CN101735477B - Additive for cellulose ester resin, cellulose ester resin composition using same, and film - Google Patents

Additive for cellulose ester resin, cellulose ester resin composition using same, and film Download PDF

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CN101735477B
CN101735477B CN2009102224519A CN200910222451A CN101735477B CN 101735477 B CN101735477 B CN 101735477B CN 2009102224519 A CN2009102224519 A CN 2009102224519A CN 200910222451 A CN200910222451 A CN 200910222451A CN 101735477 B CN101735477 B CN 101735477B
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cellulose ester
ester resin
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ester cpds
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CN101735477A (en
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三原崇
吉村洋志
桝本雅也
铃木治
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements

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Abstract

The present invention provides an additive for cellulose ester resin, which is obtained by esterification between dibasic alcohol (s1) and aromatic dicarboxylic acid compound (a2) and has a number-average molecular weight in a range of 300-3,000. The aromatic dicarboxylic acid compound (a2) is more than one component selected from terephthalic acid, terephthalic dialkyl ester, naphthalenedicarboxylic acid, naphthalenedicarboxylic dialkyl ester, diphenic acid and diphenic dialky ester. The additive for cellulose ester resin can make an optical film to have excellent optical performance and moisture-penetration resistance. Furthermore the optical film with excellent moisture-penetration resistance in high temperature and high moisture is provided.

Description

Cellulose ester resin is with additive, with its cellulose ester resin composition and film
Technical field
The present invention relates to cellulose ester resin with additive, used its cellulose ester resin composition and blooming, described cellulose ester resin additive is by can forming to the ester cpds that the bloomings such as polaroid protective film are given excellent optical property by adding in cellulose ester resin.
Background technology
In recent years, possess can clear show image and the information equipment such as the notebook computer of the liquid crystal indicator of word and TV be supplied to one after another market.About the requirement of human consumer to these information equipments, except give high functional, on the basis that meets the demands such as variation of saving spatialization, living environment, also seek slimming and lightweight and follow the wide viewing angle of large picture and high-contrast etc.
The slimming that realizes information equipment is depth (wide) attenuation of the liquid crystal indicator that will purchase on above-mentioned information equipment.Above-mentioned liquid crystal indicator roughly by have between 2 glass substrates by electrode form the layer and by liquid crystal material forms layer the laminated structure body consist of.Above-mentioned glass substrate is pasting polaroid at the opposing face of liquid crystal layer, as this polaroid, and the polaroid that usually uses the two sides bonding protective film at the polaroid that is consisted of by polyvinyl alcohol (PVA) to form.Above-mentioned polaroid protective film, the general transparency of using is high, have suitable intensity and with the cellulose ester resin film excellent in adhesion of PVA.
But above-mentioned cellulose ester resin film can not fully prevent the immersion of moisture (moisture), and there be the deteriorated of polaroid in its result, perhaps produces the problem of peeling off between polaroid and above-mentioned film.Therefore, as polaroid protective film, in the past, added the film such as softening agent such as triphenylphosphates in cellulose ester resin, used as the film with good anti-water vapour permeability.
And, as above-mentioned polaroid protective film, although according to the structure of liquid crystal indicator etc. and not identical, usually, use approximately 80 μ m left and right more of film thickness.In recent years, be accompanied by the propelling of the slimming of liquid crystal indicator, protective membrane is slimming more, as aimed film thickness approximately the research of the film of 30～50 μ m carry out.
In the research of carrying out such filming, with regard to the polaroid protective film that contains above-mentioned softening agent and above-mentioned cellulose ester resin in the past, making its film thickness be thinned to institute when requiring level, there is the significantly reduced problem of anti-water vapour permeability.
And above-mentioned softening agent because insufficient with the intermiscibility of cellulose ester resin, causes softening agent to ooze out from the film surface so be subject to sometimes the impact of heat and humidity.Thereby, when being used for liquid crystal indicator, will exist due to the impact that is subject to heat backlight etc., plasticizer exudation is surperficial to film, causes fuzzy and makes the problem that image etc. can not clear demonstration.
And about above-mentioned polaroid protective film, requirement has the surface smoothness of the excellence of the degree such as image that do not hinder clear display.So in order to obtain surface smoothness, polaroid protective film namely will contain the organic solvent solution casting film-forming shape of the cellulose ester resin composition of above-mentioned softening agent just with so-called solution casting method manufacturing, then heat drying.But because above-mentioned softening agent is low-molecular-weight compound, so easily volatilization in above-mentioned heat drying operation, the above-mentioned softening agent of volatilization will be attached to above the roller that consists of film manufacturing device etc. and cause the problem of polluting device.
Purposes, purposes such as toy or tableware beyond cellulose ester resin is used for above-mentioned polaroid protective film, oozing out with easy of above-mentioned softening agent volatilized, from beginning in the past just to be regarded as problem.As the softening agent that addresses this problem, the softening agent or the phthalic acid that have proposed take the acetylate of sugar alcohol as principal constituent are polyester (for example, with reference to patent documentation 1,2).
But; it is the resin combination of polyester and the film that obtains that moulding contains as the acetylate of the above-mentioned sugar alcohol of softening agent or phthalic acid; do not have the anti-water vapour permeability as the spendable level of polaroid protective film; and; there is the problem of still easily oozing out in these softening agent under high temperature and humidity; described phthalic acid is polyester will be that the Tetra hydro Phthalic anhydride of the concrete record of polyester and 1,3 butylene glycol react and obtain as phthalic acid.
And, it is reported and contain ester cpds that the reaction of 2-ethyl-2-butyl-1,3-PD and M-nitro benzoic acid is obtained and the film of cellulose-based resin, anti-excellent moisture permeability is (for example, with reference to patent documentation 3.)。
But, contain above-mentioned ester cpds and the film of cellulose-based resin, generally use the thickness of 80 about μ m, filming can not be kept sufficient anti-water vapour permeability in the situation of about 40～50 μ m left and right, thereby now further not universal in practical.And, because this ester cpds lower compound that is molecular weight ratio, so there is the problem of polluting the roller that consists of film manufacturing device etc. in easily volatilization in the heat drying operation in film is made.
, possesses the information equipment of liquid crystal indicator except above-mentioned slimming, according to purposes needs various characteristics also.Especially, LCD TV is starved of the wide viewing angle that is accompanied by large picture.
Wide viewing angle to liquid crystal indicator; just studying from beginning in the past; for example; give in order to give the polaroid protective film that is consisted of by cellulose ester resin the optical compensation function that is conducive to wide visual angle; proposed (for example, to refer to Patent Document 4 as the method for delayed-action activator interpolation aromatics.)。
Here, so-called optical compensation films is the film that compensates the phase differential that produces due to the liquid crystal material that consists of liquid crystal indicator, plays an important role on realizing aspect " wide viewing angle ".If can not compensation of phase poor, will exist the CF of image of demonstrating when tilted direction is seen liquid crystal panel etc. to seem and original different problem.
Therefore as optical compensation films, in order to bring into play wide viewing angle, use to have optically anisotropic film.Here, the optical property described in the present invention refers to optical anisotropy, and general optically anisotropic degree can be held according to length of delay.In the middle of the length of delay of optical compensation films, about the length of delay of film thickness direction (below, referred to as " Rth value "), generally can adjust to desirable degree of anisotropy by the material that interpolation is called as delayed-action activator.But, with regard to regard to the delayed-action activator patent documentation 4 is put down in writing, because insufficient with the intermiscibility of cellulose ester resin, ooze out and the impaired problem of the transparency so optical compensation films is placed on hot and humid existence of lower time.
In addition, the Rth value of thickness direction refers to the defined value of following formula (1).
Rth＝{(nx+ny)/2-nz}×d(nm) (1)
(in formula, nx is the specific refractory power of the slow-axis direction in face, and ny is the specific refractory power of the quick shaft direction in face, and nz is the specific refractory power of film thickness direction, and d is the thickness (nm) of film.)
Therefore; the inventor proposes; as the additive of giving excellent optical property to polaroid protective film, by two ends have aromatic group diester compound, and two ends and molecular chain in have the ester cpds of compositions of mixtures of petchem of aromatic series ring type structure (with reference to patent documentation 5.)。
But, along with the High Level of state of the art, above-mentioned optical compensation films is required more excellent optical property, that is, and high Rth value.If can obtain the optical compensation films that formed by the cellulose ester resin with excellent phase difference compensation function, usually need the above-mentioned film of 4 just can further reduce number, the realization of the filming of above-mentioned film becomes possibility, cheap and high-grade Polarizer can be provided, and then liquid crystal indicator, but being such material, present situation also do not exist now.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2000-351871 communique;
Patent documentation 2: Japanese kokai publication sho 61-276836 communique;
Patent documentation 3: TOHKEMY 2003-096236 communique;
Patent documentation 4: TOHKEMY 2000-284124 communique;
Patent documentation 5: TOHKEMY 2008-069225 communique.
