CN1817915A - Cracking light initiating agent containing high-molecular chain segment, its production and use - Google Patents
Cracking light initiating agent containing high-molecular chain segment, its production and use Download PDFInfo
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- CN1817915A CN1817915A CN 200610018289 CN200610018289A CN1817915A CN 1817915 A CN1817915 A CN 1817915A CN 200610018289 CN200610018289 CN 200610018289 CN 200610018289 A CN200610018289 A CN 200610018289A CN 1817915 A CN1817915 A CN 1817915A
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Abstract
A cracking light initiating agent containing high-molecular chain segment, its production and use are disclosed. The procedure is carried out by reacting diphenylmethane-4,4,-vulcabond or hexamethylene-vulcabond or 2,4-toluene vulcabond with cracking light initiating agent containg hydroxyl group and metacrylic acid ester containing hydroxyl group separately, obtaining two reactants, agitating and reacting the two reactants with polyester polyhydric alcohol of molecular weight 500-5000 and polyether polyhydric alcohol at 50-80DEG C to obtain the final product It is simple, has excellent dissolubility and photosensitive activity. It can be used for food packing, photo-etching material, light imaging material, photosensitive materials and three-dimensional modeling material.
Description
Technical field
The present invention relates to a kind of pbz polymer segmental crack type photoinitiator and its production and use, belong to field of light-sensitive high molecular materials.
Background technology
Photopolymerization is to utilize light as reaction power, on photosensitive compound, makes it that a series of optical physics take place by light action, photochemical reaction, generate active substance, thus the initiating activity monomer polymerization, and Ye Tai resin is converted into solid-state macromolecular material the most at last.Its polymerization characteristics are to save the energy, environmental friendliness, economical and efficient, photopolymerization device compactness, production efficiency height.In addition, photopolymerization compares to traditional polymerization technique outstanding advantage, and for example polymerized at room temperature helps the processing of heat-sensitive substrate material; Polymerization formula can be regulated by demand, guarantees product performance (as hardness, flexibility, gloss, weathering resistance etc.); Be easy to realize streamline operration, the level of automation height.Therefore photopolymerization is the advanced manufacturing technology of a kind of being described as " green technology ".
According to the difference of triggering mechanism, the photocuring process can be divided into radical photopolymerization and cationic photopolymerization.What use now is radical photopolymerization the most widely, and it is fast that it has speed, and the surface properties height is to advantages such as humidity are insensitive.But following point often appears in traditional small molecules ultraviolet radical photopolymerization initiator in application process: compatibility problem: the small molecules light trigger is the crystallization light trigger particularly, time-consuming power consumption again when dissolving disperses, after even dispersing and dissolving is complete, formula system is deposited for some time, meet low temperature, initiator may be separated out, the homogeneity and the overall performance of influence prescription; The transport property problem: the migration at a slow speed to the surface can take place in residual initiator molecule or its photolytic product in solidified coating, may cause toxicity problem, also may make the xanthochromia aggravation; The smell problem: the photolysis debris relative molecular mass of most of small molecules light triggers is low, and strong or weak peculiar smell is arranged, and when the photocuring product is used for health, packaging material for food, the smell problem of small molecules light trigger is difficult for solving.
If the small molecules light trigger is made macromolecular cpd or polymerizable structure, then above-mentioned drawback can be overcome.The macromolecular photoinitiator relative molecular mass is often higher, becomes the thickness liquid state more, and is better with the compatibility of resin system; Secondly, generally contain a plurality of initiators unit on the molecular chain, can form a plurality of free radicals simultaneously on a macromole during photoirradiation, local number of free radical can be very high.The high local concentrations effect can effectively tackle oxygen inhibition, helps quickening photopolymerization, but the probability of the mutual coupling termination of living radical also can increase in the macromole, by the design molecular structure, can reduce the intramolecularly free radical coupling.The photochemistry behavior of macromolecular photoinitiator and the mechanism of action and small molecules parent do not have the difference of essence, may be on amount difference to some extent.
Summary of the invention
The purpose of this invention is to provide a kind of pbz polymer segmental crack type photoinitiator and its production and use, resulting pbz polymer segmental crack type photoinitiator has, and light trigger and photolysis debris better with the light reactive resin consistency, that remain in the product are difficult for migration and volatilization, and its preparation cost is low, easy and simple to handle, the yield height of product.
