CN109440504A - A kind of number PVA glue, preparation method and the PRINTED FABRIC containing it - Google Patents
A kind of number PVA glue, preparation method and the PRINTED FABRIC containing it Download PDFInfo
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- CN109440504A CN109440504A CN201811466378.5A CN201811466378A CN109440504A CN 109440504 A CN109440504 A CN 109440504A CN 201811466378 A CN201811466378 A CN 201811466378A CN 109440504 A CN109440504 A CN 109440504A
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- maleic anhydride
- pva glue
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- phenylethylene
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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
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/30—Ink jet printing
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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
- D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
- D06P1/5221—Polymers of unsaturated hydrocarbons, e.g. polystyrene polyalkylene
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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
Abstract
The present invention relates to a kind of digital PVA glue, preparation method and PRINTED FABRIC containing it, the present invention is with a kind of new digital PVA glue of the Material synthesis such as the thickener of the Photocurable oligomers of 40~65wt%, the free radical activity diluent of 6~10wt%, the cationic photosensitive monomer of 6~14wt%, the free radical photo-initiation of 3~8wt%, the cation light initiator of 3~8wt%, the titanium dioxide of 12~20wt% and 1~4wt%；Present invention utilizes Photocurable oligomers resin systems, the digital PVA glue enabled carries out hybrid UV-curing reaction in fabric surface, to carry out surface covering treatment to fabric, it has comparable covering power to fabric self color, in Light Curing, with fabric adhesion-tight, good heat-resisting quantity, rub resistance, flexibility and water resistance can be provided for fabric, additionally it is possible to improve the colour vividness and printing fastness of fabric processed.
Description
Technical field
The invention belongs to fabric-treating agent field more particularly to a kind of digital PVA glue, preparation method and containing its
PRINTED FABRIC.
Background technique
Surface of cotton fabric structure and property are an important factor for influencing printing quality, to prevent from spraying on the surface of the fabric
Pattern imbibition caused by ink droplet flushing or the dye migration of thermal transfer, and the attachment fastness of ink on the fabric is improved, usually
It needs to be surface-treated cotton fabric before stamp, common textile treatment includes using sodium alginate or chitin
Fabric is pre-processed etc. fabric treating liquid is configured to, or coats the fabric-treating agent made of polymer in fabric surface
It is modified, above-mentioned processing method has fabric-treating agent and fabric adhesive force is too low, and obtained fabric washing fastness is not
The problems such as foot or fabric feeling really up to the mark, further progress is needed to improve.
The curing rate that free radical-cationic hybrid photocuring system combines radically curing is fast, price is low, Yi Jiyang
The cubical contraction of cationic cure is small, substrate adhesive force is strong, without oxygen inhibition, solidify the advantages that strong afterwards, it has also become curing field
One of research hotspot, be unable to satisfy its requirement for fabric surface adhesion in view of existing fabric-treating agent, will be free
Base-cationic hybrid photocuring system has huge potential value for fabric surface treatments field.
Traditional radical UV curing system is mostly used resin oligomers with unsaturated double-bond as fabric surface treatments
Liquid is surface-treated fabric, and the oligomer molecules amount used needs to be accurately controlled in several hundred to thousands of left and right, molecular weight
The excessive system viscosity that will lead to is excessively high, and a large amount of activated monomers need to be added and carry out viscosity reductions, so cause fabric surface treatments liquid at
The mechanical property of film properties decline, the too low fabric coating that will lead to of molecular weight reduces.The photocuring studied at present is oligomeric
Object is usually to utilize hydroxyl and carboxyl or isocyanate group etc. that step-reaction polymerization occurs, needed for introducing in polyester or polyurethane
Ultraviolet curing group, step-reaction polymerization can adjust molecular size range by controlling the ratio of reactive group, for example,
A kind of method arranged using photocuring system to fabric is disclosed in CN103526552A, has been synthesized a kind of fluorine-containing poly-
Urethane acrylate performed polymer, including will be anti-with fluorochemical polyether type glycol long-chain again after isocyanates and crylic acid hydroxy ester reaction
It should obtain performed polymer or first react isocyanates and fluorochemical polyether type glycol, then crylic acid hydroxy ester is added in system and obtains
Performed polymer and reactive diluent, photoinitiator and solvent etc. are configured to the coating of light-cured resin system and rolled by performed polymer later
It is pressed in fabric surface, irradiates the surface treatment for completing fabric after a certain period of time under ultraviolet light.Its obtained light-cured resin energy
Make that fabric has effects that preferable water repellent and refuses oily, and finishing technique process is short, low energy consumption, high-efficient, still, the above method at
This is higher, and residual volume is more after the completion of reaction for the components such as isocyanates used, toxic to human body, curing time it is longer and
Obtained fabric restricted application.
Oligomer used in cation photocuring is different from traditional photocuring system, is mostly by that will have epoxy group or second
The resin of the groups such as alkene ether makes reactive base therein under the action of light cationic initiator and optical free radical initiator
Group's simultaneous reactions, and then realize and be evenly and rapidly crosslinked, unreacted content of monomer is seldom in the product after crosslinking, is crosslinked institute
Functional group is double bond and epoxy group, small to human body toxic.For example, being disclosed in CN107621752A a kind of containing oxa-
Cyclobutane functional group and methacryloxy functional groups mix type photosensitive resin, which is blocked with double bond, side chain band oxygen
Azetidine is, it can be achieved that free radical-cationic hybrid photocuring.But photosensitive resin prepared by the invention, double bond solidification
Group can only be introduced into strand both ends, and double bond content is limited by resin molecular weight, and photocuring reaction is very slow when molecular weight is larger,
It is also poor with the caking property of fabric, therefore is not used to the surface treatment of fabric.
