CN105408779A - Polarizing plate protection film, polarizing plate and liquid crystal display device - Google Patents

Abstract

The purpose of the present invention is to provide a polarizing plate protection film which exhibits little dimensional change due to water absorption and which even when adhered to a polarizer with a water-based adhesive, can minimize the deterioration of the polarizer. This polarizing plate protection film exhibits: a tensile elasticity of 3GPa or more at 23 DEG C and 55%RH; an initial rate of elongation of 0.03 to 0.1%/min when the film has been humidified at 23+/-1 DEG C and 55%RH for 12 hours or longer, and then immersed in water at 23+/-1 DEGC; and an elongation of 0.4% or less after the immersion in water for 30 minutes.

Description

Polaroid protective film, polaroid and liquid crystal indicator

Technical field

The present invention relates to polaroid protective film, polaroid and liquid crystal indicator.

Background technology

Now, the liquid crystal indicator of the pocket of smart mobile phone, flat board etc. is popularized widely.Slimming is required for these liquid crystal indicators.

A pair polaroid that liquid crystal indicator usually has liquid crystal cell and clamped.Polaroid can have polarizer, the phase retardation film (F2 or F3) configured in its liquid crystal cell side and the diaphragm (F1 or F4) configured in the opposition side of liquid crystal cell.

As diaphragm (F1 or F4), due to for transparent, birefringence is little, it is easily bonding with polarizer etc. to stick with paste via water, therefore uses tri cellulose acetate membrane (TAC).But, because the moisture permeability of tri cellulose acetate membrane is high, therefore when being exposed under high humidity, easily there is the change in size of polarizer due to the moisture through this film.With regard to the change in size of polarizer, under high humidity, polarizer is moisture and expand; Water is extracted out from polarizer, is shunk and produce under the low humidity.The change in size of such polarizer easily produces the bending of panel (sandwich of polaroid/liquid crystal cell/polaroid); Especially, the glass plate of liquid crystal cell is thinner, easilier produces significantly.Such panel bending easily becomes the reason of the display inequality of liquid crystal indicator.

Therefore; as the diaphragm that moisture permeability is low, motion has such as cyclic olefin resin film (such as patent documentation 1), acrylic resin film (such as patent documentation 2 and 3), film (such as patent documentation 4 and 5) etc. containing acrylic resin and cellulose esters.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2004-258188 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2007-63541 publication

Patent documentation 3: Japanese Unexamined Patent Publication 2012-180423 publication

Patent documentation 4: Japanese Unexamined Patent Publication 2011-253090 publication

Patent documentation 5: Japanese Unexamined Patent Publication 2009-299075 publication

Summary of the invention

The problem that invention will solve

But, with regard to polaroid, can via water stick with paste by after diaphragm and polarizer laminating, make the sandwich that obtains dry and obtain.But if the moisture permeability of diaphragm is low, then when making above-mentioned sandwich dry, the moisture that the water entering diaphragm is stuck with paste is difficult to extract out, easily makes polarizer deterioration.Thus, there is the problem easily producing micro-red such red-deficiency at the polaroid obtained.

On the other hand, in order to the change in size of the polarizer of the reason by becoming panel bending reduces, wish that the physical strength of diaphragm is high, little by moisture caused change in size; Particularly little by moisture caused change in size.

The present invention completes in view of above-mentioned actual conditions, object for provide little by moisture caused change in size and can suppress to use water to stick with paste and bonding time the polaroid protective film of deterioration of polarizer.

For solving the means of problem

[1] polaroid protective film; wherein; tensile modulus of elasticity under 23 DEG C of 55%RH is more than 3GPa; 23 ± 1 DEG C, under 55%RH after damping more than 12 hours, in the water that impregnated in 23 ± 1 DEG C time, the elongation speed at initial stage of film is 0.03 ~ 0.1%/minute, and be less than 0.4% by the elongation of the film of film immersion in water after 30 minutes.

[2] polaroid protective film described in [1], it contains (methyl) acrylic resin.

[3] polaroid protective film described in [2], wherein, the water-octanol partition coefficient of above-mentioned (methyl) acrylic resin is more than 1.2.

[4] polaroid protective film described in any one of [1] ~ [3], relative to above-mentioned film, the cellulose esters also containing 5 ~ 25 quality %.

[5] polaroid protective film described in any one of [1] ~ [4], wherein, the water-octanol partition coefficient of above-mentioned cellulose esters is more than 0.

[6] polaroid protective film described in any one of [1] ~ [5], its contain water-octanol partition coefficient be more than 1.2 (methyl) acrylic resin and water-octanol partition coefficient be the cellulose esters of more than 0.

[7] polaroid protective film described in any one of [1] ~ [6], wherein, the thickness of above-mentioned polaroid protective film is 10 ~ 50 μm.

[8] polaroid, it contains the polaroid protective film described in any one of polarizer and [1] ~ [7].

[9] liquid crystal indicator, it contains: containing thick more than 0.3mm and less than first glass substrate of 0.7mm and the second glass substrate and the liquid crystal cell of liquid crystal layer that is configured with between above-mentioned first glass substrate and above-mentioned second glass substrate, the first polaroid that above-mentioned first glass substrate of above-mentioned liquid crystal cell is configured with, with the second polaroid be configured with on above-mentioned second glass substrate of above-mentioned liquid crystal cell, above-mentioned first polaroid contains the first polariscope, at the diaphragm F1 be configured with the face of above-mentioned liquid crystal cell opposition side of above-mentioned the first polariscope, with the diaphragm F2 that the face of the above-mentioned liquid crystal cell side at above-mentioned the first polariscope is configured with, above-mentioned second polaroid contains the second polarizer, at the diaphragm F3 that the face of the above-mentioned liquid crystal cell side of above-mentioned second polarizer is configured with, with the diaphragm F4 be configured with the face of above-mentioned liquid crystal cell opposition side at above-mentioned second polarizer, the one or both of said protection film F1 and said protection film F4 is the polaroid protective film described in any one of [1] ~ [7].

