CN109610202A - A kind of environment-protection coating printing adhesive and preparation method thereof - Google Patents
A kind of environment-protection coating printing adhesive and preparation method thereof Download PDFInfo
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- CN109610202A CN109610202A CN201811266725.XA CN201811266725A CN109610202A CN 109610202 A CN109610202 A CN 109610202A CN 201811266725 A CN201811266725 A CN 201811266725A CN 109610202 A CN109610202 A CN 109610202A
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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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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- 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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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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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
- C08G18/4829—Polyethers containing at least three hydroxy groups
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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
- C08G18/61—Polysiloxanes
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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
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
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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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
Abstract
The invention discloses environment-protection coating printing adhesives and preparation method thereof, belong to pigment printing field.Epoxidized linseed oil of the present invention is raw material, carries out open loop to it by lactic acid, so that the glue film toughness and tensile property that are formed are improved, improves the performance of adhesive；The present invention is modified adhesive with castor oil and hydroxypropyl silicone oil, the polyhydroxy of castor oil and the self-crosslinked oxidation of double bond, improve the mechanical property of glue film, there are certain microphase-separateds between siloxanes and macromolecular chain in hydroxypropyl silicone oil, the hydrophobicity of fabric surface is improved, so that its wet friction also increases；The present invention improves the adhesive force of adhesive using compoundings such as methyl methacrylate, butyl acrylates as monomer；2,2- hydroxymethyl propionic acid is added as hydrophilic monomer in the present invention before radiation polymerization, introduces carboxyl, enhances automatic emulsifying performance, improve the feature of environmental protection.The present invention solves that current printing adhesive environmental-protecting performance is poor, does, the problem that fastness to wet rubbing is low.
Description
Technical field
The invention belongs to pigment printing fields, and in particular to a kind of environment-protection coating printing adhesive and preparation method thereof.
Background technique
Pigment printing is a kind of fabric printing process, is will not have compatibility in fabric surface film forming mechanism using adhesive
With the printing method of reactive pigment adherency on the fabric.Coating is different from dyestuff, it, cannot to the mostly no reactivity of fiber
It is combined with fiber, its principle of " coloring " on fiber is mainly to anchor at fiber surface, therefore coating prints by means of adhesive
Flower is not limited by fabric fibre, is not also influenced by method for weaving, only needed after general printing fixation without washing so as to shorten
Process flow, has saved the energy, avoids pollution of the dyeing waste water to environment, therefore greatly developed.
Adhesive is the main component in pigment printing slurry, its performance directly affects the stamp process of fabric, is influenced
Fastness, feel and the style of PRINTED FABRIC.In recent years, pigment printing is quickly grown, and pigment printing product increases year by year.However,
Related chemicals such as printing adhesive for pigment printing does not catch up with the rhythm of market development also.Especially go out in the market in recent years
(dosage of the coating in print paste reaches 6-8%, even higher for existing special deep printing；And the coating dosage of general stamp often exists
3% or less), it is desirable that the dry of PRINTED FABRIC, fastness to wet rubbing reach 3-4 grades, and soft.This is undoubtedly to printing adhesive
Application performance propose very high requirement.In addition, having formulated stringent ecological spinning with the pay attention to day by day to environmental protection
Product standard limits the use of poisonous and harmful substances, such as PARA FORMALDEHYDE PRILLS(91,95) and alkyl phenol polyoxyethylene ether (APEO) have specific limit
It is fixed.Self-evident, this proposes more strict requirements to printing adhesive.
The printing adhesive prepared not release formaldehyde is disclosed at present, is also free of APEO, is belonged to Environment-friendlyadhesive adhesive, but be used for
When stamp, the dry fastness of gained PRINTED FABRIC is 2-3 grade, and fastness to wet rubbing is 2 grades, be not achieved special deep printing to do,
The requirement of fastness to wet rubbing (3-4 grades).In short, presently disclosed environment-friendly type printing adhesive or it is able to satisfy the requirement of fastness,
But it is only suitable for middle light stamp；It can be used for special deep printing, but fastness not to reach requirement.
