CN106988134A - A kind of printing adhesive and preparation method thereof, print paste and clothes - Google Patents
A kind of printing adhesive and preparation method thereof, print paste and clothes Download PDFInfo
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- CN106988134A CN106988134A CN201710247270.6A CN201710247270A CN106988134A CN 106988134 A CN106988134 A CN 106988134A CN 201710247270 A CN201710247270 A CN 201710247270A CN 106988134 A CN106988134 A CN 106988134A
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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
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- D06P1/5292—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds containing Si-atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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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)
- Textile Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a kind of printing adhesive and preparation method thereof, print paste and clothes, wherein, the printing adhesive in terms of mass fraction, including：40~70 parts of cool feeling silicone oil emulsion, 0.6~1.0 part of emulsifying agent, 36~59 parts of deionized water, 80~100 parts of soft monomer, 10~30 parts of hard monomer, 0.6~3.0 part of emulsifying agent, 0.2~0.6 part of pH buffer, 50~60 parts of deionized water, 0.2~0.6 part of initiator, 1~4 part of cross-linking monomer；So that printing adhesive not only has, viscosity is low, easy heat radiation advantage, and with higher polymerization rate, the polymer molecular weight of gained is high.
Description
Technical field
The present invention relates to light industry field of textiles, and in particular to a kind of printing adhesive and preparation method thereof.
Background technology
Pigment printing is that the pigment for not having compatibility and reactivity is adhered into fiber surface by means of adhesive and formed
A kind of special printing method of required pattern.Pigment printing has the advantages that technique is simple, save the energy and environmental pollution is small, mesh
Preceding global pigment printing fabric accounts for more than the 70% of calico total output.
In recent years, China's pigment printing there has also been very big development, but product structure is still unreasonable, in, low grade products
In the majority, profit is meagre.And the quality and class of pigment printing product are heavily dependent on the performance of pigment printing binding agent.
The water polyacrylic acid PA class adhesives used in the prior art are a major classes of printing adhesive, but pure third
The shortcomings of emulsion binding agent generally existing hot sticky cold crisp, wet-milling rubbing fastness and poor feel, to improve this kind of pigment printing bonding
The application performance of agent, especially dry and wet crock fastness, it is common to use method be exactly in the building-up process of PA adhesives with hand over
Receipts or other documents in duplicate body N hydroxymethyl acrylamide participates in copolyreaction, but it needs high temperature to bake, and the printing adhesive through baking is easy
Discharge and environmental requirement is not met to environment and the harmful free formaldehyde of human body.
Develop from improving fastness, improving feel and reducing the directions such as energy consumption, foreign binders mainly undergo four-stage.The
Four generation printing adhesives are super soft intercrossed network type adhesive, its be mutually run through by two or more polymer molecular chains and
The network structure of formation, and wherein at least one polymer molecular chain is crosslinked in the way of chemical bond.The side typically used
Formula is to be swelled second comonomer in polymer I together with crosslinking agent and initiator (or activator), makes second comonomer on the spot
It polymerize and is cross-linked to form polymer II.Interpenetrating net polymer is binary or multiple aggregation objects system, each cross-linked network phase
Mutual entanglement is very strong, so as to produce good synergy, assigns its superior performance；But, preparation technology is complex, and
Using organic silicon monomer or oligomer containing function key, there is certain limitation to the performance boost of polyacrylate, and
When being chemically reacted, the usage amount to organosilicon has certain limitations.
With development in science and technology and the improvement of people's living standards, people have higher want to the feature of garment material
Ask, comfortableness and feature become one of demand of first choice.With the development of global warming trend, people are to summer clothes
Cool and comfortable function has great demand, and the product with the refreshing function of ice is following trend.
On the premise of ensureing that product meets environmental requirement, suitable interpenetrating networks and cross-linking system, and feature are found
Composition, synthesizes the super soft dope printing adhesive for possessing cool feeling function, inierpeneirating network structure is formed during stamp, jail
Degree lifting turns into those skilled in the art's technical issues that need to address.
The content of the invention
The present invention provides a kind of printing adhesive and preparation method thereof, with solve performance boost in the prior art it is limited and
Environmentally friendly the problems such as.
The present invention provides a kind of printing adhesive, in terms of mass fraction, including：
40~70 parts of cool feeling silicone oil emulsion, 0.6~1.0 part of emulsifying agent, 36~59 parts of deionized water, soft monomer 80~100
Part, 10~30 parts of hard monomer, 0.6~3.0 part of emulsifying agent, 0.2~0.6 part of pH buffer, 50~60 parts of deionized water, initiator
0.2~0.6 part, 1~4 part of cross-linking monomer；
Wherein, 40~70 parts of the cool feeling silicone oil emulsion, 0.6~1.0 part of the emulsifying agent and the deionized water 30~
50 parts are used as the first component emulsion；
5~15 parts and described cross-linking monomer 1-4 parts add first group 40~50 parts in the soft monomer, in the hard monomer
Divide and pre-swollen liquid is formed in emulsion；
40~50 parts in the soft monomer, 5~15 parts in the hard monomer, 0.6~3.0 part of the emulsifying agent, the pH
0.2~0.6 part of buffer and 50~60 parts of the deionized water are used as the second component pre-emulsion after pre-emulsification；
0.2~0.6 part of the initiator is initiator solution with 6~9 parts of the deionized water.