On the basis of existing technology, those skilled in the art needs to develop a kind of new digital PVA glue, makes it
It can be able to carry out cation photocuring reaction in fabric surface, to be surface-treated to fabric, it is also desirable to which it solidifies
There is preferable surface adhesion and flexibility to fabric afterwards, to promote the feel and scrub performance of treated fabric.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of new digital PVA glue, light is utilized
Solidify oligomer resin system, free radical-cationic hybrid photocuring reaction can be carried out in fabric surface, to fabric
Surface covering treatment is carried out, needs to have comparable covering power to fabric self color, it is also desirable to have after its solidification to fabric
There are preferable surface adhesion and flexibility, to promote the feel and scrub performance of treated fabric.
For this purpose, one of the objects of the present invention is to provide a kind of digital PVA glue, and in percentage by weight, institute
Stating digital PVA glue includes following component:
Wherein, the weight percent of Photocurable oligomers can for 42wt%, 44wt%, 46wt%, 48wt%,
50wt%, 52wt%, 54wt%, 56wt%, 58wt%, 60wt%, 62wt% or 64wt% etc., free radical activity diluent energy
It is enough to react with free radical that is react generation, form more stable free radical, weight percent can be 6.5wt%,
7wt%, 8wt%, 8.5wt% or 9wt% etc., cationic photosensitive monomer are that chain increasing can occur by way of cationic polymerization
The monomer of long reaction, weight percent can be 7wt%, 8wt%, 10wt%, 12wt% or 13wt% etc., and free radical light draws
Hair agent can trigger the double bond in Photocurable oligomers and react with free radical activity diluent, and weight percent can be
4wt%, 5wt%, 6wt%, 7wt% or 8wt% etc., cation light initiator can trigger the epoxy in Photocurable oligomers
Base reacts with cationic photosensitive monomer, and weight percent can be 4wt%, 5wt%, 6wt%, 7wt% or 8wt%
Deng titanium dioxide can increase the covering power of slurry, set off ink-jet printed color depth, and weight percent can be
The viscosity of digital PVA glue can be improved in 13wt%, 14wt%, 16wt%, 18wt% or 19wt% etc., thickener, makes stamp edge
Apparent, weight percent can be 1.5wt%, 2wt%, 2.5wt% or 3.5wt% etc..
Preferably, the Photocurable oligomers are the benzene second containing double bond and epoxy group of acrylate and modified by cardanol
Alkene-maleic anhydride oligomers.
The modification includes introducing new structural unit in the form of copolymerization on main polymer chain and/or in polymerization owner
Small molecule compound or functional group are introduced by grafting on chain, and then change the process of the physically or chemically characteristic of original copolymer.
The oligomer typically refers to the polymer that main chain has 10~25 repetitive units, according to what is limited in the application
Type of polymer, " oligomer " in the application is polymer of the number average molecular 3000~5500.
Preferably, in parts by weight, the Photocurable oligomers are obtained by following component is reacted:
Wherein, the reaction can be that the multistep reaction of said components is utilized, and the parts by weight of styrene can be 1
Part, 3 parts, 5 parts, 7 parts, 9 parts or 11 parts etc., the parts by weight of α-methylstyrene and/or its dimer can be 31 parts, 33
Part, 35 parts, 37 parts, 39 parts, 41 parts or 43 parts etc., the parts by weight of maleic anhydride can be 23 parts, 25 parts, 27 parts, 29 parts, 31
Part, 33 parts or 35 parts etc., the parts by weight of acrylate can be 38 parts, 42 parts, 46 parts, 50 parts, 54 parts, 58 parts, 62 parts, 66
Part or 69 parts etc., the parts by weight of anacardol can be 69 parts, 74 parts, 80 parts, 85 parts, 90 parts, 95 parts or 98 parts etc., oxidant
Parts by weight can be 40 parts, 42 parts, 44 parts, 46 parts, 48 parts, 50 parts, 52 parts, 54 parts or 56 parts etc., the weight of initiator
Number can be 1.7 parts, 1.9 parts, 2.1 parts, 2.3 parts, 2.5 parts, 2.7 parts or 2.9 parts etc., and the parts by weight of catalyst can be
0.1 part, 0.2 part, 0.3 part, 0.5 part, 0.7 part, 0.9 part, 1.1 parts, 1.3 parts, 1.5 parts, 1.7 parts or 1.9 parts etc..
In the present invention, part or all of styrenic component is replaced by using α-methylstyrene and its dimer, is utilized
The steric hindrance effect for pushing away electronic action and phenyl of methyl and contain in α-methylstyrene dimer in α-methylstyrene
The stabilization of some tert-butyls, so that generating portion reactivity is less than styrene free radical in the synthetic reaction of oligomer
More stable free radical, and then control by the way that chain transfer reaction occurs during the reaction the styrene-maleic acid of synthesis
The molecular weight of acid anhydride oligomer, said components, which only need to generate free radicals by heating, can react to obtain the styrene-maleic acid
Acid anhydride oligomer, wherein not containing high toxicity component, and the smell is awful and the chain-transferring agents such as higher mercaptan of toxicity without introducing
Component, therefore it is suitable for preparing digital PVA glue.
In the present invention, the glass transition of the adjustable phenylethylene-maleic anhydride oligomer of introducing of acrylate component
Temperature (Tg), and then the flexibility of polymer is adjusted, meanwhile, acrylate component can also be by occurring transesterification with maleic anhydride
Or the reaction such as esterification, double bond is introduced in phenylethylene-maleic anhydride oligomer.