Based on this, if crock fastness environment-protection coating printing adhesive of good performance can be prepared, undoubtedly have important
Realistic meaning and economic value.
Summary of the invention
The technical problems to be solved by the invention: for current printing adhesive environmental-protecting performance it is poor, do, fastness to wet rubbing it is low
The problem of, a kind of environment-protection coating printing adhesive and preparation method thereof is provided.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of environmental protection coating material printing adhesive, including reactant, chain extender, modifying agent, mix monomer；
The reactant the preparation method comprises the following steps:
It takes epoxidized linseed oil 10 ~ 20:6 in mass ratio ~ 9 that lactic acid is added, is passed through nitrogen protection, is warming up to 70 ~ 80 DEG C and is stirred
10 ~ 12h is cooled to room temperature, and obtains cooled material, takes cooled material through rotary evaporation, and rotary evaporation obtains rotary evaporation object, and rotation is taken to steam
It sends out object 10 ~ 15:3 in mass ratio ~ 6:5 ~ 9 and dihydroxy polypropylene oxide ether, polyethylene glycol adipate glycol is added, in 30 ~ 40
DEG C 30 ~ 60min is stirred to get reactant.
The chain extender are as follows: take diethylenetriamine, N methyldiethanol amine 2 ~ 6:2 in mass ratio ~ 5:10 ~ 20 addition go from
Sub- water be stirred 30 ~ 50min to get.
The modifying agent are as follows: take castor oil 3 ~ 6:5 in mass ratio ~ 9 be added hydroxypropyl silicone oil mixing to get.
The mix monomer are as follows: according to the mass fraction, take 3 ~ 6 parts of methyl methacrylates, 6 ~ 10 parts of acetoacetyl first
Base ethyl acrylate, 2 ~ 4 parts of butyl acrylates, 3 ~ 6 parts of ethyl acrylates, 5 ~ 9 parts of acrylic acid, it is stirred 30 in 30 ~ 40 DEG C ~
50min to get.
The preparation method of the environmental protection coating material printing adhesive, includes the following steps:
(1) it takes reactant to be warming up to 100 ~ 110 DEG C of stirrings, vacuumizes 20 ~ 30min, be cooled to 65 ~ 75 DEG C, obtain cooled material a, take
Cooled material a 2 ~ 5:4 in mass ratio ~ 9 is added isophorone diisocyanate and must mix in 65 ~ 75 DEG C of 100 ~ 120min of heat preservation
Object takes 2,2- hydroxymethyl propionic acid, 1 ~ 5:8 in mass ratio ~ 15 that n-methyl-2-pyrrolidone mixing is added, obtains mixed liquor, take mixing
Liquid 3 ~ 7:80 in mass ratio ~ 100 is added in mixture and is stirred, and obtains stirring mixture；
(2) modifying agent is taken to be added dropwise in stirring mixture in 30 ~ 40 DEG C of 5 ~ 9:90 ~ 120 in mass ratio, control time for adding 50 ~
60min is stirred, then the mix monomer for being stirred amount of substance 10 ~ 20% is added dropwise, and controls 1 ~ 3h of time for adding, and stirring is mixed
It closes, mixture a must be stirred, take stirring mixture a 80 ~ 100:4 in mass ratio ~ 7 that triethylamine is added, add stirring mixture a
The acetone of quality 10 ~ 20% is stirred, and obtains mixture a, and chain extender 3 ~ 5:60 ~ 70 in mass ratio is taken to be added dropwise to mixture, control
30 ~ 50min of time for adding is warming up to 40 ~ 50 DEG C and is stirred 10 ~ 20min, nitrogen removal oxygen is passed through, in 60Co γ-rays
Radiation is lower to keep 2 ~ 4h, adjusts pH to 7 ~ 8 through triethylamine, obtains matrix object；
(3) it takes matrix object 10 ~ 15:3 in mass ratio ~ 5 that absolute ethyl alcohol and stirring mixing is added, mixture b must be stirred, take bisulfite
Deionized water is added in sodium 2 ~ 5:8 in mass ratio ~ 15, obtains mixed liquor a, 1 ~ 3:30 ~ 50 in mass ratio mixed liquor a is taken to be added dropwise to stirring
In mixture b, 30 ~ 50min of time for adding is controlled, is stirred to get environmental protection coating material printing adhesive.
