CN107955129A - A kind of imitative reactive coating stamp crosslinking agent and preparation method thereof - Google Patents
A kind of imitative reactive coating stamp crosslinking agent and preparation method thereof Download PDFInfo
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- CN107955129A CN107955129A CN201711171521.3A CN201711171521A CN107955129A CN 107955129 A CN107955129 A CN 107955129A CN 201711171521 A CN201711171521 A CN 201711171521A CN 107955129 A CN107955129 A CN 107955129A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/286—Oximes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- 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
- 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
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5285—Polyurethanes; Polyurea; Polyguanides
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
A kind of imitative reactive coating stamp crosslinking agent of the present invention and preparation method thereof, by 13 parts of 70 90 parts of hexamethylene diisocyanate trimer, 10 20 parts of polyethylene glycol, 24 parts of hydrophilic chain extender, 1 1.5 parts of trimethylolpropane, 30 40 parts of organic solvent, poly glycol monomethyl ether obtained prepolymers, crosslinking agent emulsion is made through 25 35 parts of end-blockings of methyl ethyl ketoxime, 1.5 3 parts of triethylamine neutralize, 160 230 parts of deionized water is scattered.With good dry and wet crock fastness and soaping fastness, and fabric feeling is not influenced after stamp.
Description
Technical field
The present invention relates to auxiliaries for textile dyeing and printing, and in particular to be a kind of imitative reactive coating stamp crosslinking agent and its
Preparation method.
Background technology
Pigment printing is that insoluble granules of pigments is combined to the adhesion that forms a film using adhesive to anchor at fiber surface to obtain
The printing technology of required pattern, its fabric to various fibers are applicable in, have chromatography it is complete, it is easy to operate, be easy to modulation etc.
Feature, pigment printing technique without washing, have the advantages that compared to dye printing it is energy saving, water-saving, but its feel not as contaminate
Expect stamp（Such as printing with reactive dye）Naturally it is soft, it is more prominent especially in the flower pattern of large area.The hand of pigment printing product
Sense and fastness depend on the quality of adhesive, so in order to improve the effect of pigment printing, it is necessary to select film forming is relatively soft to glue
Mixture achievees the purpose that coating imitates printing with reactive dye.
The preferably imitative reactive coating printing adhesive of quality can reach relatively soft feel at present, but due to it certainly
Body cohesive force is generally not so good as conventional pigment printing binding agent kind, and further crosslinking curing degree is limited after film forming,
Cause that the attachment fastness of imitative reactive printing coating on the fabric is poor, fastness to soaping is poor, the defects of wearing no resistance, particularly with
Some dark its dry and wet crock fastness indexs of kind are but difficult to reach 4 grades of requirement, it is necessary to add crosslinking into textile printing pigment
Agent is to improve the fastness of stamp.Common pigment printing crosslinking agent has aziridines, polyurethanes, organic silicon and melamine
Resinae etc., after these crosslinking agents add, can be in various degree play improves colorfastness to rubbing and soaping fastness, but removes
Outside polyurethanes other kinds of crosslinking agent there are toxicity it is high, not environmentally, release free formaldehyde, the easy xanthochromia of film forming, preparation
Printing paste the problems such as cannot storing.
Current existing watersoluble closed type polyurethane crosslinking agent can untie closing when heated, discharge active isocyanide
Acid esters group, reacts with the hydroxyl in adhesive agent emulsion, carboxyl, amide groups, linear copolymers is cross-linked into three-dimensional netted
The macromolecule of structure, so that the crosslinking degree and film-formation result of adhesive agent emulsion get a promotion, is particularly wet rubbing fastness
And soaping fastness is significantly improved；Hydroxyl, carboxyl, the amino to dissociate in isocyanate groups and fiber active at the same time occurs
Cross-linking reaction, makes emulsion film forming further enhance the adhesive force of fiber, is improved printing fastness.But printed to coating
After adding crosslinking agent in flower slurry adhesive agent emulsion film forming can be made to be hardened, friction coefficient increase, often dry fastness can drop
It is low, and the feel of fabric is deteriorated after stamp, and when being particularly applied to imitative reactive coating stamp, the fabric after stamp is felt hard
It is especially apparent, thus loses the meaning that coating imitates activity.
