CN104775309B - Fiber process resin combination, printed and dyed using its pigment agent and cloth and silk - Google Patents
Fiber process resin combination, printed and dyed using its pigment agent and cloth and silk Download PDFInfo
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- CN104775309B CN104775309B CN201510018627.4A CN201510018627A CN104775309B CN 104775309 B CN104775309 B CN 104775309B CN 201510018627 A CN201510018627 A CN 201510018627A CN 104775309 B CN104775309 B CN 104775309B
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Abstract
The present invention provides a kind of fiber process resin combination, pigment printing and dyeing agent and the cloth and silk of the fiber process resin combination are used, the fiber process resin combination is characterized in that, contain polymer (A) obtained from polymerizeing polymerizable monomer, the polymerizable monomer includes the polymerizable monomer (a1) with carboxyl, 0.1~5 mass % of polymerizable monomer (a2) with epoxy group and 0.1~3.5 mass % of polymerizable monomer (a3) with hydrolyzable silyl group, the range that the mass ratio [(a2)/(a3)] of the polymerizable monomer (a2) and the polymerizable monomer (a3) are 10/90~90/10.The fiber process resin combination will not generate harmful formaldehyde, it can be used in pigment printing and dyeing agent, excellent feel can be assigned to using the cloth and silk after pigment printing and dyeing agent printing and dyeing, higher washing fastness and rub resistance can be assigned to printing and dyeing portion, enhanced water resistance can also be assigned to the dyestuff weight color portion after repeatedly printed and dyed on cloth and silk pigment printing and dyeing agent and dye printing and dyeing agent.
Description
Technical field
The present invention relates to fiber process resin, the pigment of the fiber process resin is used to print and dye agent and cloth and silk, institute
Harmful formaldehyde will not be generated by stating fiber process resin, can be used in pigment printing and dyeing agent, and can print and dye to the utilization pigment agent
Cloth and silk after printing and dyeing assigns excellent feel, can assign higher washing fastness and rub resistance to printing and dyeing portion, can also be right
Repeatedly printed and dyed on cloth and silk the pigment printing and dyeing agent and dye printing and dyeing agent after dyestuff weight color portion assign enhanced water resistance.
Background technique
In the past, in order to assign washing fastness, rub resistance etc. to the adhesive resin of pigment printing and dyeing agent, use is used
The polymer of the polymerizable monomer with reactive functional groups of N- methylol (methyl) acrylamide etc.Polymer tool
There are reactive functional groups, therefore, by the cross-linking reaction of the functional group, higher washing fastness and rub resistance can be assigned,
But there are harmful formaldehyde such problems is generated when the cross-linking reaction.
As the method for solving above-mentioned Formaldehyde, proposes and utilize the object other than N- methylol (methyl) acrylamide
Matter carries out the scheme of cross-linking reaction, for example, having attempted the crosslinking agents such as Shi Yong oxazoline compound, blocked isocyanate compounds
Scheme is (referring for example to patent document 1.).But even if in the case where having used the pigment printing and dyeing agent containing these crosslinking agents,
Also excellent feel is assigned to cloth and silk and assigns higher washing fastness, rub resistance etc. to printing and dyeing portion with being unable to fully.
In addition, for previous pigment prints and dyes agent, the agent of printing dye printing and dyeing on it again after printing and dyeing on cloth and silk
In the case where or in the case where printing and dyeing pigment printing and dyeing agent on it again after printing dye prints and dyes agent, there is also pigment and
The printing and dyeing portion (hereinafter referred to as " dyestuff weight color portion " of dyestuff overlapping.) water resistance (washing fastness) reduce the problem of.
It is therefore desirable to which following fiber process resin combinations, will not generate harmful formaldehyde, can be used in
Pigment printing and dyeing agent can assign excellent feel to using the cloth and silk after pigment printing and dyeing agent printing and dyeing, can assign to printing and dyeing portion
Higher washing fastness and rub resistance, can also be to pigment printing and dyeing agent and the dye printing and dyeing agent of overlappingly having printed and dyed on cloth and silk
Dyestuff weight color portion afterwards assigns higher water resistance.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2009-150010 bulletin
Summary of the invention
Problems to be solved by the invention
Project to be solved by this invention is to provide a kind of fiber process resin combination, has used the fiber process
Harmful formaldehyde, energy will not be generated with the pigment printing and dyeing agent of resin combination and cloth and silk, the fiber process resin combination
It is enough in pigment printing and dyeing agent, excellent feel can be assigned to using the cloth and silk after pigment printing and dyeing agent printing and dyeing, it can be to printing and dyeing
Portion assigns higher washing fastness and rub resistance, can also be to pigment printing and dyeing agent and the dyestuff of overlappingly having printed and dyed on cloth and silk
Dyestuff weight color portion after printing and dyeing agent assigns higher water resistance.