For achieving the above object, technical scheme provided by the invention is: pbz polymer segmental crack type photoinitiator, make by following method: the first step, the crack type photoinitiator of hydroxyl and ditan-4,4`-vulcabond, hexamethylene diisocyanate or 2, the 4-tolylene diisocyanate in the presence of 30-60 ℃, catalyzer dibutyl tin laurate, stirring reaction 2-6 hour; Second step, the acrylate resin of hydroxyl or the methacrylate resin of hydroxyl and ditan-4,4`-vulcabond, hexamethylene diisocyanate or 2, the 4-tolylene diisocyanate 30-60 ℃, the catalyzer dibutyl tin laurate in the presence of, stirring reaction 2-6 hour; The 3rd step, get the reaction product that the first step and second step obtain, under the effect of catalyzer dibutyl tin laurate, with molecular weight be under 50-80 ℃ at polyester polyol or the polyether glycol of 500-5000 in temperature, stirring reaction makes pbz polymer segmental crack type photoinitiator.
The crack type photoinitiator of above-mentioned hydroxyl is preferably 2-hydroxyl-aminomethyl phenyl propane-1-ketone or 1-hydroxycyclohexylphenylketone.
Pbz polymer segmental crack type photoinitiator of the present invention is the product that contains following structural formula I compound, the compound that wherein may contain a spot of following structural formula II and III, but by product II and III that these are produced in preparation process do not influence the present invention as performance and effect that macromolecular photoinitiator had:
R in the formula
1For the crack type photoinitiator of hydroxyl is removed hydroxy functional group (OH) structure of remainder afterwards, as: 2-hydroxyl-aminomethyl phenyl propane-1-ketone or 1-hydroxycyclohexylphenylketone are removed the structure of hydroxy functional group (OH) back remainder; R
2Be ditan-4,4`-vulcabond (MDI), hexamethylene diisocyanate (HDI) or 2,4 toluene diisocyanate (TDI) are removed the structure of two isocyanate functional groups (NCO) back remainder, and its structure is as follows successively:
-CH
2-CH
2-CH
2-CH
2-CH
2-CH
2-
R
3For molecular weight is removed hydroxy functional group (OH) structure of remainder afterwards at polyester polyol or the polyether glycol of 500-5000; R
4Remove the structure of hydroxy functional group (OH) back remainder for the methacrylate resin of the acrylate resin of hydroxyl or hydroxyl.
The present invention also provides the preparation method of above-mentioned pbz polymer segmental crack type photoinitiator: reaction divided for three steps carried out, the first step, in the presence of 30-60 ℃, catalyzer dibutyl tin laurate, the speed that is no more than 0.8mL by per second will wait the crack type photoinitiator of the hydroxyl of mol ratio to be added drop-wise to ditan-4,4`-vulcabond, hexamethylene diisocyanate or 2, in the 4-tolylene diisocyanate, stirring reaction 2-6 hour; Second step, 30-60 ℃, the catalyzer dibutyl tin laurate in the presence of, the speed that is no more than 0.8mL by per second will wait the acrylate resin of hydroxyl of mol ratio or the methacrylate resin of hydroxyl to be added drop-wise to ditan-4,4`-vulcabond, hexamethylene diisocyanate or 2, in the 4-tolylene diisocyanate, stirring reaction 2-6 hour; The 3rd step, with the first step and second reaction product that obtain of step under the effect of catalyzer dibutyl tin laurate, with excessive molecular weight be under 50-80 ℃ at polyester polyol or the polyether glycol of 500-5000 in temperature, obtained pbz polymer segmental crack type photoinitiator in stirring reaction 2-5 hour.
The above-mentioned pbz polymer segmental of the present invention crack type photoinitiator is a kind of crack type photoinitiator of low migration, and the light trigger that can be used as light reactive resin is used for the radical photopolymerization reaction in field of light-sensitive high molecular materials.
When using pbz polymer segmental crack type photoinitiator of the present invention and carrying out polymerization, can adopt high voltage mercury lamp, electrodeless lamp source, also can adopt LASER Light Source such as Ultra-Violet Laser.
Pbz polymer segmental crack type photoinitiator of the present invention can be used as light solidifying coating material, photoetching material, photoimaging material, hologram recording material, the initiator when optical material and three-dimensional modeling material photocuring.