CN102816294A patents disclose " a kind of preparation method of watersoluble closed isocyanate crosslinking ", it is a kind of
For the water cross-linking agent of fabric coating, using isocyanates with directly being closed after hydrophilic chain extender pre-polymerization, but its structure
On from the point of view of cross-linker molecules it is smaller, and degree of branching is low, and crosslinking points are less, adhesive can be made to make film forming applied in pigment printing
It is hardened crisp, so as to influence dry fastness and stamp feel.
CN103865032A patents disclose " the watersoluble closed type polyisocyanate crosslinking agent and its system of highly branched structure
Preparation Method ", it is that the hydroxy-end capped skeleton to form dendritic is mutually blocked by isocyanates and triethanolamine, then uses isocyanic acid
Ester blocks, and polyethylene glycol chain extension, finally closes isocyanates with imidazole derivative.Its branched Chengdu is higher, has very
Good cross-linking properties, but it is smaller as the molecular weight polyethylene glycol used in soft section, and feel can still be hardened after film forming, and imidazoles
End-capping reagent to be honored as a queen in solution be solid state, can remain in cloth cover can also significantly affect feel.
The content of the invention
The object of the present invention is to provide a kind of imitative reactive coating stamp watersoluble closed type polyurethane crosslinking agent and its preparation
Method, so that imitative reactive coating stamp has good dry and wet crock fastness and soaping fastness, and does not influence fabric hand after stamp
Sense, can preferably reach the printing quality that coating imitates activity.
The imitative reactive coating stamp crosslinking agent preparation method of the present invention：
Raw material is by weight ratio：
(1) under nitrogen protection, by 70-90 parts of hexamethylene diisocyanate trimer, 10-20 parts of polyethylene glycol, hydrophilic expansion
2-4 parts of chain agent, 1-1.5 parts of trimethylolpropane, 30-40 parts of organic solvent are added in reactor, and stirring is warming up to 75-85 DEG C
When insulation reaction 1.5-2 is small；
(2) 1-3 parts of poly glycol monomethyl ether is added, in 80-85 DEG C of insulation reaction 1-1.5h, obtains prepolymer product；
(3) prepolymer product is cooled to 50-55 DEG C, 25-35 parts of end-capping reagent methyl ethyl ketoxime is added dropwise, in 50-60 DEG C of insulation reaction 2-
3h；
(4) 1.5-3 parts of neutralizer triethylamine is added, after stirring 20-30 minutes, adds the quick stirring point of 160-230 parts of deionized water
Dissipate, obtain crosslinking agent emulsion；
Appearance：Micro- bluish white emulsion
It is ionic：It is cloudy
PH value：7-8
Solid content：35±1%.
The polyethylene glycol：Molecular weight is 1000-3000；
The hydrophilic chain extender：For dihydromethyl propionic acid or dimethylolpropionic acid one；
The organic solvent：For 1-methyl-2-pyrrolidinone or N- ethyl pyrrolidone one；
The poly glycol monomethyl ether：Molecular weight is 500-1000.
Crosslinking agent of the present invention carries out water-soluble graft modification using the isocyanate trimer of trifunctional, while introduces three officials
The trimethylolpropane of energy makes the isocyanate-terminated prepolymer bone of the higher macromolecular branched structure of the performed polymer formation degree of cross linking
Frame, closes reactive isocyanate groups with sealer.As a result of the branched structure of macromolecular, friendship can be greatly improved
Join the content and crosslinking points of the active group of agent.It is added in pigment printing rubber cement when crosslinking agent, is adding with adhesive resin
Thermal deblocking obtains good cross-linking properties when curing, and makes adhesive film-formation result more preferable, the dry and wet crock fastness of fabric after stamp
And soaping fastness effectively improves.
For the present invention when synthesizing performed polymer, the rear poly glycol monomethyl ether that adds makes it graft on the end of the chain of performed polymer macromolecular
On, performed polymer is obtained end group hydrophilic radical, make it easier to self-emulsifying moisture and dissipate, while hydrophilic chain extender dosage is reduced,
Make the ionic decrease of crosslinking agent emulsion, substantially increase the water solubility and bin stability of cross-linker molecules, and be easy to
Adhesive is compounded, and slurry can not fail in long period preservation under sealing and room temperature state after compounding.