Means for solving the problems
The inventors of the present invention are studied in order to solve the above problems and in depth, as a result, it has been found that：It is following by using making
Polymer obtained from polymerizable monomer polymerization, is able to solve the above subject, thereby completing the present invention, the polymerizable monomer packet
Containing the polymerizable monomer with carboxyl, and includes the polymerizable monomer with epoxy group of specific quantity and there is water-disintegrable monosilane
The polymerizable monomer of base.
That is, the present invention provides a kind of fiber process resin combination, printed and dyed using its pigment agent and cloth and silk, the fibre
Dimension processing resin combination is characterized in that, contains polymer (A) obtained from polymerizeing polymerizable monomer, the polymerism
Monomer is comprising the polymerizable monomer (a1) with carboxyl, the polymerizable monomer (a2) with epoxy group and has water-disintegrable monosilane
The polymerizable monomer (a3) of base, wherein the polymerism in the polymerizable monomer total amount of the raw material as the polymer (A)
The ratio of monomer (a2) is the range of 0.1~5 mass %, and the ratio of the polymerizable monomer (a3) is 0.1~3.5 mass %'s
Range, the mass ratio [(a2)/(a3)] of the polymerizable monomer (a2) and the polymerizable monomer (a3) are 10/90~90/10
Range.
Invention effect
Having used the pigment of fiber process resin combination of the invention to print and dye agent will not on cloth and silk even if printing and dyeing
The original feel of cloth and silk is damaged, and the washing fastness in printing and dyeing portion, rub resistance etc. are excellent, even if after printing and dyeing are on cloth and silk again
Printing dye printing and dyeing agent on it or the agent even if pigment of printing and dyeing on it again after printing dye prints and dyes agent is printed and dyed, due to
The excellent water resistance in dyestuff weight color portion, can also obtain the dyeing cloth that the colour fading in natural feel and washing etc. is inhibited
Silks.In addition, the pigment of fiber process of the invention resin combination has been used to print and dye agent by being used in combination with dye printing and dyeing agent
And various printing and dyeing can be implemented to cloth and silk with not restricted in design.
Specific embodiment
Fiber process of the invention with resin combination containing make polymerizable monomer polymerize obtained from polymer (A)
Fiber process resin combination, the polymerizable monomer include polymerizable monomer (a1) with carboxyl, with epoxy group
Polymerizable monomer (a2) and polymerizable monomer (a3) with hydrolyzable silyl group, wherein the original as the polymer (A)
The ratio of the polymerizable monomer (a2) in the polymerizable monomer total amount of material is the range of 0.1~5 mass %, the polymerism
The ratio of monomer (a3) is the range of 0.1~3.5 mass %, the polymerizable monomer (a2) and the polymerizable monomer (a3's)
The range that mass ratio [(a2)/(a3)] is 10/90~90/10.
The polymerizable monomer (a1) is the polymerizable monomer with carboxyl, and such as (methyl) acrylic acid, clothing can be used
Health acid, crotonic acid, fumaric acid, maleic anhydride, citraconic acid etc..
The polymerizable monomer (a2) is the polymerizable monomer with epoxy group, and such as (methyl) acrylic acid contracting can be used
Water glyceride, glycidyl allyl ether etc..
The polymerizable monomer (a3) is the polymerizable monomer with hydrolyzable silyl group, and such as vinyl can be used
Methyl dimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, (the 2- methoxyl group ethoxy of vinyl three
Base) vinyl silane compounds such as silane；3 (methyl) acryloxypropyl trimethoxy silanes, 3- (methyl) acryloyl-oxy third
Ylmethyl dimethoxysilane, 3- (methyl) acryloxypropyl triethoxysilane, 3- (methyl) acryloxypropyl methyl
Diethoxy silane etc. (methyl) acryloyloxyalkyl silane compound etc..These polymerizable monomers (a3) can be used a kind,
Two or more kinds may be used.
It should be noted that in the present invention, " (methyl) acrylic acid " be a side in methacrylic acid and acrylic acid or
Both sides, " (methyl) acrylate " are one or both in methacrylate and acrylate, " (methyl) acryloyl
Base " refers to one or both in methylacryloyl and acryloyl group.
As the above-mentioned polymerizable monomer (a1) with carboxyl, the polymerizable monomer (a2) with epoxy group and there is water
The polymerizable monomer of the raw material that can be used as above-mentioned polymer (A) other than the polymerizable monomer (a3) of solution property silicyl
(a4), (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) propylene can be enumerated
(methyl) propylene such as the secondary butyl ester of acid, (methyl) tert-butyl acrylate, (methyl) isopropyl acrylate, (methyl) isobutyl acrylate
Acid alkyl ester；(methyl) benzyl acrylate etc. aromatic series (methyl) acrylate；Trimethylsiloxy ethyl (methyl) third
The silane such as olefin(e) acid ester system (methyl) acrylate；Methoxy poly (ethylene glycol) list (methyl) acrylate, methoxyl group polypropylene glycol list
(methyl) acrylate etc. alkyl polyalkylene glycols list (methyl) acrylate；Perfluor alkyl ethide (methyl) acrylate etc.