Preferably, containing free hydroxyl or amino in the acrylate, the introducing of hydroxyl and amino enables to third
Olefin(e) acid ester is grafted on phenylethylene-maleic anhydride oligomer backbone more easily by esterification, improves phenylethylene-maleic anhydride
The content of acrylic double bond in oligomer, acrylic double bond is relative to the double bond in other alkene without containing substituent group
Deng, it is easier to radical UV curing reaction occurs, so that obtained Photocurable oligomers have higher reactivity.
Preferably, the anacardol has structure as shown in Equation 1:
Wherein, x is 1 or 2, i.e., so that containing unsaturated alkane in the anacardol, the unsaturation contained in anacardol
Alkane can react under the action of oxidant generates epoxy group, and the generation of epoxy group can occur photocured cross-linked anti-
It answers, can also have an effect with the hydroxyl of fabric surface, used to improve Photocurable oligomers as fabric surface treatments liquid
When attachment fastness, the double bond such as acrylic double bond etc. with carbonyl conjugation since its cloud density is low, is not susceptible to epoxy
Change reaction and generates epoxy group.
Being modified using anacardol to phenylethylene-maleic anhydride oligomer not only can introduce epoxidation group for it,
Long alkane segment flexible can also be introduced for its side chain, to form main chain as rigidity, side chain is that the pectination of soft segment polymerize
Object, stiff backbone can provide good heat-resisting quantity and rub resistance, and the flexibility of oligomer then can be improved in flexible Long carbon chain
And water resistance.
Preferably, in parts by weight, the Photocurable oligomers are obtained by following component is reacted:
Hydroxyl in the present invention in 2-hydroxyethyl acrylate as previously described can be by low with phenylethylene-maleic anhydride
The carboxyl generated after unreacted acid anhydrides or anhydride reaction in polymers reacts, and it is living that radical UV curing is introduced in strand
Property high acrylic double bond, but the dosage of 2-hydroxyethyl acrylate should not be too large, and dosage crosses conference and makes the oligomeric of preparation
The acid value of object declines, and reduces the content of wherein carboxyl, and then reduces processed fabric in subsequent decal or dyeing course
Adhesive force.
Preferably, the styrene, α-methylstyrene, the linear dimerization body of α-methylstyrene, maleic anhydride and third
The sum of parts by weight of the different monooctyl ester of olefin(e) acid are 100 parts.
Preferably, the amount of the substance of the anacardol be less than or equal to maleic anhydride substance amount, due to maleic anhydride with
A carboxyl can be generated after anacardol reaction, and the steric hindrance of anacardol is big, phenolic hydroxyl group is low with the reactivity of carboxylic acid, generates
Carboxyl will not the reaction was continued with anacardol, excessive anacardol can make there are unreacted phenolic hydroxyl group in system, and phenolic hydroxyl group is easily sent out
Raw oxidation reaction discoloration, therefore the ratio between molal quantity of anacardol and maleic anhydride should be not more than 1:1.
Preferably, the oxidant is peroxide, further preferably metachloroperbenzoic acid.
Preferably, the initiator is radical initiator, and further preferably benzoyl peroxide and/or azo two is different
Butyronitrile.
Preferably, the catalyst is in zinc chloride, pyridine, dehydrated alcohol sodium, p-methyl benzenesulfonic acid or tetrabutyl titanate
Any one or at least two mixture.
Preferably, acid value >=20mgKOH/g of the Photocurable oligomers.
Preferably, the free radical activity diluent is isobornyl methacrylate, methacrylic acid tetrahydrofuran first
Ester, decyl acrylate, ethoxyethoxyethyl acrylate, 1,6 hexanediol diacrylate, two propylene of tripropylene glycol
Acid esters, neopentyl glycol diethoxy diacrylate, in two contracting trimethylolpropane tetra-acrylates any one or at least
Two kinds of mixture.
Preferably, the cationic photosensitive monomer is the siloxanyl monomers containing vinyl ether group.
Preferably, the cationic photosensitive monomer has structure as shown in Equation 2:
Wherein, 2,3,4 or 5 n.
Preferably, the free radical photo-initiation is benzoin dimethylether, Alpha-hydroxy phenylcyclohexyl ketone, isopropyl thioxanthone
Anthrone, 2- (4- methylthio phenyl formoxyl) -2- morpholinopropane, 2,4,6- trimethyl benzoyl diphenyl base phosphine oxide, it is bis- (2,
4,6- trimethylbenzoyl) in phenyl phosphine oxide any one or at least two mixture.
Preferably, the cation light initiator is appointing in iron arene complexes, diaryl iodonium salt or triaryl sulfonium salts
It anticipates a kind of or at least two mixtures.
Preferably, the titanium dioxide is lipophilic anatase thpe white powder.
Preferably, the thickener is oil thickeners.
The second object of the present invention is to provide a kind of preparation method of digital PVA glue, and the preparation method includes
Following steps:
The Photocurable oligomers of formula ratio, free radical activity diluent, cationic photosensitive monomer, free radical is light-initiated
Agent, cation light initiator, titanium dioxide and thickener are mixed evenly, and obtain the digital PVA glue.
Preferably, the preparation method includes the following steps:
In Photocurable oligomers, sequentially add in order while agitating formula ratio free radical activity diluent,
Cationic photosensitive monomer, free radical photo-initiation, cation light initiator and titanium dioxide continue dispersion stirring at least 30min (example
For example 35min, 50min, 80min, 120min, 150min, 180min, 210min or 240min etc.), thickener is added later,
Said mixture is stirred evenly, the digital PVA glue is obtained.
