CN105177988B - It is a kind of to solidify free radical/cationic hybrid system for the blue light that textile digital function is arranged - Google Patents
It is a kind of to solidify free radical/cationic hybrid system for the blue light that textile digital function is arranged Download PDFInfo
- Publication number
- CN105177988B CN105177988B CN201510652534.7A CN201510652534A CN105177988B CN 105177988 B CN105177988 B CN 105177988B CN 201510652534 A CN201510652534 A CN 201510652534A CN 105177988 B CN105177988 B CN 105177988B
- Authority
- CN
- China
- Prior art keywords
- parts
- free radical
- blue light
- acrylate
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The present invention relates to a kind of textile photocuring technology, especially a kind of to solidify free radical/cationic hybrid system for the blue light that textile digital function is arranged, the system includes following component in parts by weight：13 parts of cation light initiator, 12 parts of free radical photo-initiation, 0.5 1 parts of aided initiating, 10 40 parts of epoxy monomer, 36 54 parts of acrylate oligomer, wherein 24 36 parts of acrylate monomer, the summation of epoxy monomer, acrylate oligomer and acrylate monomer are 100 parts.Solidify free radical/cationic hybrid system when in use for the blue light that textile digital function is arranged, blue light light intensity >=80mw/cm2.The system can under blue light irradiation polymerizing curable, relative to single radical polymerization, can obviously reduce oxygen inhibition, the mechanical stretching performance of enhancing photopolymerization film and meet the digital low-viscosity requirement for arranging.
Description
Technical field
The present invention relates to a kind of textile photocuring technology, especially a kind of blue light arranged for textile digital function
Solidification free radical/cationic hybrid system.
Background technology
Finishing functions of textile fabrics can assign textile needed for specific function, be improve textile added value important way
Footpath, but there is non-selectivity applying, water consumption power consumption in traditional " padding a drying one to bake " technique, raw material availability is low and arranges
Dirty serious the shortcomings of.In order to solve the above problems, Shao is built medium inventor and " a kind of blue light curing formula and is being carried out using it
A kind of new functional finishing method is proposed in textile digital function method for sorting " (CN201310309592) -- textile
Blue light solidification digital function is arranged, it is advantageous that substituting traditional heat cure with blue light curing mode, energy-saving and emission-reduction, realization can
Sustainable development, and reaction speed is fast, efficiency high, ozone free discharge, and mode is flexible etc., while proposing digital function arrangement
New ideas, achievable fixed point location carries out finishing functions on demand, possesses wide market prospects.But there is condensate in the invention
It is that viscosity is bigger than normal, there is oxygen inhibition in polymerization process and the weak point such as polymeric membrane mechanical stretching strength is weaker.
Photocuring technology is the core that textile blue light solidification digital function is arranged, and current photocuring technology is broadly divided into certainly
By base photocuring and cation photocuring both technologies.Radical UV curing can be extremely short by being reacted rapidly after illumination
Time interior just curable film-forming, and the physical and mechanical properties of the cured film for obtaining is excellent, but during polymerization film formation, oxygen
Inhibition and volume contraction are two large problems, affect the performance of polymeric membrane.Relative to radical UV curing, cation photocuring by
The strong acid catalyzed polymerization of cationic species, and spike will not with illumination disappear and inactivate, initiation reaction can enter always
OK, until cationic species are all consumed, thus in the absence of oxygen inhibition problem.While the ring of monomer used by cationic polymerization
Oxide structure makes its cured product have low-down shrinkage factor, and the cured film for obtaining has excellent adaptation and chemical resistance.But
Be cation photocuring reaction curing efficiency it is not high, available monomer is also fewer, therefore cationic polymerization is subject to certain
Limitation.
