CN102483481A - Method of manufacturing optical film, optical film, deflection plate, and liquid crystal display device - Google Patents

Abstract

Disclosed is a method of manufacturing an optical film wherein a failure due to foreign matters, a black band while the film is rolled, and blocking never occur in the surface of the film, eliminating wrinkles and flaws. The method of manufacturing the optical film comprises a process of clamping a member comprising a plurality of projections onto both side edge sections of the long film in the width direction, thereby knurling the side edge sections by irregularity, and a process of taking up the film. In the process of knurling, the height of projecting portions formed by a film member clamped away by the projections when the projections are clamped onto the surface of the film is restricted by a flat portion configuring the base of the projections, so that the height of the projecting portions is determined height.

Description

The manufacturing approach of blooming, blooming, polaroid and liquid crystal indicator

Technical field

The present invention relates to manufacturing approach, blooming, polaroid and the liquid crystal indicator of blooming.

Background technology

In recent years, except that CRT, developed various display device such as LCD TV, plasma display (PDP), OLED display, their screen size maximizes.Follow giant-screenization and high image qualityization, the blooming that is used for display device is large tracts of landization also, and the requirement to film uniformity also improves in addition.As such blooming, for example have in the polaroid of liquid crystal indicator, use be used to polaroid protective film of protecting by polarizer etc.

Blooming as such display device is used particularly owing to nearest giant-screenization, needs the wide film that width 1000mm is above and then 1400mm is above.In addition, for the raising of throughput rate, the lightweight of device, the thin blooming about expectation high-speed production thickness 40 μ m.

But, broaden at the width of blooming as mentioned above, in addition, the thickness attenuation has been accelerated under the situation of speed of production simultaneously, in the stage of batching blooming, is easy to generate the flanging (the volume I is formed ま り) of roller, the distortion of film.The distortion of inhomogeneous, the film of the flanging of roller is identified in the form with the band of black (below, be called black-tape (Block ラ Star Network バ Application De)) on the circumference of roller.In addition, the flanging of roller also causes each other driving fit of film surface (below, be called obstruction) easily.The blooming that from the roller that has produced black-tape, obstruction, stretches out produces gauffer, damage etc., can not be applicable to display device, causes the reduction of yield.

For such problem, for the distortion of having batched the film under the state at blooming since preventing in the past, motion have be provided with in the Width both sides of film be called as annular knurl or embossing compare bulky part (being also referred to as knurled portions) with face.

For example, in patent documentation 1, motion has following method: make the front end of tooth be shaped as 90～130 ° dandy roll, to the extruding of the surface of film end, make the thickness volume earth deformation of film end carry out annular knurl processing.

The prior art document

Patent documentation

Patent documentation 1: the spy opens flat 11-262950 communique

Summary of the invention

The problem that invention will solve

But; Known: even use the method for patent documentation 1 to carry out annular knurl processing; Make under the velocity ratio of the batching blooming situation fast, making the batching under the longer situation of length of blooming, can not fully suppress to be rolled into black-tape under the state of roller shape, block such problem with contact.The inventor etc. concentrate on studies to these problems, and the result distinguishes, when accelerating coiling speed or increase and batch length, and the flanging grow, in the method for patent documentation 1, volume becomes big protuberance and when coiling into the roller shape, is damaged by pressure through annular knurl processing.Use Fig. 9 (a) and (b), (c), (d), describe for making the height volume of film end become big method and problem points thereof to the extruding of film surface dandy roll.Fig. 9 (a) is for implementing the skeleton diagram of the state of annular knurl processing through dandy roll 102 and the backing roll 103 that has an even surface in the end of blooming 101.Fig. 9 (b) shows the tooth 104 of dandy roll 102, for having four jiaos of section shapes of hammering the tooth of shapes into shape of smooth front end.The figure that Fig. 9 (c) has amplified for section with the film after the annular knurl processing.When the tooth 104 of the surface of film 101 extruding dandy roll 102, the membrane material of being pushed open through the tooth 104 of dandy roll 102 is pushed into the peripheral part of tooth 104, on the surface of film 101, around recess 107 and recess 107, is formed with protuberance (protrusion) 106.When the film 101 that will have such protuberance (protrusion) 106 was rolled into the roller shape, because the weight of flanging, film, shown in Fig. 9 (d), protuberance (protrusion) 106 did not tolerate its load, was damaged by pressure, the reason of become and cause black-tape, blocking such problem.Therefore, the shape of the jog that the inventor is conceived to be difficult for damaging by pressure has been accomplished the present invention.

Therefore; The object of the present invention is to provide the impurity fault that does not produce the film surface, black-tape, the obstruction under the roller shape; Blooming and the manufacturing approach thereof of non-wrinkled, damage, in addition is to provide the polaroid that has used this blooming and used the liquid crystal indicator of this polaroid.

Be used to solve the means of problem

In order to solve above-mentioned problem, the present invention has following characteristic.

1. blooming, a plurality of protuberances that formed with recess with around recess are a pair of concavo-convex blooming for the both side ends at the Width of the film of strip has formed for it,

It is characterized in that above-mentioned a pair of concavo-convex raised part is sentenced when cutting off with the surperficial parallel plane of above-mentioned film in 1/2 of the average height on the surface of the above-mentioned film of distance of this protuberance, and the sectional area S of each raised part is 2500～10000 μ m ², the mean breadth W of raised part is 3～20 μ m.

2. above-mentioned 1 described blooming is characterized in that, above-mentioned a pair of concavo-convex in, above-mentioned sectional area S μ m ²With the ratio S/H of the average height H μ m on the surface of the above-mentioned film of distance of raised part be 100～3000.

3. above-mentioned 1 or 2 described bloomings is characterized in that, above-mentioned a pair of concavo-convex in,

Above-mentioned sectional area S μ m ²With the ratio S/Y of the breadth extreme Y μ m of above-mentioned recess be 10～300.

4. the described blooming of each of above-mentioned 1～3 is characterized in that, in the both side ends of the Width of above-mentioned film with 10～300/cm ²Form above-mentioned a pair of concavo-convex.

5. the manufacturing approach of a blooming is characterized in that, have both side ends extruding at the Width of the film of strip and have the parts of a plurality of juts and give by the operation of the annular knurl of concavo-convex generation and the operation of batching above-mentioned film,

In making above-mentioned 1～4 each the method for blooming,

Above-mentioned operation of giving annular knurl; With above-mentioned jut during to the extruding of the surface of above-mentioned film; Limit with the par of the base portion that constitutes above-mentioned jut height, make the height of the height of raised part for regulation to the protuberance that forms through the membrane element of having pushed open by above-mentioned jut.

6. a polaroid is characterized in that, in the surface configuration of polarizer each described blooming of above-mentioned 1～4.

7. a liquid crystal indicator is characterized in that, has disposed above-mentioned 6 described polaroids.

The effect of invention

According to the present invention, even the wide and film change of width can be provided blooming, do not produce black-tape, obstruction, the blooming and the manufacturing approach thereof of non-wrinkled, damage yet.In addition, high-quality polaroid that has used this blooming and the liquid crystal indicator that has used this polaroid can be provided.

Description of drawings

Fig. 1 is the synoptic diagram of expression blooming of the present invention.

Fig. 2 be illustrated in protuberance height H 1/2 sentence the sectional view that the plane has cut off protuberance.

Fig. 3 is the synoptic diagram of annular knurl manufacturing procedure.

Fig. 4 is the enlarged drawing of annular knurl manufacturing procedure in the past.

Fig. 5 is the enlarged drawing of other annular knurl manufacturing procedure in the past.

Fig. 6 schematically shows the process flow diagram of device of manufacturing approach that comes the blooming of embodiment of the present invention through solution casting system embrane method.

Fig. 7 schematically shows the process flow diagram of device of manufacturing approach that comes the blooming of embodiment of the present invention through fusion curtain coating system embrane method.

Fig. 8 is the sectional view of the shape of expression jut.

Fig. 9 is the figure that is pressed into the method that height volume that dandy roll makes the film end increases on the film surface that is used to explain as technology in the past.

Embodiment

Below, the best mode that is used for embodiment of the present invention is elaborated, but the invention is not restricted to this.

In the blooming of the present invention; The both side ends of Width that is implemented in the film of strip has formed a plurality of protuberances (protrusion) that formed with recess with around recess and has been a pair of concavo-convex annular knurl processing; With a pair of concavo-convex protuberance the sentencing when cutting off of this protuberance with the surperficial parallel plane of film apart from 1/2 of the average height on the surface of film, the sectional area S of each protuberance is 2500～10000 μ m ², the mean breadth W of protuberance is 3～20 μ m.

The planimetric map of Fig. 1 (a) expression blooming 1 of the present invention has the annular knurl processing part 12 that is made up of a plurality of concavo-convex (protuberance 13, recess 14) at the side end of the Width of blooming.

Fig. 1 (b) is illustrated in the sectional view that has cut off a pair of concavo-convex (13,14) in annular knurl processing part 12 a plurality of concavo-convex of formation, at the thickness direction of blooming 1.

Fig. 2 representes to have cut off the sectional view of the protuberance 13 of Fig. 1 at 1/2 place of the height H of protuberance 13 with the surperficial parallel plane (the A-A section of Fig. 1) of blooming 1.

In the blooming of the present invention, making the mean breadth W of the protuberance in this section part is that 3～20 μ m, sectional area S are 2500～10000 μ m ²Scope, even accelerate coiling speed thus or increase in addition to batch length, the following black-tape of the state that also can suppress to be rolled into the roller shape, the generation of obstruction can obtain fold, damage few blooming.At this, so-called mean breadth W measures width W 1, W2, W3, the W4 of central portion on each limit of section shape of the protuberance 13 of Fig. 2, with its mean value as mean breadth W.In addition, not under the such dimetric situation of Fig. 2 at section shape, almost uniformly-spaced to measure 4 places, calculate its mean value.

In addition, preferred above-mentioned sectional area S (μ m ²) and the ratio S/H apart from the average height H (μ m) on the surface of film of protuberance be 100～3000.Through making S/H is this scope, can further suppress to be rolled into the black-tape under the state of roller shape, the generation of obstruction, can obtain fold, damage blooming still less.So-called average height H apart from the film surface, with almost impartial interval measure at 10 places protuberance apart from the film surface height, get its mean value.

In addition, preferred above-mentioned sectional area S μ m ²With the breadth extreme Y μ m of recess (with reference to Fig. 2.) ratio S/Y be 10～300.Through making S/Y is this scope, can further suppress to be rolled into the black-tape under the state of roller shape, the generation of obstruction, can obtain fold and damage blooming still less.The breadth extreme Y of so-called recess, shown in the sectional view of Fig. 2, the part that leaves for width in the width of recess.

In addition, at the side end of the film of having implemented annular knurl processing, preferably with 10～300/cm ²Form a pair of concavo-convex.Through with 10～300/cm ²Form a pair of concavo-convexly, can further suppress to be rolled into the black-tape under the state of roller shape, the generation of obstruction, can obtain fold, damage blooming still less.