The present invention introduces polyethylene glycol, the poly glycol monomethyl ether of the long-chain-segment of flexibility, its ether contained in performed polymer
Key can rotate freely, and the flexibility of compound is got a promotion, you can material is hardened when being effectively improved crosslinking agent curing crisp
The shortcomings that；End-capping reagent can completely be volatilized when by thermal deblocking using the relatively low methyl ethyl ketoxime of boiling point, will not be remained in and be knitted at the same time
Thing surface influences feel.
Crosslinking agent of the present invention is water-based aliphatic polyurethane, its soft non yellowing that forms a film, has good sun-resistant color jail
Degree and weatherability, formaldehydeless release when being crosslinked by thermal deblocking, recommends the adhesive compounding use with no aldehyde type, to meet environmental protection
It is required that.
Embodiment
Embodiment 1
(1) under nitrogen protection, by 70 parts of hexamethylene diisocyanate trimer, molecular weight 1000 10 parts of polyethylene glycol,
2 parts of dihydromethyl propionic acid, 1 part of trimethylolpropane, 30 parts of 1-methyl-2-pyrrolidinone are added in reactor, and stirring is warming up to 80
When DEG C insulation reaction 2 is small；
(2) 1 part of the poly glycol monomethyl ether of molecular weight 500 is added, in 80 DEG C of insulation reaction 1.5h, obtains prepolymer product；
(3) prepolymer product is cooled to 50 DEG C, 25 parts of end-capping reagent methyl ethyl ketoxime is added dropwise, in 50 DEG C of insulation reaction 3h；
(4) 1.5 parts of neutralizer triethylamine is added, reaction after twenty minutes, adds 160 parts of deionized water to be quickly dispersed with stirring, must be crosslinked
Agent emulsion.
Embodiment 2
(1) under nitrogen protection, by 70 parts of hexamethylene diisocyanate trimer, molecular weight 2000 15 parts of polyethylene glycol,
2 parts of dihydromethyl propionic acid, 1 part of trimethylolpropane, 30 parts of 1-methyl-2-pyrrolidinone are added in reactor, and stirring is warming up to 80
When DEG C insulation reaction 2 is small；
(2) 1.5 parts of the poly glycol monomethyl ether of molecular weight 500 is added, in 85 DEG C of insulation reaction 1h, obtains prepolymer product；
(3) prepolymer product is cooled to 50 DEG C, 28 parts of end-capping reagent methyl ethyl ketoxime is added dropwise, in 50 DEG C of insulation reaction 3h；
(4) 1.5 parts of neutralizer triethylamine is added, stirring after twenty minutes, adds 170 parts of deionized water to be quickly dispersed with stirring, must be crosslinked
Agent emulsion.
Embodiment 3
(1) under nitrogen protection, by 80 parts of hexamethylene diisocyanate trimer, molecular weight 2000 10 parts of polyethylene glycol,
3 parts of dihydromethyl propionic acid, 1 part of trimethylolpropane, 40 parts of N- ethyl pyrrolidones are added in reactor, and stirring is warming up to 80
When DEG C insulation reaction 2 is small；
(2) 2 parts of the poly glycol monomethyl ether of molecular weight 750 is added, in 85 DEG C of insulation reaction 1h, obtains prepolymer product；
(3) prepolymer product is cooled to 50 DEG C, 30 parts of end-capping reagent methyl ethyl ketoxime is added dropwise, in 50 DEG C of insulation reaction 3h；
(4) 2.3 parts of neutralizer triethylamine is added, stirring after twenty minutes, adds 190 parts of deionized water to be quickly dispersed with stirring, must be crosslinked
Agent emulsion.
Embodiment 4
(1) under nitrogen protection, by 80 parts of hexamethylene diisocyanate trimer, molecular weight 2000 15 parts of polyethylene glycol,
3 parts of dihydromethyl propionic acid, 1.5 parts of trimethylolpropane, 40 parts of N- ethyl pyrrolidones are added in reactor, and stirring is warming up to
When 85 DEG C of insulation reactions 1.5 are small；
(2) 2 parts of the poly glycol monomethyl ether of molecular weight 750 is added, in 85 DEG C of insulation reaction 1.5h, obtains prepolymer product；
(3) prepolymer product is cooled to 50 DEG C, 31 parts of end-capping reagent methyl ethyl ketoxime is added dropwise, in 50 DEG C of insulation reaction 3h；
(4) 2.3 parts of neutralizer triethylamine is added, stirring after twenty minutes, adds 200 parts of deionized water to be quickly dispersed with stirring, must be crosslinked
Agent emulsion.
