By using such an ink, it is possible to suppress the occurrence of ink bleeding and perform sharp printing or dyeing. Further, after the polymerization treatment, a cured product having a structural unit derived from a water-soluble ethylenically unsaturated monomer containing an ionic group and a counterion can be easily removed by washing with water or the like. Therefore, a highly safe textile printing or dyeing product can be obtained while maintaining the original texture of the fiber material and having less skin irritation.

7. Additives The textile printing or dyeing composition of the present invention may contain other additives, if necessary, as long as the effects of the present invention are not impaired. Specific examples thereof include photoinitiator aids, polymerization inhibitors, surfactants, antioxidants, chain transfer agents, fillers and the like.

Photoinitiator aids include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethylamino-p-benzoic acid ethyl ester, N, N-dimethyl. Examples thereof include tertiary amine compounds such as amino-p-benzoic acid isoamylethyl ester, N, N-dihydroxyethylaniline, triethylamine and N, N-dimethylhexylamine.

Examples of the polymerization inhibitor include (alkyl) phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiline, p-benzoquinone, and nitroso. Benzene, 2,5-di-t-butyl-p-benzoquinone, dithiobenzoyldisulfide, picric acid, cuperon, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- (3-oxyanilino-1, 3-Dimethylbutylidene) Aniline oxide, dibutyl cresol, cyclohexanone oxime cresol, guayacol, o-isopropylphenol, butyraldoxime, methylethylketoxim, cyclohexanone oxime and the like can be mentioned.

Surfactants include ethylene oxide (abbreviated as EO) 1 to 40 mol additions of phenol, EO 1 to 40 mol additions of stearate, EO 1 to 40 mol additions to higher alcohols, sorbitan palmitate monoester, sorbitan stear. Nonionic surfactants such as acid monoesters and sorbitan stearate triesters; linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), secondary alkane sulfonates (SAS), polyoxyethylene alkyl ether sulfates. Anionic surfactants such as (AES), α-olefin sulfonic acid salt (AOS), α-sulfo fatty acid ester salt (α-SF), polyoxyethylene alkyl ether sulfonate; alkyltrimethylammonium salt, dialkyldimethylammonium Cationic surfactants such as salts; Amphoteric surfactants such as alkylamino fatty acid salts and alkyl betaines; Fluoro-containing surfactants such as perfluoroalkyl EO 1-50 mol additives, perfluoroalkyl carboxylates, perfluoroalkyl betaines and the like Examples thereof include modified silicone oils such as polyether-modified silicone oils and (meth) acrylate-modified silicone oils.

As antioxidants, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, dilauryl 3,3'-thiodipropionate, Examples thereof include triphenylphosphine, octylated diphenylamine, 2,6-di-t-butyl-p-cresol, 2,2'-methylenebis (4-methyl-6-t-butylphenol) and the like.

Chain transfer agents include hydroquinone, diethylmethylamine, diphenylamine, diethyldisulfide, di-1-octyldisulfide, toluene, xylene, 1-butene, 1-nonene, dichloromethane, carbon tetrachloride, methanol, 1-butanol, ethylthiol. , 1-octylthiol, acetone, methylethylketone, 2-methyl-2-propylaldehyde, 1-pentylaldehyde, phenol, m-cresol, p-cresol, o-cresol and the like.

Fillers include alumina powder, silica powder, talc, mica, clay, aluminum hydroxide, calcium carbonate, calcium silicate, aluminum powder, copper powder, carbon fiber, glass fiber, cotton fiber, nylon fiber, acrylic fiber, rayon. Examples include fiber, microballoon, carbon black, metal sulfide, wood powder and the like.

The above additives may be used alone or in combination of two or more.
The content of the additive is preferably 0.05 to 30% by mass, more preferably 0.05 to 20% by mass, based on 100% by mass of the composition.

The textile printing or dyeing composition of the present invention can be prepared using the various components described above, and the preparation means and conditions thereof are not particularly limited. For example, a general stirring blade, an ultrasonic homogenizer, a high-speed homogenizer, etc. Examples thereof include a method of stirring and mixing using a device capable of mixing or stirring such as a high-pressure homogenizer, a planetary stirrer, a 3-roll, a ball mill, a kitty mill, a disc mill, a pin mill, and a dyno mill. After preparing the solution, filtration may be performed using various filters.

