CN102190807A - Manufacturing method of cellulose acylate film - Google Patents
Manufacturing method of cellulose acylate film Download PDFInfo
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- CN102190807A CN102190807A CN2011100524963A CN201110052496A CN102190807A CN 102190807 A CN102190807 A CN 102190807A CN 2011100524963 A CN2011100524963 A CN 2011100524963A CN 201110052496 A CN201110052496 A CN 201110052496A CN 102190807 A CN102190807 A CN 102190807A
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- KQJHEAUPUFGPOR-UHFFFAOYSA-N Cc1cccc(Nc2nc(Nc(cc3)ccc3OC)nc(Nc3cc(C)ccc3)n2)c1 Chemical compound Cc1cccc(Nc2nc(Nc(cc3)ccc3OC)nc(Nc3cc(C)ccc3)n2)c1 KQJHEAUPUFGPOR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention provides a manufacturing method of a cellulose acylate fim, wherein the cellulose film is manufactured by concentrated solution through a solution film preparing method. The cellulose acylate and a substitute with a preset structure are used in the solid content of the concentrated solution. The preset structure is the polymer of a saccharide which is polymerized through glycosidic bonds, and furthermore is a structure in which the hydrogen of a hydroxyl group of the polymer (56) is replaced by other atom groups. When the atom groups are acyl groups which are same with the cellulose acylate, the solid component which is composed of the cellulose acylate and the substitutes performs a mixture of the cellulose and the polymer, namely the acylation raw material. When drying is performed in the film which is prepared by the solution, the wet film which contains 4-100wt% of solvent is heated to a temperature in 70-150 DEG C.
Description
Technical field
The present invention relates to a kind of manufacture method of cellulose acylate film, relate in particular to a kind of manufacture method of the cellulose acylate film that uses as optical compensation films.
Background technology
Cellulose acylate film uses as optical compensation films.As optical compensation films phase retardation film is arranged.Phase retardation film will be transformed into the state to nearly linear polarization by the elliptical polarized light after the liquid crystal layer by matching with the phase differential of liquid crystal layer in the liquid-crystal display.This optical compensation films also uses as the protective membrane of polarizing coating in Polarizer sometimes.
Manufacture method as polymeric film has fusion film-forming method and solution film-forming method as everyone knows.Require excellent optical in the optical compensation films, solution film-forming can produce than fusion system film has the more cellulose acylate film of excellent optical.Therefore, cellulose acylate film is mainly made by solution film-forming method.
In optical characteristics, exist to postpone, exist in the delay of film and postpone Re and thickness direction retardation Rth in the face.Re is and the orthogonal direction of film thickness direction, i.e. delay on the face direction.Re obtains by following formula (1).And Rth is the delay on the film thickness direction, obtains by following formula (2).In addition, when when showing birefringent film incident light, there are slow axis and fast axle.In following formula (1), (2), nx is the specific refractory power on the interior slow-axis direction of face, and ny is the specific refractory power on the quick shaft direction, and nz is the specific refractory power on the film thickness direction.And d is film thickness (nm).
Re＝(nx-ny)×d (1)
Rth＝{(nx+ny)/2-nz}×d (2)
Rth even also is much accounted of in optical characteristics in the purposes of optical compensation films gradually.For example, according to the optical characteristics of other film that uses with optical compensation films or the kind of liquid crystalline cpd, the different various films of expectation Rth are so that can select optical compensation films based on Rth.
When making long film, can be for Re by prolonged treatment control the on delivery direction or width of giving based on tension force.But, in optical characteristics, problems such as wayward Rth are arranged also.For example, when making long film, as above-mentioned tension adjustment when prolonged treatment in, can't control Rth fully and can not make its raising.Even suppose and to improve Rth in the tension adjustment when prolonged treatment, because along with tension adjustment Re also changes, so can not embody the Re of expectation.
Therefore, the open 2003-344655 communique of Japanese Patent has proposed following method: improve Rth by making the compound that contains predetermined structure in the film as postponing dose.And,,, can improve to a certain degree Rth by improving degree of acetylation then as described in the open 2007-072390 communique of Japanese Patent if in cellulose acylate, be limited to cellulose acetate.And then the open 2007-084653 communique of Japanese Patent also discloses the method that embodies higher Rth.This method is for by being heated to preset temperature to film, thereby is made as the method for the film of the crystallization degree with pre-determined range of described 0.9～1.8.In the method for the open 2007-084653 communique of this Japanese Patent, in the solution film-forming process, film is carried out extension more than 10% to curtain coating direction or width.
Yet if use the delay dose in the past that proposes as in the open 2003-344655 communique of Japanese Patent, Re and Rth will change simultaneously.Therefore, if then be not suitable for will optionally control Rth the time.And, in the drying process in solution film-forming etc., also exist the Rth dose to separate out above film or gasification and adhere to problems such as freezing solidly on device.In addition, this delay dose price height causes being separated of cellulose acylate in the dope and additive sometimes.This reason that is separated into to the optical characteristics inequality of film.Therefore, delay dose in the past preferably suppresses usage quantity as far as possible.
And degree of acetylation is acyl group is defined as ethanoyl in cellulose acylate a factor.Therefore, in the method for the open 2007-072390 communique of Japanese Patent, uncontrollable Rth to cellulose acylate with acyl group different with ethanoyl.Certainly, for cellulose acetate, dependency is to a certain degree arranged between degree of acetylation and Rth.But, even, also embody mutually different Rth usually from the film that obtains separately for having the cellulose acylate of identical degree of acetylation mutually.Therefore, can't only control Rth with degree of acetylation.
On the other hand, thought in the past that the control of its value of Re was important, once be set as the target of film product classification.And the extension ratio the during extension process in the solution film-forming process is the factor of remarkably influenced Re, if change extension ratio, then Re changes.And in extension process, heating film heats up it, but also is Re to be brought the factor of remarkably influenced based on the temperature of the film of this heating.So, in order to embody the Re of expectation, although set the temperature of extension ratio or film, except Re, if want to control Rth with this factor, then the condition enactment in the extension process is extremely difficult in extension process.Therefore, if according to the method for the open 2007-084653 communique of Japanese Patent, even then can improve Rth, want the kind of the film made many more, the condition when finding extension process according to each kind is more with difficulty.