Summary of the invention
The problem that invention will solve
The problem to be solved in the present invention is, provide the cellulose ester resin that formed by ester cpds with additive and the cellulose ester resin composition that used it, described ester cpds gives excellent optical property and anti-water vapour permeability can for the film that is formed by cellulose ester resin, anti-exudative excellence under high temperature and humidity, and be difficult to volatilization in manufacturing process.
And, the invention provides the film or the blooming that are formed by above-mentioned cellulose ester resin composition.
The means of dealing with problems
The result that the inventor furthers investigate, discovery is in carrying out the resulting ester cpds of esterification with dibasic alcohol and specific aromatic dicarboxylic acid compound, the ester cpds that will have the specified range molecular weight uses with additive as cellulose ester resin, just can obtain to give the blooming that formed by cellulose ester resin optical property and the anti-water vapour permeability, the cellulose ester resin additive that is difficult to volatilize with excellence in the anti-exudative excellence under high temperature and humidity and the manufacturing process at film, thereby complete invention.
namely, the invention provides the cellulose ester resin additive, the cellulose ester resin composition that contains this additive, and the film and the blooming that are formed by this resin combination, described cellulose ester resin with additive by the number-average molecular weight of dibasic alcohol (a1) and aromatic dicarboxylic acid compound (a2) being carried out esterification and obtaining 300～3, the ester cpds of 000 scope (A) forms, described aromatic dicarboxylic acid compound (a2) is from by terephthalic acid, dimethyl terephthalate ester, naphthalic acid, the naphthalic acid dialkyl, more than a kind of selection in the group that diphenyl dicarboxylic acid and diphenyl dicarboxylic acid dialkyl form.
The invention effect
Cellulose ester resin additive of the present invention by adding in cellulose ester resin, can be given excellent optical property and anti-water vapour permeability to film.And cellulose ester resin additive of the present invention has anti-exudatively under high temperature and humidity, has the effect of the excellence that is difficult to volatilize in film manufacturing process.Further, the film by the cellulose ester resin composition that contains cellulose ester resin use additive of the present invention forms can be used for various bloomings, and is wherein very useful to the polaroid protective film that needs optical compensation function.
Embodiment
Cellulose ester resin of the present invention is described with additive ester cpds (A).
As ester cpds of the present invention (A), take its end be hydroxyl or alkyl ester group as feature, can enumerate ester cpds with structure shown in following general formula (I)～(VI) etc.
[changing 1]
Figure G2009102224519D0000051
(G in above-mentioned general formula (I) represents the residue of dibasic alcohol (a1), and T represents the residue of aromatic dicarboxylic acid compound (a2), and R represents alkyl.And n represents repeating unit, is the integer more than 1.)
In addition, above-mentioned " residue " expression following content.2 hydroxyls that " residue " of dibasic alcohol (a1) expression removes that dibasic alcohol (a1) has and remaining organic group.And, " residue " of aromatic dicarboxylic acid compound (a2) is, in the situation that aromatic dicarboxylic acid compound (a2) is aromatic carboxylic acid, expression has been removed carboxyl that aromatic carboxylic acid has and remaining organic group, in the situation that aromatic dicarboxylic acid compound (a2) is the aromatic carboxylic acid alkyl ester, expression has been removed carbalkoxy that the aromatic carboxylic acid alkyl ester has and remaining organic group.
More specifically, the n in above-mentioned general formula (I)～(VI) is so long as the integer more than 1 is just passable, the integer of preferred 1～15 scope.The mixture of above-mentioned ester cpds (A) a plurality of ester cpds that normally the n number is not identical.for example, contain with respect to whole ester cpds (A) scope that n in general formula (I)～(VI) is 1 ester cpds (A1) 25～40 quality %, n in general formula (I)～(VI) is the scope of 2 ester cpds (A2) 20～40 quality %, and the n in general formula (I)～(VI) is the ester cpds (A) of the scope of ester cpds (A3) 35～45 quality % more than 3, give more excellent optical property because can give the blooming that is formed by cellulose ester resin, and anti-water vapour permeability, anti-exudative excellence under high temperature and humidity, and ester cpds (A) in film manufacturing process is so to be difficult to volatilization preferred.
The hydroxyl value of ester cpds of the present invention (A) preferably in 0.1～200 scope, is more preferably at 1～150 scope.If the hydroxyl value of ester cpds (A) is in this scope, the anti-exudative and anti-water vapour permeability of blooming will be good.And, blooming is used for can further suppressing the deteriorated of polaroid in the situation of polaroid protective film.This hydroxyl value derives from the terminal hydroxyl of ester cpds (A) and the dibasic alcohol (a1) that uses as raw material.
Cellulose ester resin additive of the present invention is particularly in the situation that for blooming, require volatility resistance.Above-mentioned volatility resistance; as long as measure the weight loss on heating value of above-mentioned additive; for example; in the situation that be used for the polaroid protective film of blooming; cellulose ester resin uses the weight loss on heating value of additive below 1.0 quality %; the scope of preferred 0.01～1.0 quality % is more preferably the scope of 0.01～0.80 quality %, particularly preferably the scope of 0.01～0.50 quality %.If the weight loss on heating value in this scope, the weather resistance of polaroid protective film, and the recirculation of forming process and the organic solvent that uses when making film by solution casting method excellent, reach the upper and practical no problem level of making.In addition, the details of the condition determination of weight loss on heating value are recorded in embodiment.
Cellulose ester resin of the present invention with additive ester cpds (A) for give volatility resistance, with the intermiscibility of cellulose ester resin (B) and anti-exudative, its number-average molecular weight is 300～3,000 scope.And, be more preferably number-average molecular weight 330～2,700 scope.The blooming that is formed by the cellulose ester resin composition that contains the ester cpds (A) in the scope of this number-average molecular weight, have excellent optical property and anti-water vapour permeability, and also can suppress oozing out of ester cpds (A) under the high temperature conditions such as film manufacturing process, can obtain the film of the excellent in te pins of durability under wet heat condition.
If the number-average molecular weight of above-mentioned ester cpds (A) is will a large amount of remaining monomer components or low molecular weight substance below 300, so volatility resistance significantly worsens.On the other hand, if the number-average molecular weight of above-mentioned ester cpds (A) will worsen with the intermiscibility of cellulose ester resin (B) more than 3,000, so the transparency of film suffers damage, and particularly the use as blooming becomes difficulty.
In addition, the number-average molecular weight of above-mentioned ester cpds (A) can be by using tetrahydrofuran (THF) (THF) as elutriant, and (GPC) measures with gel permeation chromatography, and the value that is converted into polystyrene standard obtains.Be recorded in embodiment for detailed condition determination.
Above-mentioned ester cpds (A) can prepare by dibasic alcohol (a1) and aromatic dicarboxylic acid compound (a2) are carried out esterification, described aromatic dicarboxylic acid compound (a2) be select from the group who is formed by terephthalic acid, dimethyl terephthalate ester, naphthalic acid, naphthalic acid dialkyl, diphenyl dicarboxylic acid and diphenyl dicarboxylic acid dialkyl more than a kind.
The conversion unit of above-mentioned ester cpds of the present invention (A) can be with making with pressurization, the corresponding conversion unit of decompression.The general device that conversion unit can apparatus responds device, stirrer, rectifying tower, water cooler, be used for the pump etc. of decompression is made.
Above-mentioned ester cpds (A) can be by after for example adding above-mentioned dibasic alcohol (a1) and above-mentioned aromatic dicarboxylic acid compound (a2) and intensification in the reactor that possesses thermometer, agitator and reflux cooler, add esterifying catalyst in temperature-rise period, react under the specified temperature condition, after reaction, for the purpose of removing unreacted monomer or low molecular weight compositions and the purpose that promotes reaction, further carry out Depressor response and obtain.
Below the dibasic alcohol (a1) that uses in the present invention is illustrated.
(a1) can enumerate for example ethylene glycol as above-mentioned dibasic alcohol, 1, 2-propylene glycol (propylene glycol), 1, ammediol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 1, the 7-heptanediol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, 1, the 10-decanediol, 1, 11-undecane glycol, 1, the 12-dodecanediol, 1, the 4-cyclohexanedimethanol, neopentyl glycol, 3, 3-diethyl-1, ammediol, 3, 3-dibutyl-1, ammediol, 1, the 2-pentanediol, 1, the 3-pentanediol, 2, the 3-pentanediol, 2, the 4-pentanediol, 2-methyl-2, the 4-pentanediol, the 3-methyl isophthalic acid, the 5-pentanediol, 1, the 4-pentanediol, 1, the 2-hexylene glycol, 1, the 3-hexylene glycol, 1, the 4-hexylene glycol, 1, the 5-hexylene glycol, n-butoxy ethylene glycol, cyclohexanedimethanol, Hydrogenated Bisphenol A, two polyalcohols, Diethylene Glycol, dipropylene glycol, triethylene glycol, polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, hexylene glycol etc.These dibasic alcohol can use separately also and can will also use more than 2 kinds.