Application as above-mentioned pbz polymer segmental crack type photoinitiator, the invention provides a kind of radical photoinitiator solidified coating material, form by the light reactive resin of 40～80wt%, the reactive thinner of 15～50wt%, claim 1 described pbz polymer segmental crack type photoinitiator and the 0～3wt% auxiliary agent of 3～10wt%.
Above-mentioned light reactive resin is epoxy (methyl) acrylic resin, polyester (methyl) acrylic resin, urethane (methyl) acrylic resin, polyacrylic ester (methyl) acrylic resin, polyethers (methyl) acrylic resin etc.
Described reactive thinner is a simple function group, bifunctional, polyfunctional group (methyl) acrylate monomer.
Described auxiliary agent is this area flow agent commonly used, defoamer, oxidation inhibitor and/or uv-absorbing agent etc.
Above-mentioned radical photoinitiator solidified coating material can be pressed the method preparation, in the container of whipping device is housed, add 15%～50% reactive thinner, 3%～10% pbz polymer segmental crack type photoinitiator, 0～3% auxiliary agent, after the stirring and dissolving, add 40%～80% light reactive resin again, under 40～50 ℃ of temperature, stir to make it to mix and promptly obtain radical photoinitiator solidified coating material.
Pbz polymer segmental crack type photoinitiator of the present invention, its photosensitive activity is suitable with existing small molecules light trigger.And, because its relative molecular mass is higher, be the thickness liquid state, better with the compatibility of resin system; Secondly, generally contain a plurality of initiators unit on the molecular chain, can form a plurality of free radicals simultaneously on a macromole during photoirradiation, local number of free radical can be very high, and the high local concentrations effect can effectively tackle oxygen inhibition, helps quickening photopolymerization; The photolysis debris relative molecular mass of this photoinitiator is also higher, thus its in solidified coating seldom to the migration on surface, avoided causing the problem of toxicity, smell and xanthochromia aggravation, be particularly suitable on health, the packaging material for food.
Embodiment
Synthetic embodiment
Embodiment 1: pbz polymer segmental crack type photoinitiator [R wherein
1Remove the structure of hydroxy functional group (OH) back remainder for 2-hydroxyl-aminomethyl phenyl propane-1-ketone (1173); R
2Be the structure that 2,4 toluene diisocyanate is removed remainder after two isocyanic ester (NCO) functional group, R
3Remove the structure of hydroxy functional group (OH) back remainder for polyoxyethylene glycol (PEG) 600; R
4Remove the structure of hydroxy functional group (OH) back remainder for bisphenol A epoxy acrylate] [being abbreviated as the 1173-TDI-PEG600-TDI-bisphenol A epoxy acrylate] synthetic
(1) 1173-TDI's is synthetic
TDI 5.2g (0.03mol), the 0.6mL dibutyl tin laurate is dissolved in the ethyl acetate, at logical N
2Be heated to 50 ℃ under the condition of stirring and isolated steam, drip (pressing the speed of per second 0.4mL) 2-hydroxyl-aminomethyl phenyl propane-1-ketone (1173) 4.9g (0.03mol), reacted 3 hours; Obtain 1173-TDI.
(2) bisphenol A epoxy acrylate-TDI's is synthetic
TDI 5.2g (0.03mol), dibutyl tin laurate 0.6mL, stopper MEHQ 2mg is dissolved in the ethyl acetate, at logical N
2Be heated to 40 ℃ under the condition of stirring and isolated steam, drip (pressing the speed of per second 0.4mL) bisphenol A epoxy acrylate 7.7g (0.01mol), reacted 4 hours; Obtain bisphenol A epoxy acrylate-TDI.