Fluorine system (methyl) acrylate；Styrene, styrene derivative are (to dimetylsilyl styrene, (to ethenylphenyl)
Methyl sulfide, to hexin base styrene, to methoxy styrene, to t-butyldimethylsilyloxy base styrene, o-methyl-benzene
Ethylene, p-methylstyrene, p-tert-butylstyrene, α-methylstyrene etc.), vinyl naphthalene, vinyl anthracene, 1,1- diphenyl
The aromatic ethenyl compounds such as ethylene；(methyl) glycidyl acrylate, epoxy (methyl) acrylate, ethylene glycol two
(methyl) acrylate, diethylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylene
Glycol four (methyl) acrylate, bis- propylene acetoxypropane of 2- hydroxyl -1,3-, 2,2- bis- [4- (acryloyl-oxy methoxyl group) phenyl]
Bis- [4- (acryl-oyloxyethoxy) phenyl] propane of propane, 2,2-, dicyclopentenyl (methyl) acrylate tricyclodecyl (first
Base) (methyl) acrylic acid such as acrylate, three (acrylyl oxy-ethyl) isocyanuric acid esters, carbamate (methyl) acrylate
Ester compounds；Dimethyl aminoethyl (methyl) acrylate, diethylamino ethyl (methyl) acrylate, dimethylamino
Propyl (methyl) acrylate etc. has (methyl) acrylate of alkyl amino；(methyl) acrylamide, N, N- dimethyl propylene
The acrylamide compounds such as acrylamide, N-isopropylacrylamide, Diacetone Acrylamide；2- vinylpyridine, 4- vinylpyridine
The vinylpyridine acridine compounds such as pyridine, naphthylethen yl pyridines；1,3-butadiene, 2- methyl-1,3- butadiene, 2,3- dimethyl-
1,3-butadiene, 1,3-pentadiene, 1,3- hexadiene, 1,3- cyclohexadiene equiconjugate diene etc..These polymerizable monomers (a4)
It can be used a kind, also two or more kinds may be used.
Above-mentioned polymerism in above-mentioned polymerizable monomer (a1)~(a4) total amount of raw material as above-mentioned polymer (A)
The ratio of monomer (a2) is the range of 0.1~5 mass %, but from can be to having been used fiber process of the invention resin group
Cloth and silk print and dye of pigment printing and dyeing agent for closing object assigns superior feel, can also be higher washable to the imparting of printing and dyeing portion
It sets out in terms of washing property and rub resistance, preferably the range of 0.2~3.5 mass %, the range of more preferable 0.3~3 mass %.
Above-mentioned polymerism in above-mentioned polymerizable monomer (a1)~(a4) total amount of raw material as above-mentioned polymer (A)
The ratio of monomer (a3) is the range of 0.1~3.5 mass %, but from can be to through having used fiber process resin of the invention
Cloth and silk print and dye of pigment printing and dyeing agent of composition assigns superior feel, can also be higher resistance to the imparting of printing and dyeing portion
It sets out in terms of washing performance and rub resistance, preferably the range of 0.2~2.5 mass %, the range of more preferable 0.3~2 mass %.
In addition, from can to fiber process of the invention with resin combination assign into water it is more good dispersibility,
It sets out in terms of higher washing fastness and rub resistance can also being assigned to printing and dyeing portion, the raw material as above-mentioned polymer (A)
Above-mentioned polymerizable monomer (a1)~(a4) total amount in above-mentioned polymerizable monomer (a1) ratio preferably 0.5~5 mass %
Range, the range of more preferable 1~4 mass %, the range of further preferred 1.5~3 mass %.
In addition, the mass ratio [(a2)/(a3)] of above-mentioned polymerizable monomer (a2) and above-mentioned polymerizable monomer (a3) are 10/90
~90/10 range, but from can to used fiber process of the invention resin combination pigment print and dye agent carry out
The aspect that the cloth and silk of printing and dyeing assigns superior feel, can also assign higher washing fastness and rub resistance to printing and dyeing portion
It sets out, preferably 15/85~85/15 range.
As the manufacturing method of fiber process resin combination of the invention, for example, can be poly- using well known lotion
It is legal.