And (a1) can use aromatic diol as dibasic alcohol.Can enumerate ethylene oxide adduct such as dihydroxyphenyl propane, dihydroxyphenyl propane, propylene oxide adduct etc. as this aromatic diol.
In above-mentioned dibasic alcohol (a1), most preferred dibasic alcohol can be enumerated the material of carbonatoms 2～12 scopes.Specifically can enumerate ethylene glycol, 1,2-PD, 1,3-PD, 2-methyl isophthalic acid, ammediol, 1,2-butyleneglycol, 1,3 butylene glycol, BDO, 2,3-butyleneglycol, 1,5-pentanediol, neopentyl glycol, 1,2-encircles pentanediol, 1, and 3-encircles pentanediol, 1,4-cyclohexanediol, 1,6-cyclohexanediol etc.These dibasic alcohol can use separately also and can will also use more than 2 kinds.
And then, use 1,2-propylene glycol, 2-methyl isophthalic acid, ammediol, neopentyl glycol etc. have the dibasic alcohol of alkyl chain of branching and the ester cpds (A) that obtains, because the intermiscibility to cellulose ester resin (B) is excellent, anti-exudative also excellence when making blooming under the high temperature and humidity environment, therefore further preferred.
And, as above-mentioned dibasic alcohol (a1), and if spent glycol (a1-1) and 1,2-PD (a1-2), will obtain having the blooming of excellent optical property, i.e. polaroid protective film, so particularly preferably.
And spent glycol (a1-1) and 1, in the situation of 2-propylene glycol (a1-2), derive from ethylene glycol (a1-1) and 1 in the petchem that produces (A), mole ratio of components (a1-1)/(a1-2) of the structure unit of 2-propylene glycol (a1-2) preferred 85/15～10/90 (% by mole) scope, be more preferably 80/20～15/85 (% by mole) scope.If ethylene glycol (a1-1) and 1, mole ratio of components (a1-1)/(a1-2) of 2-propylene glycol (a1-2) is in this scope, with the intermiscibility of cellulose ester resin (B) or when making film with solution casting method because to the favorable solubility of organic solvent, so can give the sufficient transparency to film.And the performance of optical property is abundant.
In the situation that and with above-mentioned ethylene glycol (a1-1) and 1,2-PD (a1-2), also can use these dibasic alcohol other alcohols in addition.specifically can enumerate the methyl alcohol as unary alcohol, ethanol, n-butyl alcohol, the 2-butanols, hexanol, hexalin, amylalcohol, octanol, lauryl alcohol, methyl lactate, ethyl lactate is as for example 1,3-PD of di-alcohols, 1,2-butyleneglycol, 1,3 butylene glycol, BDO, 1,5-PD, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, decamethylene-glycol, 1,11-undecane glycol, 1,12-dodecanediol, 1,4 cyclohexane dimethanol, neopentyl glycol, 3,3-diethyl-1,3-PD, 3,3-dibutyl-1,3-PD, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 2-methyl-2, the 4-pentanediol, the 3-methyl isophthalic acid, the 5-pentanediol, Isosorbide-5-Nitrae-pentanediol, 1,2-hexylene glycol, 1,3-hexylene glycol, Isosorbide-5-Nitrae-hexylene glycol, 1,5-hexylene glycol, n-butoxy ethylene glycol, cyclohexanedimethanol, Hydrogenated Bisphenol A, poly-dihydric alcohol, Diethylene Glycol, dipropylene glycol, triethylene glycol, polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, hexylene glycol, dihydroxyphenyl propane, the oxyethylene affixture of dihydroxyphenyl propane, propylene oxide adduct etc.Polyvalent alcohol as other can be enumerated glycerine, Sorbitol Powder, ribitol, tetramethylolmethane.These alcohols can use separately also and can will also use more than 2 kinds.
Then, the below illustrates the aromatic dicarboxylic acid compound (a2) more than a kind of selecting from the group who is comprised of terephthalic acid, dimethyl terephthalate ester, naphthalic acid, naphthalic acid dialkyl, diphenyl dicarboxylic acid and diphenyl dicarboxylic acid dialkyl that uses in the present invention.
The above-mentioned aromatic dicarboxylic acid compound (a2) that uses in the present invention is more than a kind of selection from the group who is comprised of terephthalic acid, dimethyl terephthalate ester, naphthalic acid, naphthalic acid dialkyl, diphenyl dicarboxylic acid and diphenyl dicarboxylic acid dialkyl.
As the alkyl of above-mentioned dimethyl terephthalate ester, naphthalic acid dialkyl and diphenyl dicarboxylic acid dialkyl, can enumerate the alkyl of carbonatoms 1～8, carbonatoms more than 3 can be that straight chained alkyl can be also branched-chain alkyl.Can enumerate such as methyl, ethyl, propyl group, sec.-propyl, butyl, amyl group, hexyl, cyclohexyl, heptyl, octyl group etc. as such alkyl.And, 2 alkyl that above-mentioned aromatic dicarboxylic acid dialkyl has identical also can, difference also can.Above-mentioned aromatic dicarboxylic acid dialkyl can use separately also and can will also use more than 2 kinds.
Can enumerate such as dimethyl terephthalate (DMT), diethyl terephthalate, terephthalic acid dipropyl, dibutyl terephthalate, terephthalic acid diamyl ester, terephthalic acid dihexyl, terephthalic acid two heptyl esters etc. as above-mentioned dimethyl terephthalate ester.Preferred dimethyl terephthalate (DMT) in these dimethyl terephthalate ester, because dimethyl terephthalate (DMT) gives excellent optical property can for the blooming that is formed by the cellulose ester resin composition, so and due to the anti-exudative also excellent film that can obtain to have weather resistance under the high temperature and humidity environment.
As above-mentioned naphthalic acid dialkyl, can enumerate naphthalene diformic acid dimethyl ester, naphthalic acid diethyl ester, naphthalic acid dipropyl, naphthalic acid dibutylester, naphthalic acid diamyl ester, naphthalic acid dihexyl, naphthalic acid two heptyl esters etc.And although there is the position of substitution of many places alkyl carboxylates on these naphthalic acid dialkyls, 2,6 of preferred naphthalene become alkyl carboxylates, and further being more preferably alkyl is the NDA dimethyl ester of methyl.
As above-mentioned diphenyl dicarboxylic acid dialkyl, can enumerate '-biphenyldicarbonacid--dimethylester, diphenyl dicarboxylic acid diethyl ester, diphenyl dicarboxylic acid dipropyl, diphenyl dicarboxylic acid dibutylester, diphenyl dicarboxylic acid diamyl ester, diphenyl dicarboxylic acid dihexyl, diphenyl dicarboxylic acid two heptyl esters etc.And although there is the position of substitution of many places alkyl carboxylates on these diphenyl dicarboxylic acid dialkyls, 4,4 ' of preferred biphenyl becomes alkyl carboxylates, and further being more preferably alkyl is 4 of methyl, 4 '-'-biphenyldicarbonacid--dimethylester.
Further, in the manufacturing of above-mentioned ester cpds (A), so long as do not damaging scope of the present invention, just may be used other di-carboxylic acid or its alkyl ester compound, perhaps carbonate products.As above-mentioned di-carboxylic acid or its alkyl ester compound, can use aliphatic dicarboxylic acid or aromatic dicarboxylic acid, perhaps these alkyl ester compound.can enumerate for example succsinic acid as above-mentioned aliphatic dicarboxylic acid or its alkyl ester compound, Succinic acid dimethylester, pentanedioic acid, Methyl glutarate, hexanodioic acid, dimethyl adipate, diethylene adipate, Polycizer W 260, pimelic acid, NSC 52563, suberic acid, the suberic acid dimethyl ester, nonane diacid, dimethyl azelate, sebacic acid, dimethyl sebacate, decane dicarboxylic acid, the decane dicarboxylic acid dimethyl ester, cyclohexane cyclohexanedimethanodibasic, dimethyl hexahydrophthalate, dimeracid, the dimeracid dimethyl ester, fumaric acid, dimethyl fumarate etc.And, can enumerate phthalic acid, dimethyl phthalate, m-phthalic acid, dimethyl isophthalate etc. as aromatic dicarboxylic acid or its alkyl ester compound.Further, can enumerate methylcarbonate, diethyl carbonate, dibutyl carbonate etc. as carbonate products.These other di-carboxylic acid or its alkyl ester compound or carbonate products can use separately also and can more than 2 kinds and use.
When above-mentioned dibasic alcohol (a1) and above-mentioned aromatic dicarboxylic acid compound (a2) are carried out esterification, to promote reaction as purpose, can react under the existence of esterifying catalyst as required.