(3) the 1173-TDI-PEG600-TDI-bisphenol A epoxy acrylate is synthetic
Above-mentioned (1) 1173-TDI is joined in the container that 21.0g (0.035mol) PEG600 is housed, at logical N
2Be heated to 70-80 ℃ of reaction 1-2 hour under the condition of stirring and isolated steam.In reaction solution, add above-mentioned (2) bisphenol A epoxy acrylate-TDI then, continue at logical N
2Be heated to 70-80 ℃ of reaction 1-2 hour under the condition of stirring and isolated steam.Then reaction solution is poured in the aqueous sodium hydroxide solution, the compound of wherein excessive hydroxyl is removed in the vibration washing.Standing demix, collected organic layer, add anhydrous magnesium sulfate drying, distilling off solvent under vacuum condition at last, obtain the 1173-TDI-PEG600-TDI-bisphenol A epoxy acrylate, wherein contain a small amount of 1173-TDI-PEG600-TDI-1173 and bisphenol A epoxy acrylate-TDI-PEG600-TDI-bisphenol A epoxy acrylate by product, do not influence the present invention as performance and effect that macromolecular photoinitiator had but contain above-mentioned by product.Product is identified through infrared spectra, by monitoring hydroxyl peak O-H (3450cm
-1) to amino peak N-H (3305cm
-1) transformation and isocyanate peak NCO (2272cm
-1) disappearance, proved response is finished.
Embodiment 2: pbz polymer segmental crack type photoinitiator [R wherein
1Remove the structure of hydroxy functional group (OH) back remainder for 1-hydroxycyclohexylphenylketone (184); R
2Remove the structure of remainder after two isocyanic ester (NCO) functional group for HDI; R
3Remove the structure of hydroxy functional group (OH) back remainder for polyoxyethylene glycol (PEG) 600; R
4Remove the structure of hydroxy functional group (OH) back remainder for bisphenol A epoxy acrylate] [being abbreviated as the 184-HDI-PEG600-HDI-bisphenol A epoxy acrylate] synthetic
(1) 184-HDI's is synthetic
HDI 5.0g (0.03mol), the 0.6mL dibutyl tin laurate is dissolved in the ethyl acetate, at logical N
2Be heated to 60 ℃ under the reaction conditions under the condition of stirring and isolated steam, drip (pressing the speed of per second 0.7mL) 1-hydroxycyclohexylphenylketone (184) 4.9g (0.03mol), reacted 2 hours.
(2) bisphenol A epoxy acrylate-HDI's is synthetic
HDI 5.0g (0.03mol), dibutyl tin laurate 0.6mL, stopper MEHQ 2mg is dissolved in the ethyl acetate, at logical N
2Be heated to 60 ℃ under the condition of stirring and isolated steam, drip (pressing the speed of per second 0.7mL) bisphenol A epoxy acrylate 7.7g (0.01mol), reacted 2 hours.
(3) the 184-HDI-PEG600-HDI-bisphenol A epoxy acrylate is synthetic
Above-mentioned (1) 184-HDI is joined in the container that 21.0g (0.035mol) PEG600 is housed, at logical N
2Be heated to 50 ℃ of reactions 5 hours under the condition of stirring and isolated steam.In reaction solution, add above-mentioned (2) bisphenol A epoxy acrylate-HDI then, continue at logical N
2Be heated to 50 ℃ of reactions 5 hours under the condition of stirring and isolated steam.Then reaction solution is poured in the aqueous sodium hydroxide solution, the compound of wherein excessive hydroxyl is removed in the vibration washing.Standing demix, collected organic layer, add anhydrous magnesium sulfate drying, distilling off solvent under vacuum condition at last, obtain the 184-HDI-PEG600-HDI-bisphenol A epoxy acrylate, wherein contain a small amount of 184-HDI-PEG600-HDI-184 and bisphenol A epoxy acrylate-HDI-PEG600-HDI-bisphenol A epoxy acrylate, do not influence the present invention as performance and effect that macromolecular photoinitiator had but contain above-mentioned by product.Product is identified through infrared spectra, by monitoring hydroxyl peak O-H (3450cm
-1) to amino peak N-H (3305cm
-1) transformation and isocyanate peak NCO (2272cm
-1) disappearance, proved response is finished.
Synthesizing of embodiment 31173-MDI-PEG5000-MDI-bisphenol A epoxy acrylate
(1) 1173-MDI's is synthetic
MDI 0.03mol, the 0.6mL dibutyl tin laurate is dissolved in the ethyl acetate, at logical N
2Be heated to 30 ℃ under the condition of stirring and isolated steam, drip (pressing the speed of per second 0.2mL) 2-hydroxyl-aminomethyl phenyl propane-1-ketone (1173) 4.9g (0.03mol), reacted 6 hours; Obtain 1173-MDI.