Embodiment 5
(1) under nitrogen protection, by 90 parts of hexamethylene diisocyanate trimer, molecular weight 3000 20 parts of polyethylene glycol,
4 parts of dihydromethyl propionic acid, 1.5 parts of trimethylolpropane, 40 parts of N- ethyl pyrrolidones are added in reactor, and stirring is warming up to
When 85 DEG C of insulation reactions 1.5 are small；
(2) 2 parts of the poly glycol monomethyl ether of molecular weight 750 is added, in 80 DEG C of insulation reaction 1h, obtains prepolymer product；
(3) prepolymer product is cooled to 55 DEG C, 35 parts of end-capping reagent methyl ethyl ketoxime is added dropwise, in 60 DEG C of insulation reaction 2h；
(4) 3 parts of neutralizer triethylamine is added, stirring after twenty minutes, adds 230 parts of deionized water to be quickly dispersed with stirring, obtains crosslinking agent
Lotion.
Embodiment 6
(1) under nitrogen protection, by 80 parts of hexamethylene diisocyanate trimer, molecular weight 2000 15 parts of polyethylene glycol,
4 parts of dimethylolpropionic acid, 1 part of trimethylolpropane, 40 parts of N- ethyl pyrrolidones are added in reactor, and stirring is warming up to 80
When DEG C insulation reaction 2 is small；
(2) 3 parts of the poly glycol monomethyl ether of molecular weight 1000 is added, in 80 DEG C of insulation reaction 1.5h, obtains prepolymer product；
(3) prepolymer product is cooled to 50 DEG C, 30 parts of end-capping reagent methyl ethyl ketoxime is added dropwise, in 50 DEG C of insulation reaction 3h；
(4) 2.7 parts of neutralizer triethylamine is added, stirring after twenty minutes, adds 200 parts of deionized water to be quickly dispersed with stirring, must be crosslinked
Agent emulsion.
Testing inspection
The present embodiment 1-6 crosslinking agent product 3g are taken respectively, with deionized water 68g, thickener 4g, imitative reactive coating adhesive
20g, blueness slurry 5g, are sufficiently mixed uniformly obtained printing paste.
Using plain net scraper stamp, calico pure cotton twill（Specification is 40x40/133x72）, again by drying after stamp
150-160 DEG C of case is dried 2 minutes, is then tested.
Comparative example：Using the wider pigment printing crosslinking agent of commercially available application：FH-10（Suzhou connection contains chemistry）、CL-FF2
（The refined rhythm in Shanghai）, with slurry and printing technology is same as above.
Test structure such as following table：
Colour fastness to rubbing detects：According to GB/T 3920-2008《Textile color stability tests colour fastness to rubbing》It is right
Cloth specimen is tested after stamp.
Fastness to soaping detects：According to GB/T 3921-2008《Textile color stability tests fastness to soaping》It is right
Cloth specimen is tested after stamp.
Flexibility effective evaluation：It is subject to comprehensive evaluation result of 6 people to feel, ++++to be best ,+to be worst.
It can be seen from upper table number test data crosslinking agent product of the present invention do, wet friction color fastness effect it is good, in stamp
Addition 3% can improve dry, half grade of fastness to wet rubbing to level-one in slurry, be better than commercial product；Fastness to soaping is good, generally can
Improve soaping fastness level-one or so, hence it is evident that better than commercially available crosslinking agent product F H-10, CL-FF2；Flexibility is good, after stamp cloth specimen with
The blank control stamp cloth-like hand for not adding crosslinking agent is basically identical, hence it is evident that is better than commercially available crosslinking agent FH-10, CL-FF2.