The content of the invention
The present invention provides a kind of blue light solidification free radical/cationic hybrid system arranged for textile digital function,
The system can under blue light irradiation polymerizing curable, and with appropriate mobility, be conducive to digital spraying function to arrange, after solidification
The film formed on fabric has excellent strength, pliability and nontoxic low taste, relative to single radical polymerization, can be bright
It is aobvious to reduce oxygen inhibition, the mechanical stretching performance of enhancing polymeric membrane and meet the digital low-viscosity requirement for arranging.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of to solidify free radical/cationic hybrid system for the blue light that textile digital function is arranged, the system is included
Below component in parts by weight：Cation light initiator 1-3 parts, free radical photo-initiation 1-2 parts, aided initiating 0.5-1 parts,
Epoxy monomer 10-40 parts, acrylate oligomer 36-54 parts, wherein acrylate monomer 24-36 parts, epoxy monomer, acrylic acid
The summation of ester oligomer and acrylate monomer is 100 parts.Solidify free radical/sun for the blue light that textile digital function is arranged
Ion hybrid systems when in use, blue light light intensity >=80mw/cm2。
Later stage application of the invention can continue to use Shao builds the patent of medium people invention " a kind of blue light curing formula and is carried out using it
Textile digital function method for sorting " method for sorting in (ZL201310309592) carries out textile digital function arrangement.
The advantages of in rapid photocuring and cation photocuring based on free radical without oxygen inhibition, the present invention solidifies two kinds
Technology combines, and forms hybrid systems, and concerted reaction occurs, and forms interpenetrating networks macromolecular structure, not only reduces polymerization
System viscosity, the need for being conducive to meeting digital spray process, decreases the oxygen inhibition problem in polymerization process, is conducive to carrying
Polymerization conversion high, can also significantly increase the mechanical stretching performance of cured film.Therefore free radical/cationic hybrid light is consolidated
The foundation of change system arranges most important to textile blue light solidification digital function.
Preferably, cation light initiator is diphenyl iodine hexafluorophosphate (DPI), free radical photo-initiation is camphor tree
Brain quinone (CQ), aided initiating is 4- (dimethylamino) ethyl benzoate (EDB).
Preferably, epoxy monomer used is 3,4- epoxy-cyclohexanes formic acid 3,4- 7-oxa-bicyclo[4.1.0s methyl esters (UVR)；
Acrylate oligomer and acrylate monomer used is respectively aliphatic urethane diacrylate (Aliphatic PUA)
With hydroxy-ethyl acrylate (HEA).
Preferably, aliphatic urethane diacrylate：The weight ratio of hydroxy-ethyl acrylate is 6：4.
A kind of preparation method for solidifying free radical/cationic hybrid system for the blue light that textile digital function is arranged,
The method is：It is accurate to weigh cation light initiator, free radical photo-initiation and aided initiating, add epoxy monomer and acrylic acid
Ultrasonic disperse after ester monomer, adds the desired amount of acrylate oligomer after solid fully dissolves, and continues ultrasonic disperse, waits to mix
Zoarium system it is fully dispersed it is uniform after obtain the oil-based liquid of transparent clarification shape, the liquid is blue light solidification free radical/cation
Hybrid systems.
The beneficial effects of the invention are as follows：Relative to " a kind of blue light curing formula and the textile number work(carried out using it
Solidify free radical system using only single blue light in energy method for sorting " (CN201310309592), the present invention is consolidated using blue light
Change free radical/cationic hybrid system, significantly reduce oxygen inhibition problem present in single degree of freedom base curing system, and
The viscosity of polymerization system and the mechanical performance of enhancing cured film, simultaneous reactions efficiency high, simple operation, energy can substantially be reduced
Low, environmental protection is consumed, meets the requirement of sustainable development.
Specific embodiment
Below by specific embodiment, technical scheme is described in further detail.It should be appreciated that this hair
Bright implementation is not limited to the following examples, and any formal accommodation and/or change made to the present invention will all fall
Enter the scope of the present invention.
In the present invention, if not refering in particular to, all of part, percentage are unit of weight, equipment and raw material for being used etc.
It is commercially available or commonly used in the art.Method in following embodiments, unless otherwise instructed, is the normal of this area
Rule method.
The testing standard used in the present invention is as follows:
The testing standard of the tensile stress of film is ISO1184-1983《The measure of stretched plastic film performance》, omnipotent
Carried out in Material Testing Machine (Instron Corporation of Instron3367,1TW group).
The viscosity (before illumination) of formula is measured by rotational rheometer (MCR301, Austrian Anton Paar commerce and trade Co., Ltd),
The rheological property of different formulations is tested on the plectane of a diameter of 20mm, it is 100-200s to set shear rate change scope-1, survey
Examination temperature is 25 DEG C.
