CN105064084B - Special soft type imitates reactive coating stamp formaldehyde binder and preparation method thereof, application - Google Patents
Special soft type imitates reactive coating stamp formaldehyde binder and preparation method thereof, application Download PDFInfo
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- CN105064084B CN105064084B CN201510516465.7A CN201510516465A CN105064084B CN 105064084 B CN105064084 B CN 105064084B CN 201510516465 A CN201510516465 A CN 201510516465A CN 105064084 B CN105064084 B CN 105064084B
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Abstract
Reactive coating stamp formaldehyde binder and preparation method thereof, application are imitated the present invention relates to the special soft type of one kind, adhesive of the present invention is using the polysiloxanes of hydroxyalkyl containing acyloxy, acrylic acid, methacrylic acid, acrylic ester monomer, acrylamide, styrene, vinyl acetate, acrylonitrile, N-glycidyl acrylamide, unsaturated strongly hydrophilic monomer, reactive surfactant as raw material, under the effect of additional initiator, it is prepared from by copolymerization, condensation reaction.The adhesive of the present invention has reaches respective country standard without formaldehyde, color fastness, can be not only used for pigment printing and can also be used for fabric feeling particularly soft after pigment dyeing, stamp or dyeing, when using not roll banding, not network blocking, the advantages of property is stable, color fastness is high.
Description
Technical field
The present invention relates to imitative reactive coating printing adhesive field, in particular it relates to which a kind of special soft type imitates reactive coating print
Flower formaldehyde binder and preparation method thereof, application.
Background technology
Reactive printing is to use reactive dye, by technological processes such as stamp, drying, decatize, washing and drying, to weaving
The method that product carry out coloring arrangement.Reactive dye chromatogram used in reactive printing technology is complete, lovely luster, the color of PRINTED FABRIC
Fastness preferably, fabrics feel soft and is not touched with one's hand, and environmental protection is free of formaldehyde, is the main flow printing technique of cellulose base fiber fabric.So
And, salt need to be added when being dyed using reactive printing technology or glauber salt makees accelerant, sodium carbonate or hydrogen-oxygen need to be added during fixation
Change sodium, it is not high to there is degree of fixation, produce that COD in a large amount of coloured sewage, sewage is high, processing is difficult, technological process is numerous and diverse, production weight
Renaturation is poor, easily occurs staining during blending color, the defect such as power consumption is big, cost height (wire mark industry, 2014,9,11-14.).With
The raising of sound and people's environmental consciousness of laws and regulations, traditional reactive printing technology can not cater to the ring of sustainable development
Factoring is read, thus a kind of Novel decorating technology of low-carbon environment-friendly urgently occurs, and pigment printing is exactly to be answered under this overall situation
Transport and raw new technology.With updating and suitable for the thickener of pigment printing for pigment printing binding agent synthetic technology
Appearance so that the advantage of pigment printing increasingly protrude.For example, pigment printing only needs stamp, dries and bake, without
The process such as decatize and washing, is not limited by fibre property, is substantially shortened compared to reactive printing technological process, life cycle of the product
Greatly shorten, comprehensive energy consumption is significantly reduced, while avoiding the discharge of coloured sewage.Thus, this easy to operate, favorable reproducibility
Novel decorating technology just progressively replacing traditional reactive printing technology.At present, China's pigment printing and pigment dyeing in print
Utilization rate in dyer's sequence is in the trend of rapid growth more than 60%.
The fine or not key of pigment printing and Pigment Dyeing Quality is used adhesive.At present, in pigment printing
The adhesive generally used is high-temperature self-crosslinking adhesive, its advantage such as have color fastness relatively preferable, easy to use, but
In the presence of needing high temperature (150 DEG C) to bake, after stamp or dyeing, fabric feeling is stiff, release harmful formaldehyde, property is not during use
It is stable, the defect such as performance difference.In recent years, with environmentally friendly cry the " green that continuous improvement and developed country is constantly set
The problem of barrier ", people's release formaldehyde in use to textile, is increasingly paid attention to.Formaldehyde of many developed countries to textile
Content has all formulated strict regulation, for example, the ecological mark of Japan, German BLUE ANGEL, the green stamped signature in the U.S., Oeko Tex
100th, EcoTex, Eco-label, Toxproof and Wite SWan etc..Then, China has also formulated corresponding regulation ---
GB18401-2003 and GB18401-2010, and start to enforce on January 1st, 2010.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of property stabilization, cementability is good, fastness is good, particle diameter is small, hand
The soft special soft type of sense imitates reactive coating stamp formaldehyde binder, to overcome existing pigment printing and dyeing adhesive to contain first
Aldehyde or poor color fastness during without formaldehyde, use can not be met the need for and PRINTED FABRIC feel is stiff, pigment printing binding agent
The deficiency such as easy roll banding during for pigment dyeing.
