CN102167760A - Cationic polymerization or cation-free radical mixed polymerization type photopolymerization curing system - Google Patents
Cationic polymerization or cation-free radical mixed polymerization type photopolymerization curing system Download PDFInfo
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- CN102167760A CN102167760A CN201110053680XA CN201110053680A CN102167760A CN 102167760 A CN102167760 A CN 102167760A CN 201110053680X A CN201110053680X A CN 201110053680XA CN 201110053680 A CN201110053680 A CN 201110053680A CN 102167760 A CN102167760 A CN 102167760A
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Abstract
The invention discloses a cationic polymerization or cation-free radical mixed polymerization type photopolymerization curing system and belongs to the technical field of preparation of optically functional materials for recording imaging information. The curing system consists of 86 to 89 weight parts of sensitizing monomer, of which the terminal groups are vinyl ether and allyl ether, 1 to 4 weight parts of photopolymerization initiator and 7 to 13 weight parts of solvent. Compositions of the curing system can be applied to a nanoimprinting technology to generate corresponding images and photocureable coating or can be applied to a negative type resist to obtain a negative image. Radical photopolymerization and cation photopolymerization occur in the curing system at the same time. The curing system exerts the advantages of two kinds of polymerization and has high curing speed, low viscosity and low contractibility.
Description
Technical field
The invention belongs to the preparing technical field of image-forming information record, the photopolymerization curing system of particularly a kind of cationoid polymerisation or positively charged ion-free radical mixed polymerization with optical function material.
Background technology
Photopolymerization (claiming photocuring again) is meant that under the effect of light (ultraviolet or visible light) liquid-state oligomers (comprising monomer) forms the process of solid product through crosslinking polymerization.Ultraviolet light polymerization have do not contain organic solvent, environmental pollution is little, curing speed is fast, save the energy, the cured product performance is good, be suitable for high-speed automated production line and to the advantages such as coating of thermo-responsive base material.
Photopolymerization (photocuring) technology is widely used in coating, field (Yang Yongyuan such as the packaged material of printing ink, tackiness agent, electronic industry, photoresist material and printing material, the reparation of tooth section and biomaterial, Wu Yumin, Hu Hui, Tan Haoya. the present situation of radiation curing material and some progress [J1. photographic science and photochemistry, 2002,20 (3): 230-238.).Because of characteristics such as its curing speed is fast, less energy-consumption, non-environmental-pollution, coating performance excellences, since German Bayer AG in 1967 successfully develops ultraviolet-curing paint for the first time, obtained all over the world fast-developing (Deeker C.Kinetic study and new applieations of UV radiation curing[J] .Maeromol.; Rapid Conunun.[J] 2002,23 (18): 1067-1093).
Photopolymerization can be divided into radical polymerization and cationoid polymerisation according to the triggering mechanism difference.Under the situation that these technology constantly are employed, various polyreactions all embody its relative merits.Radical photopolymerization has some important disadvantages: at first, the radical photopolymerization oxygen inhibition is serious, easily causes surface cure bad, often will solidify inconvenient operation under inert atmosphere; Secondly, radical photopolymerization is to follow this bigger volumetric shrinkage usually.The cationic photopolymerization system has been compared following advantage with the radical photoinitiator curing system: be not subjected to oxygen quenching, polymerization chamber volumetric shrinkage little, the polymkeric substance sticking power of formation is stronger; The active centre life-span is long, and curing reaction is difficult for stopping; The more important thing is that its triggering mechanism does not relate to free radical and excited triplet state, thereby, in air atmosphere, can obtain polymerization fast and completely not by oxygen inhibition.But the cationoid polymerisation system also has the shortcoming of himself, is subjected to influence of moisture big, and polymerization velocity is slow, and performance differs and regulates etc.Make with light positively charged ion-free radical mixed light curing system and then can learn from other's strong points to offset one's weaknesses, give full play to the characteristics of free radical and cation photocuring system, thereby widen the scope of application of photocuring system, this just is called as the mixed light polymerization.