The surface drying test of cured film：The compound resin sample uniform application for preparing is taken in glass sheet surface, sample
Thickness about 2mm, the film-forming under the irradiation of visible-light curing machine.Detect by an unaided eye with qualitative filter paper wiping to be combined after judging solidification
The greasy degree of resin surface, it follows that the surface drying performance of compound resin, is generally divided into 5 grades, and series is higher, and surface is drier
It is smooth.Because oxygen is to the inhibition of radical polymerization so that cured film polymerization reaction on the solid surface is insufficient, cause cured film table
Face can stickness, greasy, the oxygen inhibition degree for judging solidification process is tested by this.
The flexible testing standard of film is GB/T1731-93《Paint film flexibility assay method》, in paint film flexibility
Tested on tester (QTX, Tianjin Hong Juli testing equipments factory).
Embodiment 1
It is accurate to weigh 0.02g DPI, 0.02g CQ, 0.02g EDB, add monomer 0.2g UVR and 0.72g HEA, ultrasound
Dispersion adds 1.08g Aliphatic PUA after solid fully dissolves, and continues ultrasonic disperse, and question response liquid is sufficiently mixed, obtains
Oil-based liquid to transparent clarification shape is blue light curing reaction liquid (i.e. of the present invention to be arranged for textile digital function
Blue light solidifies free radical/cationic hybrid system).
Embodiment 2:
Concrete scheme is with embodiment 1, difference:0.04g DPI, 0.02g CQ, 0.01g EDB accurately are weighed,
Add monomer 0.4g UVR and 0.64g HEA, ultrasonic disperse that 0.96g Aliphatic PUA are added after solid fully dissolves,
Continue ultrasonic disperse, question response liquid is sufficiently mixed, obtain the oil-based liquid i.e. blue light curing reaction liquid of transparent clarification shape.
Embodiment 3:
Concrete scheme is with embodiment 1, difference:0.05g DPI, 0.04g CQ, 0.01g EDB accurately are weighed,
Add monomer 0.6g UVR and 0.56g HEA, ultrasonic disperse that 0.84g Aliphatic PUA are added after solid fully dissolves,
Continue ultrasonic disperse, question response liquid is sufficiently mixed, obtain the oil-based liquid i.e. blue light curing reaction liquid of transparent clarification shape.
Embodiment 4:
Concrete scheme is with embodiment 1, difference:0.06g DPI, 0.03g CQ, 0.02g EDB accurately are weighed,
Add monomer 0.8g UVR and 0.48g HEA, ultrasonic disperse that 0.72g Aliphatic PUA are added after solid fully dissolves,
Continue ultrasonic disperse, question response liquid is sufficiently mixed, obtain the oil-based liquid i.e. blue light curing reaction liquid of transparent clarification shape.
Comparative example 1：
Concrete scheme is with embodiment 1, difference:0.04g DPI, 0.02g CQ, 0.01g EDB accurately are weighed,
Add monomer 0.8g HEA, ultrasonic disperse that 1.2g Aliphatic PUA are added after solid fully dissolves, continue ultrasonic disperse,
Question response liquid is sufficiently mixed, and obtains the oil-based liquid i.e. blue light curing reaction liquid of transparent clarification shape.
The preparation of cured film：Example 1-4 and solidify liquid obtained in comparative example 1 are coated in glass plate respectively, and control is thick
It is 0.3mm to spend, under nitrogen atmosphere, fixed blue light light intensity 80mw/cm2Lower irradiation 8 minutes, takes off as cured film, test
The viscosity of blue light curing reaction liquid and the mechanical stretching performance of cured film and pliability.Example 1-4 and comparative example 1 again
Obtained solidify liquid is coated in glass plate, controls thickness for 0.3mm, under air atmosphere, fixed blue light light intensity 80mw/cm2Under
Irradiation 8 minutes, takes off the surface drying of test blue light cured film (towards the side of air).
The viscosity and the ultimate strength of cured film of the blue light solidify liquid of above-described embodiment 1-4 and comparative example 1, elongation percentage,
Surface drying and pliability are listed in Table 1 below.
