CN104327206A - Two tail end hydroxyl butadiene low polymer, flexible printed board, liquid crystal alignment layer and method for removing low molecular weight component in two tail end hydroxyl butadiene low polymer - Google Patents
Two tail end hydroxyl butadiene low polymer, flexible printed board, liquid crystal alignment layer and method for removing low molecular weight component in two tail end hydroxyl butadiene low polymer Download PDFInfo
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- CN104327206A CN104327206A CN201410315779.6A CN201410315779A CN104327206A CN 104327206 A CN104327206 A CN 104327206A CN 201410315779 A CN201410315779 A CN 201410315779A CN 104327206 A CN104327206 A CN 104327206A
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- molecular weight
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/06—Butadiene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
- C08F6/12—Separation of polymers from solutions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
Abstract
The invention provides a two tail end hydroxyl butadiene low polymer of which only a high-percentage low molecular weight component is well removed under the condition that a molecular weight and the like are not changed, a flexible printed board formed by the two tail end hydroxyl butadiene low polymer and a liquid crystal alignment layer formed through flexographic printing operation via the flexible printed board. After the two tail end hydroxyl butadiene low polymer are subjected to various heating-free working procedures of solvent-adding stirring operation, standing and separating operation, and decanting operation; the low molecular weight component in a raw material is removed, and the flexible printed board is made by using the two tail end hydroxyl butadiene low polymer as a starting material. The liquid crystal alignment layer is made through the flexographic printing operation via the flexible printed board.
Description
Technical field
The present invention relates to two terminal hydroxyl divinyl oligopolymer, using the flexible printing plate that this two terminal hydroxyls divinyl oligopolymer is formed and the liquid crystal orientation film formed by carrying out flexographic printing with this flexible printing plate.
Background technology
In order to form liquid crystal orientation film on the electrode forming surface of substrate for liquid crystal panel, discussing and utilizing print process, especially flexographic printing method.
The flexible printing plate that liquid crystal orientation film is formed such as by being layeredly clipped between stiffening piece and exasperate sheet, form irradiation ultraviolet radiation under certain thickness state, carry out photopolymerization after peel off exasperate sheet and be formed as (patent documentations 1 etc.) such as the sheets of one side (printing surface) exasperate.
As photosensitive polymer combination, such as, can be used in and there is 1，2-butadiene structure and there is at end the resin combination being mixed with ethylene unsaturated monomer, Photoepolymerizationinitiater initiater etc. in the prepolymer of ethene double bond.
In addition, prepolymer is such as by making two terminal hydroxyl divinyl oligopolymer and tolylene diisocyanate and (methyl) vinylformic acid 2-hydroxypropyl acrylate etc. react to synthesize.
For liquid crystal orientation film, require its as far as possible thickness evenly, there is no pin hole etc. and thin.
But, high-precision refinement in recent years with liquid crystal panel, multifunction are required and continually develops the progressive alignment films ink containing strong solubility solvent with the flexible printing plate formed by photosensitive polymer combination in the past and combine, when forming liquid crystal orientation film by flexographic printing, there is this liquid crystal orientation film and occur uneven thickness, pin hole, the problem of wearing and tearing and so in flexible printing plate meeting short period of time during printing repeatedly.
According to the research of present inventor, the reason producing these problems is low molecular weight compositions contained in two terminal hydroxyl divinyl oligopolymer.
That is, when carrying out flexographic printing, low molecular weight compositions can be exuded in ink, and the composition of ink is changed, thus easily in liquid crystal orientation film, occurs uneven thickness and pin hole.
In addition, can be swelling when the flexible printing plate having low molecular weight compositions to ooze out prints repeatedly, strength degradation, thus easily short period of time interior wearing and tearing.
Can consider to remove this low molecular weight compositions by adding thermal distillation.
But, in this case, due to the impact of heating, have that the molecular weight of two terminal hydroxyl divinyl oligopolymer is cut off, molecular weight diminishes and occur the anxiety of variation as the Replacement rate of the hydroxyl of functional group.
And, use when there is two terminal hydroxyl divinyl oligopolymer of these problems, due to cannot synthetic prepolymer, or i.e. enable synthesis, its molecular weight is also little, therefore, there is the problem that cannot form the flexible printing plate of the printing characteristic with regulation and so on.
Patent documentation:
Patent documentation 1: Japanese Unexamined Patent Publication 2009-34913 publication
Summary of the invention
The object of the present invention is to provide when not making molecular weight change with high percent, the two terminal hydroxyl divinyl oligopolymer only eliminating low molecular weight compositions well.
In addition, the present invention aim to provide form, have the printing characteristic of regulation by this two terminal hydroxyls divinyl oligopolymer and can not the liquid crystal orientation film formed be had an impact, himself can not the flexible printing plate of very quick-wearing.
Further, the present invention aims to provide the liquid crystal orientation film that the thickness formed by carrying out flexographic printing with this flexible printing plate is even, do not have pin hole etc.
The present invention is two terminal hydroxyl divinyl oligopolymer, it is characterized in that, obtain by the following method: in the material oligomer containing low molecular weight compositions and two terminal hydroxyl divinyl oligopolymer, add the solvent high to the solvability of the above-mentioned two terminal hydroxyl divinyl oligopolymer of the solvability comparison of above-mentioned low molecular weight compositions, leave standstill after stirring, decant process is carried out to isolated supernatant liquor, removes above-mentioned low molecular weight compositions thus.