The effect of invention

According to the present invention, can provide little by moisture caused change in size and can suppress to use water to stick with paste and bonding time the polaroid protective film of deterioration of polarizer.

Accompanying drawing explanation

Fig. 1 is the figure of the relation of the elongation represented relative to the film by the elapsed time of film immersion when the water.

Fig. 2 is the schematic diagram of an example of the basic formation representing liquid crystal indicator.

Embodiment

As previously mentioned, if by the sandwich of glass substrate and polaroid from hot and humid conditional transfer to high temperature low humidity conditions, then easily there is warpage (panel bending) and make glass substrate side become convex.In order to suppress such panel bending, 1) diaphragm has the physical strength of the convergent force that can tolerate polarizer; 2) it is effective for making the convergent force of diaphragm diminish.

1) in order to improve the physical strength of diaphragm, preferred diaphragm has high tensile modulus of elasticity.But long-pending proportional due to the convergent force of diaphragm and the tensile modulus of elasticity of diaphragm and size changing amount and thickness, therefore more make the tensile modulus of elasticity of diaphragm raise, the convergent force of diaphragm more becomes greatly.Therefore, although the tensile modulus of elasticity 2 in order to improve diaphragm) convergent force of diaphragm is diminished, it is desirable to make being diminished as far as possible by moisture caused size changing amount of diaphragm.

Being depended on containing water speed (the elongation speed at initial stage) and water cut (elongation) by moisture caused size changing amount of diaphragm.Fig. 1 be represent relative to by film immersion in water time the figure of relation of elongation of film of dip time.In FIG, the elongation speed being equivalent to the film at initial stage containing water speed of film; The water cut of film is equivalent to the elongation of the film after certain hour.

In order to make to be diminished by moisture caused size changing amount, preferably making the water cut of film (elongation) and diminishing containing both water speeds (elongation speed).But if excessively make to diminish containing water speed (elongation speed), then shipwreck to extract out from film, the polaroid made using water to stick with paste easily produces micro-red (red-deficiency) (the downward arrow with reference to Fig. 1).

Therefore, in the present invention, the elongation speed of film when preferably be impregnated in water by diaphragm and elongation are adjusted to the scope of the regulation shown in oblique line portion of Fig. 1.

Particularly, with regard to diaphragm, preferably dipping and elongation after 30 minutes is less than 0.4% in the water of 23 ± 1 DEG C, is more preferably less than 0.35%, and more preferably less than 0.3%.If the elongation of diaphragm be certain below, then the water cut of film is few, and therefore the size changing amount of film is little, easily suppresses panel bending.With regard to the lower limit of the elongation of diaphragm, from order to the consideration out such as easily water moderately be extracted, can about 0.2% be set to.

With regard to diaphragm, the elongation speed at initial stage when preferably flooding in the water of 23 ± 1 DEG C is 0.03 ~ 0.1%/minute, be more preferably 0.04 ~ 0.09%/minute, more preferably 0.04%/minute more than and less than 0.08%/minute.If the elongation speed of diaphragm be certain below, then film is only large containing water speed, and the size changing amount of film therefore can be made to diminish.On the other hand, if the elongation speed of diaphragm be certain more than, then film is only little containing water speed, and therefore the water capacity is easily moderately extracted out, can be difficult to produce micro-red.

The elongation of diaphragm extends speed can according to following sequential determination.

1) under the condition of 23 ± 1 DEG C of 55%RH by diaphragm damping more than 12 hours.

2) Hitachi ハイテク society TMA/SS7100 is used the film immersion of water retting accessory will to be installed in the pure water of 23 ± 1 DEG C, taking-up and measure the elongation of film.The MD direction being determined at film of elongation is carried out.Then, obtain " elongation (%) " of the film from dipping after 30 minutes.So-called MD direction is the masking direction of film, represents the length direction of the film in coiling body; So-called TD direction is the direction that the masking direction with film is orthogonal, represents the Width of film.

3) for the measured value obtained, with transverse axis: dip time (minute), the longitudinal axis: the elongation (%) of film carries out drawing and obtaining curve.Using the curve that obtains, from dipping to the slope (slope relative to the elongation of dip time) after 2 minutes as " elongation speed (%/minute) ".

When diaphragm has slow axis in face, MD direction can be preferably in " in the face of film slow axis direction " or " direction orthogonal with slow axis direction in face "; More preferably can be in " direction orthogonal with slow axis direction in face ".

The elongation of diaphragm regulates by film composition; The elongation speed of diaphragm regulates by film composition, surface treatment.Extending speed to make the elongation of diaphragm is above-mentioned scope, preferably by relative with hydrophobicity for resin relatively high for hydrophobicity low resin combination; Or as the film surface of major component, hydrophobization process is carried out to the resin relatively low using hydrophobicity.In the example of the combination of the resin that hydrophobicity is relatively high low resin relative to hydrophobicity, the combination containing (methyl) acrylic resin described later and cellulose esters; The combination etc. of carbamate carbamide resin described later and polyester-polyurethane system plastifier.

Diaphragm, tensile modulus of elasticity under 23 DEG C of 55%RH is preferably more than 3GPa, is more preferably more than 4GPa.If the tensile modulus of elasticity of diaphragm be certain more than, then can tolerate the convergent force of polarizer, therefore easily suppress panel bending.With regard to the upper limit of the tensile modulus of elasticity of diaphragm, become difficulty from treatability and consider, can below 10GPa be set to.Diaphragm, tensile modulus of elasticity under 23 DEG C of 55%RH is preferably essentially 3GPa ~ 5GPa.

