WO2014148465A1 - カチオン化剤、水不溶性粒子の定着方法、および染色物の製造方法 - Google Patents
カチオン化剤、水不溶性粒子の定着方法、および染色物の製造方法 Download PDFInfo
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- WO2014148465A1 WO2014148465A1 PCT/JP2014/057267 JP2014057267W WO2014148465A1 WO 2014148465 A1 WO2014148465 A1 WO 2014148465A1 JP 2014057267 W JP2014057267 W JP 2014057267W WO 2014148465 A1 WO2014148465 A1 WO 2014148465A1
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Classifications
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- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
- D06P1/5242—Polymers of unsaturated N-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F126/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/22—Effecting variation of dye affinity on textile material by chemical means that react with the fibre
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/22—Effecting variation of dye affinity on textile material by chemical means that react with the fibre
- D06P5/225—Aminalization of cellulose; introducing aminogroups into cellulose
Definitions
- the present invention relates to a cationizing agent, a method for fixing water-insoluble particles, and a method for producing a dyed product.
- Fibers and fabrics are often subjected to processing such as fixing and dyeing pigments and dyes.
- dyeing of fibers and fabrics with dyes is easy to dye but has a low fading fastness.
- Dyeing with pigments has the advantage that the pigments do not fade easily and a unique texture such as casual wear can be obtained.
- the pigments are insoluble in water, many of the surfaces are difficult to penetrate into the fiber. Therefore, it is difficult to fix a large amount. For this reason, there are problems such that dark color processing is difficult and washing fastness is poor.
- Patent Document 1 discloses a polymer having a structural unit derived from a vinylamine monomer as a dye fixing agent used for a cellulose fiber dyed with a reactive dye.
- a dye fixing agent used for a cellulose fiber dyed with a reactive dye.
- the present invention provides a cationizing agent capable of efficiently fixing water-insoluble particles such as pigments on a fabric, a method for fixing water-insoluble particles using the cationizing agent, and a method for producing a dyed product.
- a cationizing agent for cationizing the fabric before fixing water-insoluble particles on the fabric A cationizing agent comprising a polymer having a structural unit (a1) derived from a vinylamine monomer represented by the following formula (1).
- the polymer having the structural unit (a1) derived from the vinylamine monomer is a hydrolyzate of a polymer having a structural unit derived from the N-vinylamide compound, A structural unit (a2) derived from an N-vinylamide compound represented by the following formula (2):
- the ratio of the structural unit (a1) to the total structural unit of the polymer is 5 to 99.9 mol%, and the ratio of the structural unit (a2) is 95 to 0.1 mol%.
- a cationization step for cationizing the fabric by attaching the cationizing agent according to [1] or [2] to the fabric, and bringing the water-insoluble particles into contact with the fabric after the cationization step.
- a group in which the pigment is composed of an azo pigment, a phthalocyanine pigment, an anthraquinone pigment, a quinacridone pigment, a perylene pigment, a perinone pigment, a dioxazine pigment, a quinophthalone pigment, a fluorescent pigment, carbon, and titanium oxide.
- water-insoluble particles such as pigments can be efficiently fixed on the fabric.
- water-insoluble particles such as pigments can be efficiently fixed on a fabric.
- a dyed product obtained by efficiently fixing a pigment on a fabric can be obtained.
- the cationizing agent of the present invention is a cationizing agent used to cationize the fabric before fixing the water-insoluble particles on the fabric.
- the cationizing agent of the present invention comprises a polymer (hereinafter referred to as “polymer (A)”) having a structural unit derived from a vinylamine monomer (hereinafter referred to as “unit (a1)”).
- the “structural unit derived from a vinylamine monomer” means a repeating unit constituting a polymer structure formed by polymerization of a vinylamine monomer, and the structure is formed on a vinyl group in the vinylamine monomer.
- the molecular structure in which the two carbons of the derived ethylene group are binding sites, but the structure is the same as this, and the structure is not limited to those using vinylamine monomer as a raw material.
- the naming of other structural units shall also follow the above.
- the unit (a1) of the polymer (A) is preferably a structural unit derived from an N-vinylamine monomer, and more specifically, a structural unit having a structure represented by the following formula (1): Preferably there is. (Wherein R 1 represents hydrogen or a methyl group)
- the polymer (A) having the unit (a1) is obtained by subjecting a vinylamide polymer (hereinafter referred to as “polymer (A) precursor”) to a modification treatment such as hydrolysis or Hoffman reaction, for example. It can be obtained by converting at least a part of the side chain of the structural unit into an amino group.
- N-vinylamide polymer a polymer having a structural unit derived from an N-vinylamide compound
- N-vinylamide polymer a polymer having a structural unit derived from an N-vinylamide compound
- acrylamide polymer a polymer having a structural unit derived from an acrylamide compound
- the polymer (A) is preferably a hydrolyzate of an N-vinylamide polymer. That is, the unit (a1) is preferably formed by hydrolyzing an N-vinylamide polymer as a polymer (A) precursor.
- N-vinylamide compound examples include N-vinylcarboxylic amide, that is, a compound represented by the following formula (i).
- R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- the compound represented by the formula (i) examples include N-vinylformamide, N-vinylacetamide, N-vinylpropionic acid amide, N-vinylbutyric acid amide, and the like.
- acrylamide compound examples include (meth) acrylamide, N-alkyl (meth) acrylamide (the alkyl group has 1 to 6 carbon atoms), N, N-dialkyl (meth) acrylamide (the alkyl group has 1 to 6 carbon atoms). ), Dialkylaminoethyl (meth) acrylamide (the alkyl group has 1 to 6 carbon atoms) and its salt or quaternized product, dialkylaminopropyl (meth) acrylamide (alkyl group has 1 to 6 carbon atoms) and its salt or Quaternized products, diacetone acrylamide and the like can be mentioned.
- the acrylamide compound When used as a raw material monomer, it is polymerized and then subjected to a Hofmann reaction, which will be described later, so that an unsubstituted or substituted carbamoyl group (—CONH 2 ) as a polymer side chain is unsubstituted or
- the unit (a1) can be formed by conversion to a substituted amino group (—NH 2).
- N-vinylformamide is preferable because the unit (a1) can be easily formed.
- the polymer (A) has a structural unit derived from a monomer other than the vinylamine monomer (hereinafter referred to as “comonomer unit”) in addition to the unit (a1) as necessary. May be.
- the arbitrary monomers which have an ethylenically unsaturated bond can be used, for example, (meth) acrylic acid and its salt, (meth) acrylic acid ester ((meth) acrylic acid) And esters of alcohol and phenol having 1 to 6 carbon atoms), (meth) acrylonitrile, N-vinylpyrrolidone, N-vinylcaprolactam, vinyl acetate and the like.