What is called mixes photocuring and be meant two or more dissimilar polyreaction is arranged (as radical polymerization and polycondensation, radical polymerization and cationoid polymerisation) process of carrying out simultaneously in same system.A kind of Special Circumstances are arranged, and polyreactions dissimilar in the system realize that by two stages such system is called dual polymerization system, is sensu lato hybrid polymer system.Hybrid polymer is different with modification by copolymerization with dual polymerization, generation be not multipolymer but high polymer alloy; Also different with blend, they are that original position forms high polymer alloy, and might obtain inierpeneirating network structure (positive N), thereby make polymerisate possess better comprehensive performance.Hybrid polymer combines the advantage of each polyreaction, shows good synergistic effect, is the novel method of polymer modification.
Summary of the invention
The invention provides the composition of the photopolymerization curing system of a kind of cationoid polymerisation or positively charged ion-free radical mixed polymerization, its core is that end group is the sensitization monomer of vinyl ether and allyl ethers, and it specifically consists of:
(1) end group of 86-89 weight part is the sensitization monomer of vinyl ether and allyl ethers;
(2) Photoepolymerizationinitiater initiater of 1-4 weight part;
(3) solvent of 7-13 weight part.
Described end group is that the sensitization monomer of vinyl ether and allyl ethers is shown below:
R in the formula
1Be the vinyl ether alkoxyl group, structural formula is
R wherein
7For H, carbonatoms are the alkyl or phenyl of 1-4, a is the integer of 1-10;
R
2Be the allyl ethers alkoxyl group, structural formula is
R wherein
8For H, carbonatoms are
The alkyl or phenyl of 1-4, b are the integer of 1-10;
R
3, R
4, R
5, R
6Be H, CH
3, phenyl or p-methylphenyl;
N is the integer of 0-10; M is the integer of 1-10.
Described end group is that the monomeric concrete structure formula of the sensitization of vinyl ether and allyl ethers is as follows: monomer A-1 is to A-24:
Monomers B-1 is to B-24:
Monomer C-1 to C-24:
Monomer D-1 to D-24:
Monomer E-1 to E-24:
Described Photoepolymerizationinitiater initiater is cationic photopolymerization initiator and radical photopolymerization initiator, is specially among mixed type triaryl fluorine metaantimmonic acid sulfosalt cation light initiator PAG201, mixed type triaryl fluorine metaantimmonic acid sulfosalt cation light initiator PAG202, triaryl fluorine metaantimmonic acid sulfosalt cation light initiator 445, radical initiator ITX, radical initiator 907, radical initiator 784, radical initiator TPO, the radical initiator BAPO one or more.
Described solvent is one or more in ethyl lactate, butylacetate, pentyl acetate, Pyruvic Acid Ethyl ester, ethylene glycol ether acetate, glycol methyl ether acetate, 1-Methoxy-2-propyl acetate, acetone, methyl iso-butyl ketone (MIBK), 2-heptanone and pimelinketone, gamma-butyrolactone, hexanaphthene, the tetrahydrofuran (THF).These solvents can fully dissolve each component, have suitable drying rate and even, slick coating is provided after solvent evaporation.
The composition of the cationoid polymerisation of the present invention's preparation or the photopolymerization curing system of positively charged ion-free radical mixed polymerization, its core contain end group be vinyl ether and allyl ethers contain the silicon photoreceptor monomer, this monomer is in the presence of radical initiator and cationic initiator common, UV-light causes generation cationoid polymerisation and radical polymerization, radical photopolymerization reaction and cationic photopolymerization promptly take place in this curing system simultaneously, this system has been brought into play the advantage of two kinds of polyreactions simultaneously, but the forgone shortcoming of two kinds of reactions reduces its susceptibility to oxygen and moisture.The composition polymerization degree height of this curing system, rate of polymerization are fast, simultaneously, siliceous monomer can improve wear resistance and anti-dry etching performance as the nano impression resist, and the surface tension that the silicon chain has reduced, make viscosity lower, film forming homogeneity improves, and this monomeric maximum absorption wavelength is at 200nm, stable to visible light, make storage and transportation comparatively convenient.The composition of this curing system can be used for nanometer embossing can produce respective image, photo-cured coating, or be used for the negative type resist and obtain the negative image.
Embodiment
Embodiment:
The proportioning of according to the form below is with the cationic photopolymerization initiator, and end group is that the sensitization monomer of vinyl ether and allyl ethers is dissolved in the solvent.