It is preferred that, the cool feeling silicone oil emulsion is amido silicon oil, polyether silicone oil or ternary polymerization silicone oil.
It is preferred that, the soft monomer is ethyl acrylate, Isooctyl acrylate monomer one of the two or two kinds and acrylic acid
The mixture of butyl ester.
It is preferred that, the butyl acrylate account for the mixture gross mass percentage range be more than or equal to 60%, it is small
In equal to 80%.
It is preferred that, the hard monomer is one or both of acrylonitrile, vinyl acetate, tertiary ethylene carbonate, styrene
With the mixture of methyl methacrylate.
It is preferred that, the methyl methacrylate account for the mixture gross mass percentage range be more than or equal to
50%, less than or equal to 70%.
It is preferred that, the emulsifying agent is that anion emulsifier is compounded with nonionic emulsifier.
It is preferred that, the anion emulsifier is neopelex, lauryl sodium sulfate, succinic acid dihexyl
Sodium sulfonate or sulfosuccinate surfactant.
It is preferred that, the nonionic emulsifier is AEO.
It is preferred that, the cross-linking monomer is GDMA or methylene-bisacrylamide.
It is preferred that, the initiator is ammonium persulfate or potassium peroxydisulfate.
It is preferred that, the pH buffer is sodium acid carbonate.
It is preferred that, regulation pH value range is more than or equal to 7.0, the ammoniacal liquor less than or equal to 7.5.
The present invention also provides a kind of preparation method of printing adhesive, including：
There is provided to prepare by cool feeling silicone oil emulsion, emulsifying agent and deionized water and obtain the first component emulsion, and will be described
First component emulsion is put into polymerization reaction kettle；
Being added into the polymerization reaction kettle with the first component emulsion includes soft monomer, hard monomer and crosslinking list
Body, is configured to pre-swollen liquid and is stirred be swelled；
The pre-swollen drop into the polymerization reaction kettle adds the initiator solution；
It is added dropwise after the emulsion in the polymerization reaction kettle meets predetermined condition by the soft monomer, hard monomer, emulsification
Agent, pH buffer and deionized water prepare obtained the second component pre-emulsion and initiator solution formation printed adhesive
Agent.
It is preferred that, the preparation condition of the first component emulsion is：
In terms of mass fraction, 40~70 parts of the cool feeling silicone oil emulsion is chosen, 0.6~1.0 part of the emulsifying agent is described to go
56~69 parts of ionized water, temperature elevating range be more than or equal to 40 DEG C, less than or equal to 45 DEG C, uniform stirring time range be more than or equal to
2.0h, less than or equal to 3.0h, then cools the temperature to less than 40 DEG C.
It is preferred that, the preparation condition of the second component pre-emulsion is：
In terms of mass fraction, selection 40~50 parts of the soft monomer, 5~15 parts of the hard monomer, the emulsifying agent 0.6~
3.0 parts, 0.2~0.6 part of the pH buffer, described 50~60 parts of uniform stirrings of deionized water obtain the pre- breast of the second component
Liquid.
It is preferred that, the configuration condition of the pre-swollen liquid is specially：
In terms of mass fraction, 80~100 parts of the first component emulsion, the soft list are added in the polymerization reaction kettle
40~50 parts of body, 5~15 parts of the hard monomer and 1~4 part of the cross-linking monomer.
It is preferred that, it is described into the polymerization reaction kettle with the first component emulsion add include soft monomer, firmly
The pre-swollen liquid that monomer and cross-linking monomer are constituted, which is stirred the condition being swelled, to be included：
The temperature elevating range for controlling the polymerization reaction kettle is more than or equal to 25 DEG C, less than or equal to 35 DEG C；Stir be swelled when
Between scope be more than or equal to 10h, less than or equal to 14h；Control again afterwards the polymerization reaction kettle temperature elevating range be more than or equal to
45 DEG C, less than or equal to 55 DEG C.
It is preferred that, it is described the initiator solution is added dropwise into the polymerization reaction kettle to be specially：
The initiator solution is 4~6 parts；
It is more than or equal to 78 DEG C, less than or equal to 80 DEG C to control the temperature range in the polymerization reaction kettle.