In addition, the present invention is flexible printing plate, it is characterized in that, is formed with above-mentioned two terminal hydroxyl divinyl oligopolymer of the present invention.
Further, the present invention is liquid crystal orientation film, it is characterized in that, is formed by carrying out flexographic printing with above-mentioned flexible printing plate of the present invention.
According to the present invention, through all not heat tracing with the stirring of solvent, standing separation and each operation of decant process, can obtain when not making the changes such as molecular weight with high percent, the two terminal hydroxyl divinyl oligopolymer eliminating low molecular weight compositions well.
That is, through stirring and standing separation operation, can from material oligomer, optionally make low molecular weight compositions stripping in solvent, and by decant process, this low molecular weight compositions be removed together with solvent.
In addition, thus by the two terminal hydroxyl divinyl oligopolymer and obtaining after using process have regulation printing characteristic and can not affect formation liquid crystal orientation film, himself also can not the flexible printing plate of very quick-wearing.
Further, by using this flexible printing plate, the liquid crystal orientation film that thickness is even, do not have pin hole etc. can be obtained.
According to the present invention, can obtain when not making the changes such as molecular weight with high percent, the two terminal hydroxyl divinyl oligopolymer only eliminating low molecular weight compositions well.
In addition, according to the present invention, can obtain forming, have the printing characteristic of regulation by this two terminal hydroxyls divinyl oligopolymer and can not the liquid crystal orientation film formed be had an impact, himself also can not the flexible printing plate of very quick-wearing.
Further, according to the present invention, can obtain the thickness that formed by carrying out flexographic printing with this flexible printing plate evenly, there is no the liquid crystal orientation film of pin hole etc.
Accompanying drawing explanation
Fig. 1 is the chart of the molecular weight distribution being presented in embodiments of the invention 1 material oligomer before removing low molecular weight compositions.
Fig. 2 is the chart of the molecular weight distribution showing two terminal hydroxyl divinyl oligopolymer after removing low molecular weight compositions in embodiment 1.
Embodiment
(two terminal hydroxyl divinyl oligopolymer)
The feature of two terminal hydroxyl divinyl oligopolymer of the present invention is, obtain by the following method: in the material oligomer containing low molecular weight compositions and two terminal hydroxyl divinyl oligopolymer, add the solvent high to the solvability of the above-mentioned two terminal hydroxyl divinyl oligopolymer of the solvability comparison of above-mentioned low molecular weight compositions, leave standstill after stirring, decant process is carried out to isolated supernatant liquor, removes above-mentioned low molecular weight compositions thus.
According to the present invention, through all not heat tracing with the stirring of solvent, standing separation and each operation of decant process, can obtain when not making the changes such as molecular weight with high percent, the two terminal hydroxyl divinyl oligopolymer eliminating low molecular weight compositions well.
As material oligomer, consider the printing characteristic etc. of the molecular weight of the prepolymer of synthesis, the flexible printing plate of formation, preferably use number-average molecular weight Mn more than 2000, the oligopolymer of less than 4000.
In addition, as the low molecular weight compositions that will remove, easy to be that to ooze out in ink etc., the composition of number-average molecular weight Mn below 1200 illustrated before can being.To the lower limit of low molecular weight compositions without particular restriction, mini-components that can be contained in material oligomer are also as removing object.
In addition, in the present invention, owing to make use of the difference of solvent to the solvability of two terminal hydroxyl divinyl oligopolymer and low molecular weight compositions, thus, although it is low sometimes to have saturation concentration, a part for two terminal hydroxyl divinyl oligopolymer is dissolved in solvent the situation of dissolving in solvent in two terminal hydroxyl divinyl oligopolymer.
And, if the amount being dissolved into two terminal hydroxyl divinyl oligopolymer in solvent is many, the yield of two terminal hydroxyl divinyl oligopolymer then after process can decline, spillage of material increases, if and the amount of dissolving in the solvent in two terminal hydroxyl divinyl oligopolymer is many, then there is the anxiety except increases such as the energy needed for desolventizing, time, costs.
Therefore, the selected of solvent just becomes important.That is, consider the intermiscibility of two terminal hydroxyl divinyl oligopolymer and low molecular weight compositions, should select to do one's utmost minimizing two terminal hydroxyl divinyl oligopolymer and be dissolved in solvent the solvent dissolved in solvent in two terminal hydroxyl divinyl oligopolymer.In addition, by selective solvent, can also adjust the removal rate of low molecular weight compositions and two terminal hydroxyl divinyl oligopolymer organic efficiency (time, removal rate, spillage of material, except the energy etc. needed for desolventizing).
Such as, as explained above, in the number-average molecular weight of material oligomer more than 2000, less than 4000 and the low molecular weight compositions that will remove when being the composition of number-average molecular weight less than 1200, consider the intermiscibility with two-component, at least one in preferred Virahol (boiling point: 82.4 DEG C), methyl ethyl ketone (boiling point: 79.5 DEG C) etc. is as solvent.
The addition of solvent can set arbitrarily, but such as relative to material oligomer 100 mass parts, preferably more than 200 mass parts, and preferably below 300 mass parts.