As the method for making blooming of the present invention; It is characterized in that; In giving the operation of annular knurl, push a plurality of juts on the surface of the side end of film and form a plurality of concavo-convex right, with jut when film pushes; Limit with the par of the base portion that constitutes jut height, make the height of the height of protuberance for regulation to the protuberance that forms through the membrane element of having pushed open by jut.

Fig. 3 (a) is the figure that schematically shows the annular knurl operation, and said annular knurl operation is through (being also referred to as the par on smooth surface 21 cylindraceous.) on have the dandy roll 61 of a plurality of juts 20 and with dandy roll 61 clamping bloomings 1 relatively the both ends of 62 pairs of bloomings 1 of backing roll of configuration carry out annular knurl processing.

Fig. 3 (b) is with on blooming, form the figure that concavo-convex formation portion has amplified through jut 20.Jut 20 forms the quadrangular pyramid shape that leading section 20a has smooth face.This jut 20 is squeezed in surface, the formation protuberance 13 of film 1.Use the top 13a of par 21 crush lobes 13 of the base portion that constitutes jut 20, height H 0 is restricted.Through limiting the height that obtains stipulating with the top 13a of the 21 pairs of protuberances 13 in par as stated, the membrane material of being pushed open by jut is thus expanded at Width when reaching certain height.Therefore, can stably form the height of protuberance 13, also can come stably to form simultaneously the value of width through maximum height limit.

Fig. 4, Fig. 5 represent not have as Fig. 3 to form with the par maximum height limit state of protuberance 13.As far as Fig. 4, Fig. 5, owing to do not limit the top 13a of protuberance 13, inequality appears in the height and the width of the protuberance that therefore forms easily.For example, as the width W 01 of the protuberance of protuberance attenuates or the convex form of the chevron that the width of narrowed width, the bottom of formation top 13a is big as Fig. 5 along the side of jut 31 Fig. 4.Therefore, the height that preferably as Fig. 3, limits protuberance is advisable.

As shown in Figure 3; The shape (front end face shape, bottom shape, height H 0 etc.) of the manufacturing approach of the blooming of the application of the invention, change jut 20 can stably form the width and the protuberance of height and the shape of recess that have in the regulation of scope of the present invention.

Promptly; Batch length even accelerate film coiling speed or increase; Also can stably form not the protuberance and the recess that can cause the shape of the regulation that protuberance damaged by pressure, therefore can suppress to have batched the obstruction under the roller state of film, the phenomenon of black-tape owing to the load that puts on top 13a.Its result can be reduced in the fold, the damage that produce on the film.

As the shape of jut, though use quadrangular pyramid that top 13a has a tabular surface as an example, also can be pyrometric cone, coniform, in addition, the top also can be for circular-arc.As long as structure for the membrane material that when being squeezed in jut on the film, with the par restriction of the base portion that constitutes jut, has been extruded.Can stably form the height with regulation and the protuberance of width through forming such structure.

Below, be described in detail for the present invention.

In the manufacturing approach of blooming of the present invention, relate to the annular knurl processing of the blooming through solution casting system embrane method or fusion curtain coating system embrane method made, at first, describe for the manufacturing approach of the blooming of the solution casting system of utilization embrane method.

In the manufacturing approach of the blooming of the solution casting system of utilization embrane method,, can use various resins as membrane material, but preferred cellulose ester wherein.

The cellulose esters of cellulose esters for having been replaced by acyl group etc. from cellulosic hydroxyl.For example, can enumerate cellulose acetate, cellulose triacetate, cellulose-acetate propionate, cellulose acetate-butyrate, the acylated cellulose of acetate propionic acid cellulose butyrate etc. has the cellulose acetate of aliphatic polyester graft side chain etc.Wherein, preferred cellulose acetate, cellulose-acetate propionate, have the cellulose acetate of aliphatic polyester graft side chain.As long as in the scope of not damaging effect of the present invention, then also can contain other substituting group.

As the example of cellulose triacetate, the degree of substitution of preferred acetyl group is more than 2.0 and below 3.0.Through making degree of substitution is this scope, can obtain good formability, and postpones (Ro) and thickness direction retardation (Rt) in the face that can obtain expecting.When the degree of substitution of acetyl group is lower than this scope, sometimes as the humidity resistance of phase retardation film, poor dimensional stability under particularly damp and hot; When degree of substitution is excessive, can not present necessary lag characteristic sometimes.

As the cellulose of the raw material of employed cellulose esters among the present invention, not special the qualification can not enumerated cotton linter, wood pulp, mestha etc.In addition, the cellulose esters that obtains thus can mix use with arbitrary proportion respectively.

Among the present invention, the number-average molecular weight of cellulose esters is when 60000～300000 scope, and the physical strength of the film that obtains is strong, and is preferred.Further preferred 70000～200000.The Mw/Mn of employed cellulose esters ratio is preferably 1.4～3.0 among the present invention, further is preferably 1.4～2.3.

The mean molecular weight of cellulose esters and molecular weight distribution can use high-speed liquid chromatography to measure, and therefore can use it to calculate number-average molecular weight (Mn), matter average molecular weight (Mw), calculate their ratio.

Condition determination is following.

Solvent: methylene chloride

Post: Shodex K806, K805, K803G (connecting 3 Showa Denko K. K's system posts uses)

Column temperature: 25 ℃

Sample solution concentration: 0.1 quality %

Detecting device: RI Model 504 (GL サ イ エ Application ス corporate system)

Pump: L6000 (Hitachi Ltd.'s system)

Flow: 1.0ml/ minute

Calibration curve: using and utilizing polystyrene standard STK s t andard polystyrene (eastern ソ one Co., Ltd.'s system) Mw is the calibration curve of 13 samples of 1,000,000 to 500.13 samples preferably almost uniformly-spaced use.

Total acyl substituted degree of cellulose esters can use 2.3～2.9, preferably can use 2.6～2.9.Total acyl substituted degree can be measured based on ASTM-D817-96.

In the present invention, can in cellulose esters, cooperate various adjuvants.

In manufacturing approach according to blooming of the present invention, preferred rubber cement (the De one プ) composition that contains cellulose esters and the adjuvant that reduces thickness direction retardation (Rt) that uses.

Among the present invention, reducing the thickness direction retardation (Rt) of blooming, is important in the meaning that the visual angle of the liquid crystal indicator that under the IPS pattern, turns round enlarges, and among the present invention, as the adjuvant that such reduction postpones, can enumerate following substances.

Generally speaking, the delay of blooming, with from the delay of cellulose esters and from the delay of adjuvant and appear.Therefore, what is called is used to reduce the adjuvant of the delay of cellulose esters, is meant the orientation of upsetting cellulose esters, self is difficult for the compound that orientation and/or the little adjuvant of polarizability anisotropy reduce thickness direction retardation (Rt) effectively.Therefore, as the adjuvant of the orientation that is used to upset cellulose esters, compare the aliphatic based compound with the aromatic series based compound.

At this,, for example can enumerate by the polyester shown in following general formula (1) or (2) as concrete delay depressant.

General formula (1) B ₁-(G-A-) mG-B ₁

General formula (2) B ₂-(G-A-) nG-B ₂

In the above-mentioned formula, B ₁Expression monocarboxylic acid composition, B ₂Expression monohydroxy alcohol composition, G representes glycol component, and A representes dicarboxylic acid component, and expression is synthetic by these materials.It is characterized in that B ₁, B ₂, G and A all do not contain aromatic rings.M, n represent repeat number.

As by B ₁Represented monocarboxylic acid composition, not special restriction can be used known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid etc.

As the example of preferred monocarboxylic acid, can enumerate following such material, but the present invention is not limited to this.

As fat family monocarboxylic acid, can preferably use the straight chain of carbon number 1～32 or have the fatty acid of side chain.Further preferred carbon number is 1～20, and preferred especially carbon number is 1～12.When containing acetate, therefore preferred with the compatibility increase of cellulose esters, also preferably acetate and other monocarboxylic acid mixing are used.

As preferred monocarboxylic acid, can enumerate the unsaturated fatty acid etc. of the saturated fatty acid, undecynic acid, oleic acid, sorbic acid, linoleic acid, leukotrienes, arachidonic acid etc. of formic acid, acetate, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, 2-methyl-cyclohexane carboxylic-acid, undecanoic acid, lauric acid, tridecylic acid, tetradecylic acid, pentadecanoic acid, hexadecylic acid, margaric acid, stearic acid, nonadecanoic acid, 20 acid, behenic acid, tetracosanoic acid, cerinic acid, carboceric acid, octacosanoic acid, triacontanoic acid, lacceroic acid etc.

As by B ₂The monohydroxy alcohol composition of expression, not special restriction can be used known alcohols.Can preferably use the straight chain of carbon number 1～32 for example or have the aliphatic saturated alcohols or the aliphatics unsaturated alcohol of side chain.Further preferred carbon number is 1～20, and preferred especially carbon number is 1～12.

As the glycol component of representing by G, can enumerate like following material, but the present invention is not limited to this.Can enumerate for example monoethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,2-butylene glycol, 1,3 butylene glycol, 1; 4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,5-pentanediol, diglycol, triethylene glycol, tetraethylene glycol etc.; Wherein, preferred monoethylene glycol, 1,2-propylene glycol, 1, ammediol, 1; 2-butylene glycol, 1,3 butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, diglycol, triethylene glycol; Further preferred use 1, ammediol, 1,4-butylene glycol, 1,6-hexanediol, diglycol.

As the dibasic acid of representing by A (dicarboxylic acid) composition; Aliphatic dibasic acid, ester ring type dibasic acid; For example as aliphatic dibasic acid; Use malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, heneicosane dicarboxylic acid, dodecanedicarboxylic acid etc., particularly as aliphatic carboxylic acid, use carbon number 4～12 carboxylic acid, be selected from least a kind carboxylic acid in these.That is, can make up the dibasic acid that uses more than 2 kinds.

Repeat number m, n in above-mentioned general formula (1) or (2) is preferably more than 1 and below 170.

The matter average molecular weight of polyester is preferably below 20000, further is preferably below 10000.Particularly the matter average molecular weight is 500～10000 polyester, and is good with the compatibility of cellulose esters, in the system film, can not cause evaporation, volatilization.

The polycondensation of polyester can be carried out through well-established law.Any means of the de-hydrogen halide of the methyl esters that for example can be through the direct reaction of above-mentioned dibasic acid and glycol, above-mentioned dibasic acid or their alkyl esters, for example dibasic acid and the polyesterification reaction of glycols or heat fusing condensation method that ester exchange reaction is carried out or these sour acid chlorides and glycol is prepared, and does not preferably utilize direct reaction but the matter average molecular weight is not very big polyester.At the high polyester of low-molecular-weight side distribution, very good with the compatibility of cellulose esters, after film forms, can obtain the also little and rich transparent cellulose ester membrane of moisture permeability.