The tensile modulus of elasticity of diaphragm can measure by following method.

Diaphragm is cut out the size of 100mm (MD direction) × 10mm (TD direction), obtain sample film.By this sample film according to JISK7127, use オ リ エ ンテック society テ Application シ ロ Application RTC-1225A, make chuck spacing be 50mm, the tensile modulus of elasticity in the MD direction that stretches in the MD direction, measures.Carry out under being determined at 23 DEG C of 55%RH.

With regard to the tensile modulus of elasticity of diaphragm, can regulate mainly through film composition and manufacturing condition.In order to improve the tensile modulus of elasticity of diaphragm, preference is as improved the degree of orientation of resin by stretching.In addition, also preferably by thermal treatment, resin is carried out densification.

1. diaphragm

Diaphragm of the present invention contains (methyl) acrylic resin or carbamate carbamide resin and other resin as required or adjuvant.

(methyl) acrylic resin

(methyl) acrylic resin can be the homopolymer of (methyl) acrylate; Or (methyl) acrylate and can with the multipolymer of other monomer of its copolymerization.Wherein, from easily regulating the considerations such as hydrophobicity, preferably (methyl) acrylate and can with the multipolymer of other monomer of its copolymerization.In the present invention, (methyl) acrylate is methacrylate or acrylate.

(methyl) acrylate is preferably (methyl) alkyl acrylate, is more preferably methyl methacrylate.

Can with the example of other the monomer of (methyl) methyl acrylate copoly, containing (methyl) acrylate beyond methyl methacrylate; The α of acrylic acid, methacrylic acid etc., beta-unsaturated acid; The dicarboxylic acids containing unsaturated group of maleic acid, fumaric acid, itaconic acid etc.; The aromatic ethenyl compound of styrene, α-methyl styrene, core substituted phenylethylene etc.; The α of vinyl cyanide, methacrylonitrile etc., alpha, beta-unsaturated nitriles; Maleic anhydride; Maleimide, N-substituted maleimide amine; Glutaric anhydride etc.Alkyl in alkyl acrylate and alkyl methacrylate can be ring-type, also can be chain.These other monomer can use individually, also two or more can be combinationally used.

(methyl) acrylate beyond methyl methacrylate can be that (methyl) is acrylic acid, the chain-like alkyl ester of carbon number 1 ~ 20; The ester ring type Arrcostab of carbon number 6 ~ 20; Or the aryl ester etc. of carbon number 6 ~ 20.In the example of the chain-like alkyl ester of (methyl) acrylic acid carbon number 1 ~ 20, containing Tert-butyl Methacrylate etc.In the example of the ester ring type Arrcostab of (methyl) acrylic acid carbon number 6 ~ 20, containing t-butyl cyclohexyl ester, methacrylic acid diamantane ester, isobornyl methacrylate etc.In the example of the aryl ester of (methyl) acrylic acid carbon number 6 ~ 20, containing benzyl methacrylate, phenoxyethyl methacrylate etc.

Wherein, extending speed to make the elongation of diaphragm is above-mentioned scope, and other monomer is preferably containing the monomer that hydrophobicity is relatively high.

The monomer that hydrophobicity is relatively high is the monomer containing aromatic rings, or can be the monomer containing ester ring type group.In the example of the monomer containing aromatic rings, the aromatic ethenyl compound containing styrene, α-methyl styrene, core substituted phenylethylene etc.In the example of the monomer containing ester ring type group, containing the alkyl methacrylate etc. with cyclic alkyl.Wherein, the monomer preferably containing aromatic rings, more preferably styrene.

With regard to styrene, according to its stereoregularity, there are random isotactic polystyrene, isotactic polystyrene, syndiotactic polystyrene etc., suitably can select according to hydrophobicity.Wherein, more preferably thermotolerance high, there is hydrophobic syndiotactic polystyrene (SPS).

Relative to form above-mentioned multipolymer entire infrastructure unit, from the relatively high monomer of hydrophobicity structural unit containing proportional, also required hydrophobicity is depended on, but be preferably 20 ~ 90 quality %, be preferably 20 ~ 80 quality %, be more preferably 20 ~ 50 quality %.If from the relatively high monomer of hydrophobicity structural unit containing proportional be in above-mentioned scope, then the hydrophobicity of easy moderately raising (methyl) acrylic resin.

Relative to form above-mentioned multipolymer entire infrastructure unit, from methyl methacrylate structural unit containing proportional be preferably 10 ~ 80 quality %, be more preferably 20 ~ 80 quality %.

With regard to the weight-average molecular weight (Mw) of (methyl) acrylic resin; from in order to make the physical strength of diaphragm be certain more than, guarantee the considerations such as mobility when film is shaped; be preferably 10,000 ~ 2,000,000, be more preferably 100,000 ~ 1,000,000.

The weight-average molecular weight (Mw) of (methyl) acrylic resin is by gel permeation chromatography.Condition determination can as following.

Solvent: methylene chloride

Post: ShodexK806, K805, K803G (Showa electrician (strain) system) 3 is connected and uses.

Column temperature: 25 DEG C

Sample solution concentration: 0.1 quality %

Detecting device: RIModel504 (GL サ イ エ Application ス society system)

Pump: L6000 (Hitachi (strain) makes)

Flow: 1.0ml/ minute

Calibration curve: use and utilize polystyrene standard STKstandard polystyrene (Dong ソ ー (strain) to make) Mw=1.0 × 10 ⁶~ 5.0 × 10 ²the calibration curve that obtains of 13 samples.With regard to 13 samples, preferably select at substantially equal intervals.