Stirring mixture is stirred condition in the step (1) are as follows: is stirred 60 ~ 90min in 65 ~ 75 DEG C.
Environmental protection coating material printing adhesive is stirred condition in the step (3) are as follows: it is stirred 1 in 20 ~ 25 DEG C ~
4h。
The present invention is compared with other methods, and advantageous effects are:
(1) epoxidized linseed oil of the present invention is raw material, carries out open loop to it by lactic acid, the linseed oil for being prepared for lactic modified is polynary
Alcohol is simultaneously compounded using dihydroxy polypropylene oxide ether, polyethylene glycol adipate glycol as reactant, forms soft segment and stamp is added
Adhesive is most radiated through 60Co γ-rays afterwards so that the glue film toughness and tensile property that are formed are improved, and is not needed to be added and be drawn
Hair agent is polymerize, and is accelerated polymerization efficiency, so that winding the even closer of combination between polymer molecule segment, is improved viscous
The performance of mixture；
(2) present invention is modified adhesive with castor oil and hydroxypropyl silicone oil, the polyhydroxy of castor oil and the oxygen of double bond
Change self-crosslinking, increases the degree of cross linking of printing adhesive, improve the mechanical property of glue film, siloxanes and high score in hydroxypropyl silicone oil
There are certain microphase-separateds between subchain, and silicon is caused to be easier to concentrate on film surface, so that the resistance to water energy of modified glue film
Power improves, and enhances macromolecule to the package of dyestuff, increases the effect of stamp fixation, while the film to be formed is had
There is preferable flatness, reduce the coefficient of friction between fiber sheath, improve dry friction color fastness, on the other hand to knit
The surface of object can reduce, and improve the hydrophobicity of fabric surface, so that its wet friction also increases；
(3) present invention is using compoundings such as methyl methacrylate, acetoacetoxyethyl methacrylate, butyl acrylates as list
Body, the later period polymerize via radiation to be introduced into binder molecule chain, so that soft in molecular chain structure, hard section block, overcomes and mutually separate
Problem, while improving the water resistance of glue film, weatherability, improve the adhesive force of adhesive；
(4) 2,2- hydroxymethyl propionic acid is added before radiation polymerization and is sealed as hydrophilic monomer, and through sodium hydrogensulfite by the present invention
End because introducing hydrophilic radical carboxyl, and makes polyurethane obtain emulsifiability, can prepare the self-emulsifying of excellent in stability
Type is aqueous to generate blocked isocyanate first is that reacting with isocyanate groups, second is that can react to be formed with hydrophilic sulphur
Acidic group, blocked isocyanate performed polymer are dissolved in water or are emulsifiable in water, form the adhesive of self-emulsifying, and it is poly- not need addition alkyl phenol
Ethylene oxide ether etc. emulsifies it, improves environmental-protecting performance.
Specific embodiment
Reactant the preparation method comprises the following steps:
It takes epoxidized linseed oil 10 ~ 20:6 in mass ratio ~ 9 that lactic acid is added, is passed through nitrogen protection, is warming up to 70 ~ 80 DEG C and is stirred
10 ~ 12h is cooled to room temperature, and obtains cooled material, takes cooled material through rotary evaporation, and rotary evaporation obtains rotary evaporation object, and rotation is taken to steam
It sends out object 10 ~ 15:3 in mass ratio ~ 6:5 ~ 9 and dihydroxy polypropylene oxide ether, polyethylene glycol adipate glycol is added, in 30 ~ 40
DEG C 30 ~ 60min is stirred to get reactant.