- the unit (a1) of the polymer (A) is formed by hydrolysis of an N-vinylamide polymer
- the acrylamide compound may be used as the other monomer.
- the unit (a1) of the polymer (A) is formed by the Hofmann reaction of an acrylamide polymer
- the N-vinylamide compound may be used as the other monomer.
- modification by hydrolysis after polymerization is not performed.
- the comonomer unit may be a structural unit (a2) derived from an N-vinylamide compound remaining without being hydrolyzed in the hydrolysis of an N-vinylamide polymer (polymer (A) precursor).
- the unit (a2) has a structure represented by the following formula (2). (Wherein R 2 represents a hydrogen atom or a methyl group, and R 3 represents an alkyl group having 1 to 6 carbon atoms)
- the comonomer unit may be a structural unit derived from an unreacted acrylamide compound in the Hoffman reaction of an acrylamide polymer (polymer (A) precursor).
- the ratio of the unit (a1) to the total structural unit (100 mol%) in the polymer (A) is preferably 5 to 99.9 mol%.
- the proportion of the unit (a1) is preferably 40 mol% or more, more preferably 70 mol% or more, and particularly preferably 95 mol% or more. Furthermore, less than 100 mol% is preferable. When the proportion of the unit (a1) is not less than the lower limit and less than the upper limit, the fixing efficiency of the water-insoluble particles becomes better.
- the ratio of the unit (a2) to the total structural unit (100 mol%) of the polymer (A) is preferably 95 to 0.1 mol%.
- the N-vinylamide compound in all the structural units (100 mol%) of the polymer (A) precursor 5 mol% is preferable, 10 mol% is more preferable, 50 mol% is further more preferable, and 70 mol% is particularly preferable.
- the proportion of the structural unit derived from the N-vinylamide compound is equal to or greater than the lower limit, the proportion of the unit (a1) formed by hydrolysis increases and the fixing efficiency of the water-insoluble particles becomes better.
- the polymerization method for obtaining the polymer (A) precursor is not particularly limited, and a known method such as aqueous solution polymerization, aqueous solution stationary adiabatic polymerization, suspension polymerization, emulsion polymerization, or optical belt continuous polymerization can be employed.
- a radical polymerization initiator can be used for the polymerization. Examples of radical polymerization initiators include redox initiators, azo initiators, and peroxides. Only 1 type may be used for a radical polymerization initiator and it may use 2 or more types together.
- the radical polymerization initiator may be water-soluble or oil-soluble. When using an oil-soluble radical polymerization initiator, it is dissolved in a water-soluble solvent and added.
- water-soluble azo initiators examples include 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane Dihydrochloride, 4,4′-azobis (4-cyanovaleric acid), and the like.
- oil-soluble azo initiator examples include 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2-methylpropionate), 2,2′-azobis (4-methoxy-2,4dimethyl) valeronitrile and the like.
- Examples of the redox initiator include a combination of ammonium peroxodisulfate and sodium sulfite, sodium hydrogen sulfite, trimethylamine, tetramethylethylenediamine and the like, a combination of t-butyl hydroperoxide, sodium sulfite, and sodium hydrogen sulfite.
- Examples of peroxides include ammonium or potassium peroxodisulfate, hydrogen peroxide, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, succinic peroxide, t-butylperoxy-2-ethylhexanoate, and the like. It is done.
- a redox initiator that initiates polymerization at a low temperature and a water-soluble azo initiator that initiates polymerization at a relatively high temperature.
- a combination of t-butyl hydroperoxide and sodium sulfite or sodium bisulfite is used as a redox initiator, and 2,2′-azobis (2-amidinopropane) dihydrochloride is used in combination as a water-soluble azo initiator. It is preferable. This makes it easy to complete the polymerization even when the polymerization temperature is greatly different at the start and end of the polymerization.
- a known photopolymerization initiator can be used.
- the amount of initiator used is preferably 100 to 10,000 ppm by mass, more preferably 500 to 5,000 ppm by mass, based on the total mass of the monomers used.
- the amount of initiator used is preferably 10 to 1,000 ppm by mass, more preferably 30 to 600 ppm by mass, based on the total mass of the monomers used. If the amount of the initiator used is not less than the lower limit, a sufficient polymerization rate can be easily obtained. If the usage-amount of an initiator is below the said upper limit, it will be easy to suppress that the molecular weight of a polymer becomes low too much.
- the molecular weight of the polymer (A) precursor is 1 N saline solution.
- 0.05 to 12 is preferably used, with the value of the reduced viscosity ( ⁇ sp / C) at 25 ° C. of an aqueous solution in which the polymer (A) precursor is dissolved to a concentration of 0.1 g / dL as an index, 0.1 to 11 is more preferable.
- the viscosity average molecular weight of the polymer (A) precursor having a structural unit derived from an N-vinylamide compound is preferably 5,000 to 5,000,000, and more preferably 10,000 to 4,000,000.
- the viscosity average molecular weight can be measured by the method described in Examples.
- Hydrolysis of the polymer (A) precursor may be performed using an acid or a base.
- a strong acid such as hydrochloric acid
- a base such as sodium hydroxide
- the amount of the acid or base used varies depending on the desired hydrolysis rate, but is usually 0.8 to 2 times equivalent to the structural unit derived from the vinylamine monomer in the target polymer (A), preferably 1 to 1.5 times equivalent.
- a substance that is more easily hydrolyzed than the N-vinylcarboxylic acid amide group coexists in the hydrolysis reaction system depending on the kind of the raw material monomer, it is naturally necessary to use an amount that offsets this excessively.
- the acid or base is preferably dissolved in advance and subjected to a hydrolysis reaction as a solution.
- a higher concentration of the solution is preferable for the reaction operation.
- the hydrolysis reaction is carried out by mixing the powdered polymer (A) precursor that has been insolubilized with an acid or base and bringing them into direct contact.
- the mixing method is not particularly limited, and a method similar to the mixing method in the insolubilization preventing treatment is appropriately used.
- it is a method of mixing in a bag, shaking mixing, a rotating container type mixer in which a container such as a cylinder, a double cone or a Y type rotates, a blade rotating type such as a ribbon mixer, a screw mixer or a disk rotating type.
- a blender such as a mixer
- a blade rotating type such as a ribbon mixer
- a screw mixer or a disk rotating type examples include a method of mixing by batch operation using a blender such as a mixer, a method of adding acid or base in the middle of transfer using a screw conveyor and mixing while continuously transferring, and the like.