It is preferred that, the predetermined condition is that blue light is presented in the emulsion in the polymerization reaction kettle.
It is preferred that, it is added dropwise after the emulsion in the polymerization reaction kettle meets predetermined condition by the soft monomer, hard list
Body, emulsifying agent, pH buffer and deionized water prepare the second obtained component pre-emulsion and the initiator solution is formed
Printing adhesive, including：
The time range that the second component pre-emulsion and the initiator solution is continuously added dropwise be more than or equal to 1.5h, it is small
In equal to 2h；It is more than or equal to 85 DEG C, less than or equal to 90 DEG C to control the temperature elevating range in the polymerization reaction kettle afterwards；Keep institute
It is more than or equal to 1h, less than or equal to 2h to state the temperature-time scope in polymerization reaction kettle；The polymerisation temperature in the kettle is dropped
Warm scope is less than or equal to 40 DEG C.
It is preferred that, the emulsion after in the polymerization reaction kettle meet predetermined condition after be added dropwise by the soft monomer,
Hard monomer, emulsifying agent, pH buffer and deionized water prepare the second obtained component pre-emulsion and the initiator solution it
After include：
The pH value that ammoniacal liquor adjusts the emulsion in the polymerization reaction kettle is added into the polymerization reaction kettle.
It is preferred that, the scope of the pH value is more than or equal to 7.0, less than or equal to 7.5.
The present invention also provides a kind of print paste, including：Using printing adhesive as described above and print as described above
Printing adhesive, mill base, thickener and water configuration prepared by the preparation method of flower adhesive is formed.
It is preferred that, the mass percent of the printing adhesive is 30%, and the mass percent of the mill base is 2.0%,
The mass percent of the thickener is 2.0%, and the mass percent of the water is 66%.
The present invention also provides a kind of clothes, and the print being made of printing adhesive as described above is provided with clothes
Flower.
Compared with prior art, the present invention has advantages below：
A kind of printing adhesive that the application is provided, regard the cool feeling silicone oil emulsion, emulsifying agent and deionized water as the
One component emulsion；The soft monomer, the hard monomer and the cross-linking monomer are added in first component emulsion and form pre-
Swelling solution；It regard soft monomer, hard monomer, emulsifying agent, pH buffer part and deionized water as the second component pre-emulsion；By initiator
It is initiator solution with the deionized water；By using emulsion polymerization way by the pre-swollen liquid and the second component emulsion with
And initiator solution carries out being mixed to form printing adhesive, so that printing adhesive not only has viscosity low, easy heat radiation
Advantage, and with higher polymerization rate, the polymer molecular weight of gained is high, in addition, using water as medium, production peace
Entirely, environmental pollution is small, with low cost；The printing adhesive stable storing of synthesis, forms inierpeneirating network structure during stamp,
Fastness is good；
Class containing APES (APEO) emulsifying agent is not used in the printing adhesive that the application is provided, and stamp is produced
The formaldehydeless release of product, belongs to environmentally friendly machine；
The printing adhesive that the application is provided is when to realizing emulsion polymerization, and the technique of use is simple, polymerization process is stable,
Workable, equipment investment is small, is conducive to large-scale industrial production；
The application provide printing adhesive there is emulsion particle interpenetrating structure, can strengthen cool feeling silicone oil (polysiloxanes) with
Compatibility between polyacrylate, makes Printing have outstanding dry, wet rubbing fastness and washing fastness, and flower-shaped wheel is cleaned up
Clear, lovely luster.
Cool feeling silicone oil (polysiloxanes) in the printing adhesive that the application is provided can be in fabric face shape after stamp
Into oriented, the coefficient of friction between fiber is reduced, PRINTED FABRIC is obtained smooth, super soft feel.Further, since adopting
Cause the Printing being made up of printing adhesive that there is coolness with cool feeling silicone oil, be suitably applied summer clothes, especially
It is the clothes that outdoor, running etc. have demand to cool feeling.
Embodiment
Many details are elaborated in the following description to fully understand the present invention.But the present invention can be with
Much it is different from other manner described here to implement, those skilled in the art can be in the situation without prejudice to intension of the present invention
Under do similar popularization, therefore the present invention is not limited to the specific embodiments disclosed below.
The application provides a kind of printing adhesive, its constituent in terms of mass fraction, including：Cool feeling silicone oil emulsion 40~
70 parts, 0.6~1.0 part of emulsifying agent, 56~69 parts of deionized water, 80~100 parts of soft monomer, 10~30 parts of hard monomer, emulsifying agent
0.6~3.0 part, 0.2~0.6 part of pH buffer, 50~60 parts of deionized water, 0.2~0.6 part of initiator, cross-linking monomer 1~4
Part；
Wherein, 40~70 parts of the cool feeling silicone oil emulsion, 0.6~1.0 part of the emulsifying agent and the deionized water are chosen
30~50 parts are used as the first component emulsion；
Choose 40~50 parts of the soft monomer, 5~15 parts of the hard monomer and be directly added into shape in first component emulsion
Into pre-swollen liquid；
Choose 40~50 parts of the soft monomer, 5~15 parts of the hard monomer, 0.6~3.0 part of the emulsifying agent, the pH
0.2~0.6 part of buffer and 50~60 parts of the deionized water are used as the second component pre-emulsion；
0.2~0.6 part of the initiator is used as initiator solution with 6~9 parts of the deionized water.