Summary of the invention
Therefore, the objective of the invention is to, a kind of method of making cellulose acylate film is provided, the usage quantity of the delay dose of use suppresses the rising of Re to this method by suppressing up to now, and optionally controls Rth.
The manufacture method of cellulose acylate film of the present invention possesses curtain coating step, drying step and heating steps.The curtain coating step be with the cellulose acylate solution casting to supporter; and peel from described supporter as solvent-laden moistening film; described cellulose acylate solution comprises substituent; described substituent has the structure that is replaced to other atomic group based on the hydrogen of the hydroxyl in the polymer of the sugar of glycosidic link, and described substituent is different with cellulose acylate.Drying step is to make cellulose acylate film by the described moistening film of drying.Heating steps is solvent containing ratio in described drying step to be reduced to described moistening film between the 4 quality % from 100 quality % heat so that reach more than 70 ℃ temperature in 150 ℃ of following scopes.
The amount of the described substituent in the preferred described cellulose acylate solution according to the film of manufacturing (nx+ny)/thickness direction retardation Rth that 2-nz} * d obtains adjusts.At this, nx is the specific refractory power on the interior slow-axis direction of the face of cellulose acylate film; Ny is the specific refractory power on the interior quick shaft direction of the face of cellulose acylate film; Nz is the specific refractory power on the film thickness direction; D is film thickness (unit is nm).
The preferred relation of obtaining the amount of thickness direction retardation Rth when carrying out described drying step and described substituent in advance with certain condition, and decide the amount of the described substituent in the described dope according to the described relation of having obtained.
Preferred described sugar is hexose.
Preferred described sugar has cyclic skeleton.
Preferred described polymer is any one in mannosans, glucomannan and the starch.
Preferred described atomic group be ethanoyl, propionyl, butyryl radicals, 2-ethylhexyl, methyl, ethyl, hydroxyethyl, carboxymethyl, sulfuryl, nitro, amino, N-acetyl and carbon number be more than 8 in the longer chain fatty acid ester group below 30 at least any one.
Preferably, make the cellulose acylate that comprises the described substituent of predetermined amount, this cellulose acylate is dissolved in described solvent and prepares described cellulose acylate solution by carrying out acidylate to comprising the described polymeric Mierocrystalline cellulose of predetermined amount.
The invention effect
According to the present invention, can simple and easy manufacturing cellulose acylate film its usage quantity by the delay dose that suppresses to use up to now suppress the rising of Re, and optionally control Rth.
Description of drawings
Fig. 1 is the concise and to the point figure that has implemented solution film-forming equipment of the present invention.
Fig. 2 is the explanatory view of the 1st form of the solids component of preparation dope.
Quality %) and the Rth of film (unit: the chart of relation nm) Fig. 3 is expression with respect to the ratio CS of the substituent of cellulose acylate (unit:.
Quality %) and reach 1 minute preset temperature of maintenance behind the preset temperature and the Rth (unit: the chart of relation nm) of the film that obtains Fig. 4 is the solvent containing ratio (unit: of the moistening film of expression when reaching preset temperature.
Fig. 5 is the concise and to the point figure of clip tenter machine.
Fig. 6 is the sectional view along the VI-VI line of Fig. 5.
Fig. 7 is the explanatory view of the 2nd form of the solids component of preparation dope.
Quality %) and the Rth of film (unit: the chart of relation nm) Fig. 8 is that expression is with respect to cellulosic polymeric ratio CP (unit:.
Embodiment
The solution film-forming equipment 10 of Fig. 1 is made film 22 by dope 11.Dope 11 is products that cellulose acylate is dissolved in solvent.Solution film-forming equipment 10 possesses casting device 15, pin tenter 16, clip tenter machine 20, kiln 25, cooling room 26 and take-up mechanism 27 successively from upstream side.Casting device 15 forms moistening film 12 by dope 11.Pin tenter 16 usefulness pins (not shown) keep each sidepiece of moistening film 12 to come dry moistening film 12.Clip tenter machine 20 usefulness clips 67 (with reference to Fig. 5) are controlled each sidepiece of moistening film 12, and to the width moistening film 12 that stretches.Kiln 25 further dry moistening films 12 and make film 22.Cooling room 26 cooling films 22.Take-up mechanism 27 coils into the roller shape with film 22.
The device for excising of strained each sidepiece of the moistening film 12 of excision also can be set between casting device 15 and pin tenter 16.In addition, also can between pin tenter 16 and clip tenter machine 20 or than clip tenter machine 20, more also dispose device for excising respectively by the downstream.The device for excising of configuration excises each sidepiece of the maintenance vestige that pin is arranged that causes because of pin tenter 16 between pin tenter 16 and clip tenter machine 20.More excising each sidepiece of controlling vestige that clip is arranged that causes because of clip tenter machine 20 than clip tenter machine 20 by the device for excising of downstream configuration.
In addition, the curtain coating supporter is not limited to cylinder 30.For example, also can use and be set up in support roll last bringing for no reason replaced cylinder 30.When endless band is used as the curtain coating supporter, by making heat-transfer medium pass through the inside of each support roll, thereby adjust the temperature of band by support roll.When making it the solidified what is called when dry casting films and carrying out dry curtain coating, use mostly to bring to replace cylinder 30.
It is parallel with the long side direction of cylinder 30 that stripper roll 35 is adapted to long side direction.Casting films 32 supports this moistening film 12 by strain moistening film 12 and stripper roll 35 to delivery direction Z1 with side face, thereby is peeled from cylinder 30 at preposition.When carrying out the cooling flow time-delay, when probably being 200～300 quality %, the solvent containing ratio of casting films 32 carries out peeling off from the cylinder 30 of casting films 32.When carrying out dry curtain coating, when probably being 15～50 quality %, the solvent containing ratio of casting films 32 carries out.
The inside of casting device 15 possesses has condenser in (electrical condenser).Condenser makes respectively the solvent condensation that becomes gas from dope 11, casting films 32,12 evaporations of moistening film.Solvent by this condenser liquefaction is directed to the retrieving arrangement that is equipped on 36 outsides, chamber, and is reclaimed by this retrieving arrangement.In addition, omit the diagram of condenser and retrieving arrangement.