The not special restriction of the control method of molecular weight can be used method in the past.For example, though according to the difference of polymerizing condition and difference, can control according to the amount of adding of these urmaterie through molecular end being carried out the method for end-blocking with monoacid or monohydroxy alcohol.At this moment, consider preferred monoacid from the stability of polymkeric substance.For example can enumerate acetate, propionic acid, butyric acid etc., but be chosen in do not distill in the polycondensation reaction remove to system and stop, material that removing of distillation easily when removing such monoacid to reaction system.Also can mix and use above material.In addition, under the situation of directly reaction, also can be utilized in and regulate the matter average molecular weight on opportunity that the amount of the water that distillation is removed in the reaction stops to react through mensuration.In addition, deflection appears in the glycol that can be through making adding or the molal quantity of dibasic acid regulates, and also can regulate through the control temperature of reaction.

By above-mentioned general formula (1) or (2) represented polyester, preferably contain 1～40 quality % with respect to cellulose esters.Especially preferably contain 5～15 quality %.

In the present invention, as reducing the adjuvant that postpones, can also enumerate following substances.

The rubber cement that uses in the manufacturing of blooming of the present invention mainly contains cellulose esters, as the polymkeric substance (polymkeric substance, acrylic acid series polymeric compounds that the ethylenically unsaturated monomer polymerization is obtained) and the organic solvent of the adjuvant that reduce to postpone.

In the present invention, in common polymerization, be difficult to control molecular weight as the polymkeric substance that reduces the adjuvant that postpones, hope with not making the excessive method of molecular weight use the method that makes molecular weight consistent as far as possible for synthetic.As this polymerization; Can enumerate the method for using the such peroxidic polymerization initiators of dicumyl peroxide, tert butyl hydroperoxide, than the method for the polymerization inhibitor that common polymerization is used the method for polymerization initiator more, except that polymerization initiator, uses the method for the chain-transferring agent of sulfhydryl compound, phenixin etc., except that polymerization initiator, used benzoquinones, dinitro benzene is such and then use and specially open compounds that 2000-128911 communique or special opens all that kind in the 2000-344823 communique perhaps and used the polymerization catalyst of this compound and organometallics to carry out the method etc. of bulk polymerization with a mercapto and secondary hydroxyl; The above any means of preferred in the present invention use, but the method for putting down in writing in preferred especially this communique.

Among the present invention,, enumerate following, but be not limited to this as the monomer of formation as the monomeric unit of the polymkeric substance of the adjuvant of useful reduction delay.

As the ethylenically unsaturated monomer unit that constitutes polymkeric substance; The adjuvant that said polymkeric substance postpones as the reduction that the ethylenically unsaturated monomer polymerization is obtained; At first; As vinyl esters, for example can enumerate vinyl acetate, propionate, vinyl butyrate, valeric acid vinyl acetate, pivalic acid vinyl acetate, vinyl caproate, capric acid vinyl acetate, vinyl laurate, tetradecylic acid vinyl acetate, hexadecylic acid vinyl acetate, stearic acid vinyl ester, cyclohexane-carboxylic acid vinyl acetate, sad vinyl acetate, metering system vinyl acetate, Vinyl crotonate, sorbic acid vinyl acetate, vinyl benzoate, cinnamic acid vinyl acetate etc.

Then; As acrylic ester, for example can enumerate methyl acrylate, ethyl acrylate, propyl acrylate (different, just), butyl acrylate (just, different, secondary, uncle), acrylic acid pentyl ester (just, different, the second month in a season), Hexyl 2-propenoate (just, different), acrylic acid heptyl ester (just, different), 2-ethyl hexyl acrylate (just, different), acrylic acid ester in the ninth of the ten Heavenly Stems (just, different), acrylic acid myristyl ester (just, different), cyclohexyl acrylate, acrylic acid-2-ethyl caproite, benzyl acrylate, phenylethyl, acrylic acid (6-caprolactone), acrylic acid (2-hydroxy methacrylate), acrylic acid (2-hydroxy propyl ester), acrylic acid (3-hydroxy propyl ester), acrylic acid (4-hydroxyl butyl ester), acrylic acid (2-hydroxyl butyl ester), acrylic acid-to hydroxymethyl phenyl ester, acrylic acid-to (2-hydroxyethyl) phenyl ester etc.; As methacrylate, can enumerate the aforesaid propylene acid esters is become the material that methacrylate forms.

And then, as unsaturated acid, for example can enumerate acrylic acid, methacrylic acid, maleic anhydride, crotonic acid, itaconic acid etc.

The polymkeric substance that is made up of above-mentioned monomer can be multipolymer, also can be homopolymer, the multipolymer of the homopolymer of preferred vinyl ester, the multipolymer of vinyl esters, vinyl esters and acrylic or methacrylic acid esters.

Among the present invention, so-called acrylic acid series polymeric compounds (abbreviating acrylic acid series polymeric compounds as) is meant the homopolymer or the multipolymer of the acrylic or methacrylic acid alkyl ester with the monomeric unit with aromatic rings or cyclohexyl.

As the acrylate monomer that does not have aromatic rings and cyclohexyl; For example can enumerate methyl acrylate, ethyl acrylate, propyl acrylate (different, just), butyl acrylate (just, different, secondary, uncle), acrylic acid pentyl ester (just, different, the second month in a season), Hexyl 2-propenoate (just, different), acrylic acid heptyl ester (just, different), 2-ethyl hexyl acrylate (just, different), acrylic acid ester in the ninth of the ten Heavenly Stems (just, different), acrylic acid myristyl ester (just, different), acrylic acid (2-Octyl Nitrite), acrylic acid (6-caprolactone), acrylic acid (2-hydroxy methacrylate), acrylic acid (2-hydroxy propyl ester), acrylic acid (3-hydroxy propyl ester), acrylic acid (4-hydroxyl butyl ester), acrylic acid (2-hydroxyl butyl ester), acrylic acid (2-methoxyl ethyl ester), acrylic acid (2-ethoxy ethyl ester) etc., or the aforesaid propylene acid esters has been become the material of methacrylate.

Acrylic acid series polymeric compounds is the homopolymer or the multipolymer of above-mentioned monomer, preferably has the above methacrylate monomer of 30 quality % unit, in addition, preferably has the above methyl methacrylate monomer of 40 quality % unit.The homopolymer of preferred especially methyl acrylate or methyl methacrylate.

Polymkeric substance, acrylic acid series polymeric compounds that above-mentioned ethylenically unsaturated monomer polymerization is obtained, all the compatibility with cellulose esters is excellent, does not have evaporation, volatilization; Throughput rate is excellent; Retention as protective film for polarizing plate is good, and moisture permeability is little, excellent in dimensional stability.

Among the present invention, under the situation of the acrylic or methacrylic acid ester monomer with hydroxyl, it is not homopolymer but the formation unit of multipolymer.At this moment, preferably in acrylic acid series polymeric compounds, contain the acrylic or methacrylic acid ester monomer unit that 2～20 quality % have hydroxyl.

In the manufacturing approach of blooming of the present invention, preferred composition of colloidal slurry contains cellulose esters and as the matter average molecular weight that reduces the adjuvant that postpones 500 or more and 3000 following acrylic acid series polymeric compounds.

In addition, in the manufacturing approach of blooming of the present invention, preferred composition of colloidal slurry contains cellulose esters and as the matter average molecular weight that reduces the adjuvant that postpones 5000 or more and 30000 following acrylic acid series polymeric compounds.

Among the present invention; The matter average molecular weight that needs only the polymkeric substance of the adjuvant that postpones as reduction is more than 500 and 3000 matter average molecular weights following, perhaps other polymkeric substance are more than 5000 and below 30000; Then good with the compatibility of cellulose esters, do not produce evaporation, volatilization in the system film.In addition, the transparency of the blooming behind the system film is excellent, and moisture permeability is also extremely low, shows excellent performance as protective film for polarizing plate.

Among the present invention,, also can preferably use the polymkeric substance that has hydroxyl at side chain as reducing the adjuvant that postpones.As monomeric unit with hydroxyl; Identical with above-mentioned monomer; But preferred acrylic or methacrylic acid esters; For example can enumerate acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxy propyl ester, acrylic acid 3-hydroxy propyl ester, acrylic acid 4-hydroxyl butyl ester, acrylic acid 2-hydroxyl butyl ester, acrylic acid-, be preferably 2-Hydroxy ethyl acrylate base and methacrylic acid-2-hydroxy methacrylate to hydroxymethyl phenyl ester, acrylic acid-become the material that methacrylic acid forms to (2-hydroxyethyl) phenyl ester or with these acrylic acid.Have the acrylic ester or the methacrylate monomers unit of hydroxyl in the polymkeric substance, contain 2～20 quality % in the preferred polymers, more preferably 2～10 quality %.

The polymkeric substance of above-mentioned that kind contains the material that the above-mentioned monomeric unit with hydroxyl of 2～20 quality % forms; Certainly not only compatibility, retention and excellent in dimensional stability, the moisture permeability with cellulose esters is little; And excellent especially with cementability as the polarizer of protective film for polarizing plate, have the effect that the permanance of polaroid improves.

In addition, among the present invention, preferably at least one the end at the main chain of above-mentioned polymkeric substance has hydroxyl.Make the method that has hydroxyl at the main chain end; So long as make the end of main chain have the just not special qualification of hydroxyl; Can obtain through following method: use the such radical polymerization initiator of azo two (2-hydroxyethyl butyric ester) with hydroxyl method, use the such chain-transferring agent of 2 mercapto ethanol with hydroxyl method, use the polymerization inhibitor with hydroxyl method, through the active ion polymerization make the method that has hydroxyl endways, use special open 2000-128911 communique or special open that kind all in the 2000-344823 communique the compound with a mercapto and secondary hydroxyl or and the method etc. of having used the polymerization catalyst of this compound and organometallics to carry out bulk polymerization, the method for putting down in writing in preferred especially this communique.The polymkeric substance of using the method relevant with this communique record to make, can preferably be used by commercially available as comprehensive ア Network ト Off ロ one シ リ one ズ that grinds chemical company's system.

The above-mentioned polymkeric substance that has hydroxyl endways and/or have the polymkeric substance of hydroxyl at side chain in the present invention, has the compatibility that significantly improves for the polymkeric substance of cellulose esters, the effect of the transparency.

Among the present invention; Adjuvant as useful reduction delay; Except above-mentioned points, ester compounds, the spy that for example can to enumerate special two glycerine of opening the record of 2000-63560 communique be polyvalent alcohol and fatty acid opens ester or ether compound, styrene oligomer that phosphate compound, spy that compound, the spy shown in the general formula (1) that tricresyl phosphate aliphatic alcohol ester compounds, spy that the spy opens the record of 2004-315613 communique open the record of 2005-41911 communique opens the record of 2004-315605 communique open the record of 2005-105139 communique, and the special polymkeric substance of opening the styrenic monomers that the 2005-105140 communique puts down in writing of sugar alcohol of the hexose of 2001-247717 communique record.

The content of additive that above-mentioned reduction postpones is that resin preferably contains 5～25 quality % with respect to cellulose esters.Be lower than 5 quality % if reduce the content of additive that postpones, then can not present the effect of the reduction delay of film, therefore not preferred.When the content of additive that reduce to postpone in addition surpasses 25 quality %, produces so-called ooze out etc., the stability in the film reduces, so not preferred.