Preferably, the Photocurable oligomers are made by the steps to obtain:
Step (1), by styrene, linear dimerization body, maleic anhydride and the propylene of α-methylstyrene, α-methylstyrene
The different monooctyl ester of acid is blended, and heats up in mixed liquor and initiator is added, carry out polymerization reaction after being warming up to reaction temperature, obtain benzene second
Alkene-maleic anhydride oligomers；
Anacardol and catalyst are added in the phenylethylene-maleic anhydride oligomer obtained in step (1) for step (2), after
Temperature of continuing rising is modified processing, obtains the phenylethylene-maleic anhydride oligomer of modified by cardanol；
Propylene is added in the phenylethylene-maleic anhydride oligomer of the modified by cardanol obtained in step (2) in step (3)
Acid -2- hydroxyethyl ester carries out esterification, obtains double bond containing phenylethylene-maleic anhydride oligomer；
Viscosity-adjusting agent is added in the double bond containing phenylethylene-maleic anhydride oligomer obtained in step (3) in step (4)
Agent and oxidant, carry out oxidation reaction, and reaction product after post treatment, obtains styrene-Malaysia containing double bond and epoxy group
Acid anhydrides oligomer, the as described Photocurable oligomers.
Preferably, the reaction temperature of polymerization reaction described in step (1) be 80~100 DEG C, for example, 82 DEG C, 84 DEG C,
86 DEG C, 88 DEG C, 90 DEG C, 92 DEG C, 94 DEG C, 96 DEG C or 98 DEG C etc..
Preferably, the reaction time of polymerization reaction described in step (1) be 30~45min, for example, 31min,
33min, 35min, 37min, 39min, 41min or 43min etc..
Preferably, the temperature of modification described in step (2) be 120~150 DEG C, for example, 125 DEG C, 130 DEG C,
135 DEG C, 140 DEG C, 145 DEG C or 148 DEG C etc..
Preferably, the time of modification described in step (2) be 5~6h, for example, 5.1h, 5.2h, 5.3h,
5.4h, 5.5h, 5.6h, 5.7h, 5.8h or 5.9h etc..
Preferably, the reaction temperature of esterification described in step (3) is 200~220 DEG C, for example, 202 DEG C, 204
DEG C, 206 DEG C, 208 DEG C, 210 DEG C, 212 DEG C, 214 DEG C, 216 DEG C or 218 DEG C etc..
Preferably, esterification described in step (3) carries out under conditions of reaction system vacuumizes.
Preferably, viscosity modifier described in step (4) is methylene chloride.
Preferably, oxidation reaction described in step (4) carries out under conditions of ice-water bath.
Preferably, the time of oxidation reaction described in step (4) be 1~3h, for example, 1.2h, 1.4h, 1.6h,
1.8h, 2.0h, 2.2h, 2.4h, 2.6h or 2.8h etc..
Preferably, post-processing described in step (4) includes being washed, filtered and being dried to reaction product.
The third object of the present invention is to provide a kind of PRINTED FABRIC, and the PRINTED FABRIC obtains as follows:
Print the digital PVA glue in fabric surface using silk-screen printing technique, carry out later it is digital ink-jet printed, most
There is the fabric of digital PVA glue and stamp to be placed under ultraviolet light irradiation surface printing afterwards and carry out curing process, obtains that treated
PRINTED FABRIC.
Preferably, heretofore described fabric is cotton fabric.
Numberical range of the present invention not only includes enumerated point value, further includes the above-mentioned numerical value not included
Arbitrary point value between range, as space is limited and for concise consideration, range described in the present invention no longer exclusive list includes
Specific point value.
Compared with prior art, the invention has the following beneficial effects:
The present invention with Photocurable oligomers, free radical activity diluent, cationic photosensitive monomer, free radical photo-initiation,
A kind of new digital PVA glue of the Material synthesis such as cation light initiator, titanium dioxide and thickener, it is solid that present invention utilizes light
Change oligomer resin system, the digital PVA glue enabled carries out hybrid UV-curing reaction in fabric surface, with to knitting
Object carries out surface covering treatment, has comparable covering power to fabric self color, in Light Curing, adheres to jail with fabric
Gu good heat-resisting quantity, rub resistance, flexibility and water resistance can be provided for fabric, additionally it is possible to improve processed knit
The colour vividness and printing fastness of object.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
Embodiment 1
Photocurable oligomers 1 are made by the steps:
Step (1), by 42g α-methylstyrene, the linear dimerization body of 0.5g α-methylstyrene, 32g maleic anhydride and
25.5g Isooctyl acrylate monomer is blended, and mixed liquor is warming up to 90 DEG C and 2g initiator azodiisobutyronitrile is added, polymerize later
45min is reacted, phenylethylene-maleic anhydride oligomer is obtained；
Step (2) is added 99.4g anacardol in the phenylethylene-maleic anhydride oligomer obtained in step (1) and 2g is urged
Agent p-methyl benzenesulfonic acid is continuously heating to 135 DEG C and is modified processing 6h, obtains the styrene-maleic acid of modified by cardanol
Acid anhydride oligomer；
18.9g is added in the phenylethylene-maleic anhydride oligomer of the modified by cardanol obtained in step (2) in step (3)
2-hydroxyethyl acrylate, 210 DEG C, vacuumize water removal under conditions of carry out esterification, obtain double bond containing styrene-
Maleic anhydride oligomers；
Viscosity-adjusting agent is added in the double bond containing phenylethylene-maleic anhydride oligomer obtained in step (3) in step (4)
Agent methylene chloride adjusts its viscosity to requirements, and 56.3g oxygen is slowly added dropwise thereto under conditions of ice-water bath and stirring later
Agent metachloroperbenzoic acid carries out oxidation reaction 2h or so, and reaction product is filtered to remove white solid, respectively with saturation
Sodium sulfite, sodium bicarbonate, sodium chloride solution wash 3 times, revolving remove solvent be placed in 50 DEG C of vacuum ovens it is dry
To constant weight, the phenylethylene-maleic anhydride oligomer containing double bond and epoxy group is obtained, the as described Photocurable oligomers 1 pass through
Theoretical calculation, acid value 40.9mgKOH/g.