Can enumerate as above-mentioned esterifying catalyst the metal of at least a kind or the organometallic compound of selecting from the group who is formed by the periodic table of elements the 2nd row (IIA family), the 4th row (IVB family), the 12nd row (IIB family), the 13rd row (IIIA family) and the 14th row (IVA family).More specifically can enumerate metals such as titanium, tin, zinc, aluminium, zirconium, magnesium, hafnium, germanium, the metallic compounds such as tetraisopropoxy titanium, four titanium butoxide, methyl ethyl diketone oxygen titanium, stannous octoate, 2 ethyl hexanoic acid tin, zinc acetylacetonate, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, tetraethoxy germanium etc.This wherein, the preferred good pure salt of titanium of storage stability that uses the ester cpds (A) that obtains with the reactivity of dibasic alcohol (a1) and aromatic dicarboxylic acid compound (a2), ease for operation, by esterification specifically has tetraisopropoxy titanium, four titanium butoxide, methyl ethyl diketone oxygen titanium etc.
And, usage quantity about above-mentioned esterifying catalyst, usually, so long as the amount that can control the reaction of above-mentioned dibasic alcohol (a1) and aromatic dicarboxylic acid compound (a2) and can suppress the painted scope of ester cpds (A) gets final product, total amount with respect to above-mentioned dibasic alcohol (a1) and aromatic dicarboxylic acid compound (a2), the scope of preferred 10～1000ppm is more preferably the scope of 20～500ppm, particularly preferably the scope of 30～300ppm.The painted words of ester cpds (A) can reduce the transparency of film, therefore in requiring the blooming purposes of high transparent, need to give special heed to.
About the period of the interpolation of above-mentioned esterifying catalyst, can add simultaneously with adding above-mentioned dibasic alcohol (a1) and aromatic dicarboxylic acid compound (a2), also can be in temperature-rise period, decompression is added at first.
And, make above-mentioned dibasic alcohol (a1) and above-mentioned aromatic dicarboxylic acid compound (a2) when reacting, in the scope that does not hinder effect of the present invention, quantize above-mentioned ester cpds (A) as purpose take collateralization, polymer, also can use 3 valencys such as glycerine, tetramethylolmethane, trimellitic acid, Pyromellitic Acid above polyvalent alcohol or carboxylic acid, the isocyanic ester such as HDI.
When making above-mentioned ester cpds (A), the scope that adds mol ratio [(a1)/(a2)] preferred 0.5/1～2/1 of dibasic alcohol (a1) and aromatic dicarboxylic acid compound (a2), be more preferably 0.8/1～1.5/1 scope.If in this scope, can make cellulose ester resin of the present invention additive ester cpds (A).If particularly add mol ratio (a1)/(a2) in 0.5/1～1/1 scope, the ratio that the end group of ester cpds (A) becomes the alkyl ester group will become many, so be difficult to be subject to the impact of atmosphere moisture, can obtain the little blooming of amplitude of fluctuation of Rth value.
Temperature of reaction during about manufacturing ester cpds (A), so long as considered the form and aspect of ester cpds of boiling point, reactivity, sublimability, the acquisition of raw material dibasic alcohol (a1) and aromatic dicarboxylic acid compound (a2), and in reaction (dehydration reaction, perhaps except alcohol reaction) in the scope of carrying out, just without any restriction, but the scope of preferred 120 ℃～300 ℃ is more preferably the scope of 150 ℃～280 ℃.Reaction times when making above-mentioned ester cpds (A) is preferred more than 2 hours, is more preferably the scope of 4～100 hours.Decompression degree when making above-mentioned ester cpds (A) is preferred 30, below 000Pa, is more preferably below 25,000Pa, and particularly preferably 5,000Pa～20, the scope of 000Pa.If in this scope, can remove rapidly unreacted monomer and low molecular weight compositions, can promote reaction.
About above-mentioned ester cpds (A), also diverse material can be made respectively separately, then with these mixing and as cellulose ester resin additive of the present invention.And cellulose ester resin additive of the present invention is so long as in the scope of not damaging effect of the present invention, also can coordinate ester cpds (A) additive in addition during manufacturing.As the kind of above-mentioned ester cpds (A) additive in addition, can enumerate the catalyst deactivation agent be used to the catalytic activity inactivation that makes esterifying catalyst, the painted antioxidant of inhibition ester cpds (A) etc.
As above-mentioned catalyst deactivation agent, can enumerate for example sequestrant, can use organic system sequestrant or inorganic chelating agent.Can enumerate such as amino acid, phenols, hydroxycarboxylic acid, diketone class, amine, oxime, phenanthroline class, pyridine compounds, disulfide, diazonium compound, thio-alcohol, porphyrin, have the phenols of nitrogen-atoms or carboxylic acid etc. as ligating atom as the organic system sequestrant.And, can enumerate phosphate cpds such as phosphoric acid, phosphoric acid ester, phosphorous acid, phosphorous acid ester as inorganic chelator.These with respect to the total amount of raw material dibasic alcohol (a1) and aromatic dicarboxylic acid compound (a2), preferably add in the scope of 10～2,000ppm and use.
Then, the cellulose ester resin composition that contains above-mentioned ester cpds (A) is described.
The cellulose ester resin (B) that is used for cellulose ester resin composition of the present invention is a part or whole esterified material of the hydroxyl that has from the Mierocrystalline cellulose that linters, wood pulp, mestha etc. obtain.This wherein, the Mierocrystalline cellulose that use will obtain from linters carries out the cellulose ester resin that esterification obtains and the film that obtains, because easily peel off from the metal support that consists of film manufacturing device, can improve the production efficiency of film, so preferred.
As, the object lesson of above-mentioned cellulose ester resin (B) can be enumerated such as cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, acetate propionate cellulose butyrate, cellulose acetate-phthalate and nitrocellulose etc.These cellulose ester resins can use separately also and can will also use more than 2 kinds.In the situation that the film that will be formed by cellulose ester resin composition of the present invention uses as blooming, particularly polaroid protective film, so because use cellulose acetate can obtain mechanical properties and the excellent film of the transparency is preferred.
As above-mentioned cellulose acetate, preferred average degree of acetylation (in conjunction with the acetic acid amount) is more preferably average degree of acetylation at the cellulosetri-acetate of the scope of 52.5～61.5 quality % at the cellulose acetate of the scope of 50.0～62.5 quality %.By using average degree of acetylation at the cellulose acetate of this scope, can improve the anti-water vapour permeability of the blooming that is formed by the cellulose ester resin composition that obtains.In addition, average degree of acetylation is, take the quality of cellulose acetate as benchmark, and the mass ratio of the acetic acid that generates by this cellulose acetate that alkalizes.
The number-average molecular weight of above-mentioned cellulose ester resin (B) is preferred 30,000～300,000, is more preferably 50,000～200,000.By using number-average molecular weight at the cellulose acetate of this scope, can improve the mechanical properties of gained film.
Cellulose ester resin composition of the present invention is preferably with respect to above-mentioned cellulose ester resin (B) 100 mass parts, contains the scope of above-mentioned ester cpds (A) 0.5～50 mass parts.And, more improve in the intermiscibility of above-mentioned cellulose ester resin (B) and above-mentioned ester cpds (A), anti-exudative situation, with respect to above-mentioned cellulose ester resin (B) 100 mass parts, be more preferably the scope that contains ester cpds (A) 1～40 mass parts.If use the cellulose ester resin composition that contains ester cpds (A) in this scope, can obtain the blooming of optical property, anti-water vapour permeability and the anti-exudative excellence under high temperature and humidity.
And cellulose ester resin composition of the present invention can add ester cpds (A) various additives in addition in not damaging scope of the present invention.
Can enumerate additives such as properties-correcting agent (comprising softening agent), UV light absorber, delayed-action activator, resin, matting agent, anti-deterioration agent (such as antioxidant, peroxide decomposer, free radical inhibitors, metal passivator, sour trapping agent etc.), dyestuff as above-mentioned various additives.And these additives add when also can dissolve, mixing above-mentioned cellulose ester resin (B) and above-mentioned ester cpds (A) in organic solvent in solution casting method described later in the lump.
Can enumerate phosphoric acid ester such as triphenylphosphate, tritolyl phosphate, cresyl diphenyl phosphate as above-mentioned properties-correcting agent (comprising softening agent); the phthalic esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, ethyl phthaloyl ethyl glycollate, butyl phthaloyl butyl glycolate, trimethylolpropane tris benzoic ether, pentaerythrite tetra-acetate, Tributyl O-acetylcitrate etc.
Can enumerate such as dihydroxy benaophenonel based compound, benzotriazole based compound, salicylate based compound, benzophenone cpd, cyanoacrylate based compound, nickel complexing salt based compound etc. as above-mentioned UV light absorber.With respect to above-mentioned cellulose ester resin (B) 100 mass parts, the scope of preferred 0.01～2 mass parts of the use level of this UV light absorber.
As above-mentioned delayed-action activator, so long as can make length of delay be the Rth value rise just without any restriction, such as enumerating liquid crystalline cpd, the Isosorbide-5-Nitrae-cyclohexanedicarboxyester ester compound such as 4-cyano group-4 '-pentylbiphenyl, having the compound of 1,3,5-triazines ring etc.With respect to above-mentioned cellulose ester resin (B) 100 mass parts, the scope of preferred 0.01～20 mass parts of the use level of this delayed-action activator, the particularly preferably scope of 1～10 mass parts.