In manufacturing approach according to blooming of the present invention; To be called good solvent for the organic solvent that above-mentioned cellulose derivative has a good solubility; In addition, will show in dissolving that main effect, the organic solvents that wherein use in a large number are called main (organic) solvent or main (organic) solvent.

Example as good solvent; Remove the ketone of acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone etc., tetrahydrofuran (THF), 1,4-diox, 1; 3-dioxolanes, 1; The ethers of 2-dimethoxy-ethane etc. outside the ester class of methyl formate, ethyl formate, methyl acetate, ethyl acetate, pentyl acetate, gamma-butyrolacton etc., can be enumerated methyl cellosolve, dimethyl-imidazolinone, dimethyl formamide, dimethyl acetamide, acetonitrile, dimethyl sulfoxide (DMSO), sulfolane, nitroethane, methylene chloride, methyl acetoacetate etc.; Preferred 1,3-dioxolanes, THF, methyl ethyl ketone, acetone, methyl acetate and methylene chloride.

In rubber cement, except that above-mentioned organic solvent, preferably contain the alcohol of the carbon number 1～4 of 1～40 quality %.These alcohol; With after the rubber cement curtain coating is on the metal support; The solvent start vaporizer, the ratio of alcohol becomes many, makes net (will be on metal support curtain coating the address of the later rubber cement film of the rubber cement of cellulose derivative be net) gelation thus; Net is toughened up, peel off the effect that becomes and be easy to that the gelation solvent uses or hour also have the dissolving of the cellulose derivative that promotes the chlorine-free organic solvent in their ratio as making from metal support.

As the alcohol of carbon number 1～4, can enumerate methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, sec-butyl alcohol, the tert-butyl alcohol, propylene glycol monomethyl ether.Wherein, also lower from excellent in stability, the boiling point of rubber cement, drying property is also good and consideration such as avirulence, preferred alcohol.These organic solvents do not have dissolubility with respect to cellulose derivative separately, are called poor solvent.

As the preferred macromolecular compound that will the satisfy such condition solvent that to be cellulose derivative dissolve with high concentration and most preferred solvent is methylene chloride: the ratio of ethanol is 95: 5～80: 20 a mixed solvent.Perhaps also can preferably use methyl acetate: 60: 40～95: 5 mixed solvent of ethanol.

In the film among the present invention, the anti-oxidant of the deterioration that also can contain plastifier, the particulate (matting agent) of giving the film flatness, the ultraviolet light absorber of giving the UVA function of giving film processing flexibility moisture resistance, prevents film etc.

As the plastifier that uses among the present invention; Not special the qualification; But in order not make film produce mist degree or not ooze out or volatilize from film, preferably have cellulose derivative, hydrolyzable polycondensation the reactive metal compound condensed polymer and can pass through interactional functional group such as hydrogen bond.

As such functional group; Hydroxyl, ether, carbonyl, ester group, carboxylic acid residues, amino, imino group, amide group, imide, cyanic acid, nitro, sulfo group, sulfonic acid moieties, phosphono, phosphonic acids residue etc. be can enumerate, carbonyl, ester group, phosphono are preferably.

Example as such plastifier; Can preferably use phosphate is that plastifier, phthalic ester are that plastifier, trimellitate are that plastifier, Pyromellitic Acid are that plastifier, polyol ester are that plastifier, ethyl glycolate are that plastifier, citrate are that plastifier, fatty acid ester are that plastifier, carboxylate are that plastifier, polyester are plastifier etc., and the non-phosphate that is preferably polyol ester especially and is plastifier, ethyl glycolate and be plastifier, multi-carboxylate and be plastifier etc. is a plastifier.

Polyol ester preferably constitutes, in molecule, has aromatic rings or cycloalkyl ring by the ester of aliphatic polyol more than the binary and monocarboxylic acid.

Employed polyvalent alcohol among the present invention is represented by following general formula (3).

General formula (3) R ₁-(OH) _n

(wherein, R ₁The organic group of expression n valency, n representes the positive integer more than 2)

As the example of preferred polyhydric alcohols, can enumerate the material that for example is described below, but the present invention is not limited to this.

As the example of preferred polyhydric alcohols, can enumerate ribitol, arabitol, monoethylene glycol, diglycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1; Ammediol, DPG, tripropylene glycol, 1,2-butylene glycol, 1,3 butylene glycol, 1; 4-butylene glycol, dibutylene glycol, 1,2,4-butantriol, 1; 5-pentanediol, 1; 6-hexanediol, hexanetriol, galactitol, sweet mellow wine, 3-methylpentane-1,3,5-triol, sheet alcohol, D-sorbite, trimethylolpropane, trimethylolethane, xylitol etc.Preferred especially triethylene glycol, tetraethylene glycol, DPG, tripropylene glycol, D-sorbite, trimethylolpropane, xylitol.

As employed monocarboxylic acid in the polyol ester of the present invention, not special restriction can be used known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylate etc.When using alicyclic monocarboxylic acid, aromatic monocarboxylate, consider from the aspect that improves moisture-penetrability, retention, preferred.

As the example of preferred monocarboxylic acid, can enumerate the material of the following stated, but the present invention is not limited thereto.

As aliphatic monocarboxylic acid, can preferably use the straight chain of carbon number 1～32 or have the fatty acid of side chain.Carbon number further is preferably 1～20, is preferably 1～10 especially.When containing acetate, increase with the compatibility of cellulose derivative, therefore preferred, also preferably mix acetate and other monocarboxylic acid uses.

As the example of preferred aliphatic monocarboxylic acid, can enumerate the saturated fatty acid of acetate, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, 2-methyl-cyclohexane carboxylic-acid, undecanoic acid, lauric acid, tridecylic acid, tetradecylic acid, pentadecanoic acid, hexadecylic acid, margaric acid, stearic acid, nonadecanoic acid, 20 acid, behenic acid, tetracosanoic acid, cerinic acid, carboceric acid, octacosanoic acid, triacontanoic acid, lacceroic acid etc.; The unsaturated fatty acid of undecenoic acid, oleic acid, sorbic acid, linoleic acid, leukotrienes, arachidonic acid etc. etc.

As the example of preferred alicyclic monocarboxylic acid, can enumerate cyclopentane-carboxylic acid, cyclohexane-carboxylic acid, cyclooctane carboxylic acid or their derivant.

Example as preferred aromatic monocarboxylate; Can enumerate the material, biphenyl carboxylic acids, the naphthalene-carboxylic acid, 1 that on the benzoic phenyl ring of benzoic acid, methyl benzoic acid etc., have imported alkyl; 2; 3, the aromatic monocarboxylate with two above phenyl ring of 4-tetralin carboxylic acid etc. or their derivant, but preferred especially benzoic acid.

The not special restriction of the molecular weight of polyol ester is preferably 300～1500, further is preferably 350～750.The big person of molecular weight is not volatile, and is therefore preferred, from moisture-penetrability, consider the little person of preferred molecular weight with the aspect of the compatibility of cellulose derivative.

The carboxylic acid that uses in the polyol ester can be a kind, also can be the mixing more than 2 kinds.In addition, all esterifications of OH base in the polyvalent alcohol also can be with the residual part of form of OH base.

Ethyl glycolate is the not special qualification of plastifier, and can preferably use the ethyl glycolate that in molecule, has aromatic rings or cycloalkyl ring is plastifier.As preferred ethyl glycolate is plastifier, can use for example BPBG, ethyl phthalylethyl glycolate, methyl phthalyl ethyl glycolate etc.

At phosphate is in the plastifier; Can use triphenyl, three cresyl phosphates, cresyl diphenyl phosphoester, octyl group diphenyl phosphoester, diphenyl xenyl phosphate, trioctylphosphine phosphate, Tributyl phosphate ester etc., be in the plastifier at phthalic ester; Can use repefral, DMEP, repefral, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dicyclohexyl phthalate etc.; In the present invention, preferably not containing phosphate in fact is plastifier.

At this, so-called " not containing in fact " is meant that phosphate is that the content of plastifier is lower than 1 quality %, is preferably 0.1 quality %, particularly preferably is and do not add.

These plastifier can use separately or mix more than 2 kinds and use.

The use amount of plastifier, preferred 1～20 quality %.Further preferred 6～16 quality % are preferably 8～13 quality % especially.The use amount of plastifier, when being lower than 1 quality % with respect to cellulose derivative, the effect that the moisture permeability of film is reduced is little, therefore not preferred; When surpassing 20 quality %, plastifier from film ooze out, the rerum natura variation of film, therefore not preferred.

In the cellulose derivative among the present invention,, preferably add the particulate of matting agent etc. in order to give flatness.As particulate, can enumerate the particulate of mineral compound or the particulate of organic compound.

As the example of the particulate of mineral compound, can enumerate the particulate of silicon dioxide, titania, aluminium oxide, zirconia, tin oxide etc.Wherein, be preferably the particulate of the compound that contains silicon atom, preferred especially silicon dioxide microparticle.As silicon dioxide microparticle, can enumerate AEROS I L 200,200V, 300, R972, R972V, R974, R202, R812, R805, OX50, TT600 of ア エ ロ ジ Le Co., Ltd. system for example etc.

As the example of the particulate of organic compound, can enumerate the particulate of acrylic resin, organic siliconresin, fluorine compounds resin, carbamate resins etc.

The primary particle size of particulate is not special to be limited, and preferred final mean grain size in film is about 0.05～5.0 μ m.Further be preferably 0.1～1.0 μ m.

The mean grain size of particulate is meant when with electron microscope, optical microscope cellulose ester membrane being observed, at the mean value of the length of the long axis direction of the particle of observation place of film.So long as in film viewed particle, can be primary particle, the offspring that also can form for primary particle cohesion, but viewed usually mostly be offspring.

As an example of assay method, to the vertical section photo at 1 film random shooting 10 place, for each cross sectional photograph, number goes out the 100 μ ms of long axis length at 0.05～5 mu m range ²In particle number.At this moment, try to achieve the mean value that institute's number goes out the long axis length of particle, will average the mean value at 10 places and the value that obtains as mean grain size.

Under the situation of particulate, the particle diameter that is added in primary particle size, the particle diameter after in solvent, disperseing, the film variations that mostly occur, importantly, control is particulate and cellulose esters complex coacervation and the particle diameter that forms in film finally.

At this, surpass under the situation of 5 μ m in the mean grain size of particulate, also become the deterioration of seeing mist degree or produce the reason of the fault under the volume state as impurity.In addition, be lower than under the situation of 0.05 μ m, be difficult to give the film flatness in the mean grain size of particulate.

Above-mentioned particulate adds use 0.04～0.5 quality %'s with respect to cellulose esters.The preferred interpolation used 0.05～0.3 quality %, and further preferred the interpolation used 0.05～0.25 quality %.The addition of particulate is 0.04 quality % when following, and the film surfaceness too becomes smoothly, owing to the rising of friction factor produces obstruction.When the addition of particulate surpassed 0.5 quality %, the friction factor on film surface excessively reduced, and produced when take-up and batched dislocation; Or the transparency of film is low, mist degree uprises; Therefore, becoming does not have as the value of liquid crystal indicator with film, and therefore above-mentioned scope is necessary.