Pigment printing and dyeing agent of the invention contains fiber process resin combination and pigment (B) of the invention.As described
Pigment (B), is not particularly limited, and organic pigment or inorganic pigment can be used.As the organic pigment, example can be enumerated
Such as：C lake red CAN'T, permanent red, bright fuchsin, calcium color lake, naphthols AS is red, benzimidazolone yellow, dual-azo yellow HR, pyrazolone is red, is condensed
The azo pigments such as azophosphine, condensation azophloxine, condensation azo palm fibre, nickel azophosphine；Phthalocyanine blue, chlorination phthalocyanine green, brominated phthalocyanine are green
Equal phthalocyanine colors；Anthraquinone Huang, bi-anthraquinone base red (Dianthraquinonyl Red), indanthrone indigo plant, thioindigo bordeaux, pyrene ketone orange
(Perinone Orange), scarlet, red, purplish red, quinacridone is red, quinacridone magenta, quinacridone are scarlet, two
Oxazine is purple, isoindolinone is yellow, quinophthalone yellow (Quinophthalone Yellow), isoindoline Huang, pyrrolo-pyrrole-dione
Fused polycycles pigment such as red etc..
In addition, as above-mentioned inorganic pigment, it can be cited for example that：Zinc oxide, titanium oxide, iron oxide red, iron oxide black, chromium oxide
Equal metal oxide pigments；The oxidation of the metal composites such as titan yellow, zinc-cologne earth, cobalt titanate green, cobalt green, cobalt blue, copper-chrome black, copper-iron oxide black
Object pigment；The chromic acid pigment such as chrome yellow, molybdate orange；Prussian blue equal ferrocyanides pigment；Cadmium yellow, cadmium red, zinc sulphide, barium sulphide etc.
Sulfide pigment；Ultramarine, calcium carbonate, cobalt violet, yellow iron oxide, carbon black etc..These organic pigments and inorganic pigment can be used 1
Kind, also two or more kinds may be used.
The use level of above-mentioned pigment (B) in pigment printing and dyeing agent of the invention is different according to required tone, usually exists
Pigment is printed and dyed the preferred range of 0.05~5 mass % in agent.In addition, cooperating above-mentioned pigment in pigment printing and dyeing agent of the invention
(B) when, preferably dispersed in water using pigment dispersing agent etc. in advance, cooperated again after forming dispersible pigment dispersion.
For pigment of the invention prints and dyes agent, adapted to assign viscosity corresponding with (Print) mode of printing and dyeing etc.
Property, printing and dyeing paste etc. can be cooperated.Printing and dyeing paste is to make pigment printing and dyeing agent thickening, assign the material to the printing adaptability of silk-screen printing etc.
Material, it can be cited for example that by sodium carboxymethylcellulose, hydroxyethyl cellulose, propoxyl group cellulose, sodium alginate, alginic acid ester,
Substance obtained by polycarboxylate etc. is dissolved or dispersed in water.
In addition to above-mentioned substance, the stones such as pH adjusting agents, the Mineral spirits such as ammonium hydroxide can be cooperated in pigment of the invention printing and dyeing agent
Oily series solvent, thickener, crosslinking agent, antioxidant, ultraviolet absorbing agent, pigment dispersing agent, water repellent agent, levelling agent, defoaming agent
Equal additives.
As the method by pigment printing and dyeing agent printing and dyeing of the invention on cloth and silk, can enumerate for example：Using roller dyeing machine, put down
Silk screen, rotary screen dyeing machine etc. and the side that silk-screen printing is carried out using the scraper plate of rubber, polyurethane resin etc. (squeegee)
Method.In addition, silk screen used in silk-screen printing it is usually used be 60~300 mesh silk screen.After printing and dyeing, at 100~150 DEG C
Drying, the heat treatment procedure for carrying out 1~5 minute carry out fixation of the pigment printing and dyeing agent on cloth and silk.
In addition, after by pigment printing and dyeing agent printing and dyeing to cloth and silk of the invention in the case where printing dye printing and dyeing agent, it can
With using after by pigment printing and dyeing agent printing and dyeing to cloth and silk of the invention, drying is primary, then the side of printing dye printing and dyeing agent
Method (Wet on Dry mode) can also use after pigment printing and dyeing agent of the invention is printed and dyed onto cloth and silk, what is do not dried
In the case of with regard to printing dye printing and dyeing agent method (Wet on Wet mode).
It prints and dyes the method on cloth and silk as by pigment printing and dyeing agent of the invention, it, can be in addition to above-mentioned silk-screen printing
Using gravure coating process, rolling method, comma rubbing method, air knife coating method, kiss-coating method, wire rod rubbing method, flow coat method etc.
Various printing processes.Further, it is also possible to which pigment of the invention is printed by dipping (plugging), spraying method, ink-jet mode etc.
Stain is coated on cloth and silk.