When addition is less than this scope, not easily with material oligomer uniform stirring, thus have and low molecular weight compositions stripping efficiently cannot be made to the anxiety in solvent.In addition, when addition exceedes this scope, the anxiety except increases such as the energy needed for desolventizing is had.
Stir and preferably implement under normal temperature (5 ~ 35 DEG C), but also can be warmed to below solvent boiling point and the scope of such as less than 60 DEG C of the variation of molecular weight illustrated by before there will not be etc. is implemented.
Churning time preferably more than 0.5 hour, less than 1.5 hours.
When churning time is less than this scope, has and low molecular weight compositions stripping efficiently cannot be made to the anxiety in solvent.In addition, even if churning time exceedes this scope, not only can not get better effect, also have the anxiety of the production efficiency decline of two terminal hydroxyl divinyl oligopolymer.
Separation by leaving standstill the solvent carried out after stirring preferably is implemented at normal temperatures.
Time of repose preferably more than 1.5 hours, less than 2.5 hours.
When time of repose is less than this scope, have the anxiety cannot isolating solvent fully from two terminal hydroxyl divinyl oligopolymer.In addition, even if exceed this scope rest time, not only can not get better effect, also have the anxiety of the production efficiency decline of two terminal hydroxyl divinyl oligopolymer.
Then, removed by standing and isolated supernatant liquor by decant process.
Decant process is preferably implemented at normal temperatures.
In the present invention, only can implement once above stirring that is illustrated and solvent, standing separation and each operation of decant process, but consider the removing efficiency improving low molecular weight compositions, preferably these operations be repeated more than secondary.
But multiplicity is preferably below three times.Even if multiplicity exceedes this scope, not only can not get better effect, also have the anxiety of the production efficiency decline of two terminal hydroxyl divinyl oligopolymer.
In the present invention, also can remove except two terminal hydroxyl divinyl oligopolymer after desolventizing such as pass through to carry out underpressure distillation etc. while stirring the solvent remained in this two terminal hydroxyls divinyl oligopolymer to by decant process.Removed by this decompression, the solvent in residual two terminal hydroxyl divinyl oligopolymer after treatment can be removed efficiently.
Decompression removing can be implemented at normal temperatures, but considers and improve removing efficiency, near the boiling point being preferably warmed to such as solvent and the scope of such as more than 75 DEG C, less than 85 DEG C of the variation of molecular weight illustrated before there will not be etc. implement.
Degree of decompression, treatment time etc. during decompression removing can be arranged arbitrarily.
(flexible printing plate)
Flexible printing plate of the present invention, except using eliminating two terminal hydroxyl divinyl oligopolymer of low molecular weight compositions through above-mentioned operation except starting raw material, can be formed samely.
Namely, using two terminal hydroxyl divinyl oligopolymer as starting raw material, synthesis has 1，2-butadiene structure and end has the prepolymer of ethene double bond, ethylene unsaturated monomer, Photoepolymerizationinitiater initiater etc. is mixed, modulation photosensitive polymer combination in this prepolymer.
Then, when described flexible printing plate is liquid crystal orientation film formation flexible printing plate, by this photosensitive polymer combination under being such as clipped in stratiform between stiffening piece and exasperate sheet, forming certain thickness state to its irradiation ultraviolet radiation, carry out photopolymerization, then, peel off exasperate sheet, the sheet of one side (printing surface) exasperate can be formed as thus.
(synthesis of prepolymer)
As by the method for two terminal hydroxyl divinyl oligopolymer synthetic prepolymers eliminating low molecular weight compositions, such as, have:
A () makes two terminal hydroxyls of vulcabond and two terminal hydroxyl divinyl oligopolymer react in advance, importing end is diisocyanate based, then the method that the compound containing ethene double bond and active hydrogen base (having the group of active hydrogen) and resultant are reacted;
B () first imports carboxyl at end of two terminal hydroxyl divinyl oligopolymer, then make to have the method that the epoxy compounds of ethene double bond and resultant react; Etc..
Wherein, the method for preferred (a).
In (a) method, utilize the urethane between the diisocyanate based and group with active hydrogen of end to react and import ethene double bond, the reaction of synthetic prepolymer can implement under the existence of the urethanation catalyst such as tertiary amine, tin compound.But also can react under the condition that there is not urethanation catalyst.To temperature of reaction without particular restriction, but preferably more than 40 DEG C, and preferably below 100 DEG C.During reaction, preferably first add suitable stopper.
As the vulcabond becoming terminal isocyanate group source, can be one or two or more kinds in aliphatic diisocyanate, the vulcabond of ester ring type compound and aromatic diisocyanate.
In addition, as the object lesson of vulcabond, can be such as hexamethylene diisocyanate (HMDI), ω, ω '-diisocyanate based-1,3-dimethyl benzene, 2,6-and/or 2,4-tolylene diisocyanate (2,6-and/or 2,4-TDI), PPDI, Xylene Diisocyanate, diphenylmethanediisocyanate (MDI), hydrogenation 2, one or two or more kinds in 6-and/or 2,4-TDI, hydrogenation MDI, dicyclohexyl dimethylmethanediisocyanate, Methionin isocyanic ester etc.
As the compound containing ethene double bond and active hydrogen base, such as, can be one or two or more kinds in (methyl) dihydroxypropyl alkylene ester, polyalkylene glycol mono (methyl) acrylate, (methyl) vinylformic acid secondary aminoalkyl ester, the monosubstituted acrylamide of N-, unsaturated carboxylic acid etc.