With regard to (methyl) acrylic resin, from the viewpoint of the elongation speed etc. regulating diaphragm, can combine with cellulose esters as described later.From in order to obtain the considerations such as the compatibility good with cellulose esters, the solubility parameter (SP value) of the Fedors of (methyl) acrylic resin is preferably close with the SP value of cellulose esters, be preferably 16.6 ~ 20.1, be more preferably 17.7 ~ 18.6.

SP value can use the parameter of Fedors to obtain by calculating.The unit of SP value is the square root of value obtained divided by cohesion energy density △ E with molar volume V, can use " (cm ³/ cal) ^1/2".The parameter of Fedors is recorded in list of references: 54th ~ 57 pages of basic science farmland on a plateau Yong Cizhu Maki bookstore (1977) of coating.

With regard to (methyl) acrylic resin, be the considerations such as above-mentioned scope from the elongation speed elongation in order to make diaphragm etc., preferably there is the hydrophobicity of appropriateness.Therefore, the water-octanol partition coefficient (LogP value) of (methyl) acrylic resin is preferably more than 1.2, is more preferably more than 1.4.The LogP value of (if methyl) acrylic resin be certain more than, then easily make the elongation of film extend speed for below certain.On the other hand, if LogP value is too high, the elongation of film speed of extending excessively diminishes sometimes, therefore can be less than 2.8.

In order to improve the LogP value of (methyl) acrylic resin, can make such as to form the monomer that hydrophobicity containing styrene etc. in the monomer of (methyl) acrylic resin is relatively high; Or improve the relatively high monomer of this hydrophobicity containing proportional.

Carbamate carbamide resin can be the resin making polyvalent alcohol (a), polyamines (b) and polyisocyanates (c) react and obtain.

Polyvalent alcohol (a) preferably comprises polycarbonate polyol (a1) containing ester ring type structure and aromatic polyester polyol (a2).

Polycarbonate polyol (a1) containing ester ring type structure can be the compound making carbonic ester or phosgene and the polyol reaction containing ester ring type structure and obtain.In the example of carbonic ester, containing dimethyl carbonate etc.In the example of the polyvalent alcohol containing ester ring type structure, containing 1,2-ring pentanediol, Isosorbide-5-Nitrae-cyclohexanediol etc.In the object lesson of the polycarbonate polyol (a1) containing ester ring type structure, containing Yu Buxingchan society UC-100 etc.

The compound that aromatic polyester polyol (a2) carries out esterification for making aklylene glycol and aromatic dicarboxylic acid or its dialkyl compound and obtains.In the example of aklylene glycol, containing ethylene glycol, 1,2-PD etc.In the example of aromatic dicarboxylic acid, containing terephthalic acid (TPA), naphthalenedicarboxylic acid etc.; In the example of the dialkyl of aromatic dicarboxylic acid, containing dimethyl terephthalate (DMT), diethyl terephthalate etc.

With regard in polyvalent alcohol (a) containing with regard to the polycarbonate polyol (a1) of ester ring type structure and the ratio of aromatic polyester polyol (a2), from the consideration such as hydrophobicity in order to make the resin obtained have appropriateness, be preferably (a1)/(a2)=90/10 ~ 60/40, be more preferably 85/15 ~ 75/25.Containing of the structural unit from polyvalent alcohol (a) in carbamate carbamide resin is proportional, relative to the total of the structural unit of polyvalent alcohol (a), polyamines (b) and polyisocyanates (c), 40 ~ 80 quality % can be set to.

Polyamines (b) is preferably the polyamines containing ester ring type structure; In its example, containing isophorone diamine, 4,4 '-dicyclohexyl methyl hydride diamines, diamino-cyclohexane etc.Containing of the structural unit from polyamines (b) in carbamate carbamide resin is proportional, relative to the total of the structural unit of polyvalent alcohol (a), polyamines (b) and polyisocyanates (c), 1 ~ 20 quality % can be set to.

Polyisocyanates (c) is preferably the polyisocyanates containing ester ring type structure; In its example, containing isophorone diisocyanate, HMDI, 2,4 or 2,6-methylcyclohexane diisocyanates etc.Containing of the structural unit from polyisocyanates (c) in carbamate carbamide resin is proportional, relative to the total of the structural unit of polyvalent alcohol (a), polyamines (b) and polyisocyanates (c), 15 ~ 50 quality % can be set to.

Carbamate carbamide resin can make such as polyvalent alcohol (a) and polyisocyanates (c) react and obtain after molecular end contains the carbamate prepolymer of isocyanate group; This carbamate prepolymer and polyamines (b) is made to react and obtain.

In these resins, from there is appropriate hydrophobicity and easily regulating the considerations such as optical characteristics, preferably (methyl) acrylic resin.

Diaphragm of the present invention can as required also containing other resin, adjuvant etc.

With regard to other resin, from by combining with (methyl) acrylic resin, easily regulate the considerations such as the elongation elongation speed of film, preferably containing cellulose esters.

Cellulose esters

Cellulose esters is the compound making at least one of cellulose and aliphatic carboxylic acid and aromatic carboxylic acid carry out esterification and obtain.That is, cellulose esters contains at least one of aliphatic acyl radical and aromatic acyl.

The carbon number of aliphatic acyl radical is preferably 2 ~ 7, is more preferably 2 ~ 4.In the example of aliphatic acyl radical, containing acetyl group, propiono, bytyry etc.The carbon number of aromatic acyl is preferably 6 ~ 24.In the example of aromatic acyl, containing benzoyl, 4-phenyl-benzoyl, trimethylbenzoyl, thienyl, naphthyl etc., be preferably benzoyl.

Wherein, in order to improve the LogP value of cellulose esters as described later, acyl group contained in cellulose esters is preferably containing aromatic acyl; From in order to make the considerations such as the hydrophobicity of cellulose esters (LogP value) not excessively uprises, more preferably also comprise aliphatic acyl radical.In acyl group contained in cellulose esters, aromatic acyl containing ratio, relative to the total of acyl group, 5 ~ 25%, preferably about 10 ~ 20% can be set to.