The dispersion of particulate is preferably handled the composition that has mixed particulate and solvent with the high pressure diverting device.The high pressure diverting device that uses among the present invention is for making the composition device of the specific conditions through creating high shear, high pressure conditions etc. in the tubule at a high speed that has mixed particulate and solvent.

Through handling with the high pressure diverting device, for example preferred maximum pressure conditions of in the tubule of caliber 1～2000 μ m, installing inside is 980N/cm ²More than.Further the inner maximum pressure conditions of preferred embodiment is 1960N/cm ²More than.This moment in addition, preferably be up to the speed of reaching and reach that 100m/sec is above, heat transfer rate reaches more than the 420kJ/h.

High pressure diverting device as above-mentioned that kind; For example can enumerate the super-high-pressure homogenization machine (trade name マ イ Network ロ Off Le イ ダ イ ザ one) or the Na ノ マ イ ザ one corporate system nanometer homogenizer of Microfluidics Corporation corporate system; In addition; Can enumerate マ Application ト Application go one リ Application type high pressure diverting device, for example homogenizer of イ ズ ミ Off one De マ シ Na リ system etc.

Among the present invention; Obtain the following cellulose ester membrane of characteristic: after particulate disperses in the solvent that contains 25～100 quality % lower alcohols; Mix with the rubber cement that in solvent, has dissolved cellulose esters (cellulose derivative), this mixed liquor curtain coating on metal support, is carried out drying system film.

At this,, be preferably 50～100 quality %, further be preferably 75～100 quality % as the ratio that contains of lower alcohol.

In addition, as the example of lower alcohols, preferably can enumerate methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols etc.

As the solvent beyond the lower alcohol, not special qualification the, employed solvent when preferably using the system film of cellulose esters.

Particulate concentration with 1～30 quality % in solvent is disperseed.When disperseing with the concentration more than it, viscosity sharply rises, and is therefore not preferred.As the particle concentration in the dispersion liquid, be preferably 5～25 quality %, further be preferably 10～20 quality %.

Consider the UVA function of preferably giving film from the viewpoint of the deterioration that prevents liquid crystal to the various bloomings of polaroid protective film, phase retardation film, optical compensation films etc.Obtain such UVA function, can in cellulose derivative, contain the ultraviolet material of absorption, the layer with UVA function also can be set on the film that constitutes by cellulose derivative.

Among the present invention; As operable ultraviolet light absorber; For example can enumerate dihydroxy benaophenonel based compound, benzotriazole based compound, salicylate based compound, benzophenone based compound, cyanoacrylate based compound, nickel complex salt based compound etc., preferred painted few benzotriazole based compound.In addition, the also preferred spy of use opens and puts down the 10-182621 communique, the spy opens the ultraviolet light absorber, the spy that put down in writing in the flat 8-337574 communique and opens the polymeric UV absorber of putting down in writing in the flat 6-148430 communique.

As ultraviolet light absorber, consider that from the viewpoint of the deterioration that prevents polarizer, liquid crystal ultraviolet absorptions below the optimal wavelength 370nm can be excellent, and consider that from the viewpoint of liquid crystal expressivity the absorption of visible light more than the optimal wavelength 400nm is few.

Among the present invention; Concrete example as useful ultraviolet light absorber; Can enumerate 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-the 3 '-tert-butyl group-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 '-(and 3 ", 4 ", 5 "; 6 "-tetrahydrochysene phthalimidomethyl) benzotriazole, 2-5 '-aminomethyl phenyl); (4-(1,1,3 for the 2-di-2-ethylhexylphosphine oxide; The 3-tetramethyl butyl)-6-(2H-benzotriazole-2-yl) phenol), the potpourri of 2-(2 '-hydroxyl-the 3 '-tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2H-benzotriazole-2-yl)-6-(straight chain and side chain dodecyl)-4-methylphenol, octyl group-3-[3-tertiary butyl-4-hydroxy-5-(chloro-2H-benzotriazole-2-yl) phenyl] propionic ester and 2-ethylhexyl-3-[3-tertiary butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl) phenyl] propionic ester etc., but be not limited to them.

In addition, as the commercially available article of ultraviolet light absorber, can preferably use チ ヌ PVC Application (TINUVIN) 109, チ ヌ PVC Application (TINUVIN) 171, チ ヌ PVC Application (TINUVIN) 326 (being チ バ ジ ヤ パ Application (strain) system).

In addition; Concrete example as the benzophenone based compound of spendable ultraviolet light absorber among the present invention; Can enumerate 2; 4-dihydroxy benaophenonel, 2,2 '-dihydroxy-4-methoxy benzophenone, 2-hydroxyl-4-methoxyl-5-diphenylsulfone ketone, two (2-methoxyls-4-hydroxyl-5-benzoyl phenylmethane) etc., but be not limited to these compounds.

Among the present invention, the use level of these ultraviolet light absorbers, with respect to cellulose esters (cellulose derivative), the scope of preferred 0.01～10 quality %, further preferred 0.1～5 quality %.When the use amount of ultraviolet light absorber was very few, the UVA effect was insufficient sometimes, and when ultraviolet light absorber was too much, the transparent deterioration of film was therefore not preferred sometimes.The material that the ultraviolet light absorber preferred thermal stability is high.

In addition, can be used for the ultraviolet light absorber of blooming of the present invention, can preferably use the spy to open flat 6-148430 communique and the special polymeric UV absorber of putting down in writing in the 2002-47357 communique (or ultraviolet-absorbing polymkeric substance) of opening.General formula (1) that can especially preferably use the spy to open to put down in writing in the flat 6-148430 communique or general formula (2), or specially open the polymeric UV absorber shown in the general formula (3) put down in writing in the 2002-47357 communique, (6), (7).

Anti-oxidant generally also is called as aging resister, preferably in the cellulose ester membrane as blooming, contains anti-oxidant.That is, under the situation of the state held of high humidity high temperature, cause deterioration sometimes as the cellulose ester membrane of blooming in liquid crystal image display device etc.Anti-oxidant has to postpone or prevent and therefore preferably in film, contains owing to be the effect that film that the phosphoric acid etc. of plastifier is caused decomposes by the halogen in the residual solvent in the film, phosphoric acid for example.

As such anti-oxidant, can preferably use the compound of hindered phenol system, for example can enumerate 2, [3-(3 for 6-di-t-butyl-paracresol, pentaerythrite-four; The 5-di-tert-butyl-hydroxy phenyl) propionic ester], triethylene glycol-two [3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester], 1,6-hexanediol-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], 2; 4-pair-(positive hot sulfenyl)-6-(4-hydroxyl-3,5-di-tert-butyl amido)-1,3; 5-triazine, 2,2-sulfo-di ethylene bis [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], octadecyl-3-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic ester, N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide), 1; 3,5-trimethyl-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, three-(3, the 5-di-tert-butyl-4-hydroxyl benzyl)-isocyanuric acid ester etc.Preferred especially 2,6-di-t-butyl-paracresol, pentaerythrite-four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], triethylene glycol-two [3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester].In addition, for example also can and use N, the phosphorus of metal passivator, three (2, the 4-di-tert-butyl-phenyl) phosphite ester (salt) of the hydrazine system of N '-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propiono] hydrazine etc. etc. is processing stabilizers.

The addition of these compounds in the preferred 1ppm～10000ppm of mass ratio, further is preferably 10～1000ppm with respect to cellulose derivative.

Below, the manufacturing approach according to blooming of the present invention is narrated in detail.Film can be made through the solution casting film-forming method.

Fig. 6 schematically shows the process flow diagram of device of manufacturing approach that comes the blooming of embodiment of the present invention through solution casting system embrane method.Need to prove, in the enforcement of the present invention, be not limited to the technology of Fig. 6.

The manufacturing approach of utilizing the blooming of solution casting system embrane method of the present invention; Possesses following operation: thermoplastic resin solution's (rubber cement) curtain coating is formed casting films (net) to metallic supporting mass 50; After making the part evaporation of solvent, the operation that net 1 is peeled off from metallic supporting mass 50; The operation that the net 1 that will peel off through stenter 53 stretches at Width; The net 1 that has stretched with 54 pairs of drying devices carries out dry operation; To net 1 both ends operation after the drying through cutting machine 56,57 cut-out both ends; After cutting off both ends, the dandy roll 61 through having jut on the surface be situated between by net 1 in the position configuration of correspondence the both ends of 62 pairs of nets 1 of the backing roll annular knurl operation of carrying out annular knurl processing; With the coiling process that batches the film (net) 1 after annular knurl is processed.

At first, in no illustrated dissolution kettle, with thermoplastic resin, for example cellulose esters be resin dissolves in the mixed solvent of good solvent and poor solvent, add adjuvant and the modulating resin solution (rubber cement) of above-mentioned plastifier, ultraviolet light absorber etc. therein.

Then; The rubber cement that will be in dissolution kettle have been adjusted through compression type quantitative gear pump for example, through conduit and liquor charging to casting head 51, drive curtain coating position on the metallic supporting mass 50 that stainless steel endless belt constitutes from casting head 51 curtain coating rubber cements in the rotation by unlimited transmission shown in Figure 6.

Need to prove; Though omit diagram, also can with through for example compression type quantitative gear pump by liquor charging be cast to the rubber cement of casting head 51 from casting head 51 have mirror process through the hard chrome plating the drum cooler of stainless steel rotation on surface on.

In the curtain coating of the rubber cement that utilizes casting head 51; The rubber cement film (net) that has had curtain coating is scraped the skill in using a kitchen knife in cookery, or the method for the contrary roll coater of utilization regulated with the roller that reverses etc. with what scraper was regulated thickness, but the shape of slit of preferred tunable tubulation head (mouthful gold) part, is easy to make the pressing die head that adds of uniform film thickness.In adding pressing die head, hanger-style die, T die head etc. are arranged, all can preferably use.

Need to prove,, the shape of slit of preferred tunable tubulation head part, be easy to make the pressing die head that adds of uniform film thickness as casting head 51.

At this, the solid component concentration of preferred cellulose ester solution (rubber cement) is 20～30 quality %.

At this, if the solid component concentration of cellulose ester solution (rubber cement) is lower than 20 quality %, then can not be fully dry on metallic supporting mass 50, the part of rubber cement film is residual on metallic supporting mass 50 when peeling off, and causes drum to pollute, and is therefore not preferred.In addition, solid component concentration surpasses at 30% o'clock, and rubber cement viscosity uprises, and stops up at rubber cement adjustment operation middle filtrator to accelerate, and uprising to metallic supporting mass 50 upper reaches time-delay pressure, becomes and can't extrude, and is therefore not preferred.

In possess the illustrated film forming apparatus that rotates the driving endless belt as metallic supporting mass 50, this band metallic supporting mass 50 holds the top moving part of endless belt metallic supporting mass 50 and a plurality of rollers of bottom moving part (omitting diagram) formation from dorsal branch therebetween and respectively by a pair of drum and configuration.