- a system in which an acid or a base is sprayed on a powdery polymer (A) precursor in a solid phase during flow or movement is preferable. Hydrolysis is usually carried out at 20 to 90 ° C.
- the reaction time varies depending on the temperature, but is usually 1 minute to 1 week. Stirring of the reaction product does not need to be continued during the reaction, and may be left after the acid or base is absorbed by the powdery polymer. The maximum time that can be left is 24 hours. Depending on the hydrolysis conditions, acid or alkali may remain. After the hydrolysis, neutralization may be performed or it may be left as it is.
- the polymer (A) as a cationizing agent of the present invention is usually used in the form of a solution (chemical solution) such as an aqueous solution.
- concentration of the polymer (A) in the solution is preferably 0.01 to 1% by mass, and more preferably 0.1 to 0.5% by mass.
- the water-insoluble particles can be efficiently fixed on the fabric.
- grains after processing with the cationizing agent of this invention has high dyeing property, and it is easy to fully exhibit the function by this water-insoluble particle
- the method for fixing water-insoluble particles of the present invention is a method for fixing water-insoluble particles to a fabric using the cationizing agent of the present invention.
- the method for fixing water-insoluble particles of the present invention includes a cationization step and a fixing step, which will be described later.
- the fabric is treated with the cationizing agent of the present invention.
- the cationization treatment for example, a method of immersing a fabric washed with water in an aqueous solution (chemical solution) containing the cationizing agent of the present invention, absorbing the cationizing agent, and washing with water can be mentioned. After absorbing the cationizing agent, the excess cationizing agent is removed by performing operations such as washing with water and dehydration.
- the cationization treatment may be performed by continuous treatment or batch treatment.
- the adhesion amount of the cationizing agent is at least the lower limit, the fixing efficiency of the water-insoluble particles tends to be high. Moreover, if the adhesion amount of the cationizing agent is less than or equal to the upper limit value, problems such as discoloration of the fabric are less likely to occur, and it is economically advantageous.
- the content of the cationizing agent in the chemical solution is preferably 0.5 to 15% by mass and more preferably 1 to 10% by mass with respect to the total mass of the chemical solution. If the content of the cationizing agent is at least the lower limit, the fixing efficiency of the water-insoluble particles tends to increase. Moreover, if content of a cationizing agent is below an upper limit, malfunctions, such as discoloration of a cloth, will not occur easily and it is economically advantageous.
- the temperature of the cationization treatment is preferably 10 to 90 ° C, more preferably 20 to 85 ° C.
- the dipping time of the fabric is preferably 1 to 60 minutes.
- the method for washing with water is not particularly limited, but it is preferably carried out with a water flow of 0.1 to 10 L / min for 1 to 60 minutes.
- An example of a typical water washing method is washing with running water of 3.6 L / min for 10 minutes.
- the method of dehydration is not particularly limited, but a centrifugal dehydration method can be used, and it is preferably performed at 1,000 to 10,000 rpm for 10 seconds to 10 minutes.
- An example of a typical dehydration method is dehydration at 3,000 rpm for 1 minute using a centrifugal dehydrator.
- the type of fiber constituting the fabric is not particularly limited. Natural fibers such as cotton, hemp, wool, and silk, regenerated fibers such as rayon, cupra, and polynosic, semi-regenerated fibers such as acetate, nylon, polyester, acrylic, and the like Synthetic fibers, fibers containing poval, aramid fibers (aromatic polyamide fibers) and the like. Of these, cotton, acrylic fiber, polyester fiber, acetate fiber and aramid fiber are preferred. Also, two or more of the above-mentioned fibers can be mixed and used.
- the fixing method of the present invention is a water-insoluble particle on a fabric formed of at least one fiber selected from the group consisting of cotton, acrylic fiber, polyester fiber, acetate fiber, and aramid fiber, which has been difficult with conventional methods. Enables efficient establishment. Further, the fixing method of the present invention is preferably applied to a suede fabric comprising ultrafine fibers. As an example of this suede fabric, there is a suede fabric having suede nappings made of ultrafine fibers of 1 dtex or less on the surface. Examples of the raw material for the ultrafine fibers include polyester, polyamide, and combinations thereof. The base material portion other than the raised portions is as described above for the fabric.
- the zeta potential (electrokinetic potential) of the fabric is preferably -100 to -1 mV. In particular, ⁇ 50 to ⁇ 1 mV is preferable.
- the zeta potential referred to here is measured when the water in which the fabric to be measured is immersed has a conductivity in the range of 100 ⁇ S / cm to 7 mS / cm at 20 ° C. The reason why the cationizing agent of the present invention exhibits a high effect is not clear, but it is considered that it has an ability to efficiently bind to a fabric having a low zeta potential due to a high functional group density as a cationic polymer. .
- the water-insoluble particles are fixed to the fabric after the cationization step.
- a specific method of the fixing treatment for example, a method of immersing the fabric after the cationization step in a dispersion in which water-insoluble particles are dispersed, fixing the water-insoluble particles, and washing with water can be given.
- the fixing process may be performed by a continuous process or a batch process.
- the water-insoluble particles generally have a particle diameter of 1 nm to 30 ⁇ m and are particles suspended in water as fine particles.
- the water-insoluble particles are typically pigments, and known organic pigments and inorganic pigments can be used as the pigment.
- the organic pigment include at least one selected from the group consisting of azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, perylene pigments, perinone pigments, dioxazine pigments, quinophthalone pigments, and fluorescent pigments.
- the inorganic pigment for example, at least one selected from the group consisting of carbon and titanium oxide can be used.
- the azo pigment referred to here is a compound having an azo group, and specific examples thereof include Pigment Yellow14 and Pigment Red57.
- the phthalocyanine pigment referred to here is a cyclic compound having a structure in which four phthalimides are cross-linked by nitrogen atoms, and specific examples thereof include Pigment Blue 16 and Pigment Green 7.
- the anthraquinone pigment here is an organic pigment derived from anthraquinone, and specific examples thereof include Pigment Red168 and Pigment Red177.
- the quinacridone pigment referred to here is a highly symmetrical heterocyclic pigment, and specific examples thereof include Pigment Violet 19, Pigment Red 122, and the like.
- the perylene pigment as used herein refers to a pigment having a structure in which two oxygen atoms constituting the six-membered ring of perylenetetracarboxylic dianhydride are eliminated. Specifically, Pigment Red 149, Pigment Red179 or the like.
- the perinone pigments mentioned here a perinone a fused ring compounds, specifically, like Pigment Orange43.
- the dioxane pigment referred to here is a pigment having two oxazine rings per molecule, and specific examples thereof include Pigment Violet 23, Pigment Violet 37, and the like.