In addition, as the object lesson of these compounds, it can be such as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polytetramethylene glycol list (methyl) acrylate, TriMethylolPropane(TMP) two (methyl) vinylformic acid, trimethylolethane two (methyl) acrylate, tetramethylol methane three (methyl) acrylate, dibromoneopentyl glycol list (methyl) acrylate, glycerol two (methyl) acrylate, (methyl) dihydroxypropyl cyclohexyl ester, (methyl) vinylformic acid mono-methyl amino ethyl ester, N-methyl (methyl) acrylamide, N-octyl group (methyl) acrylamide, vinylformic acid, methacrylic acid, methylene-succinic acid monoesters, fumaric monoalkylester, maleic mono-ester, one or two or more kinds in (methyl) glycidyl acrylate etc.
The blending ratio of two terminal hydroxyl divinyl oligopolymer and vulcabond is set as that the hydroxyl equivalent of two terminal hydroxyl divinyl oligopolymer and the diisocyanate based equivalent of vulcabond are about 1 ︰ 2.
In addition, the equivalent of the terminal isocyanate group of the resultant of reaction before the blending ratio of the compound containing ethene double bond and active hydrogen base is set as and the equivalent of active hydrogen base roughly equal.
When the molecular-weight average of the prepolymer of synthesis represents with number-average molecular weight, preferably more than 5000, and preferably below 30000.
When number-average molecular weight Mn is less than this scope, have the anxiety that the caoutchouc elasticity of flexible printing plate is insufficient.In addition, when exceeding this scope, then have the viscosity of photosensitive polymer combination to increase, the processibilities such as the mobility of aqueous photosensitive polymer combination decline or developability declines, and cause the anxiety of the operability decline of making a plate.
(ethylene unsaturated monomer)
The ethylene unsaturated monomer forming the component of photosensitive polymer combination together with prepolymer works the linking agent that prepolymer is cross-linked, as this ethylene unsaturated monomer, it can be such as vinyl pyridine, N-vinylcarbazole, (methyl) vinylformic acid or its ester, (methyl) acrylamide or derivatives thereof, vinylbenzene, Vinyl toluene, Vinylstyrene, Phthalic acid, diallyl ester, triallylcyanurate, vinyl acetate, vinyl cyanide, methylene-succinic acid, fumaric acid, maleic anhydride, toxilic acid, and one or two or more kinds in of these acid or dialkyl etc.
In addition, as (methyl) acrylic acid ester, such as, can be one or two or more kinds in one or two (methyl) acrylate (such as polypropylene glycol dimethacrylate etc.), one, two or three (methyl) acrylate of TriMethylolPropane(TMP), one, two, three or four (methyl) acrylate of tetramethylolmethane etc. of alkyl, cycloalkyl, tetrahydrofuran base, allyl group, glycidyl, list (methyl) acrylate of hydroxyalkyl, alkane glycol, polyether polyols.
In addition, as the derivative of (methyl) acrylamide, can be such as N-methylol (methyl) acrylamide, N, N ' one or two or more kinds in-alkylidene group two (methyl) acrylamide, two acetone (methyl) acrylamide etc.
In addition, list (methyl) acrylate (such as lauryl methacrylate(LMA) etc.), 1 of the monohydroxy-alcohol of the carbon numbers 8 ~ 30 such as octyl group (octyl), octyl group (capryl), nonyl, decyl, lauryl, cerul, 3-butyleneglycol, 1,8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, 1, one or two (methyl) acrylate (such as 1,3 butylene glycol dimethacrylate etc.) of the dibasic alcohol of the carbon numbers 4 ~ 30 such as the stearic glycol of 18-is especially effective in the solvent resistance improving flexible printing plate.
The printing characteristics of ethylene unsaturated monomer preferably required by flexible printing plate etc. are also with more than two kinds.
Relative to prepolymer 100 mass parts, ethylene unsaturated monomer the ratio more than 5 mass parts, below 100 mass parts can carry out fusion.Especially consider and improve the operability of plate-making, the printing characteristic etc. of flexible printing plate, preferably with the ratio fusion more than 40 mass parts, below 60 mass parts.This mix proportions when and with when more than two kinds ethylene unsaturated monomers being the ratio of these ethylene unsaturated monomers relative to prepolymer 100 mass parts.
(Photoepolymerizationinitiater initiater)
As Photoepolymerizationinitiater initiater, benzoin alkylether can be used.In addition, as benzoin alkylether, such as, can be one or two or more kinds in ethoxybenzoin, bitter almond oil camphor positive propyl ether, benzoin isobutyl ether etc.
Photoepolymerizationinitiater initiater can with more than the 0.001 quality % of total amount of prepolymer and ethylene unsaturated monomer, the ratio fusion of below 10 quality %.Especially, in order to obtain the film speed of the most applicable flexible printing plate plate-making, in above-mentioned scope, preferably with the ratio fusion of more than 0.01 quality %, below 5 quality %.
(hot stopper)
Also hot stopper can be mixed in photosensitive polymer combination.
Hot stopper can mix when mixing each composition forming photosensitive polymer combination simultaneously, but also can be incorporated in advance in each composition, especially prepolymer and the ethylene unsaturated monomer before mixing.