In this embodiment, the cool feeling silicone oil emulsion can be the polysiloxane emulsion with cooling effect, specifically can be with
Using amido silicon oil, polyether silicone oil or ternary polymerization silicone oil etc..
The soft monomer is that ethyl acrylate, Isooctyl acrylate monomer one of the two or two kinds are mixed with butyl acrylate
Compound.Wherein, the butyl acrylate account for the mixture gross mass of the soft monomer percentage range be more than or equal to 60%,
Less than or equal to 80%.
The hard monomer is one or both of acrylonitrile, vinyl acetate, tertiary ethylene carbonate, styrene and methyl-prop
The mixture of e pioic acid methyl ester.Wherein, the methyl methacrylate accounts for the percentage model of the mixture gross mass of the hard monomer
Enclose for more than or equal to 50%, less than or equal to 70%.
The emulsifying agent is that anion emulsifier is compounded with nonionic emulsifier.Wherein, the anion emulsifier can be with
It is neopelex, lauryl sodium sulfate, succinic acid dihexyl sodium sulfonate or sulfosuccinate surfactant
Deng.The nonionic emulsifier can be AEO.
The cross-linking monomer can be GDMA or methylene-bisacrylamide.
The initiator can be ammonium persulfate or potassium peroxydisulfate.
The pH buffer can be sodium acid carbonate.
Based on the above, the application provides three experiment effects for implementing the printing adhesive that explanation the application is provided,
It is specific as follows：
Embodiment 1
By cool feeling silicone oil emulsion SOFTEXS-585 40.0g, emulsifying agent 0.6g, deionized water 60g, 40 DEG C are warming up to,
Even stirring 2h, is made the first component；Butyl acrylate 30.0g, Isooctyl acrylate monomer 20.0g, methyl methacrylate 10.0g,
Acrylate pre-emulsion is made in acrylonitrile 5.0g, pH buffer 0.5g, emulsifying agent 1.5g, deionized water 50g, uniform stirring；Will
0.4g potassium peroxydisulfates dissolve in 8.0g deionized waters, are configured to initiator solution；Above-mentioned height is added into polymerization reaction kettle
Molecule organic silicon emulsion 100g, butyl acrylate 30.0g, Isooctyl acrylate monomer 20.0g, methyl methacrylate 10.0g, propylene
Nitrile 5.0g, GDMA 1.5g, are warming up to 30 DEG C.12h is swelled under stirring；50 DEG C are warming up to, is added above-mentioned
Initiator solution 6g, be warming up to emulsion in 78 DEG C, reactor to be polymerized and occur after blue light, then continuously dripped into polymerization reaction kettle
Plus remaining pre-emulsion, after 2h is continuously dripped, remaining initiator solution is added, is warming up to after 85 DEG C, insulation 1h, then will
Temperature is down to less than 40 DEG C, ammonification water regulation pH7.0~7.5, you can pigment printing binding agent needed for being made.
Wherein, GDMA contains 2 unsaturated double-bonds, and unsaturated double-bond is participated in the course of the polymerization process
Addition reaction, forms crosslinking.Emulsifying agent is by neopelex, AEO AFX-3070 compositions, weight
Than for 2：1.
Embodiment 2
By cool feeling silicone oil emulsion H-424 62.0g, deionized water 30g, 40 DEG C are warming up to, uniform stirring 2h is made first
Component；Butyl acrylate 40.0g, ethyl acrylate 10.0g, methyl methacrylate 10.0g, acrylonitrile 3.0g, styrene
Acrylate pre-emulsion is made in 2.0g, pH buffer 0.5g, emulsifying agent 1.5g, deionized water 50g, uniform stirring；By 0.35g mistakes
Potassium sulfate dissolves in 7.0g deionized waters, is configured to initiator solution；Above-mentioned macromolecule is added into polymerization reaction kettle to be had
Machine silicon emulsion 90g, butyl acrylate 40.0g, ethyl acrylate 10.0g, methyl methacrylate 10.0g, acrylonitrile 3.0g, benzene
Ethene 2.0g, GDMA 1.5g, are warming up to 30 DEG C.12h is swelled under stirring；It is warming up to 50 DEG C, in addition
The initiator solution 4.5g stated, is warming up to emulsion in 78 DEG C, reactor to be polymerized and occurs after blue light, then connect into polymerization reaction kettle
It is continuous that remaining pre-emulsion is added dropwise, after 2h is continuously dripped, remaining initiator solution is added, is warming up to after 85 DEG C, insulation 1h,
Less than 40 DEG C, ammonification water regulation pH7.0~7.5, you can pigment printing binding agent needed for being made are cooled the temperature to again.