- the quinophthalone pigment referred to here is a pigment obtained from quinaldine and phthalic anhydride, and specific examples thereof include Pigment Yellow 138 and Pigment Yellow 177.
- the fluorescent pigment referred to here is an organic pigment made of a rhodamine derivative and an inorganic pigment made of a rare earth element.
- Carbon as used herein refers to carbon fine particles having a diameter of 3 to 500 nm, and specifically includes Pigment Black 7 and the like.
- Titanium oxide as used herein refers to fine particles mainly composed of titanium dioxide, and specific examples thereof include Pigment White 6 and Pigment Yellow 7.
- the content of the pigment in the dispersion (100% by mass) is preferably 0.1 to 50% by mass, and more preferably 1 to 30% by mass. If the pigment content is at least the lower limit, the dyeing efficiency will be better. If the pigment content is less than or equal to the upper limit, color unevenness is unlikely to occur, and the pigment is easily dispersed in water.
- the temperature of the dispersion during the fixing process is preferably 40 to 90 ° C, more preferably 50 to 80 ° C.
- the immersion time of the fabric is preferably 10 to 30 minutes.
- a known fastness-improving treatment with a fixing agent such as a binder may be performed.
- the binder include polyurethane, polyester, and polyacrylate.
- the fixing step since the fixing step is performed after the cationization step with the cationizing agent of the present invention, the water-insoluble particles can be efficiently fixed to the fabric. it can.
- the fabric obtained by the fixing method of the water-insoluble particles of the present invention has a high fastness to washing and can sufficiently exhibit the function of the water-insoluble particles even after washing.
- the reason why the polymer (A) exhibits a high effect is not clear, but it has a high functional group density as a cationic polymer, and the primary amine is covalently bonded or coordinated by heat in addition to ionic bonds and hydrogen bonds. This is considered to be due to the ability to form various bonds such as bonds.
- the unit (a1) is derived from N-vinylcarboxylic acid amide
- the remaining carboxylic acid amide group is considered to contribute to fixing of the water-insoluble particles by forming a hydrogen bond or the like.
- the water-insoluble particles referred to here are particles dispersed in water at 1 g or less in 100 g of water at 25 ° C., and cannot be directly infiltrated into the fabric as an aqueous solution like a dye. For this purpose, a sufficient amount could not be adhered to the fabric surface, and the cationizing agent according to the present invention can be fixed to the fabric surface in a practical amount for the first time and dyed. It has become.
- the method for producing a dyed product of the present invention is a method for obtaining a dyed product by dyeing a fabric using a pigment as water-insoluble particles.
- the fixing step is performed after the cationization step with the cationizing agent of the present invention, the fabric can be dyed efficiently.
- the pigment and fabric those described above in relation to the fixing method of the present invention can be used.
- a method including the cationization step and the fixing step can be used as a specific method for producing a dyed product.
- N-vinylformamide is dissolved in degassed demineralized water so as to be 30% by mass, cooled to 0 ° C., t-butyl hydroperoxide 300 mass ppm, sodium bisulfite 300 mass ppm, azobisamidinopropane hydrochloride 1, Polymerization was carried out by adding 000 mass ppm. After 6 hours, a gel aqueous solution containing 30% by mass of N-vinylformamide having a molecular weight of 2 million was obtained. A part of the obtained gel was collected and pulverized, and diluted with water to obtain an aqueous solution containing 5% by mass of the gel.
- a 48% sodium hydroxide aqueous solution was added in an amount of 0.4 times mol to N-vinylformamide, and a hydrolysis reaction was performed at 70 ° C. for 4 hours. Thereafter, 35% hydrochloric acid was partially neutralized with half the amount of sodium hydroxide used for hydrolysis, and a polymer (A3) in which the proportion of unit (a1) (hydrochloride unit) was 40 mol% with respect to all the structural units. A polymer aqueous solution-3 having a polymer concentration of 4% by mass was obtained.
- the zeta potential of the fabric was measured by Nippon Fiber Industries, Ltd. Fiber Potential Analyzer Model FPA.
- Example 1 Tendon-woven cotton fabric was used as the fabric.
- the fabric (fabric zeta potential-15.7 mV) was washed with hot water at 80 ° C. for 5 minutes, and then centrifuged and dehydrated at 3,000 rpm for 1 minute. Then, it was dried at 25 ° C. for 12 hours.
- 5% by mass of the polymer (A1) in a pure content with respect to the mass of the dough was dissolved in 30 times the volume of the dough amount in water and the chemical solution Was prepared.
- the temperature of the chemical solution was set to 60 ⁇ 2 ° C., the dehydrated dough was added, and immersion treatment was performed for 20 minutes.
- the treated dough was washed with water for 10 minutes and then centrifuged and dehydrated at 3,000 rpm for 1 minute.
- 5% by mass of a pigment organic pigment Navy Blue FL2R conc manufactured by Dainichi Seika Kogyo Co., Ltd.
- the temperature of the obtained dispersion was 60 ° C. ⁇ 2 ° C., and the fabric was immersed for 20 minutes to exhaust the pigment. Thereafter, it was washed with water for 10 minutes, centrifuged at 3,000 rpm for 1 minute, and then dried at 25 ° C. for 12 hours.
- Example 2 The pigment was fixed in the same manner as in Example 1 except that Polymer aqueous solution-2 (Example 2) and Polymer aqueous solution-3 (Example 3) were used instead of Polymer aqueous solution-1.
- Examples 4 to 6 Comparative Example 2
- the pigment was fixed in the same manner as in Examples 1 to 3 and Comparative Example 1 except that the organic pigment BlackFLTR conc manufactured by Dainichi Seika Kogyo Co., Ltd. was used as the pigment.
- the evaluation results of Examples 4 to 6 and Comparative Example 2 are shown in Table 2.
- Example 7 Comparative Example 3
- the pigment was fixed in the same manner as in Example 1 and Comparative Example 1 except that inorganic pigment R-850 (titanium oxide) manufactured by Dainichi Seika Kogyo Co., Ltd. was used as the pigment.
- inorganic pigment R-850 titanium oxide
- the evaluation results of Example 7 and Comparative Example 3 are shown in Table 3.
- Example 1 except that suede-like artificial leather made of ultrafine fibers (zeta potential-45.1 mV) was used as the fabric, and organic pigments TC Brown FD and Black FLTR conc manufactured by Dainichi Seika Kogyo Co., Ltd. were used as the pigment. In the same manner as in Comparative Example 1, the pigment was fixed.
- Table 4 The evaluation results of Examples 8 to 10 and Comparative Example 4 are shown in Table 4.