In addition, the present invention also provides preparation method, the application that a kind of special soft type imitates reactive coating stamp formaldehyde binder.
The present invention the used technical scheme that solves the above problems is：Special soft type imitates reactive coating stamp formaldehyde-free adhesive
Agent, adhesive with the polysiloxanes of hydroxyalkyl containing acyloxy, acrylic acid, methacrylic acid, acrylic ester monomer, acrylamide,
Styrene, vinyl acetate, acrylonitrile, N-glycidyl acrylamide, unsaturated strongly hydrophilic monomer, reactive surfaces activity
Agent is raw material, and under the effect of additional initiator, copolymerization, condensation reaction are prepared from.
Further, the synthesis material of adhesive is made up of following weight percent composition：
Preferably, the synthesis material of described adhesive is made up of following weight percent composition：
Further preferably, the synthesis material of described adhesive is made up of following weight percent composition：
Wherein, compared with traditional hydroxy-terminated polysiloxane, the polysiloxane-modified polyacrylic acid of hydroxyalkyl containing acyloxy
Chemical property stable Si-C keys are formed during ester, without forming Si-O-C keys of facile hydrolysis, and then the steady of adhesive are improved
It is qualitative；Also, adhesive of the present invention, which is synthesized in raw materials used-polysiloxanes of hydroxyalkyl containing acyloxy, contains hydroxyalkyl,
Electron withdraw group-acyloxy of its adjacent group containing polarized so that the hydroxyl on hydroxyalkyl has suitable activity, and then
So that the preparation of adhesive is more easy；
Wherein, reactive surfactant, it is possible to decrease the water imbibition of adhesive glued membrane, increases the continuity of glued membrane, reaches
The purpose of adhesive color fastness is improved, half grade or so can be typically improved；
Wherein, N- glycidyl acrylamide is a kind of cross-linking monomer, is added in synthesized adhesive, can be by this
Crosslinked group on cross-linking monomer, plays bridging action, the crosslinking ability between enhancing adhesive and fabric, coating, so as to carry
Highly adhesive is used for every color fastness when pigment printing or dyeing.
The main component of adhesive is silicone acrylic emulsion, i.e., prepared by organosiloxane and acrylic ester monomer reaction,
Because the polyacrylate that hydroxy-terminated polysiloxane is modified contains Si-O-C keys, easily hydrolyze, regenerate silanol, spinning
The fracture of polymer molecular chain is easily caused in the long-term use of fabric, the performance of textile is influenceed.In addition, commercially available silicon third
Emulsion binding agent uses N hydroxymethyl acrylamide as cross-linking monomer mostly, in use can release formaldehyde, while newborn
Liquid particle diameter is also larger, and stability is not good, and this will influence the fastness of adhesive.
It is demonstrated experimentally that adhesive of the present invention has, formaldehydeless, property is stable, cementability is good, fastness is good, particle diameter
Small, soft advantage.
Further, the structural formula of the polysiloxanes of hydroxyalkyl containing acyloxy is：
Wherein, R isAnd R1For H or CH3At least one of, R2For CH2、C2H4、C3H6In at least one
Kind, 10≤n≤200.
Preferably, in the above-mentioned polysiloxanes of hydroxyalkyl containing acyloxy, R isR1For H, CH3In at least
One kind, R2For C2H4、C3H6At least one of.
The preparation method of above-mentioned hydroxyalkyl polysiloxanes is：With hydrogen containing siloxane, hydroxyalkyl acrylate or metering system
Sour hydroxyalkyl ester compound is raw material, adds polymerization inhibitor, catalyst made from platonic, solvent, and reaction temperature is 80~145 DEG C, passes through silicon
The hydrosilylation of hydrogen bond and unsaturated double-bond, generates the polysiloxanes crude product of hydroxyalkyl containing acyloxy；Then, washing is removed
Unreacted hydroxyalkyl acrylate or hydroxyalkyl methacrylate class compound, then vacuum distillation water removal, are filtered to remove polymerization inhibitor
Produce the polysiloxanes of hydroxyalkyl containing acyloxy.The solvent be benzene,toluene,xylene, dioxane or isopropanol at least
It is a kind of；The polymerization inhibitor is hydroquinones, 1,4-benzoquinone, methylnaphthohydroquinone, 2-TBHQ or 2,5-di-t-butyl pair
At least one of benzenediol；The catalyst made from platonic be chloroplatinic acid-ethanol solution, chloroplatinic acid-aqueous isopropanol, chloroplatinic acid-
At least one of vinylsiloxane complex compound or platinum dioxide.