A side of the drum of coiling portion or both sides are provided with the drive unit of metallic supporting mass 50 being given tension force at the two ends of metallic supporting mass 50, are with metallic supporting mass 50 to be used under the open state having applied tension force thus.

In addition, the peripheral speed of preferable alloy system supporting mass 50 is 50～150m/min.

Under situation as metallic supporting mass 50 use endless belts; Band temperature during as far as the system film; Can under the temperature of the boiling point of 0 ℃ of general temperature range～be lower than solvent, carry out curtain coating; Under mixed solvent, under the temperature of the boiling point that is lower than the minimum solvent of boiling point, carry out curtain coating, further the more preferably scope of 5 ℃～solvent boiling point-5 ℃.At this moment, need atmosphere moisture on every side is controlled at more than the dew point.

As stated on metallic supporting mass 50 surfaces by curtain coating rubber cement, through cooling gelization, gel film strength (film strength) increases, and then also can be through during this period of time drying before promoting to peel off, gel film strength (film strength) increases.

In addition, in order to improve system film speed, also can be at the casting head 51 that is provided with on the metallic supporting mass 50 more than 2, the amount branch of rubber cement come carry out multilayer system film.

In mode as metallic supporting mass 50 use endless belts; On metallic supporting mass 50; In order to make net 1 dry solidification to reaching through stripper roll 52 from metallic supporting mass 50 strippable film strengths; Preferably making its residual solvent amount that is dried in the net 1 is below the 150 quality %, more preferably 80～120 quality %.In addition, peel off preferred 0～30 ℃ of 1 o'clock net temperature of net from metallic supporting mass 50.In addition; Will net 1 just peeled off from metallic supporting mass 50 after; Cause temperature to descend rapidly from the solvent evaporation of metallic supporting mass 50 closed surface sides, or volatile ingredients such as the water vapor in the atmosphere, solvent vapour are easy to condense, the net temperature when therefore further preferably peeling off is 5～30 ℃.

At this, the residual solvent amount is represented by following formula.

Residual solvent amount (quality %)=(M-N)/N} * 100

In the formula, M representes film quality at any time, and the film that N representes mass M is 110 ℃ of dry down quality after 3 hours.

On the metallic supporting mass 50 the rubber cement film (net) that forms through the rubber cement of curtain coating on endless belt metallic supporting mass 50 is being heated, solvent evaporation to stripper roll 52 capable of using is peeled off net from metallic supporting mass 50.

In order to make solvent evaporation, the method for method and/or the method for conducting heat through liquid from the back side of metallic supporting mass 50 from the net cross air blow are arranged, conducting heat through radiation heat from the table the inside etc.

On metallic supporting mass 50, use in the mode of endless belt, the tension force of peeling off when through stripper roll 52 metallic supporting mass 50 being peeled off with net 1 is generally under 100N/m～200N/m and peels off, but than product in the past more in the blooming that pass through the present invention's making of filmization; The residual solvent amount of net 1 is many when peeling off; Stretch at throughput direction easily, so film is easily in the Width contraction, when drying overlaps with contraction; The end is curled, is folded into; Be easy to generate fold thus, therefore preferably under the minimum tension force～170N/m that can peel off, peel off, further preferably under minimum tension force～140N/m, peel off.

Making net 1 dry solidification on the metallic supporting mass 50 to strippable film strength, peel off net 1 through stripper roll 52.

Then, the net after peeling off 1 is imported the stenter 53 of stretching process.In the method for the present invention; As the stenter in the stretching process 53; Can use pin stenter and clip stenter, but wherein, use film as liquid crystal indicator; The clip stenter of preferably using the both sides of the edge portion of clip fixed network (or film) 1 and stretching, preferred because planarity, the dimensional stability of film are improved.

The residual solvent amount that preferably will get into the net (film) 1 before the stenter 53 of stretching process is 10～50 quality %.

In the stretching process, be that warm braw blows out the slit mouth and is blown into warm braw, discharges exhaust wind from the escape hole that leans on the rear section on the top of stenter 53, net 1 thus and when being stretched, be dried from the warm braw blowing out device of the forward part at the end of stenter 53.

Among the present invention, the extensibility of the net 1 in the stenter 53 is preferably 3～80%, further is preferably 6～60%.

If the extensibility of the Width of the net 1 in the stenter 53 is lower than 3%, even then use the wideest band, the device of curtain coating width, also can't obtain the wide film of width, therefore not preferred.The extensibility of the Width of the net 1 in the stenter 53 surpasses at 80% o'clock in addition, since draft temperature, the film cracking, therefore not preferred.

Need to prove that the warm braw blowing out device in the stretching process among so-called the present invention is meant that particularly the warm braw of the stenter 53 of stretching process blows out the slit mouth, but so long as the just not special qualification of the shape of heating film effectively through blowing out of warm braw.The temperature of warm braw is preferably 165～190 ℃, further is preferably 170～185 ℃.

Then, with the drying device 54 of film (net) the 1 guide-in roller conveying type after stretching, in drying device 54, the conveying roller 55 that constitutes through the free roller by non-driving is on one side carried drying.

In this drying device 54, the conveying roller of having seen through zigzag arrangement from 50～1000 side 55, net 1 wriggles and moves ahead, net 1 therebetween and be dried.In addition, the film conveyance tension in drying device 54 receives the rerum natura of rubber cement, carries the residual solvent amount in the operation, the temperature in the drying device 54 etc. to influence when peeling off and at film, but preferred 30～250N/m, further preferred 60～150N/m.80～120N/m most preferably.

Need to prove that the not special restriction of the device of dry net (or film) 1 generally waits with hot blast, infrared ray, warm-up mill, microwave and carries out.Consider from the aspect of simplicity; Preferably carry out drying with hot blast, the dry wind that for example is blown into through the warm braw inlet from the forward part at the end of drying device 54 carries out drying, carries out drying through discharging exhaust wind from the outlet of leaning on the rear section on the top of drying device 54.The temperature of dry wind is preferably 40～160 ℃, and 50～160 ℃ owing to make planarity, dimensional stability well and further preferred.

These can carry out under air atmosphere from being cast to the operation of final back drying, also can under the non-active gas atmosphere of nitrogen etc., carry out.At this moment, to implement dry atmosphere in the explosion limits concentration of considering solvent certainly.

After the drying of utilizing drying device 54; Is the width that becomes goods through a pair of cutting machine 56,57 up and down with film both ends joint-cutting; Cutting excision, form film according to the goods width after, implement annular knurl in the end of the Width of this film and process and form knurled portions; Batch, make the blooming of roller shape thus.

And; In manufacturing approach according to blooming of the present invention; The operation of implementing annular knurl processing a plurality of juts are squeezed in film side end the surface and form a plurality of concavo-convex rightly, it is characterized in that, when being squeezed in jut on the film; Limit with the par of the base portion that constitutes jut height, make the height of the height of protuberance for regulation to the protuberance that forms through the membrane element of having pushed open by jut.For this annular knurl processing, owing to be illustrated, so the explanation is here omitted.

The roller shape film of the blooming through method manufacturing of the present invention roll length more preferably more than the 500m, below the 12000m.

At this, if the length of rolling of roller shape film is more than the 500m, even faster production then is the switching time of the roller that the expense of also need not spending more has been spooled, preferred.In addition,, throughput rate is reduced even the frequency that adds the switching operation of film in man-hour at polaroid does not uprise yet, preferred.

In addition, if roller shape film roll length below 12000m, also be not easy to be damaged by pressure, produce and paste the worry of paying even the load that then causes rolling up core owing to the own wt of film becomes big, make the annular knurl height increase protuberance, therefore preferred.

Need to prove that the residual solvent amount of the film that batches through take-up mechanism 58 is below the 0.5 quality %, is preferably below the 0.1 quality %, can obtain the good film of dimensional stability thus.

As more than, through solution casting system embrane method, can make coiled into the roller shape blooming of the present invention.

Then, describe for the manufacturing approach of the blooming of fusion curtain coating film-forming method of utilizing of the present invention.

Fig. 7 is the process flow diagram of device of manufacturing approach that schematically shows the blooming that utilizes fusion curtain coating film-forming method of embodiment of the present invention.

In the manufacturing approach of the blooming that utilizes fusion curtain coating system embrane method, the thermoplastic resin of use is not as long as can limit through fusion curtain coating system embrane method system film is just special.For example can enumerate: cellulose esters, polycarbonate, the polymkeric substance that contains the ester ring type structure, polyvinyl alcohol (PVA), polyamide, polyimide, polyester etc.Wherein because photoelastic coefficient is little, the preferred cellulose ester, contain the polymkeric substance of ester ring type structure, because particularly water-intake rate is little, preferably contain the polymkeric substance of ester ring type structure.

In addition; Among the present invention; The ester that the ester that in blooming, preferably contains the ester with structure that organic acid and the pure condensation more than the ternary form as adjuvant and be plastifier, formed by polyvalent alcohol and monocarboxylic acid is plastifier, formed by polybasic carboxylic acid and monohydroxy alcohol be at least a plastifier, the phenol in the plastifier be anti-oxidant, be selected from hindered amine as light stabilizer, phosphorus is that stabilizing agent, sulphur are at least a stabilizing agent in the stabilizing agent, further in addition can also contain peroxide decomposer, free radical scavenger, metal passivator, ultraviolet light absorber, matting agent, dyestuff, pigment, the plastifier beyond further above-mentioned, the anti-oxidant beyond the hindered phenol antioxidant etc.

The manufacturing approach of utilizing the blooming of fusion curtain coating system embrane method of the present invention possesses following operation: the raw material that will contain thermoplastic resin drops in the feeding hopper 71, the operation of mixing with mixer 72; After mixing, carry out the operation of melting mixing with extruder 73; With melting mixing the operation of fused mass on from casting head 74 curtain coatings to chill roll 76; With curtain coating the operation that stretches at Width through stenter 77 of film 70; After the stretching, cut off the operation at the both ends of film 70 through cutting machine 78,79; After cutting off both ends, the 1st dandy roll 80 of conduct the 1st parts through having protuberance on the surface and have on the position corresponding with the protuberance of the 1st dandy roll with this protuberance roughly the both ends of 81 pairs of films 70 of the 2nd dandy roll of conduct the 2nd parts of the recess of similar shape carry out the annular knurl operation of annular knurl processing and annular knurl processed after the coiling process that batches of film 70.

Among the present invention, the extruder 73 that in film system film, uses can be single screw extrusion machine, also can be double screw extrusion machine.Directly make under the situation of film can't help the material pellet; Need suitable mixing degree; Therefore the preferred double screw extrusion machine that uses; Even but single screw extrusion machine, the screw rod that also can change to the mixed milling type of マ De Star Network type, ユ ニ メ Le ト type, ダ Le メ one ジ type etc. through the shape with screw rod obtains the mixing of appropriateness, makes film.No matter still in double screw extrusion machine, be provided with ventilating opening at single screw extrusion machine, hope use vacuum pump etc. is removed gas from ventilating opening.In a single day under the situation of the semi-molten thing of making pellet, candied cake of popped rice shape, single screw extrusion machine or double screw extrusion machine all can.