Moistening film 12 guides to pin tenter 16 by roller 40 from casting device 15.The sidepiece that pin tenter 16 has at moistening film 12 runs through the needle plate (not having diagram) that a plurality of pins keep.Needle plate is advanced on planned orbit.Moistening film 12 is transmitted by advancing of needle plate.Above the transmission road of moistening film 12, possess the conduit (not having diagram) that flows out dry air is arranged.It is the air outflow port of long slit-shaped that the bottom of conduit is formed with on the width of moistening film 12.By flowing out dry air from this air outflow port, thus the slowly dry moistening film 12 that is transmitted.In this pin tenter 16, preferably carry out dry so that the solvent containing ratio of moistening film 12 reaches the following scope of the above 100 quality % of 4 quality %.In addition, the solvent containing ratio in this specification sheets be meant usefulness (X-Y)/value of the so-called dry basis that Y} * 100 are obtained.X is the quality of moistening film 12, and Y is for carrying out dry quality afterwards to this moistening film 12.
In the present embodiment, after pin tenter 16 dry moistening films 12, guide to clip tenter machine 20.But, when carrying out dry curtain coating, also can not use pin tenter 16.That is, when carrying out dry curtain coating, also pin tenter 16 can be set, will guide to clip tenter machine 20 from the moistening film 12 of curtain coating device 15.To the structure and the effect of clip tenter machine 20, use other accompanying drawing to carry out aftermentioned.
Kiln 25 possesses the many rollers 41 that support moistening film 12 with side face.Have to the driving roll that rotates in a circumferential direction in these many rollers 41, and transmit moistening film 12 by the rotation of this driving roll.Supply with in the kiln 25 heated dry air is arranged.Moistening film 12 is by carrying out drying by this kiln 25.Supply with in the cooling room 26 the roughly dry air of room temperature is arranged.By make film 22 coolings that obtained by this cooling room 26.The film 22 that temperature has descended guides to take-up mechanism 27 and is batched core 42 from cooling room 26.
Dope 11 is that cellulose acylate is dissolved in the solvent and the cellulose acylate solution of preparation.As the solids component that forms film 22, except cellulose acylate, also comprise substituent in this dope 11 with predetermined structure.The amount of the substituent by adjusting this predetermined structure is controlled Rth.
Substituent with predetermined structure is meant to have hydroxyl in the polymer by glycosidic link polymeric sugar (hydrogen OH) is replaced to the so-called substituent of the structure of other atomic group.And in the polymer by glycosidic link polymeric sugar, when carboxyl or aldehyde radical, the substituent with predetermined structure is meant that having hydroxyl (OH) is replaced to the so-called substituent of the structure of other atomic group.In addition, this substituent has said structure and gets final product in dope 11, no matter whether be the substituent of two processes of replacement that has passed through the hydrogen of sugared polymerization and hydroxyl.And above-mentioned polymer is that the polymer with structure repeatedly of fundamental unit gets final product, and also can be in oligopolymer and the polymkeric substance any one.Therefore, substituent also can be any one in oligopolymer and the polymkeric substance.In addition, glycosidic link also can be any one in α-glycosidic link and the β-glycosidic link.
Use with the substituent of above-mentioned predetermined structure solids component, and as described later moistening film 12 is heated up as dope 11.Thus, even do not use the delay dose that used in the past, the Rth of cellulose acylate film is risen.This substituent can not separated out on film 22.And, because this substituent be can't help 22 gasifications of film 12 and film in the solution film-forming process, therefore can foul solution membrane equipment 10 yet.These effects are that monomer is opposite with in the past delay dose, are because above-mentioned substituent is oligopolymer or polymkeric substance.
This substituent can use simultaneously with delay dose in the past.Thus, compare, can suppress the usage quantity of in the past delay dose very low with usage quantity in the past.Its result reduces each film that is caused by in the past delay dose and the pollution of solution film-forming equipment.
Even the substituent of above-mentioned predetermined structure is contained in the dope 11, being separated of oil phase and water do not taken place in dope 11 yet.Therefore, can be manufactured on Re, Rth is not have uneven film 22 in the optical characteristics of representative.
And, when cellulose acylate is cellulosetri-acetate (TAC), in the solution film-forming process crystallization takes place.By using the substituent of said structure, can promote the crystallization of TAC.Therefore, Rth that the crystallization degree that results from makes progress rises when becoming more definite, when in order to seek crystallization moistening film 12 being heated, can more shorten heat-up time and more properly prevents the deterioration of TAC.
In addition, in the cooling flow time-delay, promote the gelation of casting films 32 by using above-mentioned substituent.The effect that therefore, the manufacturing efficient that can improve the cooling flow Yanzhong more also arranged.
More preferably the skeleton by glycosidic link polymeric sugar is a ring-type.At this, this predetermined structure is the structure different with cellulose acylate.
Above-mentioned sugar is monose, also can be in aldose and the ketose any one.And sugar also can be any one in triose (carbon number is 3), tetrose (carbon number is 4), pentose (carbon number is 5), the hexose (carbon number is 6) etc., but wherein, preferred carbon number is 6 hexose, more preferably has the sugar of cyclic skeleton as described.This is because comparing with other sugar is the structure that is similar to the unit structure of the acyl group of removing cellulose acylate most.Be similar to the unit structure of cellulose acylate, the effect that Rth is made progress is big more.
As hexose, can enumerate glucose (Glc), seminose (Man), semi-lactosi (Gal), fructose (Fru), N-acetylglucosamine (GlcNAc), glucosamine (GlcN) etc.
When having polymer by the structure of glycosidic link polymeric sugar when being polymkeric substance, as preferred polymkeric substance, mannosans, glucomannan, guar gum, starch (direct-connected starch, amylopectin), glycogen, pectin, xylan, chitin, agarose etc. are arranged.But polymer is not limited to these.Wherein particularly preferred polymkeric substance is mannosans, glucomannan and starch.These polymers are very cheap and start with easily, and can be easily and implement the replacement of the hydrogen in the hydroxyl with low cost.Therefore, resulting substituent is compared also and can be obtained very cheap and easily with delay dose in the past.
As the substituting group of the atomic group of the hydrogen that replaces above-mentioned polymeric hydroxyl, preferred ethanoyl, propionyl, butyryl radicals, 2-ethylhexyl, methyl, ethyl, hydroxyethyl, carboxymethyl, sulfuryl, nitro, amino, N-ethanoyl and comprise alkyl and carbon number is the carboxyl below 30 etc. more than 8.As comprising alkyl and carbon number is the carboxyl below 30 more than 8, and more preferably carbon number is the longer chain fatty acid ester group below 30 more than 8.In addition, this longer chain fatty acid ester group is meant the product of the ester that hydroxyl and lipid acid form.