- Example 11 Comparative Example 5
- the pigment was fixed in the same manner as in Example 1 and Comparative Example 1, except that a polyester fabric (zeta potential -20.8 mV) was used as the fabric, and an organic pigment Black FLTR conc manufactured by Dainichi Seika Kogyo Co., Ltd. was used as the pigment. I let you.
- the evaluation results of Example 11 and Comparative Example 5 are shown in Table 5.
- Example 12 Comparative Example 6
- the pigment was fixed in the same manner as in Example 1 and Comparative Example 1, except that acrylic fiber (zeta potential -26.4 mV) was used as the fabric, and organic pigment Black FLTR conc manufactured by Dainichi Seika Kogyo Co., Ltd. was used as the pigment. I let you.
- the evaluation results of Example 12 and Comparative Example 6 are shown in Table 6.
- Example 13 comparative example 7
- the pigment was fixed in the same manner as in Example 1 and Comparative Example 1 except that acetate fiber (zeta potential-3.7 mV) was used as the fabric and organic pigment Black FLTR conc manufactured by Dainichi Seika Kogyo Co., Ltd. was used as the pigment. I let you.
- the evaluation results of Example 13 and Comparative Example 7 are shown in Table 7.
- Example 14 comparative example 8
- Example 1 and Comparative Example 1 except that a para-aramid woven fabric (zeta potential—77.0 mV) was used as the fabric and an organic pigment Black FLTR conc manufactured by Dainichi Seika Kogyo Co., Ltd. was used as the pigment. The pigment was fixed.
- Table 8 shows the evaluation results of Example 14 and Comparative Example 8.
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Abstract
Description
本願は、2013年3月19日に、日本に出願された特願2013-057091号に基づき優先権を主張し、その内容をここに援用する。
例えば、特許文献1には、反応性染料で染色されたセルロース系繊維に用いる染料固着剤として、ビニルアミン単量体に由来する構成単位を有する重合体が開示されている。しかし、特許文献1の繊維加工では、顔料等の水不溶性粒子を効率良く定着させることは困難である。
[1] 布帛に水不溶性粒子を定着させる前に、該布帛をカチオン化するためのカチオン化剤であって、
下式(1)で表されるビニルアミン単量体に由来する構成単位(a1)を有する重合体からなるカチオン化剤。
(式中、R1は、水素原子又はメチル基を示す)
[2] 前記ビニルアミン単量体に由来する構成単位(a1)を有する重合体が、N-ビニルアミド化合物に由来する構成単位を有する重合体の加水分解物であって、
下式(2)で表されるN-ビニルアミド化合物に由来する構成単位(a2)を更に含み、
前記重合体の全構成単位に対する前記構成単位(a1)の割合が5~99.9モル%であって、前記構成単位(a2)の割合が95~0.1モル%で
ある、[1]に記載のカチオン化剤。
(式中、R2は、水素原子又はメチル基を示し、R3は、炭素数1~6のアルキル基を示す)
[3] 布帛に、[1]または[2]に記載のカチオン化剤を付着させることにより、布帛をカチオン化するカチオン化工程と、前記カチオン化工程の後に前記布帛に水不溶性粒子を接触させることにより、布帛に水不溶性粒子を定着させる定着工程と、を有する、水不溶性粒子の定着方法。
[4] 前記布帛が、木綿、アクリル繊維、ポリエステル繊維、アセテート繊維及びアラミド繊維からなる群より選ばれる少なくとも1種の繊維により形成される布帛である、[3]に記載の水不溶性粒子の定着方法。
[5] 前記布帛が、極細繊維からなるスエード調布帛である、[3]または[4]に記載の水不溶性粒子の定着方法。
[6] 前記布帛が-100~-1mVのゼータ電位を有する請求項3~5のいずれか一項に記載の水不溶性粒子の定着方法。
[7] 布帛に、[1]または[2]に記載のカチオン化剤を付着させることにより、布帛をカチオン化するカチオン化工程と、前記カチオン化工程の後に前記布帛に顔料を接触させることにより、布帛に顔料を定着させて布帛を染色する染色工程と、を有する染色物の製造方法。
[8] 前記顔料がアゾ系顔料、フタロシアニン系顔料、アンスラキノン系顔料、キナクリドン系顔料、ペリレン系顔料、ペリノン系顔料、ジオキサジン系顔料、キノフタロン系顔料、蛍光顔料、カーボン、及び酸化チタンからなる群より選ばれる少なくとも1種である請求項7に記載の製造方法。
本発明の水不溶性粒子の定着方法によれば、布帛に顔料等の水不溶性粒子を効率良く定着させることができる。
本発明の染色物の製造方法によれば、布帛に顔料を効率良く定着させた染色物が得られる。
本発明のカチオン化剤は、布帛に水不溶性粒子を定着させる前に、該布帛をカチオン化するために用いるカチオン化剤である。本発明のカチオン化剤は、ビニルアミン単量体に由来する構成単位(以下、「単位(a1)」という。)を有する重合体(以下、「重合体(A)」という。)からなる。「ビニルアミン単量体に由来する構成単位」とは、ビニルアミン単量体の重合により形成される重合体構造を構成する繰り返し単位を意味し、その構造は、前記ビニルアミン単量体中のビニル基に由来するエチレン基の二つの炭素が結合部位となっている分子構造であるが、これと構造が同じであれば、ビニルアミン単量体を原料とするものに制限されない。また、他の構成単位の命名についても、上記に従うものとする。