Chain extender are as follows: take diethylenetriamine, N methyldiethanol amine 2 ~ 6:2 in mass ratio ~ 5:10 ~ 20 that deionized water is added
Be stirred 30 ~ 50min to get.
Modifying agent are as follows: take castor oil 3 ~ 6:5 in mass ratio ~ 9 be added hydroxypropyl silicone oil mixing to get.
Mix monomer are as follows: according to the mass fraction, take 3 ~ 6 parts of methyl methacrylates, 6 ~ 10 parts of acetoacetyl methyl-props
Olefin(e) acid ethyl ester, 2 ~ 4 parts of butyl acrylates, 3 ~ 6 parts of ethyl acrylates, 5 ~ 9 parts of acrylic acid, it is stirred 30 in 30 ~ 40 DEG C ~
50min to get.
A kind of preparation method of environmental protection coating material printing adhesive, includes the following steps:
(1) it takes reactant to be warming up to 100 ~ 110 DEG C of 30 ~ 60min of stirring, vacuumizes 20 ~ 30min, be cooled to 65 ~ 75 DEG C, obtain cold
But object a takes cooled material a 2 ~ 5:4 in mass ratio ~ 9 that isophorone diisocyanate is added, in 65 ~ 75 DEG C of 100 ~ 120min of heat preservation,
Mixture is obtained, takes 2,2- hydroxymethyl propionic acid, 1 ~ 5:8 in mass ratio ~ 15 that n-methyl-2-pyrrolidone mixing is added, obtains mixed liquor,
It takes mixed liquor 3 ~ 7:80 in mass ratio ~ 100 to be added in mixture, is stirred 60 ~ 90min in 65 ~ 75 DEG C, must be stirred
Object；
(2) modifying agent is taken to be added dropwise in stirring mixture in 30 ~ 40 DEG C of 5 ~ 9:90 ~ 120 in mass ratio, control time for adding 50 ~
60min is warming up to 45 ~ 55 DEG C and is stirred 50 ~ 60min, then the mix monomer for being stirred amount of substance 10 ~ 20% is added dropwise, control
1 ~ 3h of time for adding is stirred 1 ~ 3h in 45 ~ 55 DEG C, must stir mixture a, takes stirring mixture a in mass ratio 80 ~ 100:
4 ~ 7 are added triethylamine, add the acetone of stirring mixture a mass 10 ~ 20%, are stirred 20 ~ 40min in 30 ~ 35 DEG C, obtain
Mixture a takes chain extender 3 ~ 5:60 ~ 70 to be in mass ratio added dropwise to mixture, controls 30 ~ 50min of time for adding, it is warming up to 40 ~
50 DEG C are stirred 10 ~ 20min, are passed through nitrogen removal oxygen, radiate 2 ~ 4h of lower holding in 60Co γ-rays, adjust through triethylamine
PH to 7 ~ 8 obtains matrix object；
(3) it takes matrix object 10 ~ 15:3 in mass ratio ~ 5 that dehydrated alcohol is added, is stirred 20 ~ 30min in 40 ~ 50 DEG C, must stir
Mixture b takes sodium hydrogensulfite 2 ~ 5:8 in mass ratio ~ 15 that deionized water is added, obtains mixed liquor a, take mixed liquor a in mass ratio 1
~ 3:30 ~ 50 are added dropwise in stirring mixture b, are controlled 30 ~ 50min of time for adding, are stirred 1 ~ 4h in 20 ~ 25 DEG C to get ring
Friendly coating printing adhesive.