Further, acrylic ester monomer is ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, acrylic acid 2-
At least one of ethylhexyl, methyl methacrylate, butyl methacrylate.
Further, the structure of reactive surfactant is：H2C=CR1R2SO4Na、H2C=CR1R2SO3Na、H2C=
CR1R2PO3At least one of Na, wherein R1、R2For the straight or branched alkyl of alkyl number >=6.
Further, the structure of unsaturated strongly hydrophilic monomer is：HR1C=CHR2SO3Na(SO4Na、PO3Na), wherein R1
And R2For the straight chained alkyl of carbon number≤6.
Further, initiator is combination or the sulfurous acid of potassium peroxydisulfate or ammonium persulfate or potassium peroxydisulfate and ammonium persulfate
The combination of hydrogen sodium and potassium peroxydisulfate or the combination of sodium hydrogensulfite and ammonium persulfate or sodium hydrogensulfite and potassium peroxydisulfate and over cure
The combination of sour ammonium.I.e. potassium peroxydisulfate, ammonium persulfate can be used as initiator separately as initiator or combination；Sodium hydrogensulfite with
Potassium peroxydisulfate combination can as initiator, sodium hydrogensulfite combined with ammonium persulfate also can as initiator, sodium hydrogensulfite and
Ammonium persulfate, potassium peroxydisulfate three combination can also be used as initiator；The ammonium persulfate, potassium peroxydisulfate are oxidant, sulfurous acid
Hydrogen sodium is reducing agent.
Special soft type imitates the preparation method of reactive coating stamp formaldehyde binder, comprises the following steps：
A, prepare core microemulsion：By acrylic ester monomer, recombination reaction surfactant, unsaturated strongly hydrophilic list
Body and deionized water are added in reactor, are warming up to 40~60 DEG C of 10~30min of emulsification at a high speed, are obtained core microemulsion；
B, prepare shell microemulsion：N- glycidyl acrylamide, acrylic or methacrylic acid or both are mixed
Thing, styrene, vinyl acetate, acrylonitrile, acrylamide, recombination reaction surfactant, unsaturated strongly hydrophilic monomer and
Deionized water is added in reaction vessel, is warming up to 40~60 DEG C of 10~30min of emulsification at a high speed, is obtained shell microemulsion；
C, preparation initiator solution：The initiator solution includes oxidizing agent solution, reductant solution, will when using
Oxidizing agent solution, reductant solution are separately added in reaction system；
D, synthesis：The core microemulsion emulsified is warming up to 60~80 DEG C, half initiator solution is added and triggers poly-
30~60min is closed,, will to continuing to react 10~30min after dripping off then to dripping remaining initiator solution and shell microemulsion
System pH is adjusted to 4.5~6.0, adds the polysiloxanes of hydroxyalkyl containing acyloxy, continues at 75~90 DEG C of 3~4h of reaction；Reaction
Less than 40 DEG C are cooled to after complete, ammonification water adjusts pH value to 7~8, filter to obtain the imitative reactive coating stamp formaldehyde binder of special soft type.
The oxidizing agent solution specifically refers to the mixed solution of ammonium persulfate solution or potassium persulfate solution or both；The reducing agent is molten
Liquid specifically refers to solution of sodium bisulfite.
Preparation method of the present invention uses " core shell emulsion polymerization " technology, and the soft monomer of easy roll banding, network blocking is made
Core, is difficult roll banding, shell is made in the hard monomer of network blocking, so as to improve the color fastness of synthesized adhesive, the present invention uses monomer
Pre-emulsification, the polymerization technique of " monomer hungry " dripping method of seeded emulsion polymerization and rear ammonia process, super microemulsion process etc., make to be closed
Into adhesive reach nanoscale.Due to the particle diameter very little of adhesive so that it strengthens the ability that coating particle is coated, so that
Reach the purpose for improving color fastness.
The adhesive prepared by the method for the invention has formaldehydeless, property stabilization, cementability is good, fastness is good, grain
Small, the soft advantage in footpath.