Embodiment 2
Photocurable oligomers 2 are made by the steps:
Step (1), by 6.5g styrene, linear dimerization body, the 22g of 30g α-methylstyrene, 1.5g α-methylstyrene
Maleic anhydride and 40g Isooctyl acrylate monomer are blended, and mixed liquor is warming up to 80 DEG C and 3g initiator dibenzoyl peroxide is added, it
Polymerization reaction 30min is carried out afterwards, obtains phenylethylene-maleic anhydride oligomer；
Step (2), be added in the phenylethylene-maleic anhydride oligomer obtained in step (1) 68.3g anacardol and
Four isobutyl of 0.08g catalyst metatitanic acid is continuously heating to 120 DEG C and is modified processing 5h, obtains the benzene second of modified by cardanol
Alkene-maleic anhydride oligomers；
18g third is added in the phenylethylene-maleic anhydride oligomer of the modified by cardanol obtained in step (2) for step (3)
Olefin(e) acid -2- hydroxyethyl ester, 200 DEG C, vacuumize water removal under conditions of carry out esterification, obtain double bond containing styrene-horse
Carry out acid anhydrides oligomer；
Viscosity-adjusting agent is added in the double bond containing phenylethylene-maleic anhydride oligomer obtained in step (3) in step (4)
Agent methylene chloride adjusts its viscosity to requirements, and 38.7g oxygen is slowly added dropwise thereto under conditions of ice-water bath and stirring later
Agent metachloroperbenzoic acid carries out oxidation reaction 1h, and reaction product is filtered to remove white solid, respectively with the Asia of saturation
Sodium sulphate, sodium bicarbonate, sodium chloride solution wash 3 times, and revolving removing solvent, which is placed in 50 DEG C of vacuum ovens, to be dried to perseverance
Weight, obtains the phenylethylene-maleic anhydride oligomer containing double bond and epoxy group, the as described Photocurable oligomers 2, by theory
It calculates, acid value 20.4mgKOH/g.
Embodiment 3
Photocurable oligomers 3 are made by the steps:
Step (1), by 12g styrene, 34g α-methylstyrene, the linear dimerization body of 1g α-methylstyrene, 36g horse
Carrying out acid anhydrides and 17g Isooctyl acrylate monomer is blended, mixed liquor is warming up to 90 DEG C and 2.2g initiator dibenzoyl peroxide is added, it
Polymerization reaction 45min is carried out afterwards, obtains phenylethylene-maleic anhydride oligomer；
Step (2) is added 89.4g anacardol in the phenylethylene-maleic anhydride oligomer obtained in step (1) and 1g is urged
Four isobutyl of agent metatitanic acid is continuously heating to 135 DEG C and is modified processing 6h, obtains styrene-Malaysia of modified by cardanol
Acid anhydrides oligomer；
29.8g is added in the phenylethylene-maleic anhydride oligomer of the modified by cardanol obtained in step (2) in step (3)
2-hydroxyethyl acrylate, 210 DEG C, vacuumize water removal under conditions of carry out esterification, obtain double bond containing styrene-
Maleic anhydride oligomers；
Viscosity-adjusting agent is added in the double bond containing phenylethylene-maleic anhydride oligomer obtained in step (3) in step (4)
Agent methylene chloride adjusts its viscosity to requirements, and 50.7g oxygen is slowly added dropwise thereto under conditions of ice-water bath and stirring later
Agent metachloroperbenzoic acid carries out oxidation reaction 2h or so, and reaction product is filtered to remove white solid, respectively with saturation
Sodium sulfite, sodium bicarbonate, sodium chloride solution wash 3 times, revolving remove solvent be placed in 50 DEG C of vacuum ovens it is dry
To constant weight, the phenylethylene-maleic anhydride oligomer containing double bond and epoxy group is obtained, the as described Photocurable oligomers 3 pass through
Theoretical calculation, acid value 45.9mgKOH/g.
Embodiment 4
Photocurable oligomers 4 are made by the steps:
Step (1), by 5g styrene, linear dimerization body, the 28g of 37.2g α-methylstyrene, 0.8g α-methylstyrene
Maleic anhydride and 29g Isooctyl acrylate monomer are blended, and mixed liquor is warming up to 90 DEG C and 1.5g initiator azodiisobutyronitrile is added, it
Polymerization reaction 45min is carried out afterwards, obtains phenylethylene-maleic anhydride oligomer；
78.3g anacardol and 1.5g are added in the phenylethylene-maleic anhydride oligomer obtained in step (1) for step (2)
Catalyst p-methyl benzenesulfonic acid is continuously heating to 135 DEG C and is modified processing 6h, obtains styrene-Malaysia of modified by cardanol
Acid anhydrides oligomer；
23.2g is added in the phenylethylene-maleic anhydride oligomer of the modified by cardanol obtained in step (2) in step (3)
2-hydroxyethyl acrylate, 210 DEG C, vacuumize water removal under conditions of carry out esterification, obtain double bond containing styrene-
Maleic anhydride oligomers；
Viscosity-adjusting agent is added in the double bond containing phenylethylene-maleic anhydride oligomer obtained in step (3) in step (4)
Agent methylene chloride adjusts its viscosity to requirements, and 44.3g oxygen is slowly added dropwise thereto under conditions of ice-water bath and stirring later
Agent metachloroperbenzoic acid carries out oxidation reaction 2h or so, and reaction product is filtered to remove white solid, respectively with saturation
Sodium sulfite, sodium bicarbonate, sodium chloride solution wash 3 times, revolving remove solvent be placed in 50 DEG C of vacuum ovens it is dry
To constant weight, the phenylethylene-maleic anhydride oligomer containing double bond and epoxy group is obtained, the as described Photocurable oligomers 4 pass through
Theoretical calculation, acid value 31.1mgKOH/g.