(2) bisphenol A epoxy acrylate-MDI's is synthetic
MDI 0.03mol, dibutyl tin laurate 0.6mL, stopper MEHQ 2mg is dissolved in the ethyl acetate, at logical N
2Be heated to 40 ℃ under the condition of stirring and isolated steam, drip (pressing the speed of per second 0.4mL) bisphenol A epoxy acrylate 7.7g (0.01mol), reacted 4 hours; Obtain bisphenol A epoxy acrylate-MDI.
(3) the 1173-MDI-PEG5000-MDI-bisphenol A epoxy acrylate is synthetic
1173-MDI joins in the container of the PEG5000 that 0.035mol is housed with above-mentioned (1), at logical N
2Be heated to 80 ℃ of reactions 1 hour under the condition of stirring and isolated steam.In reaction solution, add above-mentioned (2) bisphenol A epoxy acrylate-MDI then, continue at logical N
2Be heated to 70 ℃ of reactions 2 hours under the condition of stirring and isolated steam.Then reaction solution is poured in the aqueous sodium hydroxide solution, the compound of wherein excessive hydroxyl is removed in the vibration washing.Standing demix, collected organic layer, add anhydrous magnesium sulfate drying, distilling off solvent under vacuum condition at last, obtain the 1173-MDI-PEG5000-MDI-bisphenol A epoxy acrylate, wherein contain a small amount of 1173-MDI-PEG5000-MDI-1173 and bisphenol A epoxy acrylate-MDI-PEG5000-MDI-bisphenol A epoxy acrylate, do not influence the present invention as performance and effect that macromolecular photoinitiator had but contain above-mentioned by product.Product is identified through infrared spectra, by monitoring hydroxyl peak O-H (3450cm
-1) to amino peak N-H (3305cm
-1) transformation and isocyanate peak NCO (2272cm
-1) disappearance, proved response is finished.
Synthesizing of embodiment 41173-HDI-PEG5000-HDI-bisphenol A epoxy acrylate
Synthetic method is with embodiment 3, only replace TDI with equimolar HDI, obtain the 1173-HDI-PEG5000-HDI-bisphenol A epoxy acrylate, wherein contain a small amount of 1173-HDI-PEG5000-HDI-1173 and bisphenol A epoxy acrylate-HDI-PEG5000-HDI-bisphenol A epoxy acrylate, do not influence the present invention as performance and effect that macromolecular photoinitiator had but contain above-mentioned by product.Product is identified through infrared spectra, by monitoring hydroxyl peak O-H (3450cm
-1) to amino peak N-H (3305cm
-1) transformation and isocyanate peak NCO (2272cm
-1) disappearance, proved response is finished.
Synthesizing of embodiment 5 184-HDI-PEG5000-HDI-bisphenol A epoxy acrylates
Synthetic method is with embodiment 2, only replace PEG600 with equimolar PEG5000 in (3) step, obtain the 184-HDI-PEG5000-HDI-bisphenol A epoxy acrylate, wherein contain a small amount of 184-HDI-PEG5000-HDI-184 and bisphenol A epoxy acrylate-HDI-PEG5000-HDI-bisphenol A epoxy acrylate, do not influence the present invention as performance and effect that macromolecular photoinitiator had but contain above-mentioned by product.Product is identified through infrared spectra, by monitoring hydroxyl peak O-H (3450cm
-1) to amino peak N-H (3305cm
-1) transformation and isocyanate peak NCO (2272cm
-1) disappearance, proved response is finished.
Synthesizing of embodiment 6 184-TDI-PEG5000-TDI-bisphenol A epoxy acrylates
With waiting mole 184 to replace 1173, PEG5000 replaces PEG600, and all the other are with embodiment 1.
Synthesizing of embodiment 7 1173-TDI-Oxyester T 1136-TDI-bisphenol A epoxy acrylates
Replace PEG600 with equimolar polyester glycol Oxyester T 1136 (molecular weight is 1000), all the other are with embodiment 1; Obtain 1173-TDI-Oxyester T 1136-TDI-bisphenol A epoxy acrylate, wherein contain a small amount of 1173-TDI-OxyesterT 1136-TDI-1173 and bisphenol A epoxy acrylate-TDI-Oxyester T 1136-TDI-bisphenol A epoxy acrylate, do not influence the present invention as performance and effect that macromolecular photoinitiator had but contain above-mentioned by product.Product is identified through infrared spectra, by monitoring hydroxyl peak O-H (3450cm
-1) to amino peak N-H (3305cm
-1) transformation and isocyanate peak NCO (2272cm
-1) disappearance, proved response is finished.