Special soft type imitates the preparation method of reactive coating stamp formaldehyde binder, comprises the following steps：
A, prepare core microemulsion：By acrylic ester monomer, the polysiloxanes of hydroxyalkyl containing acyloxy, recombination reaction surface
Activating agent, unsaturated strongly hydrophilic monomer and deionized water are added in reactor, be warming up to 40~60 DEG C at a high speed emulsification 10~
30min, obtains core microemulsion；
B, prepare shell microemulsion：N- glycidyl acrylamide, acrylic or methacrylic acid or both are mixed
Thing, styrene, vinyl acetate, acrylonitrile, acrylamide, recombination reaction surfactant, unsaturated strongly hydrophilic monomer and
Deionized water is added in reactor, is warming up to 40~60 DEG C of 10~30min of emulsification at a high speed, is obtained shell microemulsion；
C, preparation initiator solution：The initiator solution includes oxidizing agent solution, reductant solution, will when using
Oxidizing agent solution, reductant solution are separately added in reaction system；
D, synthesis：The core microemulsion emulsified is warming up to 60~80 DEG C, half initiator solution is added and triggers poly-
30~60min is closed, then to the remaining initiator solution of drop and shell microemulsion, to continuing to react 10~30min after dripping off, by body
It is that pH value is adjusted to 4.5~6.0, continues at 75~90 DEG C of 3~4h of reaction；Less than 40 DEG C are cooled to after having reacted, ammonification water adjusts pH
Value filters to obtain the imitative reactive coating stamp formaldehyde binder of special soft type to 7~8.The oxidizing agent solution specifically refers to persulfuric acid
The mixed solution of ammonium salt solution or potassium persulfate solution or both；The reductant solution specifically refers to solution of sodium bisulfite.
Special soft type imitates the application of reactive coating stamp formaldehyde binder, and described adhesive is used for pigment printing, coating
Dyeing.
The adhesive prepared by the method for the invention detects the performance of product by following method of testing：
1st, fastness
Synthesized adhesive modulates mill base according to certain formula (routine), and then polyester cotton (80/20) fabric is carried out
The brushing fastness of PRINTED FABRIC is tested after manual table printing, stamp according to GB/T420-2009；According to GB/T3920-2008
Test the crock fastness of PRINTED FABRIC；According to the color fastness to washing of GB/T3921.3-2008 test fabrics.
2nd, content of formaldehyde
Synthesized adhesive is pressed into following PROCESS FOR TREATMENT fabric first：
Adhesive 300g/L, two leachings two are rolled pure cotton fabric → 100 DEG C drying → 150-160 DEG C and baked 2 minutes, then will
Gained fabric according to GB/T2912.1-2009 textile formaldehydes measure part 1:Free and hydrolysis formaldehyde (aqueous extraction method)
Content of formaldehyde in test fabric.
3rd, emulsion particle diameter
By synthesized adhesive Malvern company of Britain Zetastzer Nano ZS90 types nano particle sizes and Zeta electricity
The particle diameter of position analysis-e/or determining adhesive agent emulsion.
4th, adhesive agent emulsion stability
4.1 mechanical stability
Synthesized adhesive is rotated into 30min with 3000 turns/min centrifugation, then filters observation whether there is cohesion
Thing is generated；It is on the contrary then stablize poor without condensation product person's good mechanical stability.
4.2 chemical stability
Take the adhesive agent emulsion synthesized by 10mL to be diluted to 40mL with 1 milliliter of calcium chloride solution, stand, seen whether
Precipitation, gelatin phenomenon.There is then poor chemical stability, it is good without then stability.
5th, feel
Synthesized adhesive modulates mill base according to certain formula (routine), and then polyester cotton (80/20) fabric is carried out
Manual table printing, finally compares the feel of printed fabric with hand palpating manipulation, so as to compare the feel of adhesive indirectly.
Technique for applying of the adhesive in printing and dyeing synthesized by the present invention is as follows：
Print paste reference formulation in pigment printing technique：
Printing technology：Dry → 150~160 DEG C and bake 2~3min in fabric → stamp → 80~100 DEG C.
The prescription of pigment dyeing：
Dyeing：Dyed gray → pad → preliminary drying → hot-air seasoning (70~90 DEG C) → bakes (150~160 DEG C × 2
~3min).
To sum up, the beneficial effects of the invention are as follows：
1st, adhesive of the present invention overcomes existing pigment printing and dyeing adhesive containing formaldehyde or without formaldehyde
When poor color fastness, use can not be met the need for and PRINTED FABRIC feel is stiff, pigment printing binding agent is used for pigment dyeing
When the deficiency such as easy roll banding, meanwhile, adhesive of the invention has reaches respective country standard without formaldehyde, color fastness, both can use
Fabric feeling particularly soft, not roll banding, not network blocking etc. when using after pigment dyeing, stamp or dyeing are can also be used in pigment printing
Advantage.
2nd, the present invention polysiloxanes of hydroxyalkyl containing acyloxy used can be formed between polysiloxanes and polyacrylate
Stable Si-C the keys of chemical property, it is thus possible to improve the Long-Term Properties of its PRINTED FABRIC.