In addition, substituent also can be can't help above-mentioned atomic group and replaced all hydroxyls.For example, a part of hydroxyl also can become carboxyl or aldehyde radical.
In the 1st embodiment, be that the substituent of the acyl group of ethanoyl etc. uses as the solids component of dope 11 with cellulose acylate and substituting group.When acyl group in the cellulose acylate 51 and acyl group in the substituent 52 are made as identically when basic,, Mierocrystalline cellulose 55 and polymer 56 combined carry out acidylate 57 and get final product as Fig. 2.That is, acidylate object 54 is made the mixture of Mierocrystalline cellulose 55 and polymer 56.Thus, the form with the mixture of cellulose acylate 51 and substituent 52 obtains solids component 58.
The Mierocrystalline cellulose that obtains from softwood tree, even refining also contains above-mentioned polymer usually.This content is compared many with the Mierocrystalline cellulose that obtains from deciduous tree or velveteen.For example, mannosans is contained in from the Mierocrystalline cellulose that softwood tree obtains with the content more than 1%, but mostly is most about 0.5% from the Mierocrystalline cellulose that deciduous tree obtains in contrast, does not contain mannosans from the Mierocrystalline cellulose that velveteen obtains.
Following in the past regulation when promptly making with phase retardation film or polarization board protective film etc. as the cellulose acylate film of purposes, does not preferably contain the hemicelluloses such as mannosans that are contained in the Mierocrystalline cellulose.Therefore, reached cellulosic synthetic and refining in the mode of from Mierocrystalline cellulose, eliminating these hemicelluloses as far as possible in the past.In contrast, in the present invention, utilize above-mentioned polymers such as mannosans energetically, the substituent that will be obtained by this polymer is as the solids component of dope 11.Therefore,, then can reduce the usage quantity of the polymer 56 or the substituent 52 of new interpolation, therefore consider more preferably from viewpoints such as costs if use the Mierocrystalline cellulose that obtains from softwood tree.
When carrying out dry curtain coating, based on suppressing than the lowland from the viewpoint of the peeling force of the casting films 32 of curtain coating supporter, with its Mierocrystalline cellulose that will obtain from softwood tree or deciduous tree as raw material, the preferred Mierocrystalline cellulose that obtains from velveteen that uses.So, even the Mierocrystalline cellulose that obtains from velveteen during as raw material, the present invention is also effective.If will be from acerose Mierocrystalline cellulose as raw material, the effect that then not only has Rth to rise also has the effect that can peel off casting films 32 with less peeling force, and is therefore preferred especially.
The line segment L1 of Fig. 3, L2, L3 make mutually different substituent 52 contain situation in film 22.The longitudinal axis is represented Rth (unit: nm), then high more more up in the chart of Fig. 3.Transverse axis is with respect to the ratio of the substituent 52 of cellulose acylate 51 (below, simply be called " substituent ratio ") CS (unit: quality %), then big more towards the right side more.As shown in Figure 3, the Rth of film 22 and the proportional relation of substituent ratio CS.Therefore, substituent ratio CS is many more, then can obtain the high film of Rth 22 more.Therefore, obtain with as the corresponding substituent ratio CS of the Rth of purpose, based on the substituent ratio CS that obtains, adjust the amount of the substituent 52 in the dope 11.Like this, based on Rth, adjust the amount of the substituent 52 in the dope 11 as purpose.
In Fig. 3, following situation has been shown, i.e. the order of the line segment L1 that represents with solid line, the line segment L3 that represents with two dot chain line, the line segment L2 that represents with a long and short dash line, its obliquity diminishes gradually, and line segment L1 and line segment L3 report to the leadship after accomplishing a task.As representing that in line segment L1, L2, L3 if the structure difference of substituent 52, even substituent ratio CS is identical, the value of the Rth that is found is also different.Therefore, by the substituent that uses 52, the relation of obtaining Rth and substituent ratio CS in advance gets final product.Thus, also can obtain the relation of the amount of the substituent 52 in Rth and the dope 11 in advance.For example, will be made as Rth (P) as the Rth of purpose.Because find that the substituent of Rth (P) is the substituent 52 of line segment L1 and line segment L3, therefore wherein any one can use in solids component 58.In addition, in the time will suppressing the usage quantity of substituent 52, wherein, select the substituent 52 of the less line segment L1 of substituent ratio CS to get final product.In Fig. 3, when selecting the substituent 52 of line segment L1, about finding the substituent ratio CS of Rth (P), figure is shown with CS (P).
When in the Mierocrystalline cellulose that uses as raw material, containing polymer in advance, make this raw material can acidylate.Then, the substituent of the component of the difference of substituent ratio CS in the cellulose acylate that will be equivalent to obtain and predetermined substituent ratio CS (P) adds in the cellulose acylate that has obtained and gets final product.
About predetermined substituent, when obtaining as the concerning of the Rth of Fig. 3 and substituent ratio CS, the condition that moistening film 12 is become in a series of drying process till the film 22 is made as constant.When making film 22 with the solution film-forming equipment 10 of Fig. 1, a series of drying process is meant each operation in pin tenter 16, clip tenter machine 20 and the kiln 25, but more preferably passing on from the stripping process of cylinder 30 or between respectively installing also is considered as drying process.But, in a series of drying process, also can be only the condition of the predetermined operation in the clip tenter machine 20 is made as constant, thereby obtain the relation of Rth and substituent ratio CS.At this moment because when having used substituent 52, in a series of drying process, condition maximum effect Rth of the predetermined operation in the clip tenter machine 20.
Casting films 32 when making a certain amount of substituent 52 be contained in the dope 11 becomes the film 22 of the higher Rth of expression by intensification.But based on the opportunity of this intensification, the lifting range of Rth diminishes.Fig. 4 for the solvent containing ratio of transverse axis (unit: quality %) thus promptly reach constantly corresponding the opportunity of the temperature that moistening film 12 is heated up reach predetermined with preset temperature.In Fig. 4, reach the moistening film 12 of predetermined temperature opportunity about solvent containing ratio at transverse axis, kept its temperature 1 minute, and with the Rth (unit: nm) be made as the longitudinal axis of the film 22 that obtains.