Can enumerate such as vibrin (such as polyethylene terephthalate, polymethylmethacrylate etc.), polycarbonate resin, polyester ether resin, urethane resin, epoxy resin, tolylsulfonyl polyimide resin etc. as above-mentioned resin.
Can enumerate such as silicon oxide, titanium oxide, aluminum oxide, calcium carbonate, Calucium Silicate powder, pure aluminium silicate, Magnesium Silicate q-agent, calcium phosphate, kaolin, talcum etc. as above-mentioned matting agent.With respect to above-mentioned cellulose ester resin (B) 100 mass parts, the scope of preferred 0.1～0.3 mass parts of this matting agent.
As above-mentioned dyestuff, can use normally used known habitual dyestuff, its use level is as long as just be not particularly limited in the scope that does not hinder purpose of the present invention.
Contain the cellulose ester resin that is formed by ester cpds of the present invention (A) the cellulose ester resin composition of additive, can be used for film, further can be used for blooming.
Film of the present invention can be by being membranaceous the acquisition with above-mentioned cellulose ester resin composition molding.As forming method can enumerate such as by with above-mentioned cellulose ester resin composition with melting mixings such as forcing machines, and use T film etc. to be shaped to membranaceous method.
And, film of the present invention can also obtain by after in organic solvent, above-mentioned cellulose ester resin composition being dissolved equably, mixes, the resin solution that obtains curtain coating and dry solution casting method on the metal support being carried out moulding except above-mentioned forming method.In the situation that obtain film by solution casting method, because can suppress the orientation of the above-mentioned cellulose ester resin (B) in film in moulding process, so the film that obtains demonstrates in fact optical isotropy.The isotropic film of this display optical can as the parts of liquid-crystal display etc., be especially useful as polaroid protective film as blooming.And the film that obtains by this solution casting method because be difficult to form concavo-convex on its surface, has advantages of the surface smoothness excellence, so the melting casting method is the forming method of more desirable film.
The melting casting method comprises following operation: above-mentioned cellulose ester resin (B) and above-mentioned ester cpds (A) are dissolved in organic solvent, the resin solution that obtains is carried out the first operation of curtain coating on the metal support, the organic solvent that contains in the above-mentioned resin solution of dry curtain coating and form the second operation of film, and the film that forms on the metal support is peeled off and the 3rd operation of heat drying from the metal support.
As the metal support that uses in the first operation, can use the metal of band shape for no reason or rotating cylinder shape, for example stainless steel, its surface carried out bright finished metal support.In the above-mentioned resin solution of curtain coating, in order to sneak into foreign matter in the film that prevents from obtaining, the preferred use crossed the resin solution of filtration by strainer on above-mentioned metal support.
As the drying means in the second operation, have the wind that for example makes 30～50 ℃ of temperature ranges cross the top of above-mentioned metal support and below, evaporate approximately 50～80 quality % degree of the organic solvent that contains in the above-mentioned resin solution of curtain coating, form the method for film at above-mentioned metal support.
The 3rd operation is that the film that forms in above-mentioned the second operation is peeled off from the metal support, carries out the operation of heat drying in the temperature higher than above-mentioned the second operation.As above-mentioned heating and drying method, so for example make method that temperature rises because can make dimensional stability better preferred the temperature range of 100～160 ℃ interimly.By heat drying in the said temperature scope, almost can remove remaining organic solvent in the film that obtains in above-mentioned the second operation fully.
As the strength of solution of the cellulose ester resin composition in above-mentioned resin solution, the scope of preferred 3～50 quality % is more preferably the scope of 5～40 quality %.
As above-mentioned organic solvent, so long as can dissolving cellulos ester resin (B) and the organic solvent of above-mentioned ester cpds (A) just there is no particular limitation, for example use in the situation of cellulose acetate as cellulose ester resin (B), as the good solvent of cellulose acetate, can use such as Organohalogen compounds or dioxolane classes such as methylene dichloride.And, for this good solvent, because also can improve the production efficiency of film with lean solvents such as methyl alcohol, ethanol, 2-propyl alcohol, propyl carbinol, hexanaphthene, pimelinketone, so preferred.Mix the mass ratio in the situation of using good solvent and lean solvent, the scope of preferred good solvent/lean solvent=75/25～95/5 (quality %).
The scope of preferred 10～1, the 000 μ m of the film thickness of film of the present invention is more preferably the scope of 20～500 μ m, further the scope of preferred 30～200 μ m.And, in the situation of film of the present invention as the blooming use, the scope of preferred 10～150 μ m of this film thickness.In the situation that use as polaroid protective film in blooming; if this film thickness is in the scope of 25～100 μ m; just can seek the slimming of liquid crystal indicator, and can keep excellent film toughness, according to dimensional stability and the anti-water vapour permeability of damp and hot variation.In addition, claim sometimes in the present invention that anti-exudative and dimensional stability is weather resistance.
And blooming of the present invention can also needing be used for the polaroid protective film of optical compensation function.This polaroid protective film is according to TN (Twisted Nematic; twisted-nematic), VA (Vertically Aligned; vertical orientated), the liquid-crystal display mode such as OCB (Optically Compensatory Bend, optical compensation curved) requires the anisotropy of specified range.
Blooming of the present invention preferably has the above Rth value of 100nm, and because can derive from the phase differential of liquid crystal material by effective compensation, so be more preferably the Rth value of the scope with 100～500nm.
In order to obtain to have the optically anisotropic polaroid protective film of expectation, can realize with the cooperation ratio of additive etc. by adjusting the cellulose ester resin that formed by above-mentioned ester cpds of the present invention (A).Cellulose ester resin additive of the present invention particularly, because even a small amount of interpolation also can obtain high Rth value, so in the liquid crystal device of the liquid-crystal display modes such as the VA, the OCB that adopt the higher Rth value of requirement and TN, also can keep the Rth value of adjusting the prestige that expires under anti-exudative condition.
Why blooming of the present invention manifests excellent optical property, and its reason is considered to chemical structure and the molecular interaction thereof of above-mentioned ester cpds (A) and has made contribution.Particularly, be presumably because the cellulose ester resin that is comprised of ester cpds of the present invention (A) has the higher structure of planarity with raw material dibasic alcohol (a1) and the aromatic dicarboxylic acid compound (a2) of additive, and the effect by the aromatic dicarboxylic acid compound (a2) in ester cpds is at the intermolecular pi-pi bond that formed of polyester, so electron density is high.This planarity is high, electron-dense ester cpds (A) is seen as in the situation of indicatrix, infer because ester cpds (A) forms the high structure of anisotropy in cellulose ester resin (B), so have excellent optical property.
and, when and spent glycol (a1-1) and 1,2-propylene glycol (a1-2) is as in the situation of the cellulose ester resin that is comprised of ester cpds of the present invention (A) with the raw material dibasic alcohol (a1) of additive, think 1,2-propylene glycol (a1-2) can be to the intermiscibility of ester cpds (A) and cellulose ester resin (B), and the raising of the solvent solubility when making film is favourable, think that on the other hand the distance between C-C is short, and the ethylene glycol (a1-1) with high rectilinearity structure can be to optical anisotropy, namely, the raising of Rth value is favourable.Thereby, can infer by and spent glycol (a1-1) and 1,2-PD (a1-2), can have concurrently and improve with the intermiscibility of cellulose ester resin (B) or the solvent solubility when making film, and the effect of the optical property of performance excellence.
Water Vapour Permeability to blooming of the present invention describes.If the film thickness of blooming of the present invention is 80 μ m, the water vapour permeability of the film of cellulose ester resin (B) is for example 800～900g/m 2The 24h degree preferably can obtain 600g/m by the film that the cellulose ester resin composition forms 2The Water Vapour Permeability that 24h is following is more preferably and obtains 100～600g/m 2The Water Vapour Permeability of 24h scope.If in this scope, even being thinned to 20～60 μ m degree, the thickness of the blooming of gained also can have excellent anti-Water Vapour Permeability.
Film of the present invention, due to optical property not only, and anti-water vapour permeability, the transparency, non-volatility, anti-exudative etc. also excellent under high temperature and humidity, so can be used for such as the blooming of liquid crystal indicator or the support of silver halide photographic sensitive material etc.Here, above-mentioned blooming can be enumerated such as polaroid protective film, phase retardation film, reflector, visual angle expanded film, antiglare film, non reflecting film, electrostatic prevention film, colored filter etc.In these bloomings, have the film of characteristic and the high Rth value of excellence as above, can be used as the polaroid protective film with viewing angle compensation function and use.
Embodiment
The below enumerates embodiment and comparative example, illustrates the present invention.