(式中、R1は、水素又はメチル基を示す)
前記の単位(a1)を有する重合体(A)は、例えば、ビニルアミド重合体(以下、「重合体(A)前駆体」という。)を加水分解やホフマン反応等の変性処理に付すことによって、その構成単位の少なくとも一部の側鎖をアミノ基に変換することによって得ることができる。より具体的には、前記の構成単位(a1)は、例えば、N-ビニルアミド化合物に由来する構成単位を有する重合体(以下、「N-ビニルアミド重合体」という。)を重合体(A)前駆体として、これを加水分解することや、アクリルアミド化合物に由来する構成単位を有する重合体(以下、「アクリルアミド重合体」という。)を重合体(A)前駆体として、これをホフマン反応に付すこと等によって、前記重合体(A)前駆体の構成単位の少なくとも一部の側鎖をアミノ基に変換することによって形成することができる。
重合体(A)は、N-ビニルアミド重合体の加水分解物であることが好ましい。すなわち、単位(a1)は、N-ビニルアミド重合体を重合体(A)前駆体として、これを加水分解することにより形成することが好ましい。
前記式(i)で表される化合物としては、例えば、N-ビニルホルムアミド、N-ビニルアセトアミド、N-ビニルプロピオン酸アミド、N-ビニル酪酸アミド等が挙げられる。
前記式(i)で表される化合物を原料単量体として用いた場合、これを重合した後、後述する加水分解処理に付すことにより、重合体側鎖としての-NHCOR基を無置換又は置換されたアミノ基(-NH2)に変換し、これにより、単位(a1)を形成することができる。
前記アクリルアミド化合物を原料単量体として用いた場合、これを重合した後、後述するホフマン反応に付すことにより、重合体側鎖としての無置換又は置換されたカルバモイル基(-CONH2)を無置換又は置換されたアミノ基(-NH2)に変換することにより、単位(a1)を形成することができる。
前記他の単量体としては、エチレン性不飽和結合を有する任意の単量体を用いることができ、例えば、(メタ)アクリル酸およびその塩、(メタ)アクリル酸エステル((メタ)アクリル酸と炭素数1~6のアルコール又はフェノールとのエステル)、(メタ)アクリロニトリル、N-ビニルピロリドン、N-ビニルカプロラクタム、酢酸ビニル等が挙げられる。また、重合体(A)の単位(a1)をN-ビニルアミド重合体の加水分解により形成する場合、前記他の単量体として前記アクリルアミド化合物を用いてもよい。但し、この場合、重合後のホフマン反応による変性は行わない。また、重合体(A)の単位(a1)をアクリルアミド重合体のホフマン反応により形成する場合、前記他の単量体として前記N-ビニルアミド化合物を用いてもよい。但し、この場合、重合後の加水分解による変性は行わない。
(式中、R2は、水素原子又はメチル基を示し、R3は、炭素数1~6のアルキル基を示す)
また、前記コモノマー単位は、アクリルアミド重合体(重合体(A)前駆体)のホフマン反応において、未反応で残存したアクリルアミド化合物に由来する構成単位であってもよい。
重合にはラジカル重合開始剤を用いることができる。ラジカル重合開始剤としては、レドックス系開始剤、アゾ系開始剤、過酸化物等が挙げられる。ラジカル重合開始剤は、1種のみを使用してもよく、2種以上を併用してもよい。また、ラジカル重合開始剤は、水溶性であっても、油溶性であってもよい。油溶性のラジカル重合開始剤を用いる場合は、水溶性の溶剤に溶解して添加する。
油溶性アゾ系開始剤としては、例えば、2、2’-アゾビスイソブチロニトリル、1、1’-アゾビス(シクロヘキサンカルボニトリル)、2、2’-アゾビス(2-メチルブチロニトリル)、2、2’-アゾビス(2-メチルプロピオネ-ト)、2、2’-アゾビス(4-メトキシ-2、4ジメチル)バレロニトリル等が挙げられる。
過酸化物としては、例えば、ペルオクソ二硫酸アンモニウムあるいはカリウム、過酸化水素、ベンゾイルペルオキサイド、ラウロイルペルオキサイド、オクタノイルペルオキサイド、サクシニックペルオキサイド、t-ブチルペルオキシ-2-エチルヘキサノエート等が挙げられる。
光重合の場合は、公知の光重合開始剤が利用できる。
レドックス系開始剤の場合、開始剤の使用量は、使用する単量体の全質量に対して、10~1,000質量ppmが好ましく、30~600質量ppmがより好ましい。
開始剤の使用量が前記下限値以上であれば、充分な重合速度が得られやすい。開始剤の使用量が前記上限値以下であれば、重合体の分子量が低くなりすぎることを抑制しやすい。
N-ビニルアミド化合物に由来する構成単位を有する重合体(A)前駆体の粘度平均分子量は、5,000~5,000,000が好ましく、10,000~4,000,000がより好ましい。粘度平均分子量は、実施例に記載の方法で測定できる。
酸または塩基の使用量は、所望する加水分解率によって異なるが、目的とする重合体(A)中のビニルアミン単量体に由来する構成単位に対し、通常0.8~2倍当量、好ましくは1~1.5倍当量である。原料単量体の種類により、加水分解反応系中にN-ビニルカルボン酸アミド基よりも加水分解され易い物質が共存する場合は、当然それを相殺する量を過剰に使用する必要がある。また、酸または塩基は、予め溶解して溶液として加水分解反応に供するのが好ましい。その場合、溶液の濃度は高い方が反応操作上好ましい。
本発明の方法において、加水分解反応は、不溶化処理を行った粉体状の重合体(A)前駆体と酸または塩基を混合し直接接触させることにより行われる。混合方法としては、特に制限されず、前記の不溶化防止処理における混合方法と同様の方法が適宜使用される。具体的には、袋に入れ振り混ぜ混合する方法、円筒、二重円錐、Y型などの容器が回転する回転容器型混合機、リボン混合機、スクリュー混合機、円盤回転型などの羽根回転型の混合機などのブレンダーを使用して回分操作で混合する方法、スクリューコンベヤーを使用して移送中の途中で酸または塩基を添加し連続的に移送しつつ混合する方法などが例示される。特に、流動又は移動中の固相状態の粉体状の重合体(A)前駆体に酸または塩基を散布する方式が好ましい。
加水分解は通常20~90℃で行われる。反応時間は温度によって異なるが、通常1分から1週間である。反応物の撹拌は反応中続ける必要はなく、酸または塩基が粉体状の重合体に吸収されれば後は放置しておいてもよい。放置し得る時間は長くても24時間である。加水分解の条件によっては酸またはアルカリが残存している場合がある。
加水分解を行った後は、中和を行ってもよく、そのままでもよい。
本発明の水不溶性粒子の定着方法は、本発明のカチオン化剤を用いて、布帛に水不溶性粒子を定着させる方法である。本発明の水不溶性粒子の定着方法は、後述するカチオン化工程と定着工程とを有する。
カチオン化工程では、本発明のカチオン化剤により布帛を処理する。