8. Curing of Textile or Dyeing Composition The textile or dyeing composition of the present invention is applied to a fiber material and then cured by an electron beam to form a treated layer. For the curing, it is preferable to irradiate with light of 100 to 2000 mJ / cm ² , more preferably to irradiate with light of 100 to 1000 mJ / cm ² , and further to irradiate with light of 100 to 600 mJ / cm ² . preferable.

9. Detergency of the cured product (treated layer) after curing of the composition for printing or dyeing The composition for printing or dyeing of the present invention can be used as an ionic group by washing with warm water after being applied to a fiber material or polymerized. A cured product having a structural unit derived from a water-soluble ethylenically unsaturated monomer containing a counter ion can be easily removed. In the washing with hot water or the like, when the fiber material having the treated layer is washed by immersing it in hot water at 50 ° C., it is washed in about 10 minutes, more preferably in about 5 minutes.

10. Dye bleeding suppressing function The fiber material having the above-mentioned treated layer by the printing or dyeing composition of the present invention is excellent in the dye bleeding suppressing function. When the fiber material having the above-mentioned treated layer by the textile printing or dyeing composition of the present invention is feathered with ink, almost no bleeding occurs in the ink.

[Manufacturing method of fiber material having a treatment layer for printing or dyeing]
In the method for producing a fiber material having a treatment layer for printing or dyeing of the present invention, a treatment step of applying a treatment agent containing any of the above-mentioned textile material printing or dyeing compositions to the fiber material; It comprises a polymerization step of curing the above-mentioned treatment agent applied to a material with an electron beam to form a treatment layer.
When the textile material printing or dyeing composition contains a dye, the treated layer may be a printing layer.

As the treatment agent used in the treatment step, the printing or dyeing composition of the present invention can be used as it is (or directly), or the treatment agent is produced by mixing the medium with the above-mentioned printing or dyeing composition. You can also do it. As the medium, a hydrophilic medium is preferable.

If necessary, the treatment agent may contain other additives as long as the effects of the present invention are not impaired. Other additives include, for example, emulsion stabilizers, penetration promoters, UV absorbers, preservatives, antifungal agents, rust preventives, pH adjusters, surface tension adjusters, antifoaming agents, viscosity modifiers, dispersions. Agent, dispersion stabilizer, chelating agent, anti-drying agent (wetting agent), colorant, anti-fading agent, specific resistance adjusting agent, film adjusting agent, antioxidant, leveling agent, carrier, deep dyeing agent, catalyst, oil absorption Agents, preservatives, preservatives, plasticizers, thermosetting resins, cross-linking agents, infrared absorbers, UV absorbers, light resistance improvers, extender pigments, fluorescent whitening agents, adsorbents, antioxidants, metal ion blockers Known additives such as agents, bulking agents, hygroscopic agents, electrolytes, fragrances, antibacterial agents, deodorants, insect repellents and surfactants can be mentioned. These various additives can be added directly to the treatment agent, for example.

The content of the printing or dyeing composition in 100% by mass of the treatment agent is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and the upper limit is preferably 50% by mass or more. , 100% by mass or less is preferable.

The viscosity of the treatment agent at 25 ° C. is preferably 5 to 300 mPa · s. The surface tension is preferably 25 to 70 mN / m.

Examples of the method of applying the treatment agent to the fiber material include a pad method, a spray method, a dipping method, a coding method, and an inkjet method. Since the treatment agent containing the textile printing or dyeing composition of the present invention has a low viscosity, the inkjet method can be preferably used.

As a method of curing the above-mentioned treatment agent applied to the fiber material with an electron beam to form a treatment layer, it is preferable to irradiate with light of 100 to 2000 mJ / cm ² , and irradiate with light of 100 to 1000 mJ / cm ² . It is more preferable to irradiate with light of 100 to 600 mJ / cm ² .

When a dye is added to the textile printing or dyeing composition, for example, in the case of a cellulosic fiber material, it is preferable to perform a fixing treatment at 95 to 105 ° C. in the vicinity of saturated steam for about 4 to 12 minutes. .. Further, for amide-based fiber materials such as silk and wool, it is preferable to carry out a fixing treatment at 95 to 105 ° C. in the vicinity of saturated steam for about 20 to 40 minutes.