3rd, the particle diameter very little of adhesive of the present invention so that it strengthens the ability that coating particle is coated, so as to reach
To the purpose for improving color fastness, and adhesive prepared by the present invention in application can with additional crosslink agent (fastness enhancer),
By the crosslinked group on crosslinking agent, bridging action is played, strengthens the crosslinking ability between adhesive and fabric, coating, so that
Every color fastness that adhesive is improved when being used for pigment printing or dyeing.
4th, adhesive of the present invention is used for not permeable side, not network blocking during pigment printing, and the decorative pattern of printing is clear-cut, essence
Carefully；During for pigment dyeing, not roll banding.
Brief description of the drawings
Fig. 1 is the infared spectrum of the product end acyloxy ethoxy polysiloxanes of embodiment 1；
Fig. 2 is the infared spectrum of the product end acyloxy hydroxypropyl based polysiloxane of embodiment 2；
Fig. 3 is the infared spectrum of the product side acyloxy ethoxy polysiloxanes of embodiment 3.
Embodiment
With reference to embodiment and accompanying drawing, make detailed description further to invention, but embodiments of the present invention are not
It is limited to this.
Raw material hydroxyalkyl containing the acyloxy polysiloxanes that the present invention is used during adhesive is prepared is specially end acyl-oxygen
Base ethoxy polysiloxanes, end acyloxy hydroxypropyl based polysiloxane, side acyloxy ethoxy polysiloxanes；Hold acyloxy ethoxy
Polysiloxanes, end acyloxy hydroxypropyl based polysiloxane, the preparation method of side acyloxy ethoxy polysiloxanes are respectively such as embodiment
1st, embodiment 2, shown in embodiment 3.
Embodiment 1
Added in the 500mL three-necked flasks with thermometer, agitator and condenser pipe 100g ends hydrogen containing siloxane,
11.6g hydroxy-ethyl acrylates (C=C：Si-H mol ratios 1.0：1.0), 111.6g toluene (the 100% of reaction raw materials gross weight),
0.58g hydroquinones (the 0.05% of hydroxy-ethyl acrylate), leads to N2Displacement three times, is gradually heating to 90 DEG C, adds 11.2g's
1wt% chloroplatinic acids-ethanol solution (378ppm) makees catalyst.System is brought rapidly up, and after system temperature is stable, is gradually heating to
95 DEG C of reaction 3h, reaction is down to room temperature, washes three times and remove unreacted hydroxy-ethyl acrylate after terminating, heat up toluene after point water
Backflow band water, then raises temperature to 100 DEG C, the removed under reduced pressure toluene under -0.090MPa vacuum.Room temperature is down to, acyl-oxygen must be held by filtering
Base ethoxy polysiloxanes.Hold hydrogen containing siloxane, hydroxy-ethyl acrylate and the infrared figure for holding acyloxy ethoxy polysiloxanes
Spectrum is as shown in Figure 1.2127.48 and 912.33cm in Fig. 1 (a)-1To hold the characteristic absorption peak of Si-H keys in hydrogen containing siloxane,
1024.20 and 1091.71cm-1For the characteristic absorption peak of Si-O-Si keys, 1261.45,864.11 and 800.46cm-1For Si-
CH3The characteristic absorption peak of key.1637.56cm in Fig. 1 (b)-1And 3427.51cm-1Unsaturation C=respectively in hydroxy-ethyl acrylate
C keys and-CH2CH2In OH-OH characteristic absorption peak.It is can be found that from Fig. 1 (c)：2127.48 and 912.33cm-1Place Si-
The characteristic absorption peak of H keys disappears, in 3487.30cm-1Locate appearance-OH characteristic absorption peak, while in 1637.56cm-1Place is not
Saturation C=C characteristic absorption peak disappears, and these show by holding hydrogen containing siloxane and hydroxy-ethyl acrylate to make in platinum catalyst
Hydrosilylation under successfully synthesizes end acyloxy ethoxy polysiloxanes.Hold the red of acyloxy ethoxy polysiloxanes
Outer collection of illustrative plates is as shown in Figure 1.
Embodiment 2
Added in the 250mL three-necked flasks with thermometer, agitator and condenser pipe 100g ends hydrogen containing siloxane,
26.0g hydroxypropyl acrylates (C=C：Si-H mol ratios 2.0：1.0), 0.26g hydroquinones (the 1% of hydroxypropyl acrylate),
Logical N2Displacement three times, is gradually heating to 90 DEG C, adds 33.46g 1wt% chloroplatinic acids-aqueous isopropanol (1000ppm).System
It is brought rapidly up, after system temperature is stable, is gradually heating to 100 DEG C of reaction 3h.Room temperature is down in reaction after terminating, washed three times and removed
Excessive hydroxypropyl acrylate is removed, appropriate toluene heating water removal is added after point water.100 DEG C are then raised temperature to ,-
Removed under reduced pressure toluene under 0.090MPa vacuum.Room temperature is down to, acyloxy hydroxypropyl based polysiloxane must be held by filtering.Hold acyloxy hydroxypropyl
The infared spectrum of based polysiloxane is as shown in Figure 2.