カチオン化処理の具体的な方法としては、例えば、水洗した布帛を、本発明のカチオン化剤を含む水溶液(薬液)に浸漬し、該カチオン化剤を吸収させた後に水洗する方法が挙げられる。カチオン化剤を吸収させた後、水洗、脱水等の操作を行うことで過剰分のカチオン化剤は除去される。
カチオン化処理は、連続処理により行ってもよく、バッチ処理により行ってもよい。
カチオン化剤の含有量が下限値以上であれば、水不溶性粒子の定着効率が高くなりやすい。また、カチオン化剤の含有量が上限値以下であれば、布帛の変色等の不具合が起き難くなるうえ、経済的にも有利である。
カチオン化処理の温度は、10~90℃が好ましく、20~85℃がより好ましい。
布帛の浸漬時間は、1~60分間が好ましい。
水洗の方法としては、特に限定はしないが、0.1~10L/分の水流で1~60分で行うことが好ましい。典型的な水洗方法の1例として、3.6L/分の流水で10分間洗浄することが挙げられる。
脱水の方法としては、特に限定はしないが、遠心脱水方法を用いることができ、1,000~10,000rpmで10秒~10分で行うことが好ましい。典型的な、脱水方法の1例とし、遠心脱水機で、3,000rpm、1分間脱水することが挙げられる。
また、布帛のゼータ電位(界面動電電位)は、-100~-1mVが好ましい。特に、-50~-1mVが好ましい。ここで言うゼータ電位とは、測定しようとしている布帛を浸漬している水が、20℃で伝導率が100μS/cm~7mS/cmの範囲にあるときに測定したものである。
本発明のカチオン化剤が高い効果を発揮する理由は定かではないが、カチオンポリマーとしての高い官能基密度により、ゼータ電位の低い布帛と効率良く結合をする能力を有しているためと考えられる。
定着工程では、カチオン化工程の後に、布帛に水不溶性粒子を定着させる。
定着処理の具体的な方法としては、例えば、カチオン化工程後の布帛を、水不溶性粒子を分散させた分散液に浸漬し、該水不溶性粒子を定着させた後に水洗する方法が挙げられる。
定着処理は、連続処理で行ってもよく、バッチ処理で行ってもよい。
ここで言うアゾ系顔料とは、アゾ基を有する化合物で、具体的には、Pigment Yellow14、Pigment Red57などが挙げられる。
ここで言うフタロシアニン系顔料とは、4つのフタル酸イミドが窒素原子で架橋された構造をもつ環状化合物のことであり、具体的には、Pigment Blue16、Pigment Green7などが挙げられる。
ここで言うアントラキノン系顔料とは、アントラキノンから誘導される有機顔料のことであり、具体的には、Pigment Red168、Pigment Red177などが挙げられる。
ここで言うキナクリドン系顔料とは、対称性の高い複素環顔料のことであり、具体的には、Pigment Violet19、Pigment Red122などが挙げられる。
ここで言うペリレン系顔料とは、ペリレンテトラカルボン酸二無水物の六員環を構成している酸素原子2個を脱落させた構造を有する顔料のことであり、具体的には、Pigment Red149、Pigment Red179などが挙げられる。
ここで言うペリノン系顔料とは、縮合環化合物であるペリノンであり、具体的には、Pigment Orange43などが挙げられる。
ここで言うジオキサン系顔料とは、オキサジン環を1分子当たり2個有する顔料のことであり、具体的には、Pigment Violet23、Pigment Violet37などが挙げられる。
ここで言うキノフタロン系顔料とは、キナルジンと無水フタル酸から得られる顔料のことであり、具体的には、Pigment Yellow138、Pigment Yellow177などが挙げられる。
ここで言う蛍光顔料とは、ローダミン誘導体からなる有機顔料及び希土類元素から成る無機顔料のことである。
ここで言うカーボンとは、直径3~500nmの炭素の微粒子のことであり、具体的には、Pigment Black7などが挙げられる。
ここで言う酸化チタンとは、二酸化チタンを主体とした微粒子のことであり、具体的には、Pigment White6、Pigment Yellow7などが挙げられる。
布帛の浸漬時間は、10~30分間が好ましい。
定着工程の後には、バインダー等の固着剤による公知の堅牢度向上処理を行ってもよい。バインダーの例としてはポリウレタン、ポリエステル及びポリアクリル酸エステルが挙げられる。
重合体(A)が高い効果を発揮する理由は定かではないが、カチオンポリマーとしての高い官能基密度を有し、また1級アミンがイオン結合、水素結合の他、熱により共有結合、配位結合等、多彩な結合を形成する能力を有しているためと考えられる。さらには、単位(a1)がN-ビニルカルボン酸アミドから誘導される場合は、残余のカルボン酸アミド基も水素結合の形成等によって水不溶性粒子の定着に寄与すると考えられる。
ここで言う、水不溶性粒子とは25℃の水100gに1g以下で水に分散した粒子のことであり、染料のように水溶液として布帛に直接染み込ませることができず、従来、それ自体では着色という目的上充分な量を布帛表面に付着させることができなかったものであり、本発明によるカチオン化剤により、初めて実用的な量で布帛表面に定着させて、これを染色することが可能となったものである。
本発明の染色物の製造方法は、水不溶性粒子として顔料を用いて布帛を染色して染色物を得る方法である。
本発明の染色物の製造方法によれば、本発明のカチオン化剤によりカチオン化工程を行った後に定着工程を行うため、布帛を効率良く染色できる。 顔料及び布帛としては、本発明の定着方法に関連して前記したものを使用することができる。
また、染色物の具体的製造方法としては、前記のカチオン化工程と、前記の定着工程と、を有する方法によって行うことができる。
[分子量]
重合体の粘度平均分子量を、1N食塩水中に、重合体を濃度が0.1g/dLとなるように溶解したものの還元粘度(25℃)を測定し、ハギンズの式(還元粘度=η+0.31×η2×C。ただし、Cは濃度0.1g/dl、ηは極限粘度である。)により極限粘度を導き、極限粘度式[η]=8.31×10-5×M0.76により算出した(Mは粘度平均分子量)。
脱気脱塩水700mlを70℃に昇温し、3gのアゾビスアミジノプロパン塩酸塩を添加し、窒素気流下で3時間かけてN-ビニルホルムアミド(300g)を滴下した後、1.5gのアゾビスアミジノプロパン塩酸塩を加えてさらに3時間熟成し、重合体濃度が30質量%のN-ビニルホルムアミド重合体(重合体(A)前駆体)水溶液を得た。N-ビニルホルムアミド重合体(重合体(A)前駆体)の分子量は10万であった。
残存単量体がないことを確認した後、さらにN-ビニルホルムアミドの使用量に対して1.4倍モルの水酸化ナトリウムを用いて80℃で3時間加水分解反応を行い、全構成単位に対して単位(a1)の割合が95モル%の重合体(A1)を含む、重合体濃度が12質量%の重合体水溶液-1を得た。