Synthesizing of embodiment 8 1173-TDI-TONE Polyol 0201-TDI-bisphenol A epoxy acrylates
Replace PEG600 with equimolar polyester glycol TONE Polyol 0201 (molecular weight is 530), all the other are with embodiment 1; Obtain 1173-TDI-TONE Polyol 0201-TDI-bisphenol A epoxy acrylate, wherein contain a small amount of 1173-TDI-TONEPolyol 0201-TDI-1173 and bisphenol A epoxy acrylate-TDI-TONE Polyol 0201-TDI-bisphenol A epoxy acrylate, do not influence the present invention as performance and effect that macromolecular photoinitiator had but contain above-mentioned by product.Product is identified through infrared spectra, by monitoring hydroxyl peak O-H (3450cm
-1) to amino peak N-H (3305cm
-1) transformation and isocyanate peak NCO (2272cm
-1) disappearance, proved response is finished.
Synthesizing of embodiment 9 1173-TDI-TONE Polyol 1278-TDI-bisphenol A epoxy acrylates
Replace PEG600 with equimolar polyester glycol TONE Polyol 1278 (molecular weight is 4000), all the other are with embodiment 1; Obtain 1173-TDI-TONE Polyol 1278-TDI-bisphenol A epoxy acrylate, wherein contain a small amount of 1173-TDI-TONE Polyol 1278-TDI-1173 and bisphenol A epoxy acrylate-TDI-TONE Polyol 1278-TDI-bisphenol A epoxy acrylate, do not influence the present invention as performance and effect that macromolecular photoinitiator had but contain above-mentioned by product.Product is identified through infrared spectra, by monitoring hydroxyl peak O-H (3450cm
-1) to amino peak N-H (3305cm
-1) transformation and isocyanate peak NCO (2272cm
-1) disappearance, proved response is finished.
Embodiment 10 1173-TDI-PEG600-TDI-hydroxyl polyester acrylate PEA's is synthetic
PEA with mole hydroxyls such as containing replaces bisphenol A epoxy acrylate, and all the other are with embodiment 1; Obtain 1173-TDI-PEG600-TDI-hydroxyl polyester acrylate PEA, wherein contain a small amount of 1173-TDI-PEG600-TDI-1173 and hydroxyl polyester acrylate PEA-TDI-PEG600-TDI-hydroxyl polyester acrylate PEA, do not influence the present invention as performance and effect that macromolecular photoinitiator had but contain above-mentioned by product.Product is identified through infrared spectra, by monitoring hydroxyl peak O-H (3450cm
-1) to amino peak N-H (3305cm
-1) transformation and isocyanate peak NCO (2272cm
-1) disappearance, proved response is finished.
Application Example
Application Example 1
Under the lucifuge condition, in being housed, the Glass Containers of agitator adds the pbz polymer segmental crack type photoinitiator that 3g embodiment 1 makes, 23g aliphatic urethane acrylate resin is 40 ℃ of following stirring and dissolving, add 8g tri-propanediol diacrylate (TPGDA) again, the 8g talcum powder, 42g ground barium sulfate and 16g ground dolomite mix.Can obtain radical photoinitiator solidified coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Application Example 2
Aliphatic urethane acrylate resin (6000) 45g
TPGDA 25g
Ground dolomite 25g
The pbz polymer segmental crack type photoinitiator 3.5g that embodiment 2 makes
Oxidation inhibitor 1.5g
By preparation of Application Example 1 method and coating, obtain the high photocuring of cross-linking density and film.The preparation of 1173-HDI-PEG600-HDI-bisphenol A epoxy acrylate only substitutes 184 with equimolar 1173 with reference to embodiment 2.
Application Example 3
Aliphatic urethane acrylate resin (6000) 50g
TPGDA 19g
Ground barium sulfate 27g
The pbz polymer segmental crack type photoinitiator 4g that embodiment 3 makes
By preparation of Application Example 1 method and coating, obtain the high photocuring of cross-linking density and film.