Embodiment 3
Added in the 250mL three-necked flasks with thermometer, agitator and condenser pipe 50g sides hydrogen containing siloxane,
12.8g hydroxy-ethyl acrylates (C=C：Si-H mol ratios 1.1：1.0), 50g toluene (the 79.6% of reaction raw materials gross weight),
2-TBHQs of 0.2g (the 1.56% of hydroxy-ethyl acrylate), lead to N2Displacement three times, is gradually heating to 90 DEG C, addition
0.01g platinum dioxide (137ppm) makees catalyst.System is brought rapidly up, and after system temperature is stable, is gradually heating to 95 DEG C
React 5h.Room temperature is down in reaction after terminating, washed three times and removed excessive hydroxy-ethyl acrylate, and heat up refluxing toluene band after point water
Water.100 DEG C are then raised temperature to, the removed under reduced pressure toluene under -0.090MPa vacuum.Room temperature is down to, side acyloxy hydroxyl second is filtered to obtain
Based polysiloxane.The infared spectrum of side acyloxy ethoxy polysiloxanes is as shown in Figure 3.
Embodiment 4~8
The preparation method of adhesive described in embodiment 4~8 is basically identical, and difference essentially consists in the selection of parameter and contained
The difference of acyloxy hydroxyalkyl polysiloxanes.
Special soft type imitates the preparation method of reactive coating stamp formaldehyde binder, comprises the following steps：
A, prepare core microemulsion：By acrylic ester monomer, the polysiloxanes of hydroxyalkyl containing acyloxy, recombination reaction surface
Activating agent, unsaturated strongly hydrophilic monomer and deionized water are added in reactor, be warming up to 40~60 DEG C at a high speed emulsification 10~
30min, obtains core microemulsion；
B, prepare shell microemulsion：N- glycidyl acrylamide, acrylic or methacrylic acid or both are mixed
Thing, styrene, vinyl acetate, acrylonitrile, acrylamide, recombination reaction surfactant, unsaturated strongly hydrophilic monomer and
Deionization is added in reactor, is warming up to 40~60 DEG C of 10~30min of emulsification at a high speed, is obtained shell microemulsion；
C, preparation initiator solution：The initiator solution includes oxidizing agent solution, reductant solution, will when using
Oxidizing agent solution, reductant solution are separately added in reaction system；
D, synthesis：The core microemulsion emulsified is warming up to 60~80 DEG C, half initiator solution is added and triggers poly-
30~60min is closed, then to the remaining initiator solution of drop and shell microemulsion, to continuing to react 10~30min after dripping off, by body
It is that pH value is adjusted to 4.5~6.0, continues at 75~90 DEG C of 3~4h of reaction；Less than 40 DEG C are cooled to after having reacted, ammonification water adjusts pH
Value filters to obtain the imitative reactive coating stamp formaldehyde binder of special soft type to 7~8.
Special soft type imitates raw materials used and ratio such as table 1 when prepared by reactive coating stamp formaldehyde binder in embodiment 4~8
It is shown.
Table 1
Reaction condition is as shown in table 2 when special soft type imitates the preparation of reactive coating stamp formaldehyde binder in embodiment 4~8.
Table 2
Embodiment 9~12
The preparation method of adhesive described in embodiment 9~12 is basically identical, difference essentially consist in parameter selection and
The difference of the polysiloxanes of hydroxyalkyl containing acyloxy.
Special soft type imitates the preparation method of reactive coating stamp formaldehyde binder, comprises the following steps：
A, prepare core microemulsion：By acrylic ester monomer, the polysiloxanes of hydroxyalkyl containing acyloxy, recombination reaction surface
Activating agent, unsaturated strongly hydrophilic monomer and deionized water are added in reactor, be warming up to 40~60 DEG C at a high speed emulsification 10~
30min, obtains core microemulsion；
B, prepare shell microemulsion：N- glycidyl acrylamide, acrylic or methacrylic acid or both are mixed
Thing, styrene, vinyl acetate, acrylonitrile, acrylamide, recombination reaction surfactant, unsaturated strongly hydrophilic monomer and
Deionization is added in reactor, is warming up to 40~60 DEG C of 10~30min of emulsification at a high speed, is obtained shell microemulsion；
C, preparation initiator solution：The initiator solution will when including oxidizing agent solution, reductant solution, using
Oxidizing agent solution, reductant solution are separately added in reaction system；
D, synthesis：The core microemulsion emulsified is warming up to 60~80 DEG C, half initiator solution is added and triggers poly-
30~60min is closed, then to the remaining initiator solution of drop and shell microemulsion, to continuing to react 10~30min after dripping off, by body
It is that pH value is adjusted to 4.5~6.0, continues at 75~90 DEG C of 3~4h of reaction；Less than 40 DEG C are cooled to after having reacted, ammonification water adjusts pH
Value filters to obtain the imitative reactive coating stamp formaldehyde binder of special soft type to 7~8.