合成例1と同様にしてN-ビニルホルムアミド重合体(重合体(A)前駆体)水溶液を得た後、水酸化ナトリウムの使用量をN-ビニルホルムアミドの使用量の0.7倍モルに変更して合成例1と同様にして加水分解を行い、加水分解後に35%塩酸を加水分解に使用した水酸化ナトリウムの半分量で部分中和し、全構成単位に対して単位(a1)の割合が70モル%の重合体(A2)を含む、重合体濃度が21質量%の重合体水溶液-2を得た。
N-ビニルホルムアミドを30質量%となるように脱気脱塩水に溶かし、0℃に冷却し、t-ブチルハイドロパーオキシド300質量ppm、重亜硫酸ソーダ300質量ppm、アゾビスアミジノプロパン塩酸塩1,000質量ppmを添加して、重合を行った。6時間後、分子量200万のN-ビニルホルムアミドを30質量%含むゲル状水溶液を得た。得られたゲルを一部採取して粉砕し、水で希釈してゲルを5質量%含む水溶液とした。さらに、48%水酸化ナトリウム水溶液をN-ビニルホルムアミドに対して0.4倍モルを添加し、70℃4時間加水分解反応を行った。その後、35%塩酸を加水分解に使用した水酸化ナトリウムの半分量で部分中和し、全構成単位に対して単位(a1)(塩酸塩の単位)の割合が40モル%の重合体(A3)を含む、重合体濃度が4質量%の重合体水溶液-3を得た。
布帛として天竺織り生成り木綿生地を用いた。布帛(生地 ゼータ電位-15.7mV)を、80℃で5分湯洗いした後、3,000rpmで1分間遠心脱水した。その後、25℃で12時間乾燥させた。
合成例1で得た重合体水溶液-1を用いて、生地質量に対して純分で5質量%の重合体(A1)を、生地量に対して体積比率で30倍の水に溶かして薬液を調製した。該薬液の温度を60±2℃とし、脱水した生地を投入して、20分間浸漬処理した。処理した生地を10分水洗いし、その後、3,000rpmで1分間遠心脱水した。
次いで、生地質量に対して5質量%の顔料(大日精化工業(株)製 有機顔料Navy Blue FL2R conc)を、生地に対して体積比率で30倍の水に分散させた。得られた分散液の温度を60℃±2℃とし、20分間生地を浸漬して顔料を吸尽させた。その後、10分間水洗し、3,000rpmで1分間遠心脱水した後、25℃で12時間乾燥を行った。
重合体水溶液-1の代わりに重合体水溶液-2(実施例2)、重合体水溶液-3(実施例3)を用いた以外は、実施例1と同様にして顔料を定着させた。
重合体水溶液-1の代わりに、カチオン化剤としてEffector-DS2C(大日精化工業(株)製ジメチルアミノエチルメタクリレートメチルクロライド4級塩ホモポリマー)を8質量%含む水溶液を用いた以外は、実施例1と同様にして顔料を定着させた。
染着性は、目視により以下のように判定した。
◎:特に濃く染まっている。
○:充分な濃さで染まっている。
△:薄く染まっている。
×:ほとんど染まっていない
実施例1~3および比較例1の評価結果を表1に示す。
顔料として、大日精化工業(株)製 有機顔料BlackFLTR concを用いた以外は、実施例1~3、比較例1と同様にして顔料を定着させた。
実施例4~6および比較例2の評価結果を表2に示す。
顔料として、大日精化工業(株)製 無機顔料 R-850(酸化チタン)を用いた以外は、実施例1、比較例1と同様にして顔料を定着させた。
実施例7および比較例3の評価結果を表3に示す。
生地として極細繊維からなるスエード調の人工皮革(ゼータ電位-45.1mV)を用い、顔料として大日精化工業(株)製有機顔料TC Brown FD、Black FLTR concを用いた以外は、実施例1~3、比較例1と同様にして顔料を定着させた。
実施例8~10および比較例4の評価結果を表4に示す。
生地としてポリエステル生地(ゼータ電位-20.8mV)を用い、顔料として大日精化工業(株)製有機顔料 Black FLTR concを用いた以外は、実施例1、比較例1と同様にして顔料を定着させた。
実施例11および比較例5の評価結果を表5に示す。
生地としてアクリル繊維(ゼータ電位-26.4mV)を用い、顔料として大日精化工業(株)製有機顔料 Black FLTR concを用いた以外は、実施例1、比較例1と同様にして顔料を定着させた。
実施例12および比較例6の評価結果を表6に示す。
生地としてアセテート繊維(ゼータ電位-3.7mV)を用い、顔料として大日精化工業(株)製有機顔料 Black FLTR concを用いた以外は、実施例1、比較例1と同様にして顔料を定着させた。
実施例13および比較例7の評価結果を表7に示す。
生地としてパラ系アラミド織布(ゼータ電位-77.0mV)を用い、顔料として大日精化工業(株)製有機顔料 Black FLTR concを用いた以外は、実施例1、比較例1と同様にして顔料を定着させた。
実施例14および比較例8の評価結果を表8に示す。
特にゼータ電位が-50~-1mVの範囲にあるスエード調の人工皮革、ポリエステル繊維生地、アクリル繊維生地及びアセテート繊維生地は、顔料の定着効率が高かった。
Claims (8)
- 布帛に、請求項1または2に記載のカチオン化剤を付着させることにより、布帛をカチオン化するカチオン化工程と、前記カチオン化工程の後に前記布帛に水不溶性粒子を接触させることにより、布帛に水不溶性粒子を定着させる定着工程と、を有する、水不溶性粒子の定着方法。
- 前記布帛が、木綿、アクリル繊維、ポリエステル繊維、アセテート繊維及びアラミド繊維からなる群より選ばれる少なくとも1種の繊維により形成される布帛である、請求項3に記載の水不溶性粒子の定着方法。
- 前記布帛が、極細繊維からなるスエード調布帛である、請求項3または4に記載の水不溶性粒子の定着方法。
- 前記布帛が-100~-1mVのゼータ電位を有する請求項3~5のいずれか一項に記載の水不溶性粒子の定着方法。
- 布帛に、請求項1または2に記載のカチオン化剤を付着させることにより、布帛をカチオン化するカチオン化工程と、前記カチオン化工程の後に前記布帛に顔料を接触させることにより、布帛に顔料を定着させて布帛を染色する染色工程と、を有する染色物の製造方法。
- 前記顔料がアゾ系顔料、フタロシアニン系顔料、アンスラキノン系顔料、キナクリドン系顔料、ペリレン系顔料、ペリノン系顔料、ジオキサジン系顔料、キノフタロン系顔料、蛍光顔料、カーボン、及び酸化チタンからなる群より選ばれる少なくとも1種である請求項7に記載の製造方法。
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EP3696317A1 (en) * | 2019-02-15 | 2020-08-19 | Lenzing Aktiengesellschaft | Spun-dyed fiber and method for its manufacture |
US11008701B1 (en) | 2019-12-31 | 2021-05-18 | Industrial Technology Research Institute | Dyeing method using bio-dye and cationic modification agent utilized thereof |
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