Claims (2)
1. imitative reactive coating stamp crosslinking agent preparation method, it is characterized in that：
Raw material is by weight ratio：
(1) under nitrogen protection, by 70-90 parts of hexamethylene diisocyanate trimer, 10-20 parts of polyethylene glycol, hydrophilic expansion
2-4 parts of chain agent, 1-1.5 parts of trimethylolpropane, 30-40 parts of organic solvent are added in reactor, and stirring is warming up to 75-85 DEG C
When insulation reaction 1.5-2 is small；
(2) 1-3 parts of poly glycol monomethyl ether is added, in 80-85 DEG C of insulation reaction 1-1.5h, obtains prepolymer product；
(3) prepolymer product is cooled to 50-55 DEG C, 25-35 parts of end-capping reagent methyl ethyl ketoxime is added dropwise, in 50-60 DEG C of insulation reaction 2-
3h；
(4) 1.5-3 parts of neutralizer triethylamine is added, after stirring 20-30 minutes, adds the quick stirring point of 160-230 parts of deionized water
Dissipate, obtain crosslinking agent emulsion；
Appearance：Micro- bluish white emulsion
It is ionic：It is cloudy
PH value：7-8
Solid content：35±1%；
The polyethylene glycol：Molecular weight is 1000-3000；
The hydrophilic chain extender：For dihydromethyl propionic acid or dimethylolpropionic acid one；
The organic solvent：For 1-methyl-2-pyrrolidinone or N- ethyl pyrrolidone one；
The poly glycol monomethyl ether：Molecular weight is 500-1000.
2. the imitative reactive coating stamp crosslinking agent obtained such as claim 1 preparation method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711171521.3A CN107955129B (en) | 2017-11-22 | 2017-11-22 | Cross-linking agent for reactive pigment imitation printing and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711171521.3A CN107955129B (en) | 2017-11-22 | 2017-11-22 | Cross-linking agent for reactive pigment imitation printing and preparation method thereof |
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| Publication Number | Publication Date |
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| CN107955129A true CN107955129A (en) | 2018-04-24 |
| CN107955129B CN107955129B (en) | 2020-06-23 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108547153A (en) * | 2018-04-27 | 2018-09-18 | 东华大学 | The preparation method of wash resistant moisturizing easy-to-clean textile finishing agent and application |
| CN110452362A (en) * | 2019-08-20 | 2019-11-15 | 湖南湘江关西涂料有限公司 | Watersoluble closed isocyanate curing agent and preparation method thereof, water paint |
| CN112522973A (en) * | 2020-12-23 | 2021-03-19 | 谢德寿 | Pretreatment liquid for textiles, hydrolysis-resistant textiles and printing method thereof |
| CN112961320A (en) * | 2021-02-07 | 2021-06-15 | 武汉纺织大学 | Polyethylene glycol bridged star-linked structure polyurethane thickener and preparation method thereof |
| CN113389071A (en) * | 2021-07-02 | 2021-09-14 | 广东博科新材料有限公司 | Dry-wet rubbing fastness improver and preparation method thereof |
| CN115386061A (en) * | 2022-08-04 | 2022-11-25 | 辽宁恒星精细化工有限公司 | Heat-reactive waterborne polyurethane resin and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108547153A (en) * | 2018-04-27 | 2018-09-18 | 东华大学 | The preparation method of wash resistant moisturizing easy-to-clean textile finishing agent and application |
| CN108547153B (en) * | 2018-04-27 | 2021-07-09 | 东华大学 | Preparation method and application of washing-resistant, moisturizing and soil-release textile finishing agent |
| CN110452362A (en) * | 2019-08-20 | 2019-11-15 | 湖南湘江关西涂料有限公司 | Watersoluble closed isocyanate curing agent and preparation method thereof, water paint |
| CN112522973A (en) * | 2020-12-23 | 2021-03-19 | 谢德寿 | Pretreatment liquid for textiles, hydrolysis-resistant textiles and printing method thereof |
| CN112961320A (en) * | 2021-02-07 | 2021-06-15 | 武汉纺织大学 | Polyethylene glycol bridged star-linked structure polyurethane thickener and preparation method thereof |
| CN112961320B (en) * | 2021-02-07 | 2022-06-10 | 武汉纺织大学 | Polyethylene glycol bridged star-linked structure polyurethane thickener and preparation method thereof |
| CN113389071A (en) * | 2021-07-02 | 2021-09-14 | 广东博科新材料有限公司 | Dry-wet rubbing fastness improver and preparation method thereof |
| CN115386061A (en) * | 2022-08-04 | 2022-11-25 | 辽宁恒星精细化工有限公司 | Heat-reactive waterborne polyurethane resin and preparation method and application thereof |
| CN115386061B (en) * | 2022-08-04 | 2024-03-08 | 辽宁恒星精细化工有限公司 | Thermal reactive aqueous polyurethane resin and preparation method and application thereof |
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