As hot stopper, such as, can be one or two or more kinds in quinhydrones or derivatives thereof, benzoquinones, 2,5-phenylbenzene para benzoquinone, picric acid, two para-fluoroaniline, p methoxy phenol, 2,6 ditertiary butyl p cresol etc.
These hot stoppers preferably can not affect photo-crosslinking, can prevent the compound of heat polymerization (dark reaction).As the hot stopper of described excellent effect, quinhydrones or derivatives thereof can be used well.
In addition, as the derivative of quinhydrones, such as, can be the compound etc. that toluhydroquinone, single tertiary butylated hydroquinone etc. have 1 ~ 4 alkyl replacement on the six-ring as quinhydrones center framework.
But above-mentioned quinhydrones or derivatives thereof easily reacts because of the visible ray from luminescent lamp etc., xanthochromia occurs, and may become the reason making xanthochromia in the flexible printing plate short period of time.
Therefore, when mixing quinhydrones or derivatives thereof as hot stopper, mixed ratio is preferably set to more than 10ppm, below the 40ppm of the total amount of photosensitive polymer combination.
When mixed ratio is less than this scope, existence fully can not obtain the anxiety preventing causing heat polymerization because of thermal history, improve the effect of storage stability produced by mixing hot stopper, when exceeding this scope, then there is the anxiety of xanthochromia in the flexible printing plate easy short period of time.
(other)
In order to adjust the viscosity of photosensitive polymer combination, the caoutchouc elasticity of flexible printing plate, intensity, solvent resistance or weathering resistance etc., various additive can be mixed in photosensitive polymer combination.
As additive, such as, can be the tenderizers such as dioctyl phthalate (DOP), treated oil, whiteruss, aqueous rubber (isoprene-isobutylene rubber, divinyl rubber, styrene butadiene ribber, paracril etc.), antioxidant etc.
Curing reaction is there is in photosensitive polymer combination by the light of wavelength 200nm ~ 700nm.Photosensitive polymer combination can provide with aqueous, the various state such as sheet or tabular.
(formation of flexible printing plate)
Form the flexible printing plate of liquid crystal orientation film formation with aqueous photosensitive polymer combination, operation as in the past can be adopted.
Namely, as previously described, such as under aqueous photosensitive polymer combination being clipped in stratiform between stiffening piece and asperities sheet, forming certain thickness state to its irradiation ultraviolet radiation, carry out photopolymerization, then, peel off asperities sheet, form the sheet-like flexible press plate of one side (printing surface) exasperate thus.
In addition, when formation printing surface has the flexible printing plate of regulation printed patterns, the overlapping negative film corresponding with this printed patterns or positive, irradiation ultraviolet radiation, or, pass through laser scanning, directly corresponding with printed patterns, irradiation ultraviolet radiation, optionally makes line portion solidify thus.
Then, organic solvent, the water phase surfactant mixtures etc. such as such as normal hexane, lam-oil, benzene, toluene, trieline, tetrachloroethylene, chlorothenylpyramine, acetone, methyl ethyl ketone, ethyl acetate is used to develop as photographic developer, remove non-line portion, dry, carry out post-exposure as required again, thus be formed in flexible printing plate printing surface being formed with regulation printed patterns.
(liquid crystal orientation film)
Liquid crystal orientation film of the present invention is formed by carrying out flexographic printing with flexible printing plate of the present invention.
Such as, the one side of the transparency carriers such as soda-lime glass substrate forms the transparent electrode layer corresponding with the matrix pattern etc. of regulation, then the flexographic printing formation liquid crystal orientation film of the application of the invention flexible printing plate.
Then, prepare the transparency carrier that 2 pieces are formed with this liquid crystal orientation film, make the respective face being formed with liquid crystal orientation film in opposite directions, and liquid crystal material is sandwiched therebetween under the state making transparent electrode layer aligned in position, interfix, form duplexer, then outside two of duplexer, arrange Polarizer as required, thus form liquid crystal panel.
(embodiment)
The process of following examples, comparative example, measuring apart from outside special instruction, is implement under the condition of temperature 23 DEG C.
< embodiment 1>
Virahol (IPA) 250 mass parts is added in material oligomer (number-average molecular weight Mn=3000) 100 mass parts containing two terminal hydroxyl divinyl oligopolymer and low molecular weight compositions, stir 1 hour, then 2 hours are left standstill, supernatant liquor is separated, then, remove isolated supernatant liquor by decant process, this sequence of operations is repeated secondary, two terminal hydroxyl divinyl oligopolymer of the low molecular weight compositions that has been removed thus.
Then, while two terminal hydroxyl divinyl oligopolymer after removing supernatant liquor are under agitation warmed to 80 DEG C of limits, it is reduced pressure, the solvent that removing is residual.
Remain in the quantity of solvent in two terminal hydroxyl divinyl oligopolymer before asking calculation reduced pressure treatment by the difference of the quality before and after reduced pressure treatment, result is 12 quality %.
Then, the molecular weight distribution of two terminal hydroxyl divinyl oligopolymer after reduced pressure treatment is measured with efficient GPC device (HLC (the registered trademark)-8320GPC that Dong Cao company produces).In addition, also under similarity condition, its molecular weight distribution is measured to untreated material oligomer.Condition determination is: chromatographic column: TSKgel H
hR, moving phase: THF, reference material: polystyrene.