Embodiment 5
Photocurable oligomers 5 are made by the steps:
Step (1), by 6.5g styrene, linear dimerization body, the 22g of 30g α-methylstyrene, 1.5g α-methylstyrene
Maleic anhydride and 40g Isooctyl acrylate monomer are blended, and mixed liquor is warming up to 90 DEG C and 3g initiator dibenzoyl peroxide is added, it
Polymerization reaction 45min is carried out afterwards, obtains phenylethylene-maleic anhydride oligomer；
Step (2), be added in the phenylethylene-maleic anhydride oligomer obtained in step (1) 68.3g anacardol and
Four isobutyl of 0.08g catalyst metatitanic acid is continuously heating to 135 DEG C and is modified processing 6h, obtains the benzene second of modified by cardanol
Alkene-maleic anhydride oligomers；
18g third is added in the phenylethylene-maleic anhydride oligomer of the modified by cardanol obtained in step (2) for step (3)
Olefin(e) acid -2- hydroxyethyl ester, 210 DEG C, vacuumize water removal under conditions of carry out esterification, obtain double bond containing styrene-horse
Carry out acid anhydrides oligomer；
Viscosity-adjusting agent is added in the double bond containing phenylethylene-maleic anhydride oligomer obtained in step (3) in step (4)
Agent methylene chloride adjusts its viscosity to requirements, and 38.7g oxidant m-chloro peroxide benzene is slowly added dropwise thereto at normal temperature later
Formic acid carries out oxidation reaction 2h or so, and reaction product is filtered to remove white solid, respectively with the sodium sulfite of saturation, carbon
Sour hydrogen sodium, sodium chloride solution wash 3 times, and revolving removing solvent, which is placed in 50 DEG C of vacuum ovens, to be dried to constant weight, are contained
The phenylethylene-maleic anhydride oligomer of double bond and epoxy group, the as described Photocurable oligomers 5, by theoretical calculation, acid
Value is 20.4mgKOH/g.
Embodiment 6
Photocurable oligomers 6 are made by the steps:
Step (1), by 6.5g styrene, linear dimerization body, the 22g of 30g α-methylstyrene, 1.5g α-methylstyrene
Maleic anhydride and 40g Isooctyl acrylate monomer are blended, and mixed liquor is warming up to 90 DEG C and 2.2g initiator dibenzoyl peroxide is added,
Polymerization reaction 45min is carried out later, obtains phenylethylene-maleic anhydride oligomer；
Step (2), be added in the phenylethylene-maleic anhydride oligomer obtained in step (1) 71.7g anacardol and
Four isobutyl of 0.08g catalyst metatitanic acid is continuously heating to 135 DEG C and is modified processing 6h, obtains the benzene second of modified by cardanol
Alkene-maleic anhydride oligomers；
18g third is added in the phenylethylene-maleic anhydride oligomer of the modified by cardanol obtained in step (2) for step (3)
Olefin(e) acid -2- hydroxyethyl ester, 210 DEG C, vacuumize water removal under conditions of carry out esterification, obtain double bond containing styrene-horse
Carry out acid anhydrides oligomer；
Viscosity-adjusting agent is added in the double bond containing phenylethylene-maleic anhydride oligomer obtained in step (3) in step (4)
Agent methylene chloride adjusts its viscosity to requirements, and 40.7g oxygen is slowly added dropwise thereto under conditions of ice-water bath and stirring later
Agent metachloroperbenzoic acid carries out oxidation reaction 2h or so, and reaction product is filtered to remove white solid, respectively with saturation
Sodium sulfite, sodium bicarbonate, sodium chloride solution wash 3 times, revolving remove solvent be placed in 50 DEG C of vacuum ovens it is dry
To constant weight, the phenylethylene-maleic anhydride oligomer containing double bond and epoxy group is obtained, the as described Photocurable oligomers 3 pass through
Theoretical calculation, acid value 20.1mgKOH/g.
The Photocurable oligomers that above-described embodiment 1~6 obtains are configured to number according to component proportion described in table 1 respectively
PVA glue obtains embodiment 7~12.
The formula table of the digital PVA glue (embodiment 7~12) of table 1
Wherein, "-" is indicated without the value, and S1~S4 is respectively that there is the compound of structure as shown in Equation 2 to be respectively in its n value
When 2~5, obtained compound.
It is printed on surface of cotton fabric using the digital PVA glue that silk-screen printing technique respectively obtains embodiment 7~12, it
After carry out it is digital ink-jet printed, finally by surface printing have the cotton fabric of digital PVA glue and stamp be placed in power be 200W/cm2
Ultraviolet light irradiation under carry out curing process, obtaining that treated, PRINTED FABRIC is seen simultaneously by the feel of touching test fabric
It examines whether coating occurs xanthochromia, is compared with untreated cotton fabric, comparing result is listed in table 2.
Untreated cotton fabric is tested respectively by following test method and is obtained by embodiment 7~12 digital white
The performance of rubber cement treated cotton fabric, and test result is listed in table 2.
(1) direct-injection measure of merit
Select the aqueous pigment textile printing ink of Chee company production white to untreated cotton fabric and through above-mentioned number
Whether rubber cement treated cotton fabric carries out spray printing, smooth using 50 times of amplification sem observation linear edges.
(2) thermal transfer measure of merit
Select the thermal transfer red ink-jet spray printing of martial prowess company production on transfer paper, then respectively with untreated cotton fabric and
Through above-mentioned digital PVA glue, treated that cotton fabric carries out thermal transfer, and transfer condition is to handle 30s at 220 DEG C.