In extruder 73 and the refrigerating work procedure after extruding, preferably replace or reduce pressure with the non-active gas of nitrogen etc., reduce the concentration of oxygen thus.

Though the melt temperature of the resin in the extruder 73 is according to the thickness of the sheet material of the viscosity of resin, discharge rate, manufacturing etc. and preferred condition is different, general preferred glass transition temperature with respect to moulding material (Tg) is more than the Tg and the scope below Tg+100 ℃.Further the preferred molten temperature is more than Tg+10 ℃ and below Tg+90 ℃.Melt viscosity when extruding be 10～100000 the pool, be preferably 100～10000 the pool.In addition, preferably the hold-up time of the resin in extruder 73 weak point is in 5 minutes.In more preferably 3 minutes, most preferably be in 2 minutes.Hold-up time also receives the kind of extruder 73, the influence of extrusion condition, shortens but can wait through the degree of depth of adjustment material quantity delivered, L/D, screw rod revolution, screw slot.

The shape of the screw rod of extruder 73, revolution etc. can wait suitable the selection according to viscosity, the discharge rate of resin.Shear rate in extruder 73, be preferably 1/ second～10000/ second, more preferably 5/ second～1000/ second, most preferably be 10/ second～100/ second.In order to prevent the gear-type pump interlock, reduce main filter loading that preferably the outlet side at extruder 73 is provided with prefilter.

The filter screen of 50/80/100 mesh, the sintered filter of metal fibre for example preferably are set as required.Preferred use can online change type.

To send into extruder 73 with the starting material that mixer 72 has mixed, and for example carry out heating and melting under 250 ℃, fused mass is extruded shaping by casting head 74 according to the present invention.The fused mass of extruding from casting head 74 with 76 pairs of stainless steel system chill rolls (metal support) cool off, the surface proofreaies and correct.At this moment, film 70 and chill roll 76 preferred driving fits as making film 70 driving fits in the method for chill roll 76, use touch roll 75 to be pressed into.

Temperature that will the resin of driving fit before chill roll 76 is preferably more than the Tg, more preferably more than Tg+50 ℃.Can reduce the delay of the flow direction that the extension by bar produces through keeping high resin temperature.Preferably will be incubated resin the air port of driving fit before chill roll 76 from casting head 74 outlets at resin.As heat preserving method, can preferably utilize the induction heating that uses microwave, the radiation heat heating of using infrared heater etc.Infrared heater can utilize the far-infrared ceramic well heater of electric, gas type, oily formula or steam-type.

Chill roll 76 is to get final product more than 1, but improves flatness for the two sides for film, adopts more than 2, and preferred two sides all contacts chill roll 76.In addition, also can give the cleaning equipment of clearer etc. to chill roll 76.The temperature contrast of chill roll 76 is preferably below 0.5 ℃.Speed difference is preferably below 0.5%.The hard chrome plating can be used in chill roll 76 surfaces, but is not limited to this.Below the preferred 0.1s of surfaceness.

On the other hand, as the material of touch roll 75, can use metal or around metallic roll, batch the material of resin, rubber etc.In addition, also can use follow from width central portion to sidepiece, make vary in diameter crowned roll.

In addition, will the temperature of driving fit before touch roll 75 be preferably more than the glass transition temperature (Tg) of resin, more preferably more than Tg+50 ℃.

The temperature adjustment of chill roll 76 is preferably adjusted through the thermal medium that flows through water, wet goods in chill roll 76 inside.

Then, with cooling curing film peel off from chill roll 76, stretch at Width.Be oriented through stretching molecule.The method that stretches can preferably be used known stenter 77 etc.

Stretch, preferably plant and carry out at the even temperature branch of being controlled.Preferably in ± 2 ℃, more preferably in ± 1 ℃, in ± 0.5 ℃.

For the size changing rate of the thermoplastic resin film that reduces to make etc., film is stretched or shrink with said method.In order to shrink in the longitudinal direction, following method is for example arranged: lax or the interval of the adjacent clip of cross directional stretch machine is narrowed down gradually film is shunk at length direction through temporarily clamping width tension.The latter's method can be through using biaxial stretch-formed machine general the time, for example drives the method that clip portion comes steadily little by little the interval of adjacent clip longitudinally to narrow down with pantograph mode, linear drive mode and carry out.Also can make up as required with the stretching of any direction (bevel direction).Shrink the size changing rate that reduces blooming through all make it shrink 0.5%～10% at length direction, Width.

The change of the thickness of blooming is preferably ± 3%, further be preferably ± 1% scope.In order to reduce the thickness change; The method that on mutually orthogonal biaxially oriented, stretches is effective; The stretching ratio of mutually orthogonal biaxially oriented preferably respectively final on the curtain coating direction 1.0～2.0 times, on Width 1.01～2.5 times scope, preferably on the curtain coating direction, carry out in 1.01～1.5 times scope, scope at 1.05～2.0 times on Width.

The method that film is stretched does not have special the qualification, and for example can enumerate following method: it is poor to give a plurality of roller peripheral speeds, the method for utilizing roller peripheral speed difference vertically stretching betwixt; With clip, the fixing two ends of film 70 of pin, on working direction, expand the interval of clip, pin and the method that stretches in the vertical; The method of likewise expanding in the horizontal and stretching in the horizontal; Perhaps in the method that stretches on two directions in length and breadth to expansion simultaneously in length and breadth etc.In addition, also can make up the method for using these grades.

After utilizing the stretching of stenter 77; Utilize a pair of up and down cutting machine 78,79 with of the width cutting excision of film both ends joint-cutting for goods; After forming film according to the goods width; Implement annular knurl in the end of the Width of this film and process and form knurled portions, batch, make the blooming of roller thus with take-up mechanism 82.

And; In utilizing the manufacturing approach of blooming of the present invention, the operation of implementing annular knurl processing is expressed to the surface of the side end of film with a plurality of juts, and it is a plurality of concavo-convex right to form; It is characterized in that; When jut being squeezed in film surperficial, limit with the par of the base portion that constitutes jut height the protuberance that forms through the membrane element of having pushed open by jut, make the height of the height of raised part for regulation.For this annular knurl processing, owing to narrate, so the explanation is here omitted.

Can be like the above blooming of the present invention that has been rolled into the roller shape of making through fusion curtain coating system embrane method.

In manufacturing approach according to blooming of the present invention; Method for coiling use normally used up-coiler in arbitrary method of solution casting system embrane method or fusion curtain coating system embrane method of film gets final product; Have decide calibrated wrench method, decide tensammetry, the method for the control tension force of printing Tension Control method that tapering tensammetry, internal stress are certain etc., can these separately be used.

Below, to the polaroid that used blooming of the present invention and used the display device of this polaroid to describe.

(polaroid)

Polaroid can be made by general method.Preferably the rear side of blooming of the present invention is carried out the alkali soap processing, the blooming of having handled is fitted on the face of at least one side of in iodine solution, flooding the polarizing coating that stretches and make with fully saponified type polyvinyl alcohol water solution.Face at opposite side can use this blooming, also can use other polaroid protective film.For blooming of the present invention, be used for polaroid protective film on the face of opposite side and have preferably that to postpone Ro in the face be that 20～70nm, Rt are the phase differential of 100～400nm under 590nm.These for example can be made with the method that the spy opens 2002-71957 communique record.Perhaps preferred use to have both have the liquid-crystal compounds orientation that further makes discotic mesogenic etc. and the polaroid protective film of the optical compensation films of the optical anisotropic layer that forms.For example can open the optical anisotropic layer that forms of 2003-98348 communique record with the spy.Through using, can obtain the planarity excellence, have the polaroid of stable visual angle amplification effect with combination of optical films of the present invention.

Polaroid protective film as side is overleaf used as commercially available transparent supporting mass, can preferably use KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC8UCR-3 (コ ニ カ ミ ノ Le タ オ プ ト (strain) system) etc.

What is called is as the polarizing coating of the main composition key element of polaroid; Be the element that only light of the plane of polarization of certain orientation is passed through; Now known representational polarizing coating is the polyethenol series polarizing coating, and it has makes polyvinyl alcohol (PVA) mesentery the dyeed film of iodine and the film of the dichroic dye that dyeed.Polarizing coating can use polyvinyl alcohol water solution system film, makes its uniaxial tension and after carrying out uniaxial tension after dyeing or dyeing, and has preferably carried out the material that permanance is handled with boron compound.The single face of applying blooming of the present invention forms polaroid on the face of this polarizing coating.Preferably fit for the bonding agent of the water system of principal ingredient in order to fully saponified polyvinyl alcohol (PVA) etc.

Used the planarity of polaroid of blooming in the past poor; When seeing reflection image, confirming has tiny wavy inequality, through wavy uneven increase of endurancing under 60 ℃, 90%RH condition; With respect to this, used the planarity excellence of the polaroid of blooming of the present invention.In addition, do not increase yet,, good observability can be provided even, do not change in endurancing back angle characteristic for side overleaf has the polaroid of optical compensation films even try wavy inequality through the permanance under 60 ℃, 90%RH condition yet.

(display device)

In display device that above-mentioned polarizer group is packed into, can make the excellent display device of various observabilities.Blooming of the present invention can be preferred for the LCD of the various type of drive of reflection-type, transmission-type, transflective LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type etc.In addition, the catoptrical irregular colour of the anti-reflection layer of antireflection film of the present invention significantly reduces, and planarity is excellent in addition; Also can be preferred for plasma scope, Field Emission Display; OLED display, inorganic EL display, the various display device of Electronic Paper etc.Particularly in the display device of the giant-screen more than screen is 30 types, irregular colour, wave inequality are lacked, and watch the also not tired such effect of eyes for a long time even have.

Embodiment

Below, through embodiment the present invention is further specified, but the present invention is not limited to this.

Embodiment 1～17, comparative example 1～8

Through the manufacturing approach of utilizing the blooming of solution casting system embrane method of the present invention, make tri cellulose acetate membrane as follows.

(rubber cement forms 1)

Above-mentioned rubber cement formed 1 material and drop in the closed container,, filter while heat, stir it is dissolved fully.Filtration makes it pass through metal sintering filtrator (catch particle diameter=10 micron) after utilizing pressure filter to filter.Then, use solution casting film forming apparatus shown in Figure 6, under 35 ℃ of temperature, with rubber cement with width 1800mm equably curtain coating to the stainless steel band supporting mass of width 2000mm.In addition, use the different material of the molecular weight distribution of cellulose triacetate, use two kinds of glass temperature Tg shown in the indicator gauge 1 (℃) material.

On the stainless steel band supporting mass, making solvent evaporation to residual solvent amount is 100 quality %, peels off net from the stainless steel band supporting mass.Then, control the both ends of the Width (TD direction) of net, stretch with the Width of extensibility 10% at net with stenter.Need to prove, with the residual solvent amount of the net before the stenter that is about to get into stretching process as 30 quality %.

In the stretching process; From the warm braw blowing out device of the forward part at the end of stenter is that warm braw blows out the slit mouth and under 180 ℃ of temperature, is blown into warm braw; Discharge exhaust wind from the escape hole that leans on the rear section on the top of stenter, when net is stretched, carry out drying thus.