Application Example 4
Aliphatic urethane acrylate resin (6000) 50g
TPGDA 20g
Ground barium sulfate 26g
The pbz polymer segmental crack type photoinitiator 4g that embodiment 4 makes
By preparation of Application Example 1 method and coating, obtain the high photocuring of cross-linking density and film.
Application Example 5
Aliphatic urethane acrylate resin (6000) 48g
TPGDA 21g
Ground barium sulfate 27g
The pbz polymer segmental crack type photoinitiator 4g that embodiment 5 makes
By preparation of Application Example 1 method and coating, obtain the high photocuring of cross-linking density and film.
Application Example 6
Aliphatic urethane acrylate resin (6000) 45g
TPGDA 30g
Ground dolomite 20g
The pbz polymer segmental crack type photoinitiator 3.5g that embodiment 6 makes
Auxiliary agent 1.5g
By preparation of Application Example 1 method and coating, obtain the high photocuring of cross-linking density and film.
Application Example 7
Aliphatic urethane acrylate resin (6000) 46g
TPGDA 23g
Ground barium sulfate 27g
The pbz polymer segmental crack type photoinitiator 4g that embodiment 7 makes
By preparation of Application Example 1 method and coating, obtain the high photocuring of cross-linking density and film.
Application Example 8
Aliphatic urethane acrylate resin (6000) 60g
TPGDA 19g
Ground barium sulfate 18g
The pbz polymer segmental crack type photoinitiator 3g that embodiment 8 makes
By preparation of Application Example 1 method and coating, obtain the high photocuring of cross-linking density and film.
Application Example 9
Aliphatic urethane acrylate resin (6000) 50g
TPGDA 22g
Ground barium sulfate 25g
The pbz polymer segmental crack type photoinitiator 4g that embodiment 9 makes
By preparation of Application Example 1 method and coating, obtain the high photocuring of cross-linking density and film.
Application Example 10
Aliphatic urethane acrylate resin (6000) 50g
TPGDA 19g
Ground barium sulfate 25g
The pbz polymer segmental crack type photoinitiator 6g that embodiment 10 makes
By preparation of Application Example 1 method and coating, obtain the high photocuring of cross-linking density and film.
Claims (8)
1. pbz polymer segmental crack type photoinitiator, it is characterized in that, make by following method: the first step, the crack type photoinitiator of hydroxyl and ditan-4,4`-vulcabond, hexamethylene diisocyanate or 2, the 4-tolylene diisocyanate in the presence of 30-60 ℃, catalyzer dibutyl tin laurate, stirring reaction 2-6 hour; Second step, the acrylate resin of hydroxyl or the methacrylate resin of hydroxyl and ditan-4,4`-vulcabond, hexamethylene diisocyanate or 2, the 4-tolylene diisocyanate 30-60 ℃, the catalyzer dibutyl tin laurate in the presence of, stirring reaction 2-6 hour; The 3rd step, get the reaction product that the first step and second step obtain, under the effect of catalyzer dibutyl tin laurate, with molecular weight be under 50-80 ℃ at polyester polyol or the polyether glycol of 500-5000 in temperature, stirring reaction makes pbz polymer segmental crack type photoinitiator.
2. pbz polymer segmental crack type photoinitiator according to claim 1 is characterized in that: the crack type photoinitiator of hydroxyl is 2-hydroxyl-aminomethyl phenyl propane-1-ketone or 1-hydroxycyclohexylphenylketone.
3. the preparation method of claim 1 or 2 described pbz polymer segmental crack type photoinitiators, it is characterized in that: reaction divided for three steps carried out, the first step, in the presence of 30-60 ℃, catalyzer dibutyl tin laurate, the speed that is no more than 0.8mL by per second will wait the crack type photoinitiator of the hydroxyl of mol ratio to be added drop-wise to ditan-4, in 4`-vulcabond, hexamethylene diisocyanate or the 2,4 toluene diisocyanate, stirring reaction 2-6 hour; Second step, 30-60 ℃, the catalyzer dibutyl tin laurate in the presence of, the speed that is no more than 0.8mL by per second will wait the acrylate resin of hydroxyl of mol ratio or the methacrylate resin of hydroxyl to be added drop-wise to ditan-4,4`-vulcabond, hexamethylene diisocyanate or 2, in the 4-tolylene diisocyanate, stirring reaction 2-6 hour; The 3rd step, with the first step and second reaction product that obtain of step under the effect of catalyzer dibutyl tin laurate, with excessive molecular weight be under 50-80 ℃ at polyester polyol or the polyether glycol of 500-5000 in temperature, obtained the described pbz polymer segmental of claim 1 crack type photoinitiator in stirring reaction 1-5 hour.