In the method for producing a fiber material having a treatment layer for printing or dyeing of the present invention, the cured product having a structural unit derived from a water-soluble ethylenically unsaturated monomer containing an ionic group and a counter ion is water or the like. It has high detergency because it can be easily removed by cleaning with. Cleaning can also be performed in the fixing process. Further, preferably, the textile printing or dyeing composition of the present invention has a low viscosity, so that it can be easily applied to a fiber material and has excellent permeability to the fiber material. Further, preferably, since the treated layer is formed by polymerization and curing using an electron beam after being applied to the fiber material, bleeding when the fiber material having the treated layer is printed or dyed is suppressed.

[Manufacturing method of textile material printed or dyed]
In the method for producing a textile material printed or dyed according to the present invention, a treatment step of applying a treatment agent containing any of the above-mentioned textile material printing or dyeing compositions to the fiber material, and a treatment step.
The treatment agent applied to the fiber material in the treatment step is cured with an electron beam to obtain a cured product having a structural unit derived from a water-soluble ethylenically unsaturated monomer containing the ionic group and a counter ion. A polymerization step of forming a treatment layer containing the treatment layer and producing a fiber material having the treatment layer,
A printing step of further printing or dyeing a fiber material having the above-mentioned treated layer formed in the above-mentioned polymerization step with a dye to obtain a textile material printed or dyed.
A removal step of removing a cured product having a structural unit derived from a water-soluble ethylenically unsaturated monomer containing an ionic group and a counterion from the printed or dyed fiber material obtained in the printing step. And include.

As a printing or dyeing method, a known method can be used. Further, as a method for removing the treated layer from the printed or dyed fiber material obtained in the printing step, a method of treating with high heat or high heat steam can be applied.
As for the fixing conditions for printing or dyeing, for example, in the case of a cellulosic fiber material, it is preferable to treat the cellulosic fiber material at 95 to 105 ° C. in the vicinity of saturated steam for about 4 to 12 minutes. Further, for amide-based fiber materials such as silk and wool, it is preferable to treat them at 95 to 105 ° C. in the vicinity of saturated steam for about 20 to 40 minutes.
The treatment with the high heat or the high heat steam as a method for removing the treatment layer can be performed at the same time as the printing or dyeing fixing treatment.
The method of applying the pretreatment agent to the fiber material and the method of curing the pretreatment agent applied to the fiber material with an electron beam to form a treated layer are the same as described above.
If the dye is added to the printing or dyeing composition, the printing step can be omitted.

In the method for producing a textile material printed or dyed according to the present invention, the treated layer has high solubility in water and the like and can be easily removed from the fiber material. Further, preferably, the textile printing or dyeing composition of the present invention has a low viscosity, so that it can be easily applied to a fiber material and has excellent permeability to the fiber material. Further, since the treated layer is formed by polymerizing and curing the fiber material by using an electron beam after application to the fiber material, it is possible to produce a printed or dyed fiber material in which bleeding during printing or dyeing is suppressed.

Further, in the method for producing a textile material printed or dyed according to another embodiment, the composition for printing or dyeing the fiber material contains a dye, a pigment or both, and a water-soluble group containing the ionic group and a counter ion. A treatment step of using a composition containing a sex ethylenically unsaturated monomer and applying a treatment agent containing the composition to a fiber material, and a treatment step.
A water-soluble ethylenically unsaturated monomer containing the dye, the pigment, or both, and the ionic group and the counterion by curing the treatment agent applied to the fiber material in the treatment step with an electron beam. A polymerization step of forming a treated layer containing a cured product having a constituent unit of origin and producing a fiber material having the treated layer.
A removal step of removing a cured product having a structural unit derived from a water-soluble ethylenically unsaturated monomer containing an ionic group and a counterion from the fiber material having the treated layer obtained in the polymerization step. May include.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples as well as the present invention, and appropriate modifications are made to the extent that it can meet the purposes of the preceding and the following. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention.

<Example 1>
In 50 parts by mass of water, 10 parts by mass of potassium acrylate [manufactured by Nippon Catalyst Co., Ltd.] and 10 parts by mass of zinc acrylate [manufactured by Nippon Catalyst Co., Ltd.] as water-soluble ethylenically unsaturated monomers, polyethylene glycol [PEG200]. , Wako Pure Chemical Industries, Ltd.] 30 parts by mass, and Lucillin TPO [BASF Japan Co., Ltd.] 0.3 parts by mass as a photopolymerization initiator were added and mixed by stirring to obtain a composition for printing or dyeing. ..
0.5 g of this textile printing or dyeing composition was applied to a cotton cloth (5 cm × 5 cm), dried, and then irradiated with light of 400 mJ / cm ² to prepare a cloth having a treated layer.
A line was drawn on the cloth having the obtained treated layer using a McKee ultrafine oil-based pen [manufactured by Zebra Co., Ltd.]. A photograph of the lined cloth is shown in FIG.