The measurement result of material oligomer is shown in Fig. 1, and the measurement result of two terminal hydroxyl divinyl oligopolymer after process is shown in Fig. 2.
From Fig. 1 and Fig. 2, through all without heat with the stirring of solvent, standing separation and each operation of decant process, can when not making the changes such as the molecular weight of two terminal hydroxyl divinyl oligopolymer with high percentage, only remove low molecular weight compositions well.
That is, obtained the peak area ratio of the low molecular weight compositions of below number-average molecular weight Mn=1200 by Fig. 1, Fig. 2 respectively, then asked the removal rate calculating low molecular weight compositions by two peak area ratios, result is 100%.
In addition, asked the peak area ratio calculating low molecular weight compositions and two terminal hydroxyl divinyl oligopolymer by Fig. 2, result, low molecular weight compositions is 0%, two terminal hydroxyl divinyl oligopolymer (main component) is 100%.
Further, by the peak of the two terminal hydroxyl divinyl oligopolymer of comparison diagram 1, Fig. 2, confirm not change between the two, by removing the process of low molecular weight compositions, the non-changes such as the molecular weight of two terminal hydroxyl divinyl oligopolymer.
< embodiment 2>
Except using the methyl ethyl ketone (MEK) of same amount as except solvent, through operation similarly to Example 1, material oligomer being processed, obtaining two terminal hydroxyl divinyl oligopolymer.
In each operation, remain in the quantity of solvent in two terminal hydroxyl divinyl oligopolymer before asking calculation reduced pressure treatment by the difference of the quality before and after reduced pressure treatment, result is 28 quality %.
In addition, the removal rate calculating low molecular weight compositions is asked by the result of the molecular weight distribution using efficient GPC to record under the same conditions as example 1, be 83%, and the peak area ratio of low molecular weight compositions and two terminal hydroxyl divinyl oligopolymer is, low molecular weight compositions is 1%, two terminal hydroxyl divinyl oligopolymer (main component) is 99%.
Again rear confirmation is compared to the peak of two terminal hydroxyl divinyl oligopolymer, do not change between the two, by removing the process of low molecular weight compositions, the non-changes such as the molecular weight of two terminal hydroxyl divinyl oligopolymer.
< comparative example 1>
Except using the tetrahydrofuran (THF) (THF) of same amount as except solvent, intend processing material oligomer through the operation identical with embodiment 1, obtain two terminal hydroxyl divinyl oligopolymer, but two terminal hydroxyl divinyl oligopolymer have dissolved, cannot be separated by leaving standstill, thus abandoning the idea of carrying out follow-up test.
< comparative example 2>
The untreated material oligomer of direct use.
The removal rate calculating low molecular weight compositions is asked by the result of the molecular weight distribution using efficient GPC device to record under the same conditions as example 1, result is 0%, and the peak area ratio of low molecular weight compositions and two terminal hydroxyl divinyl oligopolymer is, low molecular weight compositions is 6%, two terminal hydroxyl divinyl oligopolymer (main component) is 94%.
The synthesis > of < prepolymer
The material oligomer making two terminal hydroxyl divinyl oligopolymer of embodiment 1,2 or comparative example 2 first with TDI (2,6-TDI and 2, the mixture of 4-TDI) reaction, add methacrylic acid 2-hydroxy propyl ester again, synthesis has 1，2-butadiene structure and end has the prepolymer of ethene double bond, number-average molecular weight Mn=15000.
Set the blending ratio of each composition, make the hydroxyl equivalent of two terminal hydroxyl divinyl oligopolymer and the diisocyanate based equivalent of vulcabond be 1 ︰ 2.In addition, setting contains the blending ratio of the compound of ethene double bond and active hydrogen base, makes the equivalent of the equivalent of the terminal isocyanate group of the resultant of reaction of two terminal hydroxyl divinyl oligopolymer and vulcabond and active hydrogen base roughly equal.
The modulation > of < photosensitive polymer combination
The lauryl methacrylate(LMA), 1 as ethylene unsaturated monomer is mixed in prepolymer 100 mass parts of synthesis, 3-butylene glycol dimethacrylate and polypropylene glycol dimethacrylate be totally 50 mass parts and benzoin isobutyl ether 2.3 mass parts as Photoepolymerizationinitiater initiater, modulation photosensitive polymer combination.
< solidified sample >
The photosensitive polymer combination modulated is clipped between 2 pieces of transparent plates of the spaced and parallel maintenance of 2mm, through transparent plate irradiation ultraviolet radiation, make photosensitive polymer combination generation photopolymerization reaction, make the flat solidified sample of thick 2mm, measure following each characteristic.
(50% modulus)
Die-cut obtained solidified sample, makes dumbbell shaped test piece, uses this dumbbell shaped test piece, obtain 50% modulus (MPa) according to JIS JIS K6251 ︰ 2010 " computation of vulcanized rubber and thermoplastic elastomer-tensile properties ".
(Shore A type hardness tester)
For obtained solidified sample, the measuring method according to recording in JIS JIS K6253-3 ︰ 2006 " computation-of vulcanized rubber and thermoplastic elastomer-hardness 3: durometer hardness " measures its Shore A type hardness tester (A type hardness tester meter hardness).