Each special soft type imitates when prepared by reactive coating stamp formaldehyde binder raw materials used and ratio such as in embodiment 9~12
Shown in table 3.
Table 3
Each special soft type imitates the reaction condition such as institute of table 4 when prepared by reactive coating stamp formaldehyde binder in embodiment 9~12
Show.
Table 4
Special soft type prepared by embodiment 4~12 is imitated reactive coating stamp formaldehyde binder and printed for polyester cotton textile coating
Colored every color fastness is as shown in table 5.
Table 5
Note：Fabric is 80 (washing)/20 (cotton) fabrics, pigment printing prescription：Coating orchid 5g, adhesive 14.7g, fastness is improved
Agent STTG-20.3g, the common 80g of synthetic thickening agent+water.
It can be learnt by table 5：Adhesive of the present invention is compared with common adhesive, and it has the following advantages that：Scrub jail
Degree is higher by 1-1.5 grades than common adhesive；Crock fastness is higher by 1-1.5 grades than common adhesive；It is soft；Formaldehydeless inspection
Go out；Particle diameter ＜ 100nm；Fastness to washing is also superior to common adhesive.
As described above, the present invention can be realized preferably.
Claims (8)
1. special soft type imitates reactive coating stamp formaldehyde binder, it is characterised in that adhesive is with the poly- silicon of hydroxyalkyl containing acyloxy
Oxygen alkane, acrylic or methacrylic acid or both mixture, acrylic ester monomer, acrylamide, styrene, acetic acid second
Alkene, acrylonitrile, N-glycidyl acrylamide, unsaturated strongly hydrophilic monomer, reactive surfactant are raw material, outside
Plus under initiator effect, copolymerization, condensation reaction are prepared from；The structural formula of the polysiloxanes of hydroxyalkyl containing acyloxy is：
Wherein, R is in the polysiloxane structure of hydroxyalkyl containing acyloxy formulaAnd R1For H or CH3In at least one
Kind, R2For-C2H4、-C3H6Or-C4H8, 10≤n≤200；
The structure of the unsaturated strongly hydrophilic monomer is：HR1C=CHR2SO3Na、HR1C=CHR2SO4Na、HR1C=
CHR2PO3Na, wherein, R in unsaturated strongly hydrophilic monomer structure formula1And R2For the straight chained alkyl of carbon number≤6.
2. special soft type according to claim 1 imitates reactive coating stamp formaldehyde binder, it is characterised in that the bonding
The synthesis material of agent is made up of following weight percent composition：
The percentage by weight sum of each component is equal to absolutely.
3. special soft type according to claim 1 or 2 imitates reactive coating stamp formaldehyde binder, it is characterised in that described
Acrylic ester monomer is ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, 2-EHA, metering system
At least one of sour methyl esters, butyl methacrylate.
4. special soft type according to claim 1 or 2 imitates reactive coating stamp formaldehyde binder, it is characterised in that described
The structure of reactive surfactant is：H2C=CR1R2SO4Na、H2C=CR1R2SO3Na、H2C=CR1R2PO3In Na at least
One kind, wherein, R in reactive surfactant structural formula1、R2For the straight or branched alkyl of alkyl number >=6.
5. special soft type according to claim 1 or 2 imitates reactive coating stamp formaldehyde binder, it is characterised in that described
Initiator is potassium peroxydisulfate or the combination of ammonium persulfate or potassium peroxydisulfate and ammonium persulfate or sodium hydrogensulfite and potassium peroxydisulfate
Combination or the combination of sodium hydrogensulfite and ammonium persulfate or the combination of sodium hydrogensulfite and potassium peroxydisulfate and ammonium persulfate.