Be made as in the time that will remain on preset temperature under one minute the situation, thereby when opportunity that moistening film 12 is heated up reach preset temperature during greater than 100 quality %, and during less than 4 quality %, as shown in Figure 4, Rth rests in the less ascensional range.In contrast, thereby be more than the 4 quality % during the following scope of 100 quality % when the opportunity that moistening film 12 is heated up reach preset temperature, Rth obviously rises.During the following scope of 100 quality %, moistening film 12 is equivalent to when transmit the inside of clip tenter machine 20 more than the solvent containing ratio is 4 quality %.Therefore, when obtaining the concerning of Rth and substituent ratio CS, the temperature that the solvent containing ratio is in the moistening film 12 in the following scope of 100 quality % more than the 4 quality % in clip tenter machine 20 is made as preset temperature, and is made as this condition constant.
As shown in Figure 4, thereby be more than the 40 quality % during the following scope of 50 quality % when the opportunity that moistening film 12 is heated up reach preset temperature, Rth rises especially significantly.And, thereby be the following scope of 40 quality % or more than the 50 quality % during the following scope of 70 quality % more than the 20 quality % when the opportunity that moistening film 12 is heated up reach preset temperature, the Rth of at least 80% when becoming the following scope of the above 50 quality % of 40 quality %.Therefore, when obtaining the concerning of Rth and substituent ratio CS, more preferably in clip tenter machine 20 be that the temperature of the moistening film 12 of the following scope of 70 quality % more than the 20 quality % is made as preset temperature, and be made as this condition constant the solvent containing ratio.When obtaining the concerning of Rth and substituent ratio CS, more preferably in clip tenter machine 20 be that the temperature of the moistening film 12 of the following scope of 50 quality % more than the 40 quality % is made as preset temperature, and be made as this condition constant the solvent containing ratio.When obtaining the concerning of Rth and substituent ratio CS, be made as preset temperature particularly preferably in the temperature that in the clip tenter machine 20 is the moistening film 12 of 40 quality %, and be made as this condition constant the solvent containing ratio.
In addition, above-mentioned preset temperature according to cellulose acylate with the substituent kind and different.For example, when cellulose acylate is TAC, when substituent was mannosans acetic acid, preset temperature was 140 ℃ of following scopes more than 90 ℃.And when cellulose acylate is Cellulose diacetate (DAC), when substituent was 1: 1 the mixture of mass ratio of xylan acetic acid and mannosans acetic acid, preset temperature was 150 ℃ of following scopes more than 100 ℃.No matter above-mentioned any situation, more preferably preset temperature is 130 ℃ of following scopes more than 90 ℃.
When cellulose acylate was TAC, TAC had the crystallization degree bigger than DAC.Therefore, the chart (do not have diagram) that the longitudinal axis of Fig. 4 is replaced to the crystallization degree of TAC has the shape identical with Fig. 4.So, under the situation that TAC is used as cellulose acylate, when the opportunity that casting films 32 is heated up and reach preset temperature more than 4 quality % during the following scope of 100 quality %, the crystallization degree obviously rises.Therefore, when obtaining the concerning of Rth and substituent ratio CS, also can be that the opportunity that reaches preset temperature is obtained on the basis with the crystallization degree of TAC.
As shown in Figure 5, clip tenter machine 20 possesses chamber 60, and this chamber should transmit the road in the mode around the transmission road of moistening film 12 and peripheral and space outerpace separates.Chamber 60 has preheating zone 61, drawing zone 62, relax zone 63 and cooling zone 64 successively from the upstream side of delivery direction Z1.Wherein, chamber 60 is not Yi Ge district 61～64 to be set in inside become separately the independently separating means of spatial mode zoning.As described later, each distinguishes 61～64 tracks and form for the effusive dry air of air chamber 71a～71d (with reference to Fig. 6) from the 1st～the 4th respectively of advancing by clip 67.
Guide rail 68 and guide rail 69 with predetermined guide rail width mutually away from.The guide rail width is certain with width W 1 in preheating zone 61.In drawing zone 62, the guide rail width is along with direction Z1 is widened to width W 2 gradually from width W1.In relax zone 63, the guide rail width is along with direction Z1 subtracts wide to width W 3 gradually from width W2.In cooling zone 64, guide rail width and width W 3 are certain.By each guide rail of setting like this, in preheating zone 61, transmit moistening film 12 with the state of Max. Clearance _M., so that keep certain width, and in drawing zone 62, the moistening film 12 that is transmitted is drawn into to width to be expanded.And, in relax zone 63, diminish but with width that the confined state of width transmits moistening film 12, and in cooling zone 64, transmit with the state that keeps certain width.
Wherein, above-mentioned " necessarily " of the guide rail width in relevant preheating zone 61 and the cooling zone 64 do not need tightly.That is, also can be following form: in preheating zone 61 and cooling zone 64, make the guide rail width spread all over upstream to downstream and be varied to roughly certain degree that can be described as a little with width W 1, width W 3 respectively respectively.And,, also may not necessarily spread all over upstream to downstream constriction gradually about the guide rail width in the relax zone 63.For example, also can be following form: spread all over upstream to downstream at relax zone 63 middle guide width and be varied to roughly certain degree that can be described as a little with width W 2.
A plurality of clips 67 are installed on (not shown) on the chain across predetermined space.This chain is installed on respectively in guide rail 68 and the guide rail 69, and moves freely along guide rail 68,69.Chain more is meshed by the rolling disc 73 of upstream side and the sprocket wheel 74 that is equipped on the downstream end of cooling zone 64 with being equipped on than preheating zone 61.By the rotation of sprocket wheel 74, chain is advanced continuously.By advancing of chain, clip 67 moves along guide rail 68,69.
Than preheating zone 61 more by upstream end, be provided with beginning based on the sidepiece of the moistening film 12 of clip 67 control control beginning mechanism (not having diagram).In the cooling zone 64 downstream side be provided with releasing based on the sidepiece of the moistening film 12 of clip 67 control control cancel system (not having diagram).According to these, moistening film 12 is more leaning on upstream end being held in clip 67 than preheating zone 61, and clip 67 moves along guide rail 68,69, thereby also distinguishes 36～39 successively to the transmission of Z1 direction by each, be subjected to predetermined processing in each district 36～39,64 downstream end is removed and is controlled in the cooling zone.