【Embodiment】
Hereinafter, the present invention is specifically described by Examples and Comparative Examples.
(synthesis example 1：The synthesis of polymer (A-1))
By n-butyl acrylate (hereinafter referred to as " BA ".) 652 mass parts, methyl methacrylate (hereinafter referred to as " MMA ".)
92 mass parts, styrene (hereinafter referred to as " St ".) 140 mass parts, acrylic acid (hereinafter referred to as " AA ".) 20 mass parts, methyl-prop
2 hydroxyl ethyl ester of olefin(e) acid (hereinafter referred to as " HEMA ".) 12 mass parts, glycidyl methacrylate (hereinafter referred to as " GMA ".) 12 matter
Measure part, vinyltriethoxysilane (hereinafter referred to as " VSi ".) 4 mass parts, 400 mass parts of water and non-ionic emulsifier
The mixing of (Di-ichi Kogyo Seiyaku Co., Ltd.'s system " Noigen EA-207D ", the distyrenated phenyl ether of polyoxyethylene) 10 mass parts
Afterwards, it is emulsified using homogenizer (Tokushu Kika Kogyo K.K's system " TK HomoDisper ") and prepares monomer emulsion.
Then, 500 mass parts of water, Bian are added in the flask for being equipped with blender, nitrogen ingress pipe and reflux condenser
It is stirred side under nitrogen atmosphere and is warming up to 50 DEG C, then by ammonium persulfate (hereinafter referred to as " APS ".) 2 mass parts and burnt sulfurous
Sour sodium (hereinafter referred to as " SMS ".) 2 mass parts are added in flask and are dissolved.Then, the monomer prepared among the above is emulsified
Object, 5 mass %APS aqueous solution, 40 mass parts and 5 mass %SMS aqueous solution, 40 mass parts were added drop-wise in flask with 3 hours.It needs
It is noted that the temperature in the flask in the dropwise addition is controlled at 50~60 DEG C.After completion of dropwise addition, in 60 DEG C of further reactions 1
Hour, obtain polymer (A-1).It is then cooled to which 25 mass % ammonium hydroxide, 7 mass parts are added and are neutralized, with resin after room temperature
The mode that component reaches 45 mass % is added water and equably mixes, and obtains the resin aqueous emulsion of polymer (A-1).
(synthesis example 2~8：Polymer (A-2)~(A-8) synthesis)
It other than using raw material shown in following tables 1, is carried out similarly with synthesis example 1, obtains polymer (A-2)
The resin aqueous emulsion of~(A-8).
It should be noted that polymer (A-1)~(A-8) resin aqueous emulsion can obtained in above-mentioned synthesis example 1~8
To be directly used as fiber process resin combination of the invention.
(compare synthesis example 1~8：Polymer (RA-1)~(RA-8) synthesis)
It other than using raw material shown in following tables 2, is carried out similarly with synthesis example 1, obtains comparing poly-
Close the resin aqueous emulsion of object (RA-1)~(RA-8).
[table 1]
[table 2]
(preparation example 1：The preparation of Mineral spirits lotion)
By Mineral spirits (ExxonMobil corporation " EXXSOL D40 ") 60 mass parts, emulsifing thickener (Dainippon Ink Chemicals
Make " RYUDYE-W REDUCER CONC 720ENF ") 5 mass parts and 35 mass parts of water mixing, use homogenizer (special machine
Industrial Co., Ltd's system " TK HomoMixer ") it is emulsified, obtain turpentine fat liquor.
(embodiment 1：The preparation of pigment printing and dyeing agent (1))
Using dispersator by resin aqueous emulsion (45 matter of resin Composition of polymer obtained in synthesis example 1 (A-1)
Measure %) 30 mass parts (being 13.5 mass parts as resin), 5 mass parts of ethylene glycol, turpentine fat liquor 60 obtained in preparation example 1
Mass parts, thickener (Dainippon Ink Chemicals's system " RYUDYE-W NT CONC 117 ") 0.5 matter of 2 mass parts and 25 mass % ammonium hydroxide
Amount part equably mixes, and further uses dispersator for black pigment dispersion liquid (Dainippon Ink Chemicals system " DEXCEL
BLACK NT-900 ", 30 mass % of pigment component) 5 mass parts equably mix, obtain pigment printing and dyeing agent (1).
(embodiment 2~8：The preparation of pigment printing and dyeing agent (2)~(8))
Instead of the resin aqueous emulsion (45 mass % of resin Composition) of polymer used in embodiment 1 (A-1), and distinguish
Using polymer obtained in synthesis example 2~8 (A-2)~(A-8), in addition to this, carries out similarly to Example 1, obtain face
Material printing and dyeing agent (2)~(8).