The manufacturing of embodiment 1 ester cpds (A-1)
Be add 1,2-PD (hereinafter referred to as " PG ") 392g and dimethyl terephthalate (DMT) (hereinafter referred to as " DMT ") 800g in the four-hole boiling flask of 3 liters and heat up to the internal capacity that possesses thermometer, agitator and reflux cooler.Will be as the titanium isopropylate of esterifying catalyst when the temperature in flask reaches 130 ℃, add 60ppm with respect to the total amount of PG and DMT, under stream of nitrogen gas stir on one side and at 185 ℃ heat up in a steamer the methyl alcohol that generates on one side, reacted 15 hours.After reaction, decompression 2 hours under about 4000Pa when temperature reaches 190 ℃ in flask, obtaining thus number-average molecular weight is 400, weight-average molecular weight be 500 ester cpds (A-1) (acid number: 0.43, hydroxyl value: 86).
The manufacturing of embodiment 2 ester cpds (A-2)
Be to add PG 940g and DMT 1 in the four-hole boiling flask of 3 liters to the internal capacity that possesses thermometer, agitator and reflux cooler, 600g also heats up.Will be as the titanium isopropylate of esterifying catalyst when the temperature in flask reaches 130 ℃, add 60ppm with respect to the total amount of PG and DMT, under stream of nitrogen gas stir on one side and at 185 ℃ heat up in a steamer the methyl alcohol that generates on one side, reacted 10 hours.After reaction, approximately reducing pressure 2 hours under 4000Pa when temperature reaches 190 ℃ in flask, further approximately reducing pressure 1 hour under 133Pa, having obtained number-average molecular weight is 1,000, and weight-average molecular weight is 1,750 ester cpds (A-2) (acid number: 0.18, hydroxyl value: 61).
The manufacturing of embodiment 3 ester cpds (A-3)
Be the four-hole boiling flask of 2 liters to internal capacity, be added in resulting ester cpds (A-2) 1 in embodiment 2,500g also heats up.Decompression 1.5 hours under about 133Pa when temperature reaches 190 ℃ in flask, having obtained number-average molecular weight is 2,200, weight-average molecular weight be 5,000 ester cpds (A-3) (acid number: 0.30, hydroxyl value: 25).
The manufacturing of embodiment 4 ester cpds (A-4)
Be the four-hole boiling flask of 1 liter to the internal capacity that possesses thermometer, agitator and reflux cooler, add PG 135g and NDA dimethyl ester (hereinafter referred to as " NDCM ") 300g and heat up.Will be as the titanium isopropylate of esterifying catalyst when the temperature in flask reaches 130 ℃, add 60ppm with respect to the total amount of PG and NDCM, under stream of nitrogen gas stir on one side and at 185 ℃ heat up in a steamer the methyl alcohol that generates on one side, reacted 15 hours.After reaction, when temperature reaches 190 ℃ in flask, approximately 18, under 000Pa, decompression is 1 hour, and having obtained number-average molecular weight is 400, weight-average molecular weight be 455 ester cpds (A-4) (acid number: 0.34, hydroxyl value: 65).
The manufacturing of embodiment 5 ester cpds (A-5)
It is the four-hole boiling flask of 3 liters to the internal capacity that possesses thermometer, agitator and reflux cooler, add the 2-methyl isophthalic acid, ammediol (hereinafter referred to as " 2-MPD ") 201g, BDO (hereinafter referred to as " Isosorbide-5-Nitrae-BD ") 201g and DMT 800g also heat up.Will be as the titanium isopropylate of esterifying catalyst when the temperature in flask reaches 130 ℃, with respect to 2-MPD, 1, the total amount of 4-BD and DMT adds 60ppm, under stream of nitrogen gas stir on one side and at 180 ℃ heat up in a steamer the methyl alcohol that generates on one side, reaction was carried out 15 hours.After reaction, decompression 2 hours under about 133Pa when temperature reaches 190 ℃ in flask, having obtained number-average molecular weight is 1,600, weight-average molecular weight be 3,600 ester cpds (A-5) (acid number: 0.62, hydroxyl value: 20).
The manufacturing of embodiment 6 ester cpds (A-6)
Be the reaction vessel that pressurizes of 5 liters to the internal capacity that possesses thermometer, agitator and reflux cooler, add PG 2,244g and terephthalic acid (hereinafter referred to as " TPA ") 3,500g also heats up.Will be as the titanium isopropylate of esterifying catalyst when the temperature in flask reaches 120 ℃, total amount with respect to PG and TPA adds 60ppm, pass into nitrogen on one side in reaction vessel, under 3.5MPa pressure heat up in a steamer the water that generates and rapidly be warming up to 250 ℃ on one side.Then, slowly open pressure, reacted 3 hours under normal pressure.After reaction, decompression 1 hour under about 133Pa when temperature reaches 190 ℃ in flask, having obtained number-average molecular weight is 740, weight-average molecular weight be 1,250 ester cpds (A-6) (acid number: 0.75, hydroxyl value: 70).
The manufacturing of embodiment 7 ester cpds (A-7)
Be the four-hole boiling flask of 3 liters to the internal capacity with thermometer, agitator, rectifying tower and reflux cooler, add ethylene glycol (hereinafter referred to as " EG ") 223g, PG 274g and DMT 1,048g also heats up.Will be as the titanium isopropylate of esterifying catalyst when the temperature in flask reaches 80 ℃, add 60ppm with respect to the total amount of EG, PG and DMT, under stream of nitrogen gas stir on one side, be warming up to 190 ℃ with the heat-up rate of 10 ℃/hour on one side.Carry out reaction in 7 hours when heating up in a steamer the methyl alcohol that generates.After reaction, when temperature reaches 190 ℃ in flask, approximately 18, under 000Pa, decompression is 2 hours, having obtained number-average molecular weight is 730, and weight-average molecular weight is 1,220 ester cpds (A-1) (acid number: 0.21, hydroxyl value: 145, weight loss on heating value: 0.15 quality %).Measure the result of NMR spectrum, mole ratio of components (a1-1)/(a1-2) of ethylene glycol (a1-1) and 1,2-PD (a1-2) be 51/49 (% by mole).
The manufacturing of embodiment 8 ester cpds (A-8)
Be the four-hole boiling flask of 3 liters to the internal capacity with thermometer, agitator, rectifying tower and reflux cooler, add EG 213g, PG 261g and DMT 1,000g also heats up.Will be as the titanium isopropylate of esterifying catalyst when the temperature in flask reaches 80 ℃, add 60ppm with respect to the total amount of EG, PG and DMT, under stream of nitrogen gas stir on one side, be warming up to 190 ℃ with the heat-up rate of 10 ℃/hour on one side.Carry out reaction in 9 hours when heating up in a steamer the methyl alcohol that generates.After reaction, when temperature reaches 190 ℃ in flask, approximately 18, under 000Pa, decompression is 2 hours, having obtained number-average molecular weight is 1,530, and weight-average molecular weight is 3,200 ester cpds (A-8) (acid number: 0.34, hydroxyl value: 90, weight loss on heating value: 0.08 quality %).Measure the result of NMR spectrum, mole ratio of components (a1-1)/(a1-2) of ethylene glycol (a1-1) and 1,2-PD (a1-2) be 53/47 (% by mole).
The manufacturing of embodiment 9 ester cpds (A-9)
Be the four-hole boiling flask of 3 liters to the internal capacity with thermometer, agitator, rectifying tower and reflux cooler, add EG 233g, PG 285g and DMT 1,165g also heats up.Will be as the titanium isopropylate of esterifying catalyst when the temperature in flask reaches 80 ℃, add 60ppm with respect to the total amount of EG, PG and DMT, under stream of nitrogen gas stir on one side, be warming up to 190 ℃ with the heat-up rate of 10 ℃/hour on one side.Heat up in a steamer the simultaneous reactions 15 hours of the methyl alcohol that generates.After reaction, when temperature reaches 190 ℃ in flask, approximately 18, under 000Pa, decompression is 2 hours, having obtained number-average molecular weight is 2,650, and weight-average molecular weight is 5,580 ester cpds (A-9) (acid number: 0.24, hydroxyl value: 59, weight loss on heating value: 0.03 quality %).Measure the result of NMR spectrum, mole ratio of components (a1-1)/(a1-2) of ethylene glycol (a1-1) and 1,2-PD (a1-2) be 52/48 (% by mole).
The manufacturing of embodiment 10 ester cpds (A-10)
Be the four-hole boiling flask of 3 liters to the internal capacity with thermometer, agitator, rectifying tower and reflux cooler, add EG 140g, PG 57g and DMT 874g and heat up.Will be as the titanium isopropylate of esterifying catalyst when the temperature in flask reaches 80 ℃, add 60ppm with respect to the total amount of EG, PG and DMT, under stream of nitrogen gas stir on one side, be warming up to 190 ℃ with the heat-up rate of 10 ℃/hour on one side.Heat up in a steamer the simultaneous reactions 10 hours of the methyl alcohol that generates.After reaction, when temperature reaches 190 ℃ in flask, approximately 18, under 000Pa, decompression is 2 hours, having obtained number-average molecular weight is 730, and weight-average molecular weight is 1,220 ester cpds (A-10) (acid number: 0.43, hydroxyl value: 121, weight loss on heating value: 0.22 quality %).Measure the result of NMR spectrum, mole ratio of components (a1-1)/(a1-2) of ethylene glycol (a1-1) and 1,2-PD (a1-2) be 78/22 (% by mole).