<Examples 2 to 9>
For each of Examples 2 to 9, a cloth having a textile or dyeing composition and a treated layer was prepared in the same manner as in Example 1 except that the formulations (parts by mass) shown in Table 1 below were changed. In Table 1, AA (acrylic acid) and MEA (methoxyethyl acrylate) are manufactured by Nippon Shokubai Co., Ltd., lactic acid is manufactured by Wako Pure Chemical Industries, Ltd., and propionic acid, ethylene glycol, diethylene glycol, and triethylene glycol are (). Irgacure 184 and Irgacure 2959 manufactured by Nippon Shokubai Co., Ltd. were manufactured by BASF Japan Co., Ltd., and other commercially available products similar to the above were used.
A line was drawn on the cloth having the obtained treated layer in the same manner as in Example 1.

<Comparative Example 1>
A line was drawn on an untreated cotton cloth (5 cm × 5 cm) in the same manner as in Example 1.

<Comparative Example 2>
A cloth having a composition for printing or dyeing and a treated layer was prepared in the same manner as in Example 1 except that the composition (part by mass) shown in Table 1 below was changed. In Table 1, ACMO (acryloylmorpholine) was manufactured by Tokyo Chemical Industry Co., Ltd., and other commercially available products similar to the above were used.
A line was drawn on the cloth having the obtained treated layer in the same manner as in Example 1. A photograph of the lined cloth is shown in FIG.

The lined cloths produced in Examples 1 to 9 and Comparative Examples 1 and 2 were evaluated by the following evaluation methods.

(I) Feathering The lined cloths prepared in Examples 1 to 9 and Comparative Examples 1 and 2 were visually observed and evaluated for feathering according to the following criteria. The results are shown in Table 1.
○: No ink bleeding △: Somewhat blurry ×: Blurred

(Ii) Detergency evaluation The detergency was evaluated by immersing the lined cloths prepared in Examples 1 to 9 and Comparative Examples 1 and 2 in warm water at 50 ° C. The evaluation criteria are as follows. The results are shown in Table 1.
◯: Ink drops within 5 minutes △: Ink drops within 10 minutes over 5 minutes ×: It takes more than 10 minutes to remove ink

The textiles for printing or dyeing of Examples 1 to 9 and the cloth having a treated layer prepared by using the compositions were excellent in both feathering and detergency.

According to the textile material printing or dyeing composition of the present invention, a textile material for printing or dyeing having excellent detergency, a fiber material having a treatment layer for printing or dyeing having excellent detergency, and highly washed. Textile materials that have been printed or dyed can be provided.

Claims (4)

A composition used for printing or dyeing textile materials.
Contains a water-soluble ethylenically unsaturated monomer containing an ionic group and a counterion ,
The water-soluble ethylenically unsaturated monomer contains a monovalent salt of acrylic acid .
Textile material printing or dyeing composition. The composition for textile printing or dyeing according to claim 1, further comprising a photopolymerization initiator. A treatment step of applying the treatment agent containing the composition for printing or dyeing the fiber material according to claim 1 or 2 to the fiber material.
A polymerization step of curing the treatment agent applied to the fiber material in the treatment step with an electron beam to form a treatment layer, and a polymerization step.
including,
A method for producing a textile material having a processing layer for printing or dyeing. A treatment step of applying the treatment agent containing the composition for printing or dyeing the fiber material according to claim 1 or 2 to the fiber material.
The treatment agent applied to the fiber material in the treatment step is cured with an electron beam to obtain a cured product having a structural unit derived from a water-soluble ethylenically unsaturated monomer containing the ionic group and a counter ion. A polymerization step of forming a treatment layer containing the treatment layer and producing a fiber material having the treatment layer,
A printing step of further printing or dyeing the fiber material having the treated layer formed in the polymerization step with a dye to obtain a textile material printed or dyed.
A removal step of removing a cured product having a structural unit derived from a water-soluble ethylenically unsaturated monomer containing the ionic group and a counterion from the printed or dyed fiber material obtained in the printing step. Including,
A method for producing a textile material that has been printed or dyed.

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