In the object lesson of cellulose esters, containing cellulose-acetate propionate, acetic acid cellulose benzoate, acetate propionate cellulose benzoate, acetic acid diphenic acid cellulose, acetate propionate diphenic acid cellulose etc., consider from the hydrophobicity with appropriateness, preferred acetic acid cellulose benzoate etc.

Total degree of substitution of the acyl group of cellulose esters is more than 2.0, is preferably more than 2.5, is more preferably more than 2.7, more preferably more than 2.8.The upper limit of total degree of substitution of acyl group can be set to such as 3, preferably 2.95.In order to improve the hydrophobicity (LogP value) of cellulose esters, preference is as improved total degree of substitution of acyl group.

With regard to the degree of substitution of the acyl group of cellulose esters, can measure by the method specified in ASTM-D817-96.

With regard to the weight-average molecular weight of cellulose esters, in order to obtain certain above physical strength, being preferably 50,000 ~ 500,000, being more preferably 100,000 ~ 300,000, more preferably 150,000 ~ 250,000.The molecular weight distribution (weight-average molecular weight Mw/ number-average molecular weight Mn) of cellulose esters is preferably 1.0 ~ 4.5.The weight-average molecular weight of cellulose esters and molecular weight distribution, measure by gel permeation chromatography (GPC) in the same manner as aforementioned.

With regard to cellulose esters, from the elongation speed elongation in order to make diaphragm etc. in considerations such as above-mentioned scopes, preferably there is the hydrophobicity of appropriateness.Therefore, the water-octanol partition coefficient (LogP value) of cellulose esters is preferably more than 0, is more preferably more than 0.5, and more preferably more than 1.0.If the LogP value of cellulose esters be certain more than, such as, easily obtain appropriate hydrophobicity when combine with (methyl) acrylic resin.If the LogP value of cellulose esters is too high, likely reduces with the compatibility of (methyl) acrylic resin, therefore can be set to less than 6.5.

In order to improve the LogP value of cellulose esters, as described above, aromatic acyl can be contained; Or improve this aromatic acyl containing proportional.

The LogP value of cellulose esters is preferably less than 8 with the absolute value of the difference of the LogP value of (methyl) acrylic resin, is more preferably less than 6.If the difference of LogP value be certain below, then cellulose esters is easily compatible with (methyl) acrylic resin, easily obtains the additive effect of cellulose esters.

With regard to the content of cellulose esters, all relative to diaphragm, be preferably 5 ~ 25 quality %, be more preferably 5 ~ 15 quality %.By making the content of cellulose esters for more than certain, the elongation easily improving diaphragm extends speed (particularly elongation).By making the content of cellulose esters for below certain, the elongation that can control diaphragm exceedingly raises.

In the example of adjuvant, containing plastifier, ultraviolet light absorber, matting agent (particulate) etc.

Plastifier contains Polyester plastifier, phthalic ester system plastifier, phosphate plasticizer, acrylic acid series plastifier etc.They can use individually, also can be used in combination of two or more.

Polyester plastifier contains the repetitive of the condensation product from dicarboxylic acid and glycol.

Dicarboxylic acid can be aliphatic dicarboxylic acid, ester ring type dicarboxylic acid or aromatic dicarboxylic acid.The carbon number of aliphatic dicarboxylic acid is preferably 4 ~ 20, is more preferably 4 ~ 12.In the example of aliphatic dicarboxylic acid, containing malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, heneicosane dicarboxylic acid, dodecanedicarboxylic acid etc.

The carbon number of aromatic dicarboxylic acid is preferably 8 ~ 20, is more preferably 8 ~ 12.In the example of aromatic dicarboxylic acid, containing 1,2-phthalic acid (phthalic acid), 1,3-phthalic acid (m-phthalic acid), Isosorbide-5-Nitrae-phthalic acid (terephthalic acid (TPA)), 1,5-naphthalenedicarboxylic acid, 1,4-dimethylaniline dicarboxylic acid (1, the acid of 4-キ シ リ デ Application ジ カ Le ボ Application) etc., be preferably Isosorbide-5-Nitrae-phthalic acid (terephthalic acid (TPA)).

The carbon number of ester ring type dicarboxylic acid is preferably 6 ~ 20, is more preferably 6 ~ 12.In the example of ester ring type dicarboxylic acid, containing 1,3-cyclobutane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, Isosorbide-5-Nitrae-cyclohexanediacetic etc.

Can be a kind of for obtaining the dicarboxylic acid of petchem, also can be more than two kinds.For obtaining the dicarboxylic acid of petchem, from the hydrophobicity in order to improve transparent substrate layer or improve and the consideration such as the compatibility of cellulose esters, preferably containing aromatic dicarboxylic acid, more preferably containing both aromatic dicarboxylic acid and aliphatic dicarboxylic acid.

Glycol can be aliphatic diol, alkyl ether glycol, ester ring type glycol or aromatic diol.

The carbon number of aliphatic diol is preferably 2 ~ 20, is more preferably 2 ~ 12.In the example of aliphatic diol, containing ethylene glycol, 1,2-PD, 1,3-PD, 1,2-butylene glycol, 1,3-BDO, 1,2-PD etc.The carbon number of alkyl ether glycol is preferably 4 ~ 20, is more preferably 4 ~ 12.In the example of alkyl ether glycol, containing polytetramethylene ether diol, poly-ether glycol and polytrimethylene ether glycol etc.

The carbon number of ester ring type glycol is preferably 4 ~ 20, is more preferably 4 ~ 12.In the example of ester ring type glycol, containing Isosorbide-5-Nitrae-cyclohexanediol, 1,4-CHDM etc.