Embodiment 1
Reactant the preparation method comprises the following steps:
It takes epoxidized linseed oil 10:6 in mass ratio that lactic acid is added, is passed through nitrogen protection, is warming up to 70 DEG C and is stirred 10h, it is cooling
To room temperature, cooled material is obtained, takes cooled material through rotary evaporation, rotary evaporation obtains rotary evaporation object, takes rotary evaporation object in mass ratio
Dihydroxy polypropylene oxide ether, polyethylene glycol adipate glycol is added in 10:3:5, is stirred 30min in 30 DEG C to get anti-
Answer agent.
Chain extender are as follows: take diethylenetriamine, N methyldiethanol amine 2:2:10 in mass ratio that deionized water stirring is added mixed
Close 30min to get.
Modifying agent are as follows: take castor oil 3:5 in mass ratio be added hydroxypropyl silicone oil mixing to get.
Mix monomer are as follows: according to the mass fraction, take 3 parts of methyl methacrylates, 6 parts of acetoacetate methacrylic acid second
Ester, 2 parts of butyl acrylates, 3 parts of ethyl acrylates, 5 parts of acrylic acid, be stirred in 30 DEG C 30min to get.
A kind of preparation method of environmental protection coating material printing adhesive, includes the following steps:
(1) it takes reactant to be warming up to 100 DEG C of stirring 30min, vacuumizes 20min, be cooled to 65 DEG C, obtain cooled material a, take cooled material
A 2:4 in mass ratio is added isophorone diisocyanate and obtains mixture in 65 DEG C of heat preservation 100min, take 2,2- hydroxymethyl propionic acid
N-methyl-2-pyrrolidone mixing is added in 1:8 in mass ratio, obtains mixed liquor, takes mixed liquor 3:80 in mass ratio that mixture is added
In, it is stirred 60min in 65 DEG C, obtains stirring mixture；
(2) it takes modifying agent to be added dropwise in stirring mixture in 30 DEG C of 5:90 in mass ratio, controls time for adding 50min, be warming up to
45 DEG C are stirred 50min, then the mix monomer for being stirred amount of substance 10% is added dropwise, and control time for adding 1h, stir in 45 DEG C
1h is mixed, mixture a must be stirred, takes stirring mixture a 80:4 in mass ratio that triethylamine is added, adds stirring mixture a matter
The acetone of amount 10%, is stirred 20min in 30 DEG C, obtains mixture a, chain extender 3:60 in mass ratio is taken to be added dropwise to mixture, controls
Time for adding 30min processed is warming up to 40 DEG C and is stirred 10min, is passed through nitrogen removal oxygen, radiates lower protect in 60Co γ-rays
2h is held, pH to 7 is adjusted through triethylamine, obtains matrix object；
(3) it takes matrix object 10:3 in mass ratio that dehydrated alcohol is added, is stirred 20min in 40 DEG C, mixture b must be stirred, taken
Deionized water is added in sodium hydrogensulfite 2:8 in mass ratio, obtains mixed liquor a, takes mixed liquor a 1:30 to be in mass ratio added dropwise to stirring mixed
It closes in object b, controls time for adding 30min, be stirred 1h in 20 DEG C to get environmental protection coating material printing adhesive.
Embodiment 2
Reactant the preparation method comprises the following steps:
It takes epoxidized linseed oil 15:7 in mass ratio that lactic acid is added, is passed through nitrogen protection, is warming up to 75 DEG C and is stirred 11h, it is cooling
To room temperature, cooled material is obtained, takes cooled material through rotary evaporation, rotary evaporation obtains rotary evaporation object, takes rotary evaporation object in mass ratio
Dihydroxy polypropylene oxide ether, polyethylene glycol adipate glycol is added in 13:5:7, is stirred 40min in 35 DEG C to get anti-
Answer agent.
Chain extender are as follows: take diethylenetriamine, N methyldiethanol amine 5:4:15 in mass ratio that deionized water stirring is added mixed
Close 40min to get.
Modifying agent are as follows: take castor oil 4:7 in mass ratio be added hydroxypropyl silicone oil mixing to get.