(comparative example 1~8：The preparation of pigment printing and dyeing agent (R1)~(R8))
Instead of the resin aqueous emulsion (45 mass % of resin Composition) of polymer used in embodiment 1 (A-1), and distinguish
Using polymer obtained in synthesis example 1~8 (RA-1)~(RA-8) is compared, in addition to this, carry out similarly to Example 1,
Obtain the pigment compared printing and dyeing agent (R1)~(R8).
(production that cloth and silk is used in evaluation)
The silk of rectangular shape using automatic silk screen dyeing machine (TsujiJing Ran machine Industrial Co., Ltd system) and using 135 mesh
Net respectively prints printing and dyeing agent (1)~(8) of pigment obtained in the above embodiments 1~8 and comparative example 1~8 and (R1)~(R8)
Contaminate mono- De of cotton dimity (Cotton Block ロ of B4 size) on.Then, right with Pad-Dryer (TsujiJing Ran machine Industrial Co., Ltd system)
Cotton dimity after printing and dyeing carries out the drying of 100 DEG C, 1 minute, the heat treatment of 150 DEG C, 2 minutes is then carried out, to be commented
Valence cloth and silk.
(evaluation of feel)
By touch it is above-mentioned obtained in evaluation cloth and silk, evaluated according to standard below.
○：The soft sense of touch of the boundary line of the printing and dyeing face of being not felt by and cloth.
△：Slightly experience the sense of touch of the degree of the boundary line of printing and dyeing face and cloth.
×：The hard sense of touch of the boundary line of printing and dyeing face and cloth can be experienced.
(evaluation of washing fastness)
For evaluation cloth and silk obtained in above-mentioned, according to JIS L 0844：2005 A-4 method repeats 30 examinations
After testing, according to JIS L 0801：2004 criterion that change is utilized and fades with the visual sense method of the progressive series of greys, with 1 grade~5 grades
To determine grade.It should be noted that 1 grade, to fade at most, closer to 5 grades, then fades fewer in grade.
(evaluation of rub resistance)
For evaluation cloth and silk obtained in above-mentioned, according to JIS L 0849：2004, it is tried using vibration shape colorfastness to rubbing is learned
Machine is tested, the test of dry type and wet type is carried out, then according to JIS L 0801：2004 view for having used change to fade with the progressive series of greys
The criterion of sense method determines grade with 1 grade~5 grades.It should be noted that 1 grade most to fade, closer to 5 in grade
Grade, then fade fewer.
(preparation example 2：The preparation of dye printing and dyeing agent)
Using dispersator by 10 mass parts of water, 4 mass % sodium alginate aqueous solution, 20 mass parts, 6 mass % carboxylic first
40 mass parts of turpentine fat liquor, 2 mass parts of sodium bicarbonate, urea obtained in 20 mass parts of base cellulose aqueous solution, preparation example 1
10 mass parts and dyestuff (Nippon Kayaku K. K's system " Kayacion Red P-BN Liquid33 " or " Kayacion
Blue P-NFB Liquid50 ") 5 mass parts equably mix, it obtains for dyestuff and with the dye printing and dyeing agent of processing.
(through dyestuff and with processing after evaluation cloth and silk production)
Using automatic silk screen dyeing machine (TsujiJing Ran machine Industrial Co., Ltd system), the silk of the rectangular shape of 135 mesh is utilized
Net arrives printing and dyeing agent (1)~(8) of pigment obtained in the above embodiments 1~8 and comparative example 1~8 and (R1)~(R8) printing and dyeing
After on the cotton dimity of B4 size, next, dye printing and dyeing agent obtained in preparation example 2 is continuous in the same manner as pigment printing and dyeing agent
Printing and dyeing are twice.Then, 100 DEG C are carried out, after drying in 1 minute with Pad-Dryer (TsujiJing Ran machine Industrial Co., Ltd system), carried out
100 DEG C, 8 minutes vaporization process, make dyestuff color development.Then, 10 minutes are washed with 80 DEG C of warm water to rinse the dye that do not catch
After material, its natural drying is made to obtain the evaluation cloth and silk after dyestuff weight color processing.
(evaluation of dyestuff weight color processing cloth and silk)
For the evaluation cloth and silk after dyestuff obtained above weight color processing, in the same manner as the evaluation of above-mentioned washing fastness
It is tested, the water resistance in evaluation dyestuff weight color portion.
Used the printing and dyeing of pigment obtained in the above embodiments 1~8 and comparative example 1~8 agent (1)~(8) and (R1)~
(R8) evaluation result is shown in table 3 and table 4.