Then; Film after stretching is imported drying device; The conveying roller that on one side this film is constituted through the free roller by 500 non-drivings in drying device is carried and is carried out drying on one side, and said free roller is made up of the minute surface conveying roller (face length 2200mm, diameter 110mm) of surfaceness (Rmax) 0.8 μ m.Making the film conveyance tension in the drying device is 80N/m.In drying device, the dry wind that the temperature that is blown into through the warm braw inlet from the forward part at its end is 150 ℃ makes its drying.

After utilizing the drying of drying device, be width 1600mm with film both ends joint-cutting through upper and lower a pair of cutting machine, the cutting excision.

Then, the right ends portion from the film behind the joint-cutting being carried out annular knurl from the end to the width of 30mm respectively processes.

Annular knurl processing, the dandy roll 61 through having jut on the surface and be situated between by film relatively with dandy roll 61 that the backing roll 62 of configuration carries out.

Fig. 8 representes to be used for the section shape of the jut of dandy roll 61.As the shape of jut, to use the bottom surface be to have length L 1 on one side and be to have length L 2 on one side and implement annular knurl processing with quadrangle, the height on the limit of the identical or different length of L2 as the quadrangular pyramid of h with the face of the quadrangle on the limit of the identical or different length of L1, front end.At this moment, limit with the par of the base portion that constitutes jut height the protuberance that on face, forms.The value of length and height h on dimetric each limit that makes the face of this bottom surface and front end changes and on the film surface, forms concavo-convexly, implements to have the mean breadth W shown in the table 1, the annular knurl processing of the value of the ratio S/Y of the breadth extreme Y of ratio S/H, sectional area S and the recess of sectional area S, sectional area S and average height H.Need to prove that mean breadth W, sectional area S, recess breadth extreme Y are for sentencing the value of the plane parallel with the film surface when cutting off (with reference to Fig. 2 at 1/2 of the height of protuberance.)。

In addition, the concavo-convex number that forms on the knurled portions surface becomes the number shown in the table 1.

After the annular knurl processing, blooming is batched on the cylindrical duct of diameter 600mm, make length 3000m, thickness 50 μ mm, the embodiment 1～17 of width m1600, the blooming of comparative example 1～8.

(evaluation)

For the embodiment 1～17 that makes through above-mentioned method, the blooming of comparative example 1～8; Have or not the black-tape that produces under the roller state through visual the observation, with complete unacknowledged situation as ◎, confirm as pettiness but as the situation of the no problem level of goods as zero, situation about having confirmed as △, confirm a large amount of situation as *.In addition; Observation has or not the obstruction of generation when the roller state stretches out blooming, with complete unacknowledged situation as ◎, confirm to pettiness but as the situation of the no problem level of goods as zero, situation about having confirmed as △, will produce the film distortion, the situation of breaking as *.Observe black-tape, when blocking, on film, produce fold, impurity with the △ level, can not use as goods.Evaluation result is shown in table 1.

[table 1]

By table 1 result; When embodiment 1～5 is compared with comparative example 1～8; Distinguish: in the manufactured blooming of annular knurl surface a pair of concavo-convex; With a pair of concavo-convex when cutting off at 1/2 place apart from the average height on the surface of film of this protuberance with the surperficial parallel plane of film, the sectional area S of protuberance is preferably 2500～10000 μ m ², protuberance mean breadth W be preferably 3～20 μ m.In addition, when embodiment 3 and embodiment 6～9 are compared, distinguish sectional area S μ m ²Be preferably 100～3000 with ratio S/H apart from the average height H μ m on the surface of the film of protuberance.In addition, when embodiment 3 and embodiment 10～13 are compared, distinguish sectional area S μ m ²Be preferably 10～300 with the ratio S/Y of recess breadth extreme Y μ m.In addition, when embodiment 3 and embodiment 14～17 are compared, distinguish in the zone of having implemented annular knurl processing, preferably with 10～300/cm ²Form a pair of concavo-convex.

Use the blooming of making in the foregoing description 1～17 and the comparative example 1～8, make polaroid as follows, further, these polaroids liquid crystal of packing into is represented panel (liquid crystal indicator), observability is estimated.

According to following method, be each one polaroid of making polaroid of the present invention and comparative example as polaroid protective film of KC8UCR5 (コ ニ カ ミ ノ Le タ オ プ ト Co., Ltd. system) of optical compensation films with the blooming of embodiment 1～17 and comparative example 1～8 with as cellulose esters.

(a) making of polarizing coating

Will be in polyvinyl alcohol (PVA) (being designated hereinafter simply as PVA) 100 mass parts of 99.95 moles of % of saponification degree, the degree of polymerization 2400 impregnation glycerine 10 mass parts and water 170 materials in parts by mass carry out melting mixing; After the deaeration; Melt extrude on metallic roll from the T die head, make film.Then, carry out the dried heat processing and obtain the PVA film.The average thickness of the PVA film that obtains is that 40 μ m, moisture rate are 4.4%, the film width is 3m.

Then according to the preparatory swelling of the following stated, dye, utilize damp process uniaxial tension, fixingly handle, dry, heat treated order is handled above-mentioned PVA film continuously and make the polarizing coating film.

The PVA film was soaked in 30 ℃ water 30 seconds and carries out preparatory swelling, in 35 ℃ the WS of iodine concentration 0.4g/L, potassium iodide concentration 40g/L, soaked 3 minutes.Then; The tension force that in 50 ℃ the WS of boric acid concentration 4%, is putting on film is to carry out uniaxial tension to 6 times under the condition of 700N/m, dipping 5 minutes in 30 ℃ the WS of potassium iodide concentration 40g/L, boric acid concentration 40g/L, zinc oxide concentration 10g/L and fix processing.Then, take out the PVA film, under 40 ℃, carry out heated-air drying, and then under 100 ℃, heat-treated 5 minutes.The average thickness of the polarizing coating that obtains is 13 μ m, and for polarization property, transmissivity is 43.0%, degree of polarization is 99.5%, dichroic ratio is 40.1.

(b) making of polaroid

Then, according to following operation 1～5, applying polarizing coating film and protective film for polarizing plate are made the polaroid of polaroid of the present invention and comparative example.

Operation 1: optical compensation films and blooming were flooded 90 seconds down at 60 ℃ in the sodium hydroxide solution of 3mol/L, then, wash, make its drying.

Likewise, optical compensation films was flooded 90 seconds under 60 ℃ temperature in the sodium hydroxide solution of 3mol/L, then, washing makes its drying.

Operation 2: above-mentioned polarizing coating film was flooded 1～2 second in the polyvinyl alcohol (PVA) bonding agent groove of solid constituent 2 quality %.

Operation 3: remove lightly in operation 2 attached to the bonding agent of the surplus on the polarizing coating film, be used in alkali treatment in the operation 1 optical compensation films and blooming it is sandwiched, carry out laminated configuration.

Operation 4: with the roller of 2 rotations at 20～30N/cm ²Pressure under fit with the speed of about 2m/min.Note this moment bubble is implemented with getting into.

Operation 5: in the dryer of 80 ℃ of temperature, the sample of making in the operation 4 was carried out dried 2 minutes, make polaroid.

Peel off to exactissima diligentia the most surperficial polaroid of commercially available display panels (VA type), paste the of the present invention polaroid corresponding and the polaroid of comparative example above that with the polarization direction.

(observability evaluation)

The liquid crystal panel of liquid crystal panel of the present invention that obtains as stated and comparative example is configured on the desk of floor 80cm height, on the top of floor 3m height with 10 groups of 1.5m arranged spaced with 40W * 2 piece daylight straight tube fluorescent lamp (FLR40SD/M-X Panasonic Electric Equipment Industrial Co.,Ltd system) as 1 group.At this moment, the estimator is configured to go up towards the rear mode that occurs above-mentioned fluorescent light at the top from estimator's head when the liquid crystal panel display surface is positive.Liquid crystal panel is from tilting with respect to 25 ° of the vertical direction of desk and be shining into fluorescent light, watching easness (observability) to be described below carrying out classification and estimate screen.

A: do not receive the influence that is shining into of nearest fluorescent light, can clearly read the font literal below 8 greatly down

B: the influence that be shining into by fluorescent light nearby, but do not receive to influence at a distance, also can read the literal of font size below 8 reluctantly

C: the influence that be shining into by fluorescent light at a distance is difficult to read the literal of font size below 8

D: the influence that be shining into by fluorescent light is big, and the part that is shining into can not be read the literal of font size below 8

Evaluation result is following: the evaluation result that is incorporated with the liquid crystal panel of the polaroid that has used the blooming of making in the embodiments of the invention 1～17 is the above evaluation result of grade B, and is good.Relative therewith, the evaluation result that is incorporated with the liquid crystal panel of the polaroid that has used in the comparative example 1～8 blooming of making is the evaluation result of grade D.

The explanation of symbol

1,70 films, net

12 annular knurl machined surfaces

13 protuberances

14 recesses

21 pars

50 metallic supporting masses

51,74 casting heads

52 stripper roll

53,77 stenters

54 drying devices

55 conveying rollers

56,57,78,79 cutting machines

58,82 take-up mechanisms

61,80 dandy rolls

62,81 backing rolls

71 feeding hoppers

72 mixers

73 extruders

75 touch rolls

76 chill rolls

Claims (7)

1. blooming, a plurality of protuberances that formed with recess with around recess are a pair of concavo-convex blooming for the both side ends at the Width of the film of strip has formed for it,

It is characterized in that said a pair of concavo-convex said protuberance is sentenced when cutting off with the surperficial parallel plane of said film in 1/2 of the average height on the surface of the said film of distance of this protuberance, and the sectional area S of each said protuberance is 2500～10000 μ m ², the mean breadth W of said protuberance is 3～20 μ m.

2. blooming according to claim 1 is characterized in that, said a pair of concavo-convex in,

Said sectional area S μ m ²With the ratio S/H of the average height H μ m on the surface of the said film of distance of said protuberance be 100～3000.

3. blooming according to claim 1 and 2 is characterized in that, said a pair of concavo-convex in,

Said sectional area S μ m ²With the ratio S/Y of the breadth extreme Y μ m of said recess be 10～300.

4. according to each described blooming of claim 1～3, it is characterized in that, in the both side ends of the Width of said film with 10～300/cm ²Form said a pair of concavo-convex.

5. the manufacturing approach of a blooming is characterized in that, have both side ends extruding at the Width of the film of strip and have the parts of a plurality of juts and give by the operation of the annular knurl of concavo-convex generation and the operation of batching said film,

In making each the method for blooming of claim 1～4,

Said operation of giving annular knurl; With said jut during to the extruding of the surface of said film; The height of the protuberance that will form through the membrane element of having been pushed open by said jut with the par of the base portion that constitutes said jut limits, and makes the height of the height of said protuberance for regulation.

6. a polaroid is characterized in that, in the surface configuration of polarizer each described blooming of claim 1～4.

7. a liquid crystal indicator is characterized in that, has disposed the described polaroid of claim 6.

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