Curing system is coated on the salt sheet, and the warm air drying film forming is put on the horizontal sample platform of real-time infrared spectroscopy instrument.At room temperature use pointolite directional illumination sample, the adjusting ultraviolet ray intensity is 30mW/cm
2, gather infrared data simultaneously.Its polymerization situation is as follows:
Table 1 cationic initiator causes the polymerization situation of curing system down
P-1: mixed type triaryl fluorine metaantimmonic acid sulfosalt cation light initiator PAG201;
P-2: mixed type triaryl fluorine metaantimmonic acid sulfosalt cation light initiator PAG202;
P-3: triaryl fluorine metaantimmonic acid sulfosalt cation light initiator 445;
P-4: radical initiator ITX;
P-5: radical initiator 907;
P-6: radical initiator 784;
P-7: radical initiator TPO;
P-8: radical initiator BAPO.
As can be seen from the table, the main effect of solvent is dissolved monomer and initiator, makes final film forming even, so need only volatility solvent preferably; Initiator concentration accounts for 2.7% of system and is advisable, and promptly the quality of initiator accounts for 3% of initiator and monomer total mass, the two complete polymerizations of key of vinyl ether this moment, and allyl ethers is partially polymerized.
The according to the form below proportioning is with the cationic photopolymerization initiator, and radical photopolymerization initiator and end group are that the sensitization monomer of vinyl ether and allyl ethers is dissolved in the solvent.
Curing system is coated on the salt sheet, and the warm air drying film forming is put on the horizontal sample platform of real-time infrared spectroscopy instrument.At room temperature use pointolite directional illumination sample, the adjusting ultraviolet ray intensity is 30mW/cm
2, gather infrared data simultaneously.Its polymerization situation is as follows:
The polymerization situation of curing system under the table 2 mixed light initiator.
P-1: mixed type triaryl fluorine metaantimmonic acid sulfosalt cation light initiator PAG201;
P-2: mixed type triaryl fluorine metaantimmonic acid sulfosalt cation light initiator PAG202;
P-3: triaryl fluorine metaantimmonic acid sulfosalt cation light initiator 445;
P-4: radical initiator ITX;
P-5: radical initiator 907;
P-6: radical initiator 784;
P-7: radical initiator TPO;
P-8: radical initiator BAPO.
As can be seen from Table 2, behind the adding radical initiator, the polymerization degree increases, and the P-4 effect is best and cationic initiator cooperates, and can make the complete polymerization of monomer.Though polymerization time increases, rate of polymerization is still very high comparatively speaking.
The viscosity of sample is measured with capillary viscosimeter.
The mensuration of the monomer polymerization speed and the polymerization degree is by the REAL TIME INFRARED THERMAL IMAGE instrument it to be measured.Promptly simultaneously sample is carried out ultraviolet light irradiation and infrared detection.The high-energy ultraviolet electric light source that is mainly 365nm with emission wavelength shines sample by fiber orientation, and light intensity is 30mW/cm
2, record by light intensity meter.In the photopolymerization process, data gathering is spaced apart 1.59s, and acquisition resolution is 4cm
-1By the RT-FTIR technology, the characteristic peak 1617cm of the two keys of monitoring vinyl ether and allyl ethers
-1And 1647cm
-1Changing conditions, thereby kinetic parameters such as the polymerization degree of obtaining and rate of polymerization.Two key characteristic peaks of vinyl ether and allyl ethers are because gathering is nearer, and being overlapped into a peak can not separate.But in certificate and process, from infared spectrum as can be seen, along with the growth of time shutter, 1616cm
-1Reduce gradually, expose 1647cm
-1The peak.According to the detection at auxiliary character peak, under independent cationic initiator, the complete polymerization of two keys of vinyl ether, two key small part polymerization of allyl ethers; Under the mixing of cationic initiator and radical initiator causes, two kinds of all polymerizations fully of two keys.
Claims (5)
1. the composition of the photopolymerization curing system of a cationoid polymerisation or positively charged ion-free radical mixed polymerization is characterized in that it specifically consists of:
(1) end group of 86-89 weight part is the sensitization monomer of vinyl ether and allyl ethers;
(2) Photoepolymerizationinitiater initiater of 1-4 weight part;
(3) solvent of 7-13 weight part.