The manufacturing of embodiment 11 ester cpds (A-11)
Be the four-hole boiling flask of 3 liters to the internal capacity with thermometer, agitator, rectifying tower and reflux cooler, add EG 248g, PG 912g and DMT 1,243g also heats up.Will be as the titanium isopropylate of esterifying catalyst when the temperature in flask reaches 80 ℃, add 60ppm with respect to the total amount of EG, PG and DMT, under stream of nitrogen gas stir on one side, be warming up to 190 ℃ with the heat-up rate of 10 ℃/hour on one side.Heat up in a steamer the simultaneous reactions 10 hours of the methyl alcohol that generates.After reaction, when temperature reaches 190 ℃ in flask, approximately 18, under 000Pa, decompression is 2 hours, having obtained number-average molecular weight is 1,500, and weight-average molecular weight is 3,150 ester cpds (A-11) (acid number: 0.43, hydroxyl value: 121, weight loss on heating value: 0.22 quality %).Measure the result of NMR spectrum, mole ratio of components (a1-1)/(a1-2) of ethylene glycol (a1-1) and 1,2-PD (a1-2) be 21/79 (% by mole).
The manufacturing of embodiment 12 ester cpds (A-12)
Be the autoclave of 1 liter to the internal capacity with thermometer, agitator, rectifying tower and reflux cooler, pressurization variable valve, add EG 158g, PG 194g and TPA498g and heat up.When reaching 80 ℃, the temperature in flask will add 60ppm with respect to the total amount of EG, PG and TPA as the titanium isopropylate of esterifying catalyst, under the pressurized state of 3.5MPa, stir under the nitrogen of circulation on one side, with the heat-up rate of 100 ℃/hour be warming up to 250 ℃ on one side.Heat up in a steamer the simultaneous reactions 3 hours of the water that generates.After reaction, slowly return to normal pressure, when temperature reaches 190 ℃ in flask approximately 18, under 000Pa, decompression is 2 hours, and having obtained number-average molecular weight is 1,250, weight-average molecular weight is 2,400 ester cpds (A-12) (acid number: 0.20, hydroxyl value: 83, weight loss on heating value: 0.18 quality %).Measure the result of NMR spectrum, mole ratio of components (a1-1)/(a1-2) of ethylene glycol (a1-1) and 1,2-PD (a1-2) be 42/58 (% by mole).
The manufacturing of embodiment 13 ester cpds (A-13)
Be the four-hole boiling flask of 2 liters to the internal capacity with thermometer, agitator and reflux cooler, add EG 155g, PG 190g and NDCM 610g and heat up.When reaching 80 ℃, the temperature in flask will add 60ppm with respect to the total amount of EG, PG and NDCM as the titanium isopropylate of esterifying catalyst, under stream of nitrogen gas stir on one side, be warming up to 190 ℃ with the heat-up rate of 10 ℃/hour on one side.Heat up in a steamer the simultaneous reactions 10 hours of the methyl alcohol that generates.After reaction, when temperature reaches 190 ℃ in flask, approximately 18, under 000Pa, decompression is 2 hours, having obtained number-average molecular weight is 360, weight-average molecular weight be 390 ester cpds (A-13) (acid number: 0.43, hydroxyl value: 118, weight loss on heating value: 0.34 quality %).Measure the result of NMR spectrum, mole ratio of components (a1-1)/(a1-2) of ethylene glycol (a1-1) and 1,2-PD (a1-2) be 50/50 (% by mole).
The manufacturing of comparative example 1 ester cpds (A-14)
Be the four-hole boiling flask of 1 liter to internal capacity, be added in ester cpds (A-3) 700g that obtains in embodiment 3 and heat up.Decompression 2 hours under about 133Pa when the temperature in flask reaches 190 ℃, having obtained number-average molecular weight is 3,300, weight-average molecular weight be 9,600 ester cpds (A-14) (acid number: 0.45, hydroxyl value: 15).
The manufacturing of comparative example 2 ester cpds (A-15)
Be the four-hole boiling flask of 2 liters to the internal capacity with thermometer, agitator, rectifying tower and reflux cooler, add EG 186g, PG 228g and DMT 970g and heat up.When reaching 80 ℃, the temperature in flask will add 60ppm with respect to the total amount of EG, PG and DMT as the titanium isopropylate of esterifying catalyst, under stream of nitrogen gas stir on one side, be warming up to 190 ℃ with the heat-up rate of 10 ℃/hour on one side.Heat up in a steamer the simultaneous reactions 10 hours of the methyl alcohol that generates.After reaction, when temperature reaches 190 ℃ in flask, approximately 18, under 000Pa, decompression is 3 hours, having obtained number-average molecular weight is 3,150, and weight-average molecular weight is 8,200 ester cpds (A-15) (acid number: 0.65, hydroxyl value: 15, weight loss on heating value: 0.08 quality %).Measure the result of NMR spectrum, mole ratio of components (a1-1)/(a1-2) of ethylene glycol (a1-1) and 1,2-PD (a1-2) be 51/49 (% by mole).
The manufacturing of comparative example 3 ester cpds (A-16)
Be the four-hole boiling flask of 3 liters to the internal capacity that possesses thermometer, agitator and reflux cooler, add PG 468g, DMT 524g and M-nitro benzoic acid (hereinafter referred to as " BzA ") 733g and heat up.When reaching 130 ℃, the temperature in flask will add 60ppm with respect to the total amount of PG, DMT and BzA as the titanium isopropylate of esterifying catalyst, stir under stream of nitrogen gas on one side, from 170 ℃ heat-up rates with 10 ℃/hour be warmed up to 220 ℃ one side and heat up in a steamer the water, the methyl alcohol that generate on one side.React after 10 hours, decompression 4 hours under about 133Pa when temperature reaches 190 ℃ in flask, having obtained number-average molecular weight is 450, weight-average molecular weight be 800 ester cpds (A-16) (acid number: 0.32, hydroxyl value: 7).
The manufacturing of comparative example 4 ester cpds (A-17)
Be the four-hole boiling flask of 3 liters to the internal capacity that possesses thermometer, agitator and reflux cooler, add EG 670g and hexanodioic acid (hereinafter referred to as " AA ") 1461g and heat up.Will be as the titanium isopropylate of esterifying catalyst when the temperature in flask reaches 70 ℃, total amount with respect to EG and AA adds 60ppm, stir under stream of nitrogen gas on one side, from 150 ℃ heat-up rates with 15 ℃/hour be warmed up to 220 ℃ one side and heat up in a steamer the water that generates on one side.React after 7 hours, decompression 3 hours under about 1330Pa when temperature reaches 195 ℃ in flask, having obtained number-average molecular weight is 1,000, weight-average molecular weight be 1,850 ester cpds (A-17) (acid number: 0.55, hydroxyl value: 113).
The manufacturing of comparative example 5 ester cpds (A-18)
Be the four-hole boiling flask of 3 liters to the internal capacity that possesses thermometer, agitator and reflux cooler, add 1,3 butylene glycol (hereinafter referred to as " 1,3-BD ") 670g and Tetra hydro Phthalic anhydride (hereinafter referred to as " PA ") 1461g and heat up.Will be as the titanium isopropylate of esterifying catalyst when the temperature in flask reaches 70 ℃, with respect to 1, the total amount of 3-BD and PA adds 60ppm, under stream of nitrogen gas stir, be warmed up to 220 ℃ of one side from 150 ℃ of heat-up rates with 15 ℃/hour and heat up in a steamer the water that generates and meanwhile.React after 7 hours, decompression 3 hours under about 1330Pa when temperature reaches 195 ℃ in flask, having obtained number-average molecular weight is 710, weight-average molecular weight be 1,350 ester cpds (A-18) (acid number: 0.55, hydroxyl value: 123).
Measure number-average molecular weight (Mn), weight-average molecular weight (Mw), acid number, hydroxyl value and the weight loss on heating value of the ester cpds (A-1)～(A-18) that obtains in the above embodiments 1～13 and comparative example 1～5 by following method.In addition, hydroxyl value is to measure according to the standard of JIS K 0070-1992.
The measuring method of the number-average molecular weight of ester cpds (Mn) and weight-average molecular weight (Mw)
Use gel permeation chromatography (GPC) determinator (TOSOH Co., Ltd's system " HLC-8330 "), under following condition determination, measure number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polystyrene standard conversion of ester cpds.