4. the pbz polymer segmental crack type photoinitiator described in the claim 1 is used in field of light-sensitive high molecular materials.
5. a radical photoinitiator solidified coating material is characterized in that: be made up of the light reactive resin of 40～80wt%, the reactive thinner of 15～50wt%, claim 1 described pbz polymer segmental crack type photoinitiator and the 0～3wt% auxiliary agent of 3～10wt%.
6. radical photoinitiator solidified coating material as claimed in claim 5 is characterized in that: light reactive resin is epoxy acrylic resin or epoxy methacrylic resin, polyester acrylic resin or polyester methacrylic resin, polyurethane acrylic resin or urethane methacrylic resin, polyacrylic ester acrylic resin or polyacrylic ester methacrylic resin, polyoxyalkylene acrylate resin or polyethers methacrylic resin.
7. radical photoinitiator solidified coating material as claimed in claim 5 is characterized in that: reactive thinner is simple function group, bifunctional or multi-functional acrylate's monomer or methacrylate monomer.
8. radical photoinitiator solidified coating material as claimed in claim 5 is characterized in that: auxiliary agent is flow agent, defoamer, oxidation inhibitor and/or uv-absorbing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100182895A CN100386346C (en) | 2006-01-24 | 2006-01-24 | Cracking light initiating agent containing high-molecular chain segment, its production and use |
Applications Claiming Priority (1)
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| CN100386346C CN100386346C (en) | 2008-05-07 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805512A (en) * | 2009-02-12 | 2010-08-18 | 拜尔材料科学股份公司 | Prepolymer polyurethane formulations for the production of holographic films |
| CN107987252A (en) * | 2017-11-17 | 2018-05-04 | 深圳市嘉卓成科技发展有限公司 | A kind of preparation method and water-soluble photoinitiator of self-emulsifying aqueous photoinitiator |
| CN109776756A (en) * | 2019-01-21 | 2019-05-21 | 深圳市道尔顿电子材料有限公司 | A kind of dual modified epoxy acrylate and its photoresist |
| CN115558112A (en) * | 2021-07-01 | 2023-01-03 | 国科广化韶关新材料研究院 | Low-migration silicon-containing macromolecular photoinitiator and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020016226A1 (en) * | 2000-06-08 | 2002-02-07 | Lord Corporation | UV curable coating for golf balls |
| CN1304506C (en) * | 2004-11-22 | 2007-03-14 | 中国化工建设总公司常州涂料化工研究院 | Ultraviolet curable paint for transfer of coating |
-
2006
- 2006-01-24 CN CNB2006100182895A patent/CN100386346C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805512A (en) * | 2009-02-12 | 2010-08-18 | 拜尔材料科学股份公司 | Prepolymer polyurethane formulations for the production of holographic films |
| CN101805512B (en) * | 2009-02-12 | 2014-03-05 | 拜尔材料科学股份公司 | Prepolymer polyurethane formulations for the production of holographic films |
| CN107987252A (en) * | 2017-11-17 | 2018-05-04 | 深圳市嘉卓成科技发展有限公司 | A kind of preparation method and water-soluble photoinitiator of self-emulsifying aqueous photoinitiator |
| CN109776756A (en) * | 2019-01-21 | 2019-05-21 | 深圳市道尔顿电子材料有限公司 | A kind of dual modified epoxy acrylate and its photoresist |
| CN115558112A (en) * | 2021-07-01 | 2023-01-03 | 国科广化韶关新材料研究院 | Low-migration silicon-containing macromolecular photoinitiator and preparation method and application thereof |
| CN115558112B (en) * | 2021-07-01 | 2023-08-08 | 国科广化韶关新材料研究院 | Low-migration silicon-containing macromolecular photoinitiator and preparation method and application thereof |
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| Publication number | Publication date |
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| CN100386346C (en) | 2008-05-07 |
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