The viscosity of the blue light curing reaction liquid of table 1 and the ultimate strength of cured film, elongation percentage, surface drying and pliability compare
As shown in Table 1, the addition of epoxy monomer UVR can obviously reduce the viscosity of blue light solidify liquid, strengthen mechanical stretching
Can be with surface drying, and the increase measured with UVR, viscosity is less and less, and ultimate strength and fracture elongation are increasing,
Surface drying is better.This is, because the viscosity of UVR is very low, to be added in comparative example 1 and play diluting effect, meets later stage digital function
The low-viscosity requirement of clearing system.The UVR for adding simultaneously, the UVR converging networks by forming fragility after blue light solidification, can be with bullet
Property radical polymerization network interpenetrating together, this mutually interspersed elastic network chain serves the transmission of dispersive stress and strain
Effect, effectively reduces stickiness flowing of the radical polymerization network in stretching, prevents crackle after UVR converging network stress
Extension, improves tensile strength and elongation at break, greatly the mechanical performance of lifting cured film.Due to used camphorquinone/
The component of salt compounded of iodine/tertiary amine three triggers system and free radical/cationic hybrid polymerization system, can effectively improve oxygen inhibition and ask
Topic, the surface drying on lifting cured film surface.
Currently preferred blue light curing formula is it is contemplated that the wearability of textile, i.e., solidify in fabric face blue light
Film afterwards should be that pliability is excellent, have certain tensile strength, so be pullled by external force or during wrinkle in fabric, film
There is certain deformation recovery capability, be unlikely to the phenomenon that embrittlement occurs.
Blue light is successfully mixed curing technology and is incorporated into textile dyeing and finishing field by the present invention, instead of traditional heat cure
Mode, with reaction speed is fast, the clear superiority such as energy-saving and emission-reduction and radiationless harm, and with curing system is mixed, with low
Oxygen hinders, the advantage of low-viscosity and enhancing mechanical properties.
Embodiment described above is a kind of preferably scheme of the invention, not makees any formal to the present invention
Limitation, also has other variants and remodeling on the premise of without departing from the technical scheme described in claim.
Claims (4)
- It is 1. a kind of to solidify free radical/cationic hybrid system for the blue light that textile digital function is arranged, it is characterised in that：Should System includes following component in parts by weight：Cation light initiator 1-3 parts,Free radical photo-initiation 1-2 parts,Aided initiating 0.5-1 parts,Epoxy monomer 10-40 parts,Acrylate oligomer 36-54 parts,Acrylate monomer 24-36 parts,Wherein the summation of epoxy monomer, acrylate oligomer and acrylate monomer is 100 parts；Epoxy monomer used is 3,4- epoxy-cyclohexane formic acid 3,4- 7-oxa-bicyclo[4.1.0 methyl esters（UVR）；Acrylic acid used Ester oligomer and acrylate monomer are respectively aliphatic urethane diacrylate（Aliphatic PUA）With acrylic acid hydroxyl second Ester（HEA）.
- 2. blue light according to claim 1 solidifies free radical/cationic hybrid system, it is characterised in that：Cationic photopolymerization draws Hair agent is diphenyl iodine hexafluorophosphate（DPI）, free radical photo-initiation is camphorquinone（CQ）, aided initiating is 4- (diformazans Amino) ethyl benzoate（EDB）.
- 3. blue light according to claim 1 solidifies free radical/cationic hybrid system, it is characterised in that：Aliphatic poly ammonia Ester diacrylate：The weight ratio of hydroxy-ethyl acrylate is 6：4.