Mix monomer are as follows: according to the mass fraction, take 5 parts of methyl methacrylates, 8 parts of acetoacetate methacrylic acid second
Ester, 3 parts of butyl acrylates, 5 parts of ethyl acrylates, 7 parts of acrylic acid, be stirred in 35 DEG C 40min to get.
A kind of preparation method of environmental protection coating material printing adhesive, includes the following steps:
(1) it takes reactant to be warming up to 105 DEG C of stirring 50min, vacuumizes 25min, be cooled to 70 DEG C, obtain cooled material a, take cooled material
A 4:7 in mass ratio is added isophorone diisocyanate and obtains mixture in 70 DEG C of heat preservation 110min, take 2,2- hydroxymethyl propionic acid
N-methyl-2-pyrrolidone mixing is added in 4:12 in mass ratio, obtains mixed liquor, takes mixed liquor 5:90 in mass ratio that mixture is added
In, it is stirred 70min in 60 DEG C, obtains stirring mixture；
(2) it takes modifying agent to be added dropwise in stirring mixture in 35 DEG C of 7:100 in mass ratio, controls time for adding 52min, be warming up to
50 DEG C are stirred 55min, then the mix monomer for being stirred amount of substance 15% is added dropwise, and control time for adding 2h, stir in 40 DEG C
2h is mixed, mixture a must be stirred, takes stirring mixture a 90:5 in mass ratio that triethylamine is added, adds stirring mixture a matter
The acetone of amount 15%, is stirred 30min in 32 DEG C, obtains mixture a, chain extender 4:65 in mass ratio is taken to be added dropwise to mixture, controls
Time for adding 40min processed is warming up to 45 DEG C and is stirred 15min, is passed through nitrogen removal oxygen, radiates lower protect in 60Co γ-rays
3h is held, pH to 7.5 is adjusted through triethylamine, obtains matrix object；
(3) it takes matrix object 13:4 in mass ratio that dehydrated alcohol is added, is stirred 25min in 45 DEG C, mixture b must be stirred, taken
Deionized water is added in sodium hydrogensulfite 4:12 in mass ratio, obtains mixed liquor a, mixed liquor a 2:40 in mass ratio is taken to be added dropwise to stirring
In mixture b, time for adding 40min is controlled, is stirred 3h in 22 DEG C to get environmental protection coating material printing adhesive.
Embodiment 3
Reactant the preparation method comprises the following steps:
It takes epoxidized linseed oil 20:9 in mass ratio that lactic acid is added, is passed through nitrogen protection, is warming up to 80 DEG C and is stirred 12h, it is cooling
To room temperature, cooled material is obtained, takes cooled material through rotary evaporation, rotary evaporation obtains rotary evaporation object, takes rotary evaporation object in mass ratio
Dihydroxy polypropylene oxide ether, polyethylene glycol adipate glycol is added in 15:6:9, is stirred 60min in 40 DEG C to get anti-
Answer agent.
Chain extender are as follows: take diethylenetriamine, N methyldiethanol amine 6:5:20 in mass ratio that deionized water stirring is added mixed
Close 50min to get.
Modifying agent are as follows: take castor oil 6:9 in mass ratio be added hydroxypropyl silicone oil mixing to get.
Mix monomer are as follows: according to the mass fraction, take 6 parts of methyl methacrylates, 10 parts of acetoacetate methacrylic acids
Ethyl ester, 4 parts of butyl acrylates, 6 parts of ethyl acrylates, 9 parts of acrylic acid, be stirred in 40 DEG C 50min to get.