As shown in Figure 6, conduit 71 is arranged at the top of transmitting the road, so that become roughly certain with the interval on the transmission road of moistening film 12.Be formed with the slit 77 that extends to the width Z2 of moistening film 12 in the bottom of conduit 71, slit 77 is provided with a plurality of on the Z1 direction.In addition, transmit the road below the conduit (not having diagram) that has with conduit 71 same structures also can be set so that become roughly necessarily with the interval of transmitting the road, and in this conduit, each slit is formed at top.In addition, make delivery direction Z1 and width Z2 quadrature.
The inside of conduit 71 is the 1st～the 4th to give air chamber 71a～71d by a plurality of plate 78 zonings that separate.In addition, among Fig. 6, the 1st and the 2nd slit 77 to air chamber 71a, 71b respectively has a plurality of, and the 3rd and the 4th respectively has one for the slit 77 of air chamber 71c, 71d.But, be not limited thereto respectively for the quantity of each slit 77 among air chamber 71a～71d.That is, also can 1 slit 77 be set for air chamber 71b for air chamber 71a or the 2nd, and a plurality of slits 77 be set for air chamber 71d for air chamber 71c or the 4th the 3rd the 1st.
The the 1st～the 4th of gas supply part 72 conductive pipe 71 supply with dry air for air chamber 71a～71d.Gas supply part 72 possesses tempering machine (not having diagram), and this tempering machine is controlled independently and is supplied to the 1st～the 4th temperature of giving each dry air of air chamber 71a～71d respectively.The dry air that is adjusted to preset temperature according to this tempering machine is supplied to for air chamber 71a～71d by the 1st～the 4th respectively and respectively distinguishes 61～64.
According to from the 2nd supply of giving the dry air of air chamber 71b, heat moistening film 12 at drawing zone 62, so that become preset temperature.
And according to from the 1st supply of giving the dry air of air chamber 71a, heating in advance enters the moistening film 12 before the drawing zone 62.By heating based on this preheating zone 61, begin the tensile while in the drawing zone 62 rapidly, when in drawing zone 62, stretching, on width Z2, give more uniform tension force.
In relax zone 63, except by controlling the Max. Clearance _M. of both sides, also by the heating of dry air of air chamber 71c is suitably lax to residue in inner stress (unrelieved stress) based on giving from the 3rd.In this lax operation, the molecular orientation in the moistening film 12 is made as the state of being expected.
In cooling zone 64, in lax operation, become the moistening film 12 of the molecular orientation of being expected by the dry air cooling.By this cooling, molecule is fixed with the state of orientation of being expected.In addition, among Fig. 6,, omit the diagram of clip 67 or rolling disc 73, sprocket wheel 74 for fear of numerous and diverse.
In order in film 22, to manifest Rth, in pin tenter 16 or clip tenter machine 20, keep the temperature of moistening film 12 to make it to become preset temperature as purpose.The hold-time that the temperature of moistening film 12 is held in preset temperature is to get final product general 1 minute such short period of time.So, being used to manifest temperature as the Rth of purpose, to remain the extremely short time just enough.According to this, can suppress the change of Re.Therefore, the mode of the Re that is expected to manifest determines on the basis of the various conditions in the clip tenter machine 20 that the temperature that the Rth that only expects in order to manifest implements the short period of time in above-mentioned opportunity keeps getting final product.In addition, in kiln 25, can the scope below 200 ℃ promotes crystallization more than 155 ℃ by moistening film 12 is made as.But in these cases, the gasification that is contained in the additive in the moistening film 12 is remarkable, in addition, causes cut in the week of roller 41 in the face of moistening film 12 easily, may not be preferred.
In above-mentioned the 1st embodiment, Mierocrystalline cellulose 55 and polymer 56 are carried out acidylate 57 together, and obtain solids component 58 with the form of the mixture of cellulose acylate 51 and substituent 52.But the method that obtains solids component 58 can be following the 2nd embodiment.With with cellulose acylate and substituting group be the substituent of identical acyl group situation about using as the solids component of dope 11 as an example.As shown in Figure 7, implement the 1st acidylate 61 of acylated cellulose 55 and the 2nd acidylate 62 of acylation polymerized body 56 respectively independently.The substituent 52 that can obtain with the cellulose acylate 51 that obtained by the 1st acidylate 61 with by the 2nd acidylate 62 is together as solids component 58.It is the situation of the substituent 52 of the acyl group different with cellulose acylate that this method can be applied to use substituting group.
In the 1st and the 2nd embodiment, obtain the relation of substituent ratio and Rth in advance, but replace this form, also can be used as following the 3rd embodiment.In the 3rd embodiment, obtain Rth and polymer 56 relation in advance with respect to the ratio of Mierocrystalline cellulose 55 (below, be called the polymer ratio) CP.Line segment L4, L5, L6 shown in Figure 8 be, mutually different polymer 56 carries out acidylate 57 with Mierocrystalline cellulose 55 separately, and each Rth (unit: chart nm) when using resulting each solids component 58 to make films 22.Transverse axis is a polymer ratio (unit: quality %).The solids component 58 that uses among the solids component 58 that uses in the L4 that represents with solid line and the L1 of Fig. 3 is identical.And in the L5 that represents with a long and short dash line, the L6 that represents with two dot chain line, the solids component 58 that uses among L2, the L3 of the solids component 58 of Shi Yonging and Fig. 3 is identical separately.
As shown in Figure 8, the Rth of film 22 and the proportional relation of polymer ratio CP.In addition, L4, L5, L6 become identical relation with L1, L2, the L3 of Fig. 3 respectively.So, polymer ratio CP and substituent ratio CS and Rth between have identical relation.Therefore; can be by obtaining and the corresponding polymer ratio CP of Rth (Rth among Fig. 8 (P)) as purpose; and adjust the amount of the polymer 56 in the acidylate object 54, thereby adjust the amount of the substituent 52 in the dope 11 according to the polymer ratio CP (P) that obtained.
In the 1st～the 3rd embodiment, be use cellulose acylate and substituent situation as solids component 58.But, in dope 11, can add other material in addition.For example can enumerate softening agent, UV light absorber and delustering agent etc.
The present invention is especially effective when manufacturing requires the optical compensation films such as phase retardation film of high Rth.