2. the composition of the photopolymerization curing system of a kind of cationoid polymerisation according to claim 1 or positively charged ion-free radical mixed polymerization, described end group are that the sensitization monomer of vinyl ether and allyl ethers is shown below:
R in the formula
1Be the vinyl ether alkoxyl group, structural formula is
R wherein
7For H, carbonatoms are the alkyl or phenyl of 1-4, a is the integer of 1-10;
R
2Be the allyl ethers alkoxyl group, structural formula is
R wherein
8For H, carbonatoms are
The alkyl or phenyl of 1-4, b are the integer of 1-10;
R
3, R
4, R
5, R
6Be H, CH
3, phenyl or p-methylphenyl;
N is the integer of 0-10; M is the integer of 1-10.
3. the composition of the photopolymerization curing system of a kind of cationoid polymerisation according to claim 1 or positively charged ion-free radical mixed polymerization, described end group are that the monomeric concrete structure formula of the sensitization of vinyl ether and allyl ethers is as follows: monomer A-1 is to A-24:
Monomers B-1 is to B-24:
Monomer C-1 to C-24:
Monomer D-1 to D-24:
Monomer E-1 to E-24:
4. according to the composition of the photopolymerization curing system of claim 2 or 3 described a kind of cationoid polymerisations or positively charged ion-free radical mixed polymerization, described Photoepolymerizationinitiater initiater is cationic photopolymerization initiator and radical photopolymerization initiator, is specially mixed type triaryl fluorine metaantimmonic acid sulfosalt cation light initiator PAG201, mixed type triaryl fluorine metaantimmonic acid sulfosalt cation light initiator PAG202, triaryl fluorine metaantimmonic acid sulfosalt cation light initiator 445, radical initiator ITX, radical initiator 907, radical initiator 784, radical initiator TPO, among the radical initiator BAPO one or more.
5. the composition of the photopolymerization curing system of a kind of cationoid polymerisation according to claim 4 or positively charged ion-free radical mixed polymerization, described solvent are one or more in ethyl lactate, butylacetate, pentyl acetate, Pyruvic Acid Ethyl ester, ethylene glycol ether acetate, glycol methyl ether acetate, 1-Methoxy-2-propyl acetate, acetone, methyl iso-butyl ketone (MIBK), 2-heptanone and pimelinketone, gamma-butyrolactone, hexanaphthene, the tetrahydrofuran (THF).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105223777A (en) * | 2014-05-30 | 2016-01-06 | 青岛科技大学 | A kind of stereolithography rapid prototyping mixes type polysiloxane group photosensitive resin composition and its preparation method and application |
| CN109135392A (en) * | 2017-06-15 | 2019-01-04 | 常州强力电子新材料股份有限公司 | A kind of double sulfosalt photoinitiators |
| CN111039973A (en) * | 2019-12-30 | 2020-04-21 | 江苏奥克化学有限公司 | Organic silicon modified enol compound and preparation method thereof |
| WO2020082480A1 (en) * | 2018-10-23 | 2020-04-30 | 武汉华星光电半导体显示技术有限公司 | Photosensitive resin composition, display device, and a method for preparing photosensitive resin composition |
-
2011
- 2011-03-07 CN CN201110053680XA patent/CN102167760A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105223777A (en) * | 2014-05-30 | 2016-01-06 | 青岛科技大学 | A kind of stereolithography rapid prototyping mixes type polysiloxane group photosensitive resin composition and its preparation method and application |
| CN109135392A (en) * | 2017-06-15 | 2019-01-04 | 常州强力电子新材料股份有限公司 | A kind of double sulfosalt photoinitiators |
| WO2020082480A1 (en) * | 2018-10-23 | 2020-04-30 | 武汉华星光电半导体显示技术有限公司 | Photosensitive resin composition, display device, and a method for preparing photosensitive resin composition |
| US11520231B2 (en) | 2018-10-23 | 2022-12-06 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Flexible display substrate and method for manufacturing the same |
| CN111039973A (en) * | 2019-12-30 | 2020-04-21 | 江苏奥克化学有限公司 | Organic silicon modified enol compound and preparation method thereof |
| CN111039973B (en) * | 2019-12-30 | 2023-04-07 | 江苏奥克化学有限公司 | Organic silicon modified enol compound and preparation method thereof |
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Application publication date: 20110831 |