A kind of preparation method of environmental protection coating material printing adhesive, includes the following steps:
(1) it takes reactant to be warming up to 110 DEG C of stirring 60min, vacuumizes 30min, be cooled to 75 DEG C, obtain cooled material a, take cooled material
A 5:9 in mass ratio is added isophorone diisocyanate and obtains mixture in 75 DEG C of heat preservation 120min, take 2,2- hydroxymethyl propionic acid
N-methyl-2-pyrrolidone mixing is added in 5:15 in mass ratio, obtains mixed liquor, takes mixed liquor 7:100 in mass ratio that mixing is added
In object, it is stirred 90min in 75 DEG C, obtains stirring mixture；
(2) it takes modifying agent to be added dropwise in stirring mixture in 40 DEG C of 9:120 in mass ratio, controls time for adding 60min, be warming up to
55 DEG C are stirred 60min, then the mix monomer for being stirred amount of substance 20% is added dropwise, and control time for adding 3h, stir in 55 DEG C
3h is mixed, mixture a must be stirred, takes stirring mixture a 100:7 in mass ratio that triethylamine is added, adds stirring mixture a matter
The acetone of amount 20%, is stirred 40min in 35 DEG C, obtains mixture a, chain extender 5:70 in mass ratio is taken to be added dropwise to mixture, controls
Time for adding 50min processed is warming up to 50 DEG C and is stirred 20min, is passed through nitrogen removal oxygen, radiates lower protect in 60Co γ-rays
4h is held, pH to 8 is adjusted through triethylamine, obtains matrix object；
(3) it takes matrix object 15:5 in mass ratio that dehydrated alcohol is added, is stirred 30min in 50 DEG C, mixture b must be stirred, taken
Deionized water is added in sodium hydrogensulfite 5:15 in mass ratio, obtains mixed liquor a, mixed liquor a 3:50 in mass ratio is taken to be added dropwise to stirring
In mixture b, time for adding 50min is controlled, is stirred 4h in 25 DEG C to get environmental protection coating material printing adhesive.
Comparative example 1: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking reactant.
Comparative example 2: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking chain extender.
Comparative example 3: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking modifying agent.
Comparative example 4: the environmental protection coating material printing adhesive of Wuxi City company production.
Embodiment and comparative example are tested according to GB/T3920-2008, GB/T2912.1-1998 standard, test knot
Fruit is as shown in table 1.
Table 1:
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Dry fastness (grade) | 5 | 4 | 4-5 | 4 | 4-3 | 4-3 | 3 |
| Fastness to wet rubbing (grade) | 5 | 4 | 4-5 | 3-4 | 3 | 3 | 2-3 |
| Content of formaldehyde (ppm) | 9.3 | 9.7 | 9.5 | 11.2 | 10.1 | 10.9 | 18.3 |
| Stiffness (cm) | 3.2 | 3.7 | 3.5 | 4.2 | 4.1 | 4.7 | 5.8 |
In conclusion the dry of environmental protection coating material printing adhesive of the invention, fastness to wet rubbing reach 5 grades, it is better than commercial product；
Stiffness is smaller to illustrate that adhesive of the invention influences less original style of fabric, i.e., cotton fabric still maintains soft hand
Sense.In addition, cloth cover formaldehyde content is less than 20ppm with the fabric of adhesive stamp of the invention, meets most stringent of environmental protection and want
It asks, is worth promoting.
The foregoing is merely preferred modes of the invention, are not intended to limit the invention, all in spirit and original of the invention
Within then, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of environmental protection coating material printing adhesive, which is characterized in that including reactant, chain extender, modifying agent, mix monomer；
The reactant the preparation method comprises the following steps:
It takes epoxidized linseed oil 10 ~ 20:6 in mass ratio ~ 9 that lactic acid is added, is passed through nitrogen protection, is warming up to 70 ~ 80 DEG C and is stirred
10 ~ 12h is cooled to room temperature, and obtains cooled material, takes cooled material through rotary evaporation, and rotary evaporation obtains rotary evaporation object, and rotation is taken to steam
It sends out object 10 ~ 15:3 in mass ratio ~ 6:5 ~ 9 and dihydroxy polypropylene oxide ether, polyethylene glycol adipate glycol is added, in 30 ~ 40
DEG C 30 ~ 60min is stirred to get reactant.