Post: " TSK gel SuperHZM-M " * 2 and
" TSK ge1 SuperHZ-2000 " * 2
Guard column: " TSK SuperH-H "
Developing solvent: tetrahydrofuran (THF)
Flow velocity: 0.35mL/ minute
The measuring method of mole ratio of components (a-1)/(a-2) of ethylene glycol (a-1) and 1,2-PD (a-2)
Use 1The H-NMR device (Jeol Ltd., JNM-LA300), by analyzing chloroform-d (CDCl of ester cpds 3) solution, calculate mole ratio of components (a-1)/(a-2) (unit: % by mole) of ethylene glycol (a-1) unit in the material that forms above-mentioned ester cpds and 1,2-PD (a-2) unit.
The condition determination of weight loss on heating
(Toyo Co., Ltd.'s essence mechanism is made " SB-P " model, internal capacity 45 * 45 * 50cm of manufacturing at the gear aging tester 3) in add the approximately ester cpds of 50g, under nitrogen atmosphere, with 140 ℃ of heating quality measurement after 60 minutes, measure the weight loss on heating value according to the rate of mass reduction before and after heating.Here, be used in the situation of polaroid protective film, especially excellent as long as the weight loss on heating value of ester cpds probably just can be said volatility below 0.5 quality %.
The characteristic value of the ester cpds (A-1)～(A-18) of acquisition in the above embodiments 1～13 and comparative example 1～5 is illustrated in table 1～3.
The evaluation that is formed by the cellulose ester resin composition is with the making of film
With ester cpds (A-1)～(A-18) 1g and cellulosetri-acetate (the degree of acetylation 61 quality % that obtain in the above embodiments 1～13 and comparative example 1～5; the polymerization degree 265) 10g; mix with the mixed solvent that is formed by methylene dichloride 81g and methyl alcohol 9g and stir equably, modulation rubber cement liquid.These each rubber cement liquid are distinguished curtain coating into about the thickness of 1mm on sheet glass, after at room temperature dry 16 hours, 50 ℃ of dryings 30 minutes, further 120 ℃ of dryings 30 minutes, obtained film thickness approximately the evaluation of 80 μ m with film (F-1)～(F-18).
And, as a comparative example 6, replace above-mentioned ester cpds, use triphenylphosphate (hereinafter referred to as " the TPP ") 1g to carry out same operation, obtained film thickness approximately the evaluation of 80 μ m with film (F-19).Further, as a comparative example 7, only carry out same operation with cellulosetri-acetate, obtained film thickness approximately the evaluation of 80 μ m with film (F-20).
The anti-exudative evaluation method of film
The above-mentioned film that obtains is cut into the size of 30mm * 40mm, placed 120 hours in the fixed temperature and humidity of 85 ℃ of temperature, relative humidity 90%.Then, whether the surface of the above-mentioned film of visual observation is oozed out according to following standard evaluation ester cpds etc.
A: do not observe exudate on the surface of film.
B: observed exudate on the surface of film.
Do not observe the excellent in te pins of durability of the film of exudate etc., in situation about particularly using as polaroid protective film, can be described as the film of the damp and hot excellent in te pins of durability of polaroid protective film.
In addition, use the film after above-mentioned film carries out anti-exudative test evaluation, take the intermiscibility of judgement cellulose ester resin and ester cpds as purpose, the transparency for above-mentioned film, use turbidimeter (Japanese electric look Industrial Co., Ltd make " ND-1001DP " model), according to the standard of JIS K 7105, measure the mist value of film.In addition, be used in the situation of polaroid protective film, preferred below 1% from practicality mist value, be more preferably below 0.5% from practicality.
The measuring method of the length of delay of the thickness direction of film (Rth value)
Use automatic double refraction meter (prince's instrumentation machine Co., Ltd.'s system " KOBRA-WR "), measure the length of delay (Rth value) of the thickness direction of above-mentioned film.Condition determination is after damping under the environment of 23 ℃ of temperature, relative humidity 20% is more than 12 hours, measures under equivalent environment.The Rth value of above-mentioned film is although according to purposes and difference, as long as probably more than 130nm, use with regard to can be used as the polaroid protective film with optical compensation function.
The measuring method of the Water Vapour Permeability of film
According to the method that JIS Z 0208 puts down in writing, measure the Water Vapour Permeability of above-mentioned film, and be converted into the thickness of 80 μ m.Condition determination is 25 ℃ of temperature, relative humidity 90%.The Water Vapour Permeability of the film that is only formed by the cellulosetri-acetate that uses in the present embodiment in addition, is 800g/m 224h degree (with reference to the comparative example 9 in table 2) is so as long as coordinated cellulose ester resin of the present invention below value, just can say as polaroid protective film to have excellent anti-water vapour permeability at this with the Water Vapour Permeability of the film of additive.
Used in embodiment 1～13 cellulose ester resin of the present invention that obtains to be illustrated in table 1 and 2 with the evaluation result of the film (F-1)～(F-13) of additive.And, the film (F-14)～(F-18) of the ester cpds that obtains in comparative example 1～5, the film (F-19 that the replacement ester cpds has used TPP will have been used, comparative example 6) and what all do not have the evaluation result of the film (F-20, comparative example 7) that coordinates to be illustrated in table 3.
Table 1
Figure G2009102224519D0000241
Table 2
Figure G2009102224519D0000251
Table 3
Figure G2009102224519D0000252
From table 1 and 2 the expression results as can be known, cellulose ester resin of the present invention additive ester cpds, the weight loss on heating value is 0.03～0.45 quality %, and is very low.And used as can be known cellulose ester resin of the present invention with the anti-exudative and anti-excellent moisture permeability of the film (F-1)～(F-13) of additive, also can keep high transparent even preserve under hot and humid environment.Further the Rth value of film is 115～291nm as can be known, is very high value, and is exceedingly useful as blooming.
And, by the following content as can be known of the result shown in table 3.
Comparative example 1 and 2 is to use over the example of cellulose ester resin of the present invention with the ester cpds of the upper limit 3,000 of the number-average molecular weight of additive ester cpds.Coordinate the film (F-14) of this ester cpds and (F-15), because the non-constant of the intermiscibility of cellulose ester resin and ester cpds, thus there is the problem that film can gonorrhoea, and anti-exudative also bad.In addition, the mist value of film (F-14), film (F-14) and Rth (F-15) can not measure because of the gonorrhoea of film.And, because can not measure these values, so do not measure Water Vapour Permeability.
Comparative example 3 is as the raw material of cellulose ester resin of the present invention with the additive ester cpds, also to use aromatic series monocarboxylic acid M-nitro benzoic acid terminal hydroxyl to be carried out the example of end-blocking except the aromatic dicarboxylic acid compound.The film (F-16) that coordinates this ester cpds although anti-exudative and anti-Water Vapour Permeability is good, is not seen the raising of Rth value.
Comparative example 4 is that as the raw material of cellulose ester resin of the present invention with the additive ester cpds, the aromatic dicarboxylic acid compound that uses in replacement the present invention uses the example of the ester cpds of aliphatic dicarboxylic acid.The film (F-17) that has coordinated this ester cpds although anti-exudative and anti-Water Vapour Permeability is good, is not seen the raising of Rth value.
Comparative example 5 is, as the raw material of cellulose ester resin of the present invention with the additive ester cpds, uses the example of the ester cpds of the aromatic dicarboxylic acid different from the aromatic dicarboxylic acid compound stipulated in the present invention.The film (F-18) that coordinates this ester cpds although anti-exudative and anti-Water Vapour Permeability is good, is not seen the raising of Rth value.
Comparative example 6 is to replace cellulose ester resin of the present invention to use the example of TPP with the additive ester cpds.The film (F-19) that has coordinated as can be known this TPP, TPP also is exuded to the problem on film surface in a large number even exist at room temperature.And do not see the raising of the Rth value of film.
Comparative example 7 is not coordinate the evaluation Example of the film (F-20) of any ester cpds etc.Although this is excellent by the film transparency that cellulose ester resin forms, the Rth value is very low.

Claims (4)

1. cellulose ester resin additive, it is characterized in that, by the number-average molecular weight of dibasic alcohol and aromatic dicarboxylic acid compound being carried out esterification and obtaining 300～3, the ester cpds of 000 scope forms, described aromatic dicarboxylic acid compound is from by terephthalic acid, dimethyl terephthalate ester, naphthalic acid, the naphthalic acid dialkyl, more than a kind of selection in the group that diphenyl dicarboxylic acid and diphenyl dicarboxylic acid dialkyl form, the hydroxyl value of described ester cpds is in 1～150 scope, described dibasic alcohol is ethylene glycol and 1, the 2-propylene glycol, described ethylene glycol and 1, mole ratio of components of 2-propylene glycol is in 85/15～10/90 scope.
2. a cellulose ester resin composition, is characterized in that, with respect to cellulose ester resin 100 mass parts, contains ester cpds 0.5～50 mass parts claimed in claim 1.
3. a film, is characterized in that, formed by cellulose ester resin composition claimed in claim 2.
4. a blooming, is characterized in that, formed by cellulose ester resin composition claimed in claim 2.
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