It should be noted that adding ammoniacal liquor the emulsion in polymerization reaction kettle can be made to be in alkalescent or neutrality, one side
Polymerisation can be stopped, because environment reacts stopping in acidity after pH changes when the initiator potassium persulfate used is reacted；
On the other hand emulsion-stabilizing can be made.
GDMA contains 2 unsaturated double-bonds, and unsaturated double-bond participates in addition in the course of the polymerization process
Reaction, forms crosslinking.Emulsifying agent is by anion emulsifier neopelex, lauryl sodium sulfate, non-ionic emulsifier
Agent AEO AFX-3070 is constituted, and weight ratio is 1.8：0.2：1.
Embodiment 3
By cool feeling silicone oil emulsion SOFTEX S-009 50.0g, emulsifying agent 1.5g, deionized water 50.0g, 40 DEG C are warming up to,
Uniform stirring 2h, is made the first component；Butyl acrylate 40.0g, Isooctyl acrylate monomer 5.0g, methyl methacrylate 5.0g,
Styrene 3.0g, methylene-bisacrylamide 1.5g, pH buffer 0.5g, emulsifying agent 1.6g, deionized water 50g, uniform stirring
Acrylate pre-emulsion is made；0.5g potassium peroxydisulfates are dissolved in 9.0g deionized waters, initiator solution is configured to；To polymerization
Above-mentioned the macromolecule organic silicon emulsion 100g, butyl acrylate 40.0g, Isooctyl acrylate monomer 5.0g, methyl are added in reactor
Methyl acrylate 5.0g, styrene 3.0g, methylene-bisacrylamide 1.0g are warming up under 30 DEG C, stirring and are swelled 12h；Heating
To 50 DEG C, above-mentioned initiator solution 6g is added, emulsion in 80 DEG C, reactor to be polymerized is warming up to and occurs after blue light, then to poly-
Close in reactor and remaining pre-emulsion is continuously added dropwise, after 2h is continuously dripped, add remaining initiator solution, be warming up to 85
DEG C, after insulation 1.5h, then cool the temperature to less than 40 DEG C, ammonification water regulation pH7.0~7.5, you can pigment printing needed for being made
Adhesive.
Wherein, methylene-bisacrylamide contains 2 unsaturated double-bonds, and unsaturated double-bond participates in addition in the course of the polymerization process
Reaction, forms crosslinking.Emulsifying agent is by neopelex, succinic acid dihexyl sodium sulfonate, AEO
1307th, 1309 composition, weight ratio is 3：1：1：1.
Performance evaluation in above three embodiment on printing adhesive, see the table below：
Properties detection method is as follows in upper table：
(1) formaldehyde test is tested according to GB/T2912.1-1998.
(2) feel test is by subjective touch, and 1 is expressed as that feel is poor, and 2 are expressed as feel typically, and 3 to be expressed as feel good
Good, 4 represent soft comfortable, and 5 represent that feel is extremely excellent.
(3) cool feeling test maximum heat absorption rate, weighs the radiating rate of fabric, and numerical value is bigger, and cool feeling effect is better.
(4) crock fastness is tested according to GB/T3920-19970, and fastness to washing is tested according to GB/T420-1990.
It can be seen that, the embodiment of the present invention detects formaldehydeless release, imitated with good feel and ice sense from above-mentioned test
Really.The printing adhesive provided by the application prepare acquisition pigment printing can effectively solve feel and crock fastness,
Between washing fastness the problem of contradiction.
Based on the above, a kind of print paste that the application can also be provided, the print paste can be by using
The printing adhesive that the application is provided is formulated, and formula during specific preparation can be in the following way：
The print paste that the application is provided, using the mass percent of printing adhesive, (solid content is about for 30%
50%), mill base mass percent is 2.0%, and thickener qualities percentage is 2.0%, and water quality percentage is 66%.Wherein institute
Stating printing adhesive can be prepared using the preparation method of printing adhesive as described above.
A kind of printing adhesive that the application is provided, it is formaldehydeless environment-friendly products, passes through the printing adhesive system
Printing there is coolness, super soft, smooth feel, with outstanding dry, wet rubbing fastness and washing fastness, and flower
Shape is clear-cut, lovely luster, is suitably applied summer clothes, and especially outdoor, running etc. has the clothes of demand to cool feeling.