50 experimenters are randomly selected, are respectively compared original image and the pattern after fabric surface transfer, evaluation turns
Clarity and vividness after print, clarity and vividness evaluation are divided into 5 grades, and 5 grades are optimal thermal transfer effect.
(3) color fastness is tested
According to the benefit of method described in standard GB/T/T 3920-2008 " textile colour fastness to rubbing test method "
With colour fastness to rubbing tester to untreated cotton fabric and treated that cotton fabric carries out does through above-mentioned digital PVA glue/wet rub
Wipe color fastness detection.
Table 2 is through digital PVA glue treated fabric test Comparative result table
As can be known from Table 2, through the obtained digital PVA glue of the present invention, treated that cotton fabric is soft, tack-free, knits
Pattern edge that object surface is obtained by ink-jet direct-injection or thermal transfer is clear, without imbibition, and printing is bright-colored, and xerotripsis fastness is greater than
4 grades, wet rubbing fastness is greater than 3~4 grades, prints vividness and fastness is substantially better than untreated cotton fabric.
By in embodiment 8, embodiment 11 and embodiment 12 it is found that when the photocuring in the obtained digital PVA glue of the present invention
When oligomer acid value is lower, through the treatment fluid treated cotton fabric dry and wet rubbing fastness and in terms of performance under
Drop.
From in the comparison of embodiment 12 and embodiment 8 it is found that when anacardol and horse in the obtained digital PVA glue of the present invention
When carrying out the ratio between molal quantity of acid anhydrides greater than 1:1, excessive phenolic hydroxyl group may can aoxidize in Light Curing, cause Huang
Become, is rubescent, after the high-temperature process of thermal transfer, the form and aspect which will lead to printed patterns generate deviation.
In conclusion the present invention is with Photocurable oligomers, free radical activity diluent, cationic photosensitive monomer, free radical
A kind of new digital PVA glue of the Material synthesis such as photoinitiator, cation light initiator, titanium dioxide and thickener, present invention benefit
With Photocurable oligomers resin system, the digital PVA glue enabled is anti-in fabric surface progress hybrid UV-curing
It answers, to carry out surface covering treatment to fabric, has comparable covering power to fabric self color, in Light Curing, with
Fabric adhesion-tight can provide good heat-resisting quantity, rub resistance, flexibility and water resistance, additionally it is possible to mention for fabric
The colour vividness and printing fastness of high fabric processed.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of number PVA glue, which is characterized in that in percentage by weight, the number PVA glue includes following component:
2. number PVA glue according to claim 1, which is characterized in that the Photocurable oligomers are acrylate and waist
The modified phenylethylene-maleic anhydride oligomer containing double bond and epoxy group of fruit phenol.
3. number PVA glue according to claim 1 or 2, which is characterized in that in parts by weight, the photocuring
Oligomer is obtained by following component is reacted:
Preferably, free hydroxyl or amino are contained in the acrylate；
Preferably, the anacardol has structure as shown in Equation 1:
Wherein, x is 1 or 2；
Preferably, in parts by weight, the Photocurable oligomers are obtained by following component is reacted:
Preferably, the styrene, α-methylstyrene, α-methylstyrene linear dimerization body, maleic anhydride and acrylic acid
The sum of parts by weight of different monooctyl ester are 100 parts.
4. number PVA glue according to claim 3, which is characterized in that the amount of the substance of the anacardol is less than or equal to horse
Carry out the amount of the substance of acid anhydrides.
5. it is according to claim 3 number PVA glue, which is characterized in that the oxidant be peroxide, preferably between
Chloroperoxybenzoic acid；
Preferably, the initiator is radical initiator, further preferably two isobutyl of benzoyl peroxide and/or azo
Nitrile；
Preferably, the catalyst is appointing in zinc chloride, pyridine, dehydrated alcohol sodium, p-methyl benzenesulfonic acid or tetrabutyl titanate
It anticipates a kind of or at least two mixtures.
6. digital PVA glue described according to claim 1~one of 5, which is characterized in that the acid value of the Photocurable oligomers
≥20mgKOH/g；
Preferably, the free radical activity diluent is isobornyl methacrylate, Tetrahydrofurfuryl Methacrylate, the last of the ten Heavenly stems
Base acrylate, ethoxyethoxyethyl acrylate, 1,6 hexanediol diacrylate, tripropylene glycol diacrylate,
Any one in neopentyl glycol diethoxy diacrylate, two contracting trimethylolpropane tetra-acrylates or at least two
Mixture；
Preferably, the cationic photosensitive monomer is the siloxanyl monomers containing vinyl ether group；
Preferably, the cationic photosensitive monomer has structure as shown in Equation 2:
Wherein, 2,3,4 or 5 n；
Preferably, the free radical photo-initiation is benzoin dimethylether, Alpha-hydroxy phenylcyclohexyl ketone, isopropyl thioxanthone anthracene
Ketone, 2- (4- methylthio phenyl formoxyl) -2- morpholinopropane, 2,4,6- trimethyl benzoyl diphenyl base phosphine oxide, it is bis- (2,4,
6- trimethylbenzoyl) in phenyl phosphine oxide any one or at least two mixture；
Preferably, the cation light initiator is any one in iron arene complexes, diaryl iodonium salt or triaryl sulfonium salts
Kind or at least two mixture；
Preferably, the titanium dioxide is lipophilic anatase thpe white powder；
Preferably, the thickener is oil thickeners.
7. a kind of preparation method of the digital PVA glue as described in one of claim 1~6, which is characterized in that the preparation side
Method includes the following steps:
By the Photocurable oligomers of formula ratio, free radical activity diluent, cationic photosensitive monomer, free radical photo-initiation, sun
Ionic photoinitiator, titanium dioxide and thickener are mixed evenly, and obtain the digital PVA glue.