The carbon number of aromatic diol is preferably 6 ~ 20, is more preferably 6 ~ 12.In the example of aromatic diol, containing 1,2-dihydroxy benzenes (catechol), 1,3-dihydroxy benzenes (resorcinol), Isosorbide-5-Nitrae-dihydroxy benzenes (quinhydrones) etc.Can be a kind of for obtaining the glycol of petchem, also can be more than two kinds.For obtaining the glycol of petchem preferably containing aliphatic diol.

Wherein, the petchem of the repetitive containing the condensation product from the dicarboxylic acid containing aromatic dicarboxylic acid and aliphatic dicarboxylic acid and aliphatic diol, good from the viewpoint of the transparency of the film containing it, preferably.

For the molecular end of petchem, can as required with monocarboxylic acid or monohydroxy alcohol end-blocking.

Monocarboxylic acid can be aliphatics monocarboxylic acid, ester ring type monocarboxylic acid or aromatic series monocarboxylic acid.The monocarboxylic carbon number of aliphatics can be preferably 2 ~ 30, can be more preferably 2 ~ 4.In the example of aliphatic carboxylic acid, containing acetic acid, propionic acid etc.In the monocarboxylic example of ester ring type, containing cyclohexyl monocarboxylic acid etc.In the monocarboxylic example of aromatic series, containing benzoic acid, p-tert-butyl benzoic acid, adjacent toluic acid, a toluic acid, to toluic acid, mesitylenic acid, ethyl benzoate, n-propylbenzene formic acid, aminobenzoic acid, acetoxy-benzoic acid, phenyl acetic acid, 3-phenylpropionic acid etc.

Monohydroxy alcohol can be aliphatic monobasic alcohol, ester ring type monohydroxy alcohol or aromatic monoalcohols.The carbon number of aliphatic monobasic alcohol is 1 ~ 30, can be preferably 1 ~ 3.In the example of aliphatic monobasic alcohol, containing methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol etc.In the example of ester ring type monohydroxy alcohol, containing cyclohexanol etc.In the example of aromatic monoalcohols, containing benzylalcohol, 3-phenyl propanol etc.

In the object lesson of petchem, containing following material.In Table 1, TPA represents: terephthalic acid (TPA), and PA represents: phthalic acid, and SA represents: succinic acid, and AA represents: hexane diacid.

In the example of phthalic ester system plastifier, containing diethyl phthalate, phthalic acid dimethoxy-ethyl ester, repefral, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, terephthalic acid (TPA) dicyclohexyl maleate etc.

In the example of phosphate plasticizer, containing triphenyl phosphate, tricresyl phosphate (toluene) ester, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate and tributyl phosphate etc.

Acrylic acid series plastifier can not have homopolymer or the multipolymer of aromatic rings (methyl) acrylate monomer in molecule.Wherein, preferably not there is aromatic rings, there is (methyl) acrylate X of hydrophilic radical and not there is aromatic rings, not there is the multipolymer of (methyl) acrylate Y of hydrophilic radical.

Not there is aromatic rings, having in the example of (methyl) acrylate X of hydrophilic radical, containing (methyl) acrylic acid (2-hydroxyethyl) ester, (methyl) acrylic acid (2-hydroxypropyl) ester, (methyl) acrylic acid (3-hydroxypropyl) ester, (methyl) acrylic acid (4-hydroxybutyl) ester, (methyl) acrylic acid (2-hydroxybutyl) ester etc.

Not there is aromatic rings, do not have in the example of (methyl) acrylate Y of hydrophilic radical, containing methyl acrylate, ethyl acrylate, acrylic acid propyl group is (iso-, n-) ester, acrylic acid butyl is (n-, iso-, secondary-, uncle-) ester, acrylic acid amyl group is (n-, iso-, secondary-) ester, acrylic acid hexyl is (n-, iso-) ester, acrylic acid heptyl is (n-, iso-) ester, acrylic acid octyl group is (n-, iso-) ester, nonylphenol acrylate is (n-, iso-) ester, acrylic acid myristyl is (n-, iso-) ester, acrylic acid (2-ethylhexyl) ester etc.

In the multipolymer of (methyl) acrylate Y and Y, from (methyl) acrylate X structural unit can be X:Y=1:1 ~ 1:99 with the structural unit from (methyl) acrylate Y containing ratio (mol ratio).

The weight-average molecular weight of acrylic acid series plastifier is preferably 500 ~ 30000, is more preferably 500 ~ 10000.Weight-average molecular weight is that the acrylic acid series plastifier in above-mentioned scope is good with the compatibility of (methyl) acrylic resin etc., is also difficult to volatilize in masking.

Polyester-urethane system plastifier

Polyester-urethane system plastifier can use preferably as the plastifier of carbamate carbamide resin.Polyester-urethane system plastifier is reaction by polyester and diisocyanate and the polyester-urethane obtained, and has the repetitive represented by following general formula (1).

[changing 1]

General formula (1)

In general formula (1), l represents the integer of 2 ~ 4; M represents the integer of 2 ~ 4; N represents 1 ~ 100.R represents at following shown structural unit; Phenyl ring in following structural unit also can have the substituting group of alkyl etc.

[changing 2]

Polyester for obtaining polyester-urethane system plastifier can make glycol and dibasic acid react the polyester obtaining, have at two ends hydroxyl.In the example of glycol, containing ethylene glycol, 1,3-PD and BDO etc.; In the example of dibasic acid, containing succinic acid, glutaric acid and hexane diacid etc.The polymerization degree n of polyester is preferably 1 ~ 100.The molecular weight of polyester is preferably 1000 ~ 4500.