Based on the above, the application also provides a kind of preparation method of printing adhesive, including：
There is provided to prepare by cool feeling silicone oil emulsion, emulsifying agent and deionized water and obtain the first component emulsion, and will be described
First component emulsion is put into polymerization reaction kettle；
Being added into the polymerization reaction kettle with the first component emulsion includes soft monomer, hard monomer and crosslinking list
Body, the pre-swollen liquid being configured to and being stirred is swelled；
The initiator solution is added dropwise in the pre-swollen liquid into the polymerization reaction kettle；
Being added dropwise after the emulsion in the polymerization reaction kettle meets predetermined condition includes the soft monomer, hard monomer, emulsification
Agent, pH buffer and deionized water prepare obtained the second component pre-emulsion and initiator solution formation printed adhesive
Agent.
Also provided for the application in a kind of implementation of the preparation method of printing adhesive, the first component emulsion is matched somebody with somebody
Condition processed is：
In terms of mass fraction, 40~70 parts of the cool feeling silicone oil emulsion is chosen, 0.6~1.0 part of the emulsifying agent is described to go
30~50 parts of ionized water, temperature elevating range be more than or equal to 40 DEG C, less than or equal to 45 DEG C, uniform stirring time range be more than or equal to
2.0h, less than or equal to 3.0h, then cools the temperature to less than 40 DEG C.
The preparation condition of the second component pre-emulsion is：
In terms of mass fraction, selection 40~50 parts of the soft monomer, 5~15 parts of the hard monomer, the emulsifying agent 0.6~
3.0 parts, 0.2~0.6 part of the pH buffer, described 50~60 parts of uniform stirrings of deionized water.
The preparation condition of the pre-swollen liquid is：First component added into polymerization reaction kettle in terms of mass fraction
1~4 part of 80~100 parts of emulsion, 40~50 parts of soft monomer, 5~15 parts of hard monomer and cross-linking monomer, and be stirred and be swelled.
The condition that is swelled of stirring is：Temperature elevating range be more than or equal to 25 DEG C, less than or equal to 35 DEG C, in this embodiment,
Preferably it is warming up to 30 DEG C；The time range being swelled under stirring may be greater than equal to 10h, less than or equal to 14h, in this implementation
In, preferably 12h；It is more than or equal to 45 DEG C, less than or equal to 55 DEG C, in this embodiment, preferably to control temperature elevating range again afterwards
To be warming up to 50 DEG C.
Afterwards, 4~6 parts of initiator solution is added dropwise to the polymerization reaction kettle, controls the heating in the polymerization reaction kettle
More than or equal to 78 DEG C, less than or equal to 80 DEG C, after predetermined condition is met, i.e., temperature range is：Breast in the polymerization reaction kettle
Liquid occurs after blue light, then the second component pre-emulsion of continuous dropwise addition and remaining initiator solution, institute into the polymerization reaction kettle
It is more than or equal to 1.5h, less than or equal to 2h to state the time range being continuously added dropwise；The heating in the polymerization reaction kettle is controlled afterwards
Scope is more than or equal to 85 DEG C, less than or equal to 90 DEG C；After the polymerization reaction kettle is incubated 1~2h, then cool the temperature to 40 DEG C
Hereinafter, including 40 DEG C, you can possess the printing adhesive of the super soft intercrossed network type structure of cool feeling function needed for being made.
It should be noted that so-called intercrossed network type structure is interpenetrating polymer networks (Interpenetrating
Polymer Networks, abbreviation IPN or IPNs) it is the network as formed by mutually running through two or more polymer molecular chains
Structure, and wherein at least one polymer molecular chain is crosslinked in the way of chemical bond.IPNs structures multiple network it
Between chemical covalent bonds are not present, but be combined with each other by physics " topological key ", be that a kind of special macromolecular ring body space is opened up
Flutter form.The internetwork compatibilities of IPNs are essentially from internal active force, if different group has close Van der Waals repulsion half
Footpath, then interpenetrating structure just can be formed between these networks.
The preparation method for the printing adhesive that the application is provided, is also to employ intercrossed network type structure in preparation process
Form mode realizes, i.e.,：Each particle includes a micro- interpenetrating polymer networks.This polymer network is typically shell-core knot
Further crosslinking can occur after structure, film forming, between particle.The preparation process of shell core emulsion interpenetrating polymer networks is as follows：It is first
Polymer I is first prepared using emulsion polymerization, as " seed " emulsion, monomer II, crosslinking are then added in polymer I emulsions
Agent and initiator, monomer II polymerize on the surface of " seed " emulsion particle, ultimately form shell core emulsion IPNs.In this application
The first component emulsion by the way that the first component emulsion is put into polymerization reaction kettle, and is added equivalent to seed emulsion
Soft/duroelasts formation micelle, carries out reaction to addition initiator solution and the second component pre-emulsion and ultimately forms shell core emulsion
IPNs。
Although the present invention is disclosed as above with preferred embodiment, it is not for limiting the present invention, any this area skill
Art personnel without departing from the spirit and scope of the present invention, can make possible variation and modification, therefore the guarantor of the present invention
The scope that shield scope should be defined by the claims in the present invention is defined.