[table 3]
| Table 3 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Pigment printing and dyeing agent | (1) | (2) | (3) | (4) | (5) | (6) | (7) | (8) |
| Used polymer | (A-1) | (A-2) | (A-3) | (A-4) | (A-5) | (A-6) | (A-7) | (A-8) |
| Feel | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Washing fastness | 4 grades | 4 grades | 4 grades | 4 grades | 4 grades | 4 grades | 4 grades | 4 grades |
| Rub resistance (dry type) | 4 grades | 4 grades | 4 Grade | 4 grades | 4 grades | 4 grades | 4 grades | 4 grades |
| Rub resistance (wet type) | 3 grades | 3 grades | 3 Grade | 3 grades | 3 grades | 3 grades | 3 grades | 3 grades |
| The water resistance in dyestuff weight color portion | 4 grades | 4 grades | 4 Grade | 4 grades | 4 grades | 4 grades | 4 grades | 4 grades |
[table 4]
| Table 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 |
| Pigment printing and dyeing agent | (R1) | (R2) | (R3) | (R4) | (R5) | (R6) | (R7) | (R8) |
| Used polymer | (RA-1) | (RA-2) | (RA-3) | (RA-4) | (RA-5) | (RA-6) | (RA-7) | (RA-8) |
| Feel | ○ | ○ | △ | △ | △ | △ | △ | △ |
| Washing fastness | 2 grades | 3 grades | 3 grades | 3 grades | 3 grades | 3 grades | 3 grades | 3 grades |
| Rub resistance (dry type) | 3 grades | 3 grades | 3 grades | 3 grades | 3 grades | 3 grades | 3 grades | 3 grades |
| Rub resistance (wet type) | 2 grades | 2 grades | 2 grades | 2 grades | 2 grades | 2 grades | 2 grades | 2 grades |
| The water resistance in dyestuff weight color portion | 2 grades | 2 grades | 3 grades | 3 grades | 3 grades | 3 grades | 3 grades | 3 grades |
Evaluation result as shown in Table 1 can be confirmed：Through having used fiber process resin combination of the invention
The cloth and silk that pigment printing and dyeing agent is printed and dyed will not damage the original feel of cloth and silk, and washing fastness, rub resistance are excellent, and will
Dye printing and dyeing agent repeatedly print and dye after the water resistance of part (dyestuff weight color portion) also there is no problem.
On the other hand, comparative example 1 is the pigment containing the polymer that the polymerizable monomer (a2) with epoxy group is not used
The example of printing and dyeing agent, can be confirmed：Compared with pigment of the invention prints and dyes agent, washing fastness, rub resistance and dyestuff weight color
The water resistance in portion is deteriorated.
Comparative example 2 is the pigment print containing the polymer that the polymerizable monomer (a3) with hydrolyzable silyl group is not used
The example of stain, can be confirmed：Compared with pigment of the invention prints and dyes agent, washing fastness, rub resistance and dyestuff weight color portion
Water resistance be deteriorated.
Comparative example 3 be containing with epoxy group polymerizable monomer (a2) ratio be more than as the upper limit 5 mass % and
Polymerizable monomer (a2) and the mass ratio of the polymerizable monomer (a3) with hydrolyzable silyl group with epoxy group are also being advised
The example of the pigment printing and dyeing agent of polymer outside fixed range, can be confirmed：Compared with pigment of the invention prints and dyes agent, damage
The water resistance of cloth and silk original feel, washing fastness, rub resistance and dyestuff weight color portion is deteriorated.
Comparative example 4 is that the ratio containing the polymerizable monomer (a3) with hydrolyzable silyl group is more than as the upper limit
3.5 mass % and the polymerizable monomer (a2) with epoxy group and the polymerizable monomer (a3) with hydrolyzable silyl group
Mass ratio also the polymer outside defined range pigment printing and dyeing agent example, can be confirmed：It is printed with pigment of the invention
Stain is compared, and the original feel of cloth and silk is compromised, and the water resistance of washing fastness, rub resistance and dyestuff weight color portion is deteriorated.
Although comparative example 5 is to polymerize containing the polymerizable monomer (a2) with epoxy group with hydrolyzable silyl group
Property monomer (a3) mass ratio within the limits prescribed but the ratio of the polymerizable monomer (a2) with epoxy group is more than as upper
The example of the pigment printing and dyeing agent of the polymer of 5 mass % of limit, can be confirmed：Compared with pigment of the invention prints and dyes agent, damage
The original feel of cloth and silk is done harm to, the water resistance of washing fastness, rub resistance and dyestuff weight color portion is deteriorated.
Although comparative example 6 is to polymerize containing the polymerizable monomer (a2) with epoxy group with hydrolyzable silyl group
Property monomer (a3) mass ratio within the limits prescribed but the ratio of the polymerizable monomer (a3) with hydrolyzable silyl group is super
The example for crossing the pigment printing and dyeing agent of the polymer of the 3.5 mass % as the upper limit, can be confirmed：It prints and dyes with pigment of the invention
Agent is compared, and the original feel of cloth and silk is compromised, and the water resistance of washing fastness, rub resistance and dyestuff weight color portion is deteriorated.