With regard to the diisocyanate for obtaining polyester-urethane system plastifier, the polymethylene isocyanates of ethylidene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate etc., p-phenylene vulcabond, toluene diisocyanate, right can be enumerated, right ' the aromatic diisocyanate of-methyl diphenylene diisocyanate, 1,5-naphthalene diisocyanate etc., m-XDI etc.Wherein, with regard to toluene diisocyanate, m-XDI, tetramethylene diisocyanate, good with the compatibility of cellulose esters after due to polyurethane-reinforcement, therefore preferably.

The weight-average molecular weight of polyester-urethane system plastifier is preferably 2000 ~ 50000, is more preferably 5000 ~ 15000.

With regard to the total of the content of these plastifier, relative to the total (total of (methyl) acrylic resin and carbamate carbamide resin) of resinous principle becoming major component, be preferably 0.5 ~ 30 quality %, be more preferably 5 ~ 20 quality %.If the content of plastifier is that in above-mentioned scope, then film does not ooze out, easily obtain plasticized effect.

For making the elongation of diaphragm speed of extending be in the example of above-mentioned scope, preferred film composition, containing 1) LogP value is (methyl) acrylic resin of more than 1.2 and the combination of cellulose esters; 2) (methyl) acrylic resin and LogP value are the combination of the cellulose esters of more than 0; 3) LogP value be more than 1.2 (methyl) acrylic resin and LogP value be the combination etc. of the cellulose esters of more than 0.Wherein, by the elongation of diaphragm, speed of extending is adjusted to preferred scope due to easy, therefore preferably 3) LogP value be more than 1.2 (methyl) acrylic resin and LogP value be the combination of the cellulose esters of more than 0.

Ultraviolet light absorber

Ultraviolet light absorber can be benzotriazole based compound, 2-dihydroxy benaophenonel based compound or phenyl salicylate based compound etc.In their example, containing 2-(5-methyl-2-hydroxy phenyl) benzotriazole, 2-[2-hydroxyl-3, two (the α of 5-, α-dimethylbenzyl) phenyl]-2H-benzotriazole, 2-(3,5-bis--tert-butyl-2-hydroxy phenyl) benzophenone of triazole type, ESCALOL 567,2-hydroxyl-4-octyloxybenzophenone, 2,2 '-dihydroxy-4-methoxy benzophenone etc. of benzotriazole etc.

Wherein, with regard to the ultraviolet light absorber that molecular weight is more than 400 because for higher boiling, be difficult to volatilization, hot forming time be also difficult to disperse, therefore easily just effectively obtain weatherability with more a small amount of interpolation.Therefore, the molecular weight of ultraviolet light absorber is preferably 250 ~ 1000, is more preferably 400 ~ 800.Be in the example of the ultraviolet light absorber of more than 400 at molecular weight, containing 2-[2-hydroxyl-3, two (the α of 5-, α-dimethylbenzyl) phenyl]-2 benzotriazole, 2,2-di-2-ethylhexylphosphine oxide [4-(1,1,3, the 3-tetrabutyl)-6-(2H-benzotriazole-2-base) phenol] etc.

With regard to the content of ultraviolet screener, in diaphragm, in mass ratio, be preferably 0.001% ~ 5%, be more preferably 0.1 ~ 3%.

Matting agent

Matting agent can give sliding to diaphragm.Matting agent can be inorganic particles or organic fine particles.

In the example of mineral compound forming inorganic particles, containing silicon dioxide, titania, aluminium oxide, zirconia, calcium carbonate, calcium carbonate, talcum, clay, burn till porcelain earth, burn till calcium silicate, afwillite, alumina silicate, magnesium silicate, calcium phosphate etc.Wherein, from the little consideration of the increase of the mist degree of film, preferred silicon dioxide.

In the example of silicon dioxide, containing ア エ ロ ジ Le 200V, ア エ ロ ジ Le R972V, ア エ ロ ジ Le R972, R974, R812, R202, (above Japanese ア エ ロ ジ Le (strain) manufactures), シ ー ホ ス タ ー KEP-10, KEP-30, KEP-50 (above for Nippon Shokubai Co., Ltd manufactures) etc.

To the shape of particle, there is no particular restriction, can be unsetting, needle-like, flat, spherical etc.Wherein, well consider from the transparency of the transparent substrate layer obtained, preferably spherical particle.

With regard to the size of particle, if close to the wavelength of visible ray, then light scattering, the transparency reduce, and therefore the preferred wavelength than visible ray is little, is more preferably less than 1/2 of the wavelength of visible ray.If the size of particle is too small, then sometimes slides and can not get improving, be therefore preferably the scope of 80nm to 180nm.The size of so-called particle, when particle is the condensed matter of 1 particle, means the size of condensed matter.In addition, when particle is not spherical, the diameter of a circle suitable with its projected area is meaned.

With regard to the content of matting agent, relative to the total (total of (methyl) acrylic resin and carbamate carbamide resin) of resinous principle becoming major component, about 0.05 ~ 1.0 quality % can be set to, preferably can be set to 0.1 ~ 0.8 quality %.

With regard to diaphragm, from order to elongation speed when impregnated in water is easily adjusted to the considerations such as above-mentioned scope, surface treatment can be implemented as required.Such as, based on film hydrophobicity deficiency situation (situations of such as low for LogP value (methyl) acrylic resin film etc.) under, hydrophobization process can be carried out to the surface of this film.With regard to hydrophobization process, can contact with modifier (such as 3H-tetrafluoro propionyl chloride etc.) and carry out after such as corona treatment carried out to film surface, in the presence of a catalyst.

With regard to the thickness of diaphragm, reduce diaphragm convergent force in, be preferably certain below; Reduce water through in, be preferably certain more than.Therefore, the thickness of diaphragm is preferably 10 ~ 80 μm, is more preferably 10 ~ 70 μm, more preferably 10 ~ 50 μm, is particularly preferably 10 ~ 40 μm.