Claims (26)
1. a kind of printing adhesive, it is characterised in that in terms of mass fraction, including：
40~70 parts of cool feeling silicone oil emulsion, 0.6~1.0 part of emulsifying agent, 36~59 parts of deionized water, 80~100 parts of soft monomer, firmly
10~30 parts of monomer, 0.6~3.0 part of emulsifying agent, 0.2~0.6 part of pH buffer, 50~60 parts of deionized water, initiator 0.2~
0.6 part, 1~4 part of cross-linking monomer；
Wherein, 30~50 parts of 40~70 parts of the cool feeling silicone oil emulsion, 0.6~1.0 part of the emulsifying agent and the deionized water
It is used as the first component emulsion；
5~15 parts and described cross-linking monomer 1-4 parts add described first group 40~50 parts in the soft monomer, in the hard monomer
Divide and pre-swollen liquid is formed in emulsion；
40~50 parts in the soft monomer, 5~15 parts in the hard monomer, 0.6~3.0 part of the emulsifying agent, the pH buffering
0.2~0.6 part of agent and 50~60 parts of the deionized water are used as the second component pre-emulsion after pre-emulsification；
0.2~0.6 part of the initiator is initiator solution with 6~9 parts of the deionized water.
2. printing adhesive according to claim 1, it is characterised in that：The cool feeling silicone oil emulsion is amido silicon oil, is gathered
Ether silicone oil or ternary polymerization silicone oil.
3. printing adhesive according to claim 1, it is characterised in that：The soft monomer is ethyl acrylate, acrylic acid
The mixture of different monooctyl ester one of the two or two kinds and butyl acrylate.
4. printing adhesive according to claim 3, it is characterised in that：The butyl acrylate accounts for the total matter of the mixture
The percentage range of amount is more than or equal to 60%, less than or equal to 80%.
5. printing adhesive according to claim 1, it is characterised in that：The hard monomer is acrylonitrile, vinyl acetate, uncle
The mixture of one or both of ethylene carbonate, styrene and methyl methacrylate.
6. printing adhesive according to claim 5, it is characterised in that：The methyl methacrylate accounts for the mixture
The percentage range of gross mass is more than or equal to 50%, less than or equal to 70%.
7. printing adhesive according to claim 1, it is characterised in that：The emulsifying agent be anion emulsifier with it is non-from
Sub- emulsifying agent compounding.
8. printing adhesive according to claim 7, it is characterised in that：The anion emulsifier is detergent alkylate sulphur
Sour sodium, lauryl sodium sulfate, succinic acid dihexyl sodium sulfonate or sulfosuccinate surfactant.
9. printing adhesive according to claim 7, it is characterised in that：The nonionic emulsifier is fatty alcohol polyoxy second
Alkene ether.
10. printing adhesive according to claim 1, it is characterised in that：The cross-linking monomer is dimethacrylate second
Diol ester or methylene-bisacrylamide.
11. printing adhesive according to claim 1, it is characterised in that：The initiator is ammonium persulfate or persulfuric acid
Potassium.
12. printing adhesive according to claim 1, it is characterised in that：The pH buffer is sodium acid carbonate.
13. printing adhesive according to claim 12, it is characterised in that including：Adjust pH value range more than or equal to
7.0, the ammoniacal liquor less than or equal to 7.5.
14. a kind of preparation method of printing adhesive, it is characterised in that including：
There is provided to prepare by cool feeling silicone oil emulsion, emulsifying agent and deionized water and obtain the first component emulsion, and by described first
Component emulsion is put into polymerization reaction kettle；
Being added into the polymerization reaction kettle with the first component emulsion includes soft monomer, hard monomer and cross-linking monomer,
It is configured to pre-swollen liquid and is stirred be swelled；
The pre-swollen drop into the polymerization reaction kettle adds the initiator solution；
It is added dropwise after the emulsion in the polymerization reaction kettle meets predetermined condition and passes through the soft monomer, hard monomer, emulsifying agent, pH
Buffer and deionized water prepare obtained the second component pre-emulsion and initiator solution formation printing adhesive.
15. the preparation method of printing adhesive according to claim 14, it is characterised in that the first component emulsion
Preparation condition is：
In terms of mass fraction, 40~70 parts of the cool feeling silicone oil emulsion, 0.6~1.0 part of the emulsifying agent, the deionization are chosen
56~69 parts of water, temperature elevating range be more than or equal to 40 DEG C, less than or equal to 45 DEG C, uniform stirring time range be more than or equal to
2.0h, less than or equal to 3.0h, then cools the temperature to less than 40 DEG C.