[embodiment]
[experiment 1]～[experiment 16]
[making of cellulose acylate dope]
In mixing tank, drop into following constituent, and stir heating the time, dissolve or disperse each composition to modulate dope 11.The dope 11 that modulates is 11 kinds of the sample number A-1～A-11 shown in the table 1.In addition, the solvent of each dope 11 of A-1～A-11 consists of as follows.The mode that each dope 11 of A-1～A-11 becomes 20 quality % with the concentration of the solids component shown in the table 1 58 is adjusted concentration and is transferred liquid.Solids component 58 shown in the table 1 promptly is the delustering agent in cellulose acylate, Re dose, Rth dose, polyester glycol, the delustering agent dispersion liquid.In addition, in A-1～A-11,, therefore in table 1, put down in writing into 0 (zero) owing to do not use the Re dose." CA " expression cellulose acylate in table 1, " AA " represents hexanodioic acid (C6), " EG " represents ethylene glycol (C2), " PG " expression 1,2-propylene glycol (C3).
Methylene dichloride (the 1st solvent composition) 100 mass parts
Methyl alcohol (the 2nd solvent composition) 19 mass parts
1-butanols 1 mass parts
[modulation of delustering agent dispersion liquid]
In order to modulate each dope of table 1, modulate the delustering agent dispersion liquid in advance.Drop into following constituent in the dispersion machine (not shown) and stir, disperse each composition and modulate the delustering agent dispersion liquid of table 1.
The composition of delustering agent dispersion liquid
Silica dioxide granule dispersion liquid (median size 16nm) 10.0 mass parts
" AEROSIL R972 ", Japanese AEROSIL Co., Ltd. make
Methylene dichloride 72.8 mass parts
Methyl alcohol 3.9 mass parts
Butanols 0.5 mass parts
Cellulose acylate solution 10.3 mass parts
In addition, to above-mentioned " cellulose acylate solution ", use the identical cellulose acylate of each cellulose acylate respectively with the table 1 that in answering synthetic A-1～A-11, uses as the composition of delustering agent dispersion liquid.That is, " CA " in the table 1 of each dope of A-1～A-11 is identical mutually with the cellulose acylate that uses in " delustering agent dispersion liquid ".
Prescription as above-mentioned " the cellulose acylate solution " of the character of delustering agent dispersion liquid is as follows.
Methylene dichloride (the 1st solvent composition) 100 mass parts
Methyl alcohol (the 2nd solvent composition) 19 mass parts
1-butanols 1 mass parts
Used following compound as the Re dose.
[Chemical formula 1]
[table 1]
By solution film-forming equipment 10 and use dope 11 with as following mode produce cellulose acylate film.Be cooled on-5 ℃ the cylinder 30, from the curtain coating mouth curtain coating dope 11 of curtain coating mould 31.The state that is roughly 70 quality % with the solvent containing ratio is peeled off casting films 32.Keep the two side ends of the width of moistening film 12 with pin tenter (Japanese Patent discloses the pin tenter of putting down in writing among Fig. 3 of flat 4-1009 communique) 16 pin.In pin tenter, remain under the state of the temperature shown in the table 2 in the temperature that with the solvent containing ratio is the moistening film 12 under 4～100 quality %, when being about 3% mode and keeping a side the interval of pin and the pin of the side end of keeping the opposing party of side end with the horizontal stretching ratio of (perpendicular to the direction of delivery direction Z1), dry moistening film 12.Afterwards, further dry by between the roller 41 of kiln 25, transmitting, produce the film 22 that thickness is about 60 μ m respectively.
[the optical characteristics evaluation method of cellulose acylate film 22]
Implement the evaluation of the optical characteristics of resulting film 22 in order to following method.
[Rth that prolongs that prolongs Re and thickness direction in the face]
From resulting each film 22, the sample test portion of 30mm * 40mm.At 25 ℃, 60%RH (relative humidity) damping test portion 2 hours down, and in double refraction instrument KOBRA21ADH (manufacturing of prince's instrumentation equipment Co., Ltd.) automatically, measure Re (λ) to the light of embrane method line direction incident wavelength λ nm.And, be benchmark with length of delay 3 direction detections, in automatic double refraction instrument KOBRA21ADH, import the default 1.48 and the thickness of mean refractive index and calculate Rth (λ).Length of delay 3 direction detections is meant, described Re (λ), be tilting axis with the slow axis in the face, from tilt with respect to embrane method line direction+40 ° the light of direction incident wavelength λ nm and the length of delay measured, and be tilting axis, from tilt-40 ° the light of direction incident wavelength λ nm and the length of delay measured with respect to embrane method line direction with the slow axis in the face.
" the rising ratio % of the Re (nm) with the CA monomer during as benchmark " of table 2 reaches " the rising ratio % of the Rth (nm) with the CA monomer during as benchmark " and will contain polyester glycol and delustering agent with table 1 ratio and not contain the Re dose and the monomeric Re of cellulose acylate (nm) of Rth dose and Rth (nm) calculate as benchmark.
(film planar)
Planar according to mist degree evaluation of measuring gained film.Carried out mist degree mensuration.Following mensuration of carrying out each mist degree: after rolling at film two sided coatings Liquid Paraffin and with sheet glass, utilize mist degree determinator (HGM-2DP, SUGA trier) for 60% time and test portion 400mm * 80mm is measured according to JIS K-6714 25 ℃ of relative humidity.To have only the Liquid Paraffin that film is not clipped in the middle and the measured value of sheet glass to be made as blank.Estimate its result according to following benchmark, and its result is recorded in the table 2.
A: mist degree is below 1.0
B: mist degree is greater than 1.0 and be below 1.3
C: mist degree is greater than 1.3 and be below 1.5
D: mist degree is more than 1.5
[table 2]
[comparative experiments 1]～[comparative experiments 6]
As with respect to comparative experiments of the present invention, implemented comparative experiments 1～comparative experiments 6.At first, use cellulose acylate, other solids component and solvent to modulate the dope of sample number as A-12, A-13 with experiment 1～experiment 16 identical methods.In addition, the concentration of the solvent of A-12, A-13 composition and solids component is formed identical with the solvent in experiment 1～experiment 16.Each cellulose acylate that uses in the delustering agent dispersion liquid of A-12, A-13 is identical with A-12, the A-13 of table 1 " CA ".
With the solvent containing ratio is that the temperature of the moistening film 12 of 4～100 quality % remains the temperature shown in the comparative experiments 1～comparative experiments 4 of table 2, in addition carries out in the same manner with experiment 1～experiment 16 and makes film.