Although comparative example 7 and 8 is containing the polymerizable monomer (a2) with epoxy group and with hydrolyzable silyl group
The ratio of polymerizable monomer (a3) within the limits prescribed but the polymerizable monomer with epoxy group (a2) with have water-disintegrable first
The example of the pigment printing and dyeing agent of polymer of the mass ratio of the polymerizable monomer (a3) of silylation outside defined range, can be true
Recognize：Compared with pigment of the invention prints and dyes agent, the original feel of cloth and silk, washing fastness, rub resistance and dyestuff weight are compromised
The water resistance in color portion is deteriorated.
Claims (4)
1. a kind of fiber process resin combination is the fiber process resin combination containing polymer A, the polymerization
Object A is to make comprising the polymerizable monomer a1 with carboxyl, the polymerizable monomer a2 with epoxy group and have water-disintegrable monosilane
Obtained from the polymerizable monomer polymerization of the polymerizable monomer a3 of base,
It wherein, is 0.1 as the ratio of the polymerizable monomer a2 in the polymerizable monomer total amount of the raw material of the polymer A
The range of~5 mass %, the ratio of the polymerizable monomer a3 are the range of 0.1~3.5 mass %, the polymerizable monomer a2
10/90~90/10 range is expressed as with a2/a3 with the mass ratio of the polymerizable monomer a3,
The polymerizable monomer a1 be (methyl) acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride or citraconic acid, it is described
Polymerizable monomer a2 is (methyl) glycidyl acrylate or glycidyl allyl ether.
The agent 2. a kind of pigment is printed and dyed, contains fiber process resin combination described in claim 1 and pigment B.
3. a kind of cloth and silk is the cloth and silk printed and dyed through pigment as claimed in claim 2 printing and dyeing agent.
It is further repeatedly to have printed and dyed the cloth and silk of dye printing and dyeing agent to cloth and silk as claimed in claim 3 4. a kind of cloth and silk.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-005110 | 2014-01-15 | ||
| JP2014005110A JP6201767B2 (en) | 2014-01-15 | 2014-01-15 | Resin composition for textile processing, pigment printing agent and fabric using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104775309A CN104775309A (en) | 2015-07-15 |
| CN104775309B true CN104775309B (en) | 2018-11-30 |
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| CN201510018627.4A Active CN104775309B (en) | 2014-01-15 | 2015-01-14 | Fiber process resin combination, printed and dyed using its pigment agent and cloth and silk |
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| JP (1) | JP6201767B2 (en) |
| CN (1) | CN104775309B (en) |
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| CN113563512B (en) * | 2021-08-01 | 2022-08-19 | 苏州依司特新材料科技有限公司 | Anti-rewetting dispersant for reactive dye and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1265407A (en) * | 1999-02-16 | 2000-09-06 | 大日精化工业株式会社 | Pigment dispersion, writing tool and printer storing the same in them thereof |
| JP2002302876A (en) * | 2001-04-06 | 2002-10-18 | Nippon Carbide Ind Co Inc | Water-dispersible resin composition for fiber processing |
| JP2003165915A (en) * | 2001-11-29 | 2003-06-10 | Dainippon Ink & Chem Inc | Aqueous resin composition |
| JP2005139340A (en) * | 2003-11-07 | 2005-06-02 | Nippon Carbide Ind Co Inc | Aqueous composition of acrylic copolymer for textile printing |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06313088A (en) * | 1993-04-30 | 1994-11-08 | Sk Kaken Co Ltd | Water-based resin dispersion and coating composition using the same |
| JP3971770B2 (en) * | 2005-04-18 | 2007-09-05 | 三菱鉛筆株式会社 | Colorant composition and coloring method |
-
2014
- 2014-01-15 JP JP2014005110A patent/JP6201767B2/en active Active
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1265407A (en) * | 1999-02-16 | 2000-09-06 | 大日精化工业株式会社 | Pigment dispersion, writing tool and printer storing the same in them thereof |
| JP2002302876A (en) * | 2001-04-06 | 2002-10-18 | Nippon Carbide Ind Co Inc | Water-dispersible resin composition for fiber processing |
| JP2003165915A (en) * | 2001-11-29 | 2003-06-10 | Dainippon Ink & Chem Inc | Aqueous resin composition |
| JP2005139340A (en) * | 2003-11-07 | 2005-06-02 | Nippon Carbide Ind Co Inc | Aqueous composition of acrylic copolymer for textile printing |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6201767B2 (en) | 2017-09-27 |
| JP2015132027A (en) | 2015-07-23 |
| CN104775309A (en) | 2015-07-15 |
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