6. a kind of special soft type as claimed in claim 1 or 2 imitates the preparation method of reactive coating stamp formaldehyde binder, it is special
Levy and be, comprise the following steps：
A, prepare core microemulsion：By acrylic ester monomer, recombination reaction surfactant, unsaturated strongly hydrophilic monomer and
Deionized water is added in reactor, is warming up to 40~60 DEG C of 10~30min of emulsification at a high speed, is obtained core microemulsion；
B, prepare shell microemulsion：By N- glycidyl acrylamide, acrylic or methacrylic acid or both mixture, benzene
Ethene, vinyl acetate, acrylonitrile, acrylamide, recombination reaction surfactant, unsaturated strongly hydrophilic monomer and deionization
Water is added in reaction vessel, is warming up to 40~60 DEG C of 10~30min of emulsification at a high speed, is obtained shell microemulsion；
C, preparation initiator solution：The initiator solution includes oxidizing agent solution, reductant solution, will oxidation when using
Agent solution, reductant solution are separately added in reaction system；
D, synthesis：The core microemulsion emulsified is warming up to 60~80 DEG C, half initiator solution is added and triggers polyase 13 0
~60min, then to dripping remaining initiator solution and shell microemulsion, to continuing to react 10~30min after dripping off, by system
PH value is adjusted to 4.5~6.0, adds the polysiloxanes of hydroxyalkyl containing acyloxy, continues at 75~90 DEG C of 3~4h of reaction；After having reacted
Less than 40 DEG C are cooled to, ammonification water adjusts pH value to 7~8, filter to obtain the imitative reactive coating stamp formaldehyde binder of special soft type.
7. a kind of special soft type as claimed in claim 1 or 2 imitates the preparation method of reactive coating stamp formaldehyde binder, it is special
Levy and be, comprise the following steps：
A, prepare core microemulsion：By acrylic ester monomer, the polysiloxanes of hydroxyalkyl containing acyloxy, recombination reaction surface-active
Agent, unsaturated strongly hydrophilic monomer and deionized water are added in reactor, are warming up to 40~60 DEG C of 10~30min of emulsification at a high speed,
Obtain core microemulsion；
B, prepare shell microemulsion：By N- glycidyl acrylamide, acrylic or methacrylic acid or both mixture, benzene
Ethene, vinyl acetate, acrylonitrile, acrylamide, recombination reaction surfactant, unsaturated strongly hydrophilic monomer and go from
Son is added in reactor, is warming up to 40~60 DEG C of 10~30min of emulsification at a high speed, is obtained shell microemulsion；
C, preparation initiator solution：The initiator solution includes oxidizing agent solution, reductant solution, will oxidation when using
Agent solution, reductant solution are separately added in reaction system；
D, synthesis：The core microemulsion emulsified is warming up to 60~80 DEG C, half initiator solution is added and triggers polyase 13 0
~60min, then to the remaining initiator solution of drop and shell microemulsion, to continuing to react 10~30min after dripping off, by system pH
Value is adjusted to 4.5~6.0, continues at 75~90 DEG C of 3~4h of reaction；Less than 40 DEG C are cooled to after having reacted, ammonification water adjusts pH value to 7
~8, filter to obtain the imitative reactive coating stamp formaldehyde binder of special soft type.
8. a kind of special soft type as claimed in claim 1 or 2 imitates the application of reactive coating stamp formaldehyde binder, its feature exists
In described adhesive is used for pigment printing, pigment dyeing.
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| CN105625055A (en) * | 2016-03-03 | 2016-06-01 | 张耀忠 | Environment-friendly printing adhesive |
| CN106567262A (en) * | 2016-11-03 | 2017-04-19 | 东莞市联洲知识产权运营管理有限公司 | Formaldehyde-free adhesive for pigment dyeing and preparation method thereof |
| CN108425255A (en) * | 2018-02-09 | 2018-08-21 | 合肥聚合工贸有限公司 | The method that segmented emulsion polymerization generates high-performance macromolecule printing adhesive |
| CN110591018B (en) * | 2019-01-28 | 2021-10-22 | 四川益欣科技有限责任公司 | V-type polydimethylsiloxane hydrophobic association emulsion polymerization printing thickener, preparation method and application |
| CN111647128B (en) * | 2020-06-24 | 2021-11-12 | 义乌市渊泰新材料有限公司 | Preparation method of formaldehyde-free textile color fixing agent |
| CN113445333A (en) * | 2021-06-25 | 2021-09-28 | 江苏泰慕士针纺科技股份有限公司 | High-washability activity-imitation flash-printing knitted environment-friendly fabric |
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| CN101121771A (en) * | 2006-08-11 | 2008-02-13 | 汉高股份两合公司 | Acryloxyalkoxysilicane modified acrylic acid ester polymerization emulsion and its preparation method and application |
| CN104141249B (en) * | 2014-06-25 | 2016-05-11 | 广西科技大学 | Photocurable composite coating print paste composition and preparation method and processing method |
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