And in addition the dope 11 of curtain coating A-1, and be that the temperature of the moistening film of 4～100 quality % remains the comparative experiments 5 of table 2, the temperature shown in the comparative experiments 6 with the solvent containing ratio carries out in the same manner with experiment 1～experiment 16 and makes film.
The film that obtains in comparative experiments 1～comparative experiments 6 has respectively been implemented and experiment 1～experiment 16 identical evaluations.Evaluation result is as shown in table 2.
As shown in table 2, according to the present invention, can suppress the rising of Re and Rth is optionally risen, in addition, possess good planar film 22 by adjusting the content of substituent 52, can accessing.
Claims (8)
1. the manufacture method of a cellulose acylate film, this method possesses following steps:
(A) curtain coating step, wherein with the cellulose acylate solution casting to supporter, and peel from described supporter as solvent-laden moistening film, described cellulose acylate solution comprises substituent, described substituent has the structure that is replaced to other atomic group based on the hydrogen of the hydroxyl in the polymer of the sugar of glycosidic link, and described substituent is different with cellulose acylate;
(B) drying step is wherein made cellulose acylate film by the described moistening film of drying; And
(C) heating steps wherein is reduced to described moistening film between the 4 quality % to solvent containing ratio in described drying step from 100 quality % and heats so that reach more than 70 ℃ temperature in 150 ℃ of following scopes.
2. the manufacture method of cellulose acylate film as claimed in claim 1, wherein,
The amount of the described substituent in the described cellulose acylate solution according to the film of manufacturing (nx+ny)/thickness direction retardation Rth that 2-nz} * d obtains adjusts;
At this,
Nx is the specific refractory power on the interior slow-axis direction of the face of cellulose acylate film,
Ny is the specific refractory power on the interior quick shaft direction of the face of cellulose acylate film,
Nz is the specific refractory power on the film thickness direction,
D is a film thickness, and unit is nm.
3. the manufacture method of cellulose acylate film as claimed in claim 2, wherein,
Obtain the relation of the amount of thickness direction retardation Rth when carrying out described B step and described substituent in advance, and decide the amount of the described substituent in the described dope according to the described relation of having obtained with certain condition.
4. the manufacture method of cellulose acylate film as claimed in claim 1, wherein,
Described sugar is hexose.
5. the manufacture method of cellulose acylate film as claimed in claim 1, wherein,
Described sugar has cyclic skeleton.
6. the manufacture method of cellulose acylate film as claimed in claim 1, wherein,
Described polymer is any one in mannosans, glucomannan and the starch.
7. the manufacture method of cellulose acylate film as claimed in claim 1, wherein,
Described atomic group be ethanoyl, propionyl, butyryl radicals, 2-ethylhexyl, methyl, ethyl, hydroxyethyl, carboxymethyl, sulfuryl, nitro, amino, N-ethanoyl and carbon number be more than 8 in the longer chain fatty acid ester group below 30 at least any one.
8. the manufacture method of cellulose acylate film as claimed in claim 1, wherein,
By carrying out acidylate to comprising the described polymeric Mierocrystalline cellulose of predetermined amount, make the cellulose acylate that comprises the described substituent of predetermined amount, this cellulose acylate is dissolved in described solvent and prepares described cellulose acylate solution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP049305/2010 | 2010-03-05 | ||
| JP2010049305A JP5636200B2 (en) | 2010-03-05 | 2010-03-05 | Method for producing cellulose triacetate film |
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| CN102190807B CN102190807B (en) | 2015-01-21 |
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Cited By (3)
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|---|---|---|---|---|
| CN103304829A (en) * | 2012-03-09 | 2013-09-18 | 富士胶片株式会社 | Method and apparatus for producing cellulose acylate film |
| CN111527032A (en) * | 2017-12-27 | 2020-08-11 | 富士胶片株式会社 | Packaging material and method of use thereof |
| CN112739723A (en) * | 2018-10-15 | 2021-04-30 | 国立大学法人大阪大学 | Cyclic oligosaccharide and process for producing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007072390A (en) * | 2005-09-09 | 2007-03-22 | Fujifilm Corp | Cellulose acylate film, and optical compensation film, polarizing plate, and liquid crystal display device using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2559073B2 (en) * | 1990-04-19 | 1996-11-27 | 富士写真フイルム株式会社 | Method for producing cellulose triacetate film |
| JP2001122980A (en) * | 1999-08-17 | 2001-05-08 | Konica Corp | Cellulose ester film, protective film for polarizing plate and member for liquid crystal display |
| JP2002265637A (en) * | 2001-03-14 | 2002-09-18 | Fuji Photo Film Co Ltd | Cellulose ester film |
| JP5012369B2 (en) * | 2007-09-27 | 2012-08-29 | コニカミノルタアドバンストレイヤー株式会社 | Manufacturing method of optical film |
| JP5012378B2 (en) * | 2007-09-30 | 2012-08-29 | コニカミノルタアドバンストレイヤー株式会社 | Manufacturing method of optical film |
| JP5223351B2 (en) * | 2008-01-21 | 2013-06-26 | コニカミノルタアドバンストレイヤー株式会社 | Method for producing cellulose ester film |
| JP2011132443A (en) * | 2009-12-25 | 2011-07-07 | Fujifilm Corp | Molding material, molding, and method for producing the same, and housing for electric and electronic equipment |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007072390A (en) * | 2005-09-09 | 2007-03-22 | Fujifilm Corp | Cellulose acylate film, and optical compensation film, polarizing plate, and liquid crystal display device using same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304829A (en) * | 2012-03-09 | 2013-09-18 | 富士胶片株式会社 | Method and apparatus for producing cellulose acylate film |
| CN111527032A (en) * | 2017-12-27 | 2020-08-11 | 富士胶片株式会社 | Packaging material and method of use thereof |
| CN111527032B (en) * | 2017-12-27 | 2022-06-14 | 富士胶片株式会社 | Packaging material and method of use thereof |
| CN112739723A (en) * | 2018-10-15 | 2021-04-30 | 国立大学法人大阪大学 | Cyclic oligosaccharide and process for producing the same |
| CN112739723B (en) * | 2018-10-15 | 2023-02-17 | 国立大学法人大阪大学 | Cyclic oligosaccharide and process for producing the same |
Also Published As
| Publication number | Publication date |
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| CN102190807B (en) | 2015-01-21 |
| JP2011183606A (en) | 2011-09-22 |
| JP5636200B2 (en) | 2014-12-03 |
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