- 4. a kind of blue light solidification free radical/cation for the arrangement of textile digital function according to claim 1 is mixed The preparation method of miscellaneous system, it is characterised in that：Cation light initiator, free radical photo-initiation and aided initiating accurately are weighed, Ultrasonic disperse after epoxy monomer and acrylate monomer is added, the desired amount of acrylate oligomers are added after solid fully dissolves Thing, continues ultrasonic disperse, system to be mixed it is fully dispersed it is uniform after obtain the oil-based liquid of transparent clarification shape, the liquid is indigo plant Photocuring free radical/cationic hybrid system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510652534.7A CN105177988B (en) | 2015-10-10 | 2015-10-10 | It is a kind of to solidify free radical/cationic hybrid system for the blue light that textile digital function is arranged |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510652534.7A CN105177988B (en) | 2015-10-10 | 2015-10-10 | It is a kind of to solidify free radical/cationic hybrid system for the blue light that textile digital function is arranged |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105177988A CN105177988A (en) | 2015-12-23 |
| CN105177988B true CN105177988B (en) | 2017-05-31 |
Family
ID=54900385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510652534.7A Active CN105177988B (en) | 2015-10-10 | 2015-10-10 | It is a kind of to solidify free radical/cationic hybrid system for the blue light that textile digital function is arranged |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105177988B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317263B (en) * | 2016-08-23 | 2017-12-22 | 浙江理工大学 | Visible light initiation system and its process for photocuring in a kind of medical photocuring hydrogel |
| CN111234685B (en) * | 2020-03-04 | 2021-09-21 | 浙江理工大学 | Photo-curing textile coating agent with anti-oxidation resistance characteristic and processing method of imitation leather coating thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396698A (en) * | 2013-07-19 | 2013-11-20 | 浙江理工大学 | Blue-ray curing formula and textile digital functional finishing method utilizing same |
-
2015
- 2015-10-10 CN CN201510652534.7A patent/CN105177988B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396698A (en) * | 2013-07-19 | 2013-11-20 | 浙江理工大学 | Blue-ray curing formula and textile digital functional finishing method utilizing same |
Non-Patent Citations (1)
| Title |
|---|
| "自由基-阳离子混杂光固化环氧/丙烯酸酯协同效应的研究";王亦农;《高分子通报》;20120715(第7期);第111-115页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105177988A (en) | 2015-12-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xiang et al. | Stretchable and fatigue-resistant materials | |
| CN106496438B (en) | A kind of amidation graphene oxide modified polycarboxylic acid water-reducing agent and preparation method thereof | |
| CN106478895A (en) | Compound polycarboxylate water-reducer of a kind of graphene oxide and preparation method thereof | |
| CN108047386A (en) | It is a kind of for flexible photosensitive resin of 3D printing and preparation method thereof | |
| CN110551296B (en) | Pectin-based double-physical crosslinked hydrogel and preparation method and application thereof | |
| CN107286340B (en) | Copolymerized transparent nylon and preparation method thereof | |
| CN105143384B (en) | Pressure sensing type adhesive composite and the pressure sensing type adhesive sheet using it | |
| CN102321424A (en) | Preparation method for light-heat dual-cured woodware UV varnish coating | |
| CN109206634A (en) | Gelatin-based high intensity hydrogel and preparation method thereof | |
| CN106867431B (en) | Aqueous, environmental protective plastic cement race track adhesive and preparation method thereof | |
| CN102643591A (en) | Resin composition for thermal transfer protection layer, thermal transfer film using resin composition and thermal transfer method | |
| CN105177988B (en) | It is a kind of to solidify free radical/cationic hybrid system for the blue light that textile digital function is arranged | |
| CN100545176C (en) | Poly-(vinyl-acetic ester) emulsion and preparation method thereof | |
| CN112876613B (en) | Preparation method of high-strength light cellulose-based bionic protection material | |
| CN109082202A (en) | A kind of environment protection type high-strength polyaniline composite coating and preparation method thereof | |
| CN102604368A (en) | NCO replaced crosslinking cured joint filling material for concrete pavement | |
| WO2019119428A1 (en) | Flexible photosensitive resin for 3d printing and preparation method therefor | |
| CN103396698A (en) | Blue-ray curing formula and textile digital functional finishing method utilizing same | |
| CN109868084A (en) | A kind of UV aggretion type POSS modified acroleic acid ester pressure-sensitive and preparation method | |
| Sun et al. | Endowing water-based polyacrylics adhesives with enhanced water-resistant capability by integrating with tannic acid | |
| CN106543375B (en) | High-molecular antistatic agent and preparation method and application thereof | |
| CN104761673A (en) | Carbomer and preparation method thereof | |
| Wu et al. | Photo-curing preparation of biobased underwater adhesives with hydrophobic chain-ring interlace structure for protecting adhesion | |
| CN107325246B (en) | Modified polyurethane oligomer, preparation method thereof and application thereof in photocuring digital ink-jet printing | |
| CN102212309B (en) | Method for preparing unsaturated polyester polyurethane block copolymer solventless coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220609 Address after: 312000 Room 202, building 1, east of Dong'Er Road, Ma'an street, Keqiao District, Shaoxing City, Zhejiang Province Patentee after: Zhejiang zhongdiefang New Material Technology Co.,Ltd. Address before: 310018 Room 303, building 18, Key Laboratory of the Ministry of education, Xiasha campus, Zhejiang University of technology, No. 928, No. 2 street, Xiasha Higher Education Park, Hangzhou, Zhejiang Province Patentee before: ZHEJIANG SCI-TECH University |