Diaphragm can be monofilm, also can be stacked film.When diaphragm is stacked film, the whole layer preferably forming diaphragm have aforesaid composition (preferably, LogP to be certain above cellulose esters with LogP be certain more than the combination of (methyl) acrylic resin).

On diaphragm of the present invention, do not damaging the scope of effect of the present invention, as required also can other functional layer of further stacked anti-reflection layer etc.

The physical property of diaphragm

(mist degree)

The haze value of diaphragm is preferably less than 3.0%, is more preferably less than 2.0%, and more preferably less than 1.0%, be particularly preferably less than 0.5%.The mist degree of diaphragm can measure according to JISK-7136, use haze meter (nephelometer) (model: NDH2000, Japanese electric look (strain) manufacture).

(delay)

With regard to diaphragm, the delay R in direction in the face measured under the condition of mensuration wavelength 590nm, 23 DEG C of 55%RH ₀preferably meet 0≤R ₀≤ 20nm, more preferably meets 0nm≤R ₀≤ 10nm.Diaphragm, preferably meet 0nm≤Rth≤80nm at the delay Rth measuring the thickness direction measured under the condition of wavelength 590nm, 23 DEG C of 55%RH, more preferably meet 0nm≤Rth≤50nm.There is the diaphragm of such length of delay, as described later, can preferably use as the diaphragm (F1 or F4) of liquid crystal indicator.R ₀regulate by the composition, stretching condition etc. of film with Rth.

Postpone R ₀defined by following formula respectively with Rth.

Formula (I): R ₀=(nx-ny) × d (nm)

Formula (II): Rth={ (nx+ny)/2-nz} × d (nm)

(in formula (I) and (II),

In the face that nx represents diaphragm, on direction, refractive index becomes the refractive index on maximum slow axis direction x; Refractive index on direction y orthogonal with above-mentioned slow axis direction x on direction in the face that ny represents diaphragm; Nz represents the refractive index on the thickness direction z of diaphragm; D (nm) represents the thickness of diaphragm)

Postpone R ₀can be obtained by such as following method with Rth.

1) under 23 DEG C of 55%RH, damping is carried out to diaphragm.The mean refractive index of the optical compensation films after damping is measured with Abbe refractometer etc.

2) R when making the light of mensuration wavelength 590nm incide the diaphragm after damping abreast with this film normal to a surface is measured with KOBRA21DH, prince's measurement (strain) ₀.

3) KOBRA21ADH is passed through; using the slow axis in the face of diaphragm as sloping shaft (turning axle), measure the length of delay R (θ) when making the light of mensuration wavelength 590nm incident relative to the normal to a surface of diaphragm from the angle (incident angle (θ)) of θ.With regard to the mensuration of length of delay R (θ), can θ be 0 ° ~ 50 ° scope, every 10 ° carry out 6 points.With regard to the slow axis in the face of diaphragm, can be confirmed by KOBRA21ADH.

4) by the R determined ₀and R (θ) and aforesaid mean refractive index and thickness, by KOBRA21ADH, calculate nx, ny and nz, calculate the Rth measured under wavelength 590nm.The mensuration postponed can be carried out under 23 DEG C of 55%RH conditions.

In the face of diaphragm slow axis and film Width formed by angle θ 1 (angle of orientation) be preferably-1 ° ~+1 °, be more preferably-0.5 ° ~+0.5 °.The mensuration of the angle of orientation θ 1 of diaphragm can use automatic birefringence meter KOBRA-WR (prince measures machine) to measure.

The full light transmittance of diaphragm is preferably more than 80%, is more preferably more than 90%, and more preferably more than 93%.

Diaphragm can adopt solution film-forming method or melting masking method to make.Wherein, owing to easily obtaining the film etc. that planarity is high, the fault of linear is few, therefore preferred solution the tape casting.

Utilize the manufacture of the diaphragm of the present invention of solution casting method to carry out preferably through following operation: 1) to make above-mentioned each component dissolves obtain the operation of rubber cement liquid, 2 in solvent) by this rubber cement liquid curtain coating to the operation in the metal support of ring-type, 3) will the glue slurry dried of curtain coating be made and the operation peeled off from metal support of the membranoid substance obtained.

1) dissolution process

With regard to organic solvent useful in the preparation of rubber cement liquid, as long as above-mentioned each composition of (methyl) acrylic resin, carbamate carbamide resin etc. is dissolved simultaneously, then can unrestrictedly use.

Such as, as chlorine-based organic solvent, methylene chloride can be enumerated.As chlorine-free organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, DOX, Isosorbide-5-Nitrae-two 2 can be enumerated, 3,3-hexafluoro-1-propyl alcohol, 1,3-bis-fluoro-2-propyl alcohol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propyl alcohol, 2,2, the fluoro-1-propyl alcohol of 3,3,3-five, nitroethane etc.Wherein, preferred methylene chloride, methyl acetate, ethyl acetate, acetone etc.

In rubber cement, except above-mentioned organic solvent, the aliphatic alcohol of the straight or branched of the carbon number 1 ~ 4 preferably containing 1 ~ 40 quality %.By making containing alcohol in rubber cement liquid, membranoid substance gelation, become easy from the stripping of metal support.

As the aliphatic alcohol of the straight or branched of carbon number 1 ~ 4, methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, sec-butyl alcohol, the tert-butyl alcohol can be enumerated.Wherein, from the stability of rubber cement, boiling point also lower, drying property might as well etc. consideration, preferred alcohol.

With regard to the dissolving of cellulose esters etc., there are the method for carrying out at ambient pressure, the method for carrying out below the boiling point of main