2. environmental protection coating material printing adhesive according to claim 1, which is characterized in that the chain extender are as follows: take divinyl
Triamine, N methyldiethanol amine 2 ~ 6:2 in mass ratio ~ 5:10 ~ 20 be added deionized water be stirred 30 ~ 50min to get.
3. environmental protection coating material printing adhesive according to claim 1, which is characterized in that the modifying agent are as follows: take castor oil
3 ~ 6:5 in mass ratio ~ 9 be added hydroxypropyl silicone oil mixing to get.
4. environmental protection coating material printing adhesive according to claim 1, which is characterized in that the mix monomer are as follows: press quality
Number meter takes 3 ~ 6 parts of methyl methacrylates, 6 ~ 10 parts of acetoacetoxyethyl methacrylate, 2 ~ 4 parts of butyl acrylates, 3
~ 6 parts of ethyl acrylates, 5 ~ 9 parts of acrylic acid, be stirred in 30 ~ 40 DEG C 30 ~ 50min to get.
5. a kind of preparation method of the environmental protection coating material printing adhesive as described in claim 1 ~ 4 any one, which is characterized in that
The preparation method includes the following steps:
(1) it takes reactant to be warming up to 100 ~ 110 DEG C of stirrings, vacuumizes 20 ~ 30min, be cooled to 65 ~ 75 DEG C, obtain cooled material a, take
Cooled material a 2 ~ 5:4 in mass ratio ~ 9 is added isophorone diisocyanate and must mix in 65 ~ 75 DEG C of 100 ~ 120min of heat preservation
Object takes 2,2- hydroxymethyl propionic acid, 1 ~ 5:8 in mass ratio ~ 15 that n-methyl-2-pyrrolidone mixing is added, obtains mixed liquor, take mixing
Liquid 3 ~ 7:80 in mass ratio ~ 100 is added in mixture and is stirred, and obtains stirring mixture；
(2) modifying agent is taken to be added dropwise in stirring mixture in 30 ~ 40 DEG C of 5 ~ 9:90 ~ 120 in mass ratio, control time for adding 50 ~
60min is stirred, then the mix monomer for being stirred amount of substance 10 ~ 20% is added dropwise, and controls 1 ~ 3h of time for adding, and stirring is mixed
It closes, mixture a must be stirred, take stirring mixture a 80 ~ 100:4 in mass ratio ~ 7 that triethylamine is added, add stirring mixture a
The acetone of quality 10 ~ 20% is stirred, and obtains mixture a, and chain extender 3 ~ 5:60 ~ 70 in mass ratio is taken to be added dropwise to mixture, control
30 ~ 50min of time for adding is warming up to 40 ~ 50 DEG C and is stirred 10 ~ 20min, nitrogen removal oxygen is passed through, in 60Co γ-rays
Radiation is lower to keep 2 ~ 4h, adjusts pH to 7 ~ 8 through triethylamine, obtains matrix object；
(3) it takes matrix object 10 ~ 15:3 in mass ratio ~ 5 that absolute ethyl alcohol and stirring mixing is added, mixture b must be stirred, take bisulfite
Deionized water is added in sodium 2 ~ 5:8 in mass ratio ~ 15, obtains mixed liquor a, 1 ~ 3:30 ~ 50 in mass ratio mixed liquor a is taken to be added dropwise to stirring
In mixture b, 30 ~ 50min of time for adding is controlled, is stirred to get environmental protection coating material printing adhesive.
6. the preparation method of environmental protection coating material printing adhesive according to claim 5, which is characterized in that the step (1)
Middle stirring mixture is stirred condition are as follows: is stirred 60 ~ 90min in 65 ~ 75 DEG C.
7. the preparation method of environmental protection coating material printing adhesive according to claim 5, which is characterized in that the step (3)
Middle environmental protection coating material printing adhesive is stirred condition are as follows: is stirred 1 ~ 4h in 20 ~ 25 DEG C.
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