8. preparation method according to claim 7, which is characterized in that the preparation method includes the following steps:
In Photocurable oligomers, sequentially add in order while agitating formula ratio free radical activity diluent, sun from
Sub- photosensitive monomer, free radical photo-initiation, cation light initiator and titanium dioxide continue dispersion stirring at least 30min, Zhi Houjia
Enter thickener, stir evenly said mixture, obtains the digital PVA glue.
9. preparation method according to claim 7 or 8, which is characterized in that the Photocurable oligomers are as follows
It is prepared:
Step (1), styrene, α-methylstyrene, the linear dimerization body of α-methylstyrene, maleic anhydride and acrylic acid is different
Monooctyl ester is blended, and heats up in mixed liquor and initiator is added, carry out polymerization reaction after being warming up to reaction temperature, obtain styrene-horse
Carry out acid anhydrides oligomer；
Step (2) anacardol and catalyst is added in the phenylethylene-maleic anhydride oligomer obtained in step (1), after of continuing rising
Temperature is modified processing, obtains the phenylethylene-maleic anhydride oligomer of modified by cardanol；
Acrylic acid -2- is added in the phenylethylene-maleic anhydride oligomer of the modified by cardanol obtained in step (2) for step (3)
Hydroxyethyl ester carries out esterification, obtains double bond containing phenylethylene-maleic anhydride oligomer；
Step (4), be added in the double bond containing phenylethylene-maleic anhydride oligomer obtained in step (3) viscosity modifier and
Oxidant, carries out oxidation reaction, and reaction product after post treatment, obtains the phenylethylene-maleic anhydride containing double bond and epoxy group
Oligomer, the as described Photocurable oligomers；
Preferably, the reaction temperature of polymerization reaction described in step (1) is 80~100 DEG C；
Preferably, the reaction time of polymerization reaction described in step (1) is 30~45min；
Preferably, the temperature of modification described in step (2) is 120~150 DEG C；
Preferably, the time of modification described in step (2) is 5~6h；
Preferably, the reaction temperature of esterification described in step (3) is 200~220 DEG C；
Preferably, esterification described in step (3) carries out under conditions of reaction system vacuumizes；
Preferably, viscosity modifier described in step (4) is methylene chloride；
Preferably, oxidation reaction described in step (4) carries out under conditions of ice-water bath；
Preferably, the time of oxidation reaction described in step (4) is 1~3h；
Preferably, post-processing described in step (4) includes being washed, filtered and being dried to reaction product.
10. a kind of PRINTED FABRIC, which is characterized in that the PRINTED FABRIC obtains as follows:
The digital PVA glue as described in one of claim 1~6 is printed in fabric surface using silk-screen printing technique, is carried out later
It is digital ink-jet printed, finally there is the fabric of digital PVA glue and stamp to be placed under ultraviolet light irradiation surface printing and carries out at solidification
Reason, obtains the PRINTED FABRIC.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023165945A1 (en) * | 2022-03-03 | 2023-09-07 | Basf Se | Water-borne polymer, a method for making the same and the applications thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186743A (en) * | 2007-11-16 | 2008-05-28 | 北京化工大学 | Ultraviolet light solidifying copolymer emulsion and preparation method thereof |
| CN102093782A (en) * | 2011-03-30 | 2011-06-15 | 北京神彩优维喷墨材料科技有限公司 | Ultraviolet-cured digital painting ink and preparation method thereof |
| CN102492330A (en) * | 2011-12-02 | 2012-06-13 | 中山大学 | Ultraviolet (UV) photocurable inkjet ink for glass substrate and preparation method for UV photocurable inkjet ink |
| CN102516864A (en) * | 2011-12-07 | 2012-06-27 | 华南理工大学 | Composite aqueous UV coating |
| CN103526552A (en) * | 2013-05-03 | 2014-01-22 | 江南大学 | Photo-curing-based water and oil repellent finishing method for fabric |
| CN104530789A (en) * | 2015-01-19 | 2015-04-22 | 广东希贵光固化材料有限公司 | Cationic photocureable coating for transfer printing film |
| CN105294936A (en) * | 2015-10-19 | 2016-02-03 | 杭州龙勤新材料科技有限公司 | Bi-functionality-degree acrylic ester cross-linking agent and application thereof to 3D printing |
-
2018
- 2018-12-03 CN CN201811466378.5A patent/CN109440504B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186743A (en) * | 2007-11-16 | 2008-05-28 | 北京化工大学 | Ultraviolet light solidifying copolymer emulsion and preparation method thereof |
| CN102093782A (en) * | 2011-03-30 | 2011-06-15 | 北京神彩优维喷墨材料科技有限公司 | Ultraviolet-cured digital painting ink and preparation method thereof |
| CN102492330A (en) * | 2011-12-02 | 2012-06-13 | 中山大学 | Ultraviolet (UV) photocurable inkjet ink for glass substrate and preparation method for UV photocurable inkjet ink |
| CN102516864A (en) * | 2011-12-07 | 2012-06-27 | 华南理工大学 | Composite aqueous UV coating |
| CN103526552A (en) * | 2013-05-03 | 2014-01-22 | 江南大学 | Photo-curing-based water and oil repellent finishing method for fabric |
| CN104530789A (en) * | 2015-01-19 | 2015-04-22 | 广东希贵光固化材料有限公司 | Cationic photocureable coating for transfer printing film |
| CN105294936A (en) * | 2015-10-19 | 2016-02-03 | 杭州龙勤新材料科技有限公司 | Bi-functionality-degree acrylic ester cross-linking agent and application thereof to 3D printing |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023165945A1 (en) * | 2022-03-03 | 2023-09-07 | Basf Se | Water-borne polymer, a method for making the same and the applications thereof |
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