(swelling ratio)
After measuring the quality of obtained solidified sample, it is remained in liquid temperature in the METHYLPYRROLIDONE of 23 DEG C and flood 24 hours, after proposition, again measure its quality.Then, through type (1):
(mathematical expression 1)
Obtain swelling ratio (%).Can say, the swelling ratio of solidified sample is less, and the flexible printing plate obtained with same photosensitive polymer combination weares and teares in the short period of time because the swelling strength degradation caused is less, more not easily.
(oozing out of low molecular weight compositions)
Using obtained solidified sample liquid temperature remain on 23 DEG C, as be used for liquid crystal orientation film ink model normal hexane in dipping propose after 4 hours, measure the concentration (%) of the low molecular weight compositions be exuded in normal hexane with gas chromatography mass analyser (Shimadzu Seisakusho Ltd. produce GCMS-QP2010SE).
Can say, the concentration being exuded to the low molecular weight compositions in normal hexane from solidified sample is less, and the flexible printing plate obtained with same photosensitive polymer combination more not easily occurs because low molecular weight compositions is exuded to the ink composition change caused in ink.
< flexible printing plate >
Stiffening piece (PET sheet across the spaced and parallel maintenance of 2mm is clipped in by with the identical photosensitive polymer combination used in the making of solidified sample, thick 0.35mm) and the asperities sheet (SHILKLON (registered trademark) that great Cang industrial produces, arithmetic average roughness Ra:1.0 ~ 1.5 μm) between, irradiation ultraviolet radiation carries out photopolymerization in this state, then, peel off asperities sheet, obtain the flexible printing plate of the sheet of the liquid crystal orientation film printing of one side (printing surface) exasperate thus.
< press quality >
Obtained flexible printing plate is loaded flexible printing machine (Nakan Techno Products together with Wang Wen Gun ﹟ 400, model G2) in, use this flexible printing machine, on this one side being formed with the glass substrate of the transparent electrode layer (chromium vapor-deposited film) corresponding with the matrix pattern etc. of regulation at one side on flexible printing liquid crystal orientation film ink after, dry, form liquid crystal orientation film, aforesaid operations is implemented 10,000 times continuously.
Then, to the liquid crystal orientation film formed, by visual observation, whether it there is uneven thickness, pin hole, by the quality of following standard evaluation press quality.
◎: from the 1st to the 10,000, have no uneven thickness and pin hole in liquid crystal orientation film.
Zero: from the 1st, in liquid crystal orientation film, find uneven thickness and pin hole, but these phenomenons disappear reaching in the process of the 150th.
×: from the 1st, find uneven thickness and pin hole in liquid crystal orientation film, even if more than 150, these phenomenons disappear not yet.
(wearing and tearing of flexible printing plate)
After continuous printing 10,000, remove residual ink from flexible printing plate, dry, ask the quality after calculating printing.Further, through type (2):
(mathematical expression 2)
Obtain the decrement (%) of quality that start at from the quality before continuous printing, that caused by wearing and tearing, by the wearability of following standard evaluation flexible printing plate.
◎: decrement is below 0.05%.
Zero: decrement is more than 0.05%, below 0.10%.
×: decrement is more than 0.10%.
< comprehensive evaluation >
By press quality test and flexible printing plate these two evaluation results of wearability based on, according to following standard, comprehensive evaluation is carried out to flexible printing plate.
◎: two sides are ◎.
Zero: zero and ◎ or two sides be all zero.
×: have a side for × or two Fang Douwei ×.
Above result is shown in table 1.
Table 1
From table 1 embodiment 1,2, the result of comparative example 2, through all without heating with the stirring of solvent, standing separation and each operation of decant process, can when not making the changes such as the molecular weight of the two terminal hydroxyl divinyl oligopolymer as main component with high percent, well only remove in material oligomer contained by low molecular weight compositions.
But, from embodiment 1,2, the result of comparative example 1, in order to remove low molecular weight compositions through above-mentioned each operation from two terminal hydroxyl divinyl oligopolymer, the poorly soluble solvent this two terminal hydroxyls divinyl oligopolymer and low molecular weight compositions to appropriateness should be selected.
Find in addition, use and eliminate two terminal hydroxyl divinyl oligopolymer of low molecular weight compositions, can form the printing characteristic with regulation and can not have an impact to the liquid crystal orientation film of formation, himself also can not the flexible printing plate of very quick-wearing.
Claims (11)
1. liang terminal hydroxyl divinyl oligopolymer, it obtains by the following method: in the material oligomer containing low molecular weight compositions and two terminal hydroxyl divinyl oligopolymer, add the solvent that the solvability of two terminal hydroxyl divinyl oligopolymer described in the solvability comparison to described low molecular weight compositions is high, leave standstill after stirring, decant process is carried out to isolated supernatant liquor, removes described low molecular weight compositions.
2. two terminal hydroxyl divinyl oligopolymer according to claim 1, is characterized in that, by described solvent under reduced pressure removing residual after described decant process being obtained.
3. two terminal hydroxyl divinyl oligopolymer according to claim 1, is characterized in that, the number-average molecular weight Mn of described material oligomer more than 2000, less than 4000.
4. two terminal hydroxyl divinyl oligopolymer according to claim 1, is characterized in that, described low molecular weight compositions is the composition of number-average molecular weight Mn below 1200.