16. the preparation method of printing adhesive according to claim 14, it is characterised in that the second component pre-emulsion
Preparation condition be：
In terms of mass fraction, 40~50 parts of the soft monomer, 5~15 parts of the hard monomer, the emulsifying agent 0.6~3.0 are chosen
Part, 0.2~0.6 part of the pH buffer, described 50~60 parts of uniform stirrings of deionized water obtain the second component pre-emulsion.
17. the preparation method of printing adhesive according to claim 14, it is characterised in that the configuration of the pre-swollen liquid
Condition is specially：
In terms of mass fraction, 80~100 parts of the first component emulsion, the soft monomer 40 are added in the polymerization reaction kettle
~50 parts, 5~15 parts of the hard monomer and 1~4 part of the cross-linking monomer.
18. the preparation method of printing adhesive according to claim 14, it is characterised in that described to described first
The pre-swollen liquid that the interior addition of the polymerization reaction kettle of component emulsion includes soft monomer, hard monomer and cross-linking monomer composition is stirred
Mixing the condition being swelled includes：
The temperature elevating range for controlling the polymerization reaction kettle is more than or equal to 25 DEG C, less than or equal to 35 DEG C；Stir the time model being swelled
Enclose for more than or equal to 10h, less than or equal to 14h；Control again afterwards the polymerization reaction kettle temperature elevating range be more than or equal to 45 DEG C,
Less than or equal to 55 DEG C.
19. the preparation method of printing adhesive according to claim 14, it is characterised in that described to the polymerisation
The initiator solution is added dropwise in kettle is specially：
The initiator solution is 4~6 parts；
It is more than or equal to 78 DEG C, less than or equal to 80 DEG C to control the temperature range in the polymerization reaction kettle.
20. the preparation method of printing adhesive according to claim 14, it is characterised in that the predetermined condition is described
Blue light is presented in emulsion in polymerization reaction kettle.
21. the preparation method of printing adhesive according to claim 14, it is characterised in that treat in the polymerization reaction kettle
Emulsion meet after predetermined condition be added dropwise by the soft monomer, hard monomer, emulsifying agent, pH buffer and deionized water preparation institute
The the second component pre-emulsion obtained and initiator solution formation printing adhesive, including：
The time range that the second component pre-emulsion and the initiator solution is continuously added dropwise be more than or equal to 1.5h, less than etc.
In 2h；It is more than or equal to 85 DEG C, less than or equal to 90 DEG C to control the temperature elevating range in the polymerization reaction kettle afterwards；Keep described poly-
It is more than or equal to 1h, less than or equal to 2h to close the temperature-time scope in reactor；To greenhouse cooling model in the polymerization reaction kettle
Enclose for less than or equal to 40 DEG C.
22. the preparation method of printing adhesive according to claim 14, it is characterised in that described to treat the polymerisation
Emulsion in kettle meets to be added dropwise after predetermined condition is matched somebody with somebody by the soft monomer, hard monomer, emulsifying agent, pH buffer and deionized water
Include after the second obtained component pre-emulsion of system and the initiator solution：
The pH value that ammoniacal liquor adjusts the emulsion in the polymerization reaction kettle is added into the polymerization reaction kettle.
23. the preparation method of printing adhesive according to claim 22, it is characterised in that the scope of the pH value is big
In equal to 7.0, less than or equal to 7.5.
24. a kind of print paste, it is characterised in that including：Using the printed adhesive as described in claim 1 to 13 any one
Printing adhesive prepared by the preparation method of agent and the printing adhesive as described in claim 14 to 23 any one, mill base,
Thickener and water configuration are formed.
25. print paste according to claim 24, it is characterised in that the mass percent of the printing adhesive is
30%, the mass percent of the mill base is 2.0%, and the mass percent of the thickener is 2.0%, the quality hundred of the water
Divide than being 66%.
26. a kind of clothes, it is characterised in that using the printed adhesive as described in claim 1 to 13 any one on clothes
Printing adhesive prepared by the preparation method of agent and the printing adhesive as described in claim 14 to 23 any one is made
Stamp.
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| CN107447551A (en) * | 2017-08-16 | 2017-12-08 | 辽宁恒星精细化工有限公司 | Cotton towel fabric hydrophilic acrylic ester coating printing adhesive and preparation method thereof |
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| CN113896844A (en) * | 2021-11-19 | 2022-01-07 | 湖北分聚新材料有限公司 | Carboxylic styrene-butadiene latex for carpet and preparation method thereof |
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| CN107385732A (en) * | 2017-07-31 | 2017-11-24 | 安踏（中国）有限公司 | A kind of preparation method of cotton fabric, fabric, clothes and a kind of dressing liquid |
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