5. two terminal hydroxyl divinyl oligopolymer according to any one of Claims 1 to 4, it is characterized in that, described solvent is be selected from least one in Virahol and methyl ethyl ketone.
6. flexible printing plate, it is formed with above-mentioned two terminal hydroxyl divinyl oligopolymer according to claim 1.
7. liquid crystal orientation film, it is formed by carrying out flexographic printing with above-mentioned flexible printing plate according to claim 6.
8. from two terminal hydroxyl divinyl oligopolymer, remove the method for low molecular weight compositions, comprise the operation of the material oligomer prepared containing low molecular weight compositions and two terminal hydroxyl divinyl oligopolymer,
In described material oligomer, add the high solvent of the solvability of two terminal hydroxyl divinyl oligopolymer described in the solvability comparison to described low molecular weight compositions and the operation stirred,
The operation left standstill after stirring,
To the operation of being carried out decant process by standing and isolated supernatant liquor.
9. method according to claim 8, is characterized in that, after being also included in described decant process, decompression removes the operation of described residual solvent.
10. method according to claim 8, is characterized in that, described agitating procedure carries out more than 0.5 hour, less than 1.5 hours.
11. methods according to claim 8, is characterized in that, described standing operation carries out more than 1.5 hours, less than 2.5 hours.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-151931 | 2013-07-22 | ||
| JP2013151931A JP6164686B2 (en) | 2013-07-22 | 2013-07-22 | Method for producing both-end hydroxyl group butadiene oligomer, method for producing flexographic printing plate, and method for producing liquid crystal alignment film |
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| Publication Number | Publication Date |
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| CN104327206A true CN104327206A (en) | 2015-02-04 |
| CN104327206B CN104327206B (en) | 2018-11-16 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201410315779.6A Active CN104327206B (en) | 2013-07-22 | 2014-07-03 | Two terminal hydroxyl butadiene oligomer, flexible printing plate, liquid crystal orientation film and the method that low molecular weight compositions are removed from two terminal hydroxyl butadiene oligomer |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6164686B2 (en) |
| KR (1) | KR20150011308A (en) |
| CN (1) | CN104327206B (en) |
| TW (1) | TWI610954B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106814541A (en) * | 2015-11-30 | 2017-06-09 | 乐凯华光印刷科技有限公司 | A kind of ageing-resistant flexographic plate and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101923300B1 (en) | 2017-02-24 | 2018-11-29 | (주)켐베이스 | Photosensitive resin composition for a flexographic printing plate comprising polycarbonate diol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5231274B2 (en) * | 1975-04-18 | 1977-08-13 | ||
| US4518770A (en) * | 1984-01-30 | 1985-05-21 | Atlantic Richfield Company | Process for the preparation of polyhydroxybutadienes |
| JPH01146920A (en) * | 1987-12-03 | 1989-06-08 | Idemitsu Petrochem Co Ltd | Liquid polymer composition |
| JP2002196479A (en) * | 2000-12-26 | 2002-07-12 | Toyobo Co Ltd | Photosensitive resin composition and original plate for flexograpy board |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5039703B2 (en) * | 1973-05-17 | 1975-12-18 | ||
| US4442039A (en) * | 1980-05-30 | 1984-04-10 | The B. F. Goodrich Company | Process for treating hydroxyl terminated liquid polymers |
| GB8320904D0 (en) * | 1983-08-03 | 1983-09-07 | Rubber & Plastic Res Ass | Transformations within polymers |
| JPH01146911A (en) * | 1987-12-03 | 1989-06-08 | Idemitsu Petrochem Co Ltd | Preparation of liquid diene polymer |
| JPH01225673A (en) * | 1988-03-04 | 1989-09-08 | Idemitsu Petrochem Co Ltd | Water-based paint |
| JP2009235296A (en) * | 2008-03-28 | 2009-10-15 | Asahi Kasei E-Materials Corp | Low polarity prepolymer and photosensitive resin composition containing it |
-
2013
- 2013-07-22 JP JP2013151931A patent/JP6164686B2/en active Active
-
2014
- 2014-07-01 KR KR20140081792A patent/KR20150011308A/en not_active Application Discontinuation
- 2014-07-03 CN CN201410315779.6A patent/CN104327206B/en active Active
- 2014-07-04 TW TW103123083A patent/TWI610954B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5231274B2 (en) * | 1975-04-18 | 1977-08-13 | ||
| US4518770A (en) * | 1984-01-30 | 1985-05-21 | Atlantic Richfield Company | Process for the preparation of polyhydroxybutadienes |
| JPH01146920A (en) * | 1987-12-03 | 1989-06-08 | Idemitsu Petrochem Co Ltd | Liquid polymer composition |
| JP2002196479A (en) * | 2000-12-26 | 2002-07-12 | Toyobo Co Ltd | Photosensitive resin composition and original plate for flexograpy board |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106814541A (en) * | 2015-11-30 | 2017-06-09 | 乐凯华光印刷科技有限公司 | A kind of ageing-resistant flexographic plate and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201504267A (en) | 2015-02-01 |
| TWI610954B (en) | 2018-01-11 |
| CN104327206B (en) | 2018-11-16 |
| KR20150011308A (en) | 2015-01-30 |
| JP2015021098A (en) | 2015-02-02 |
| JP6164686B2 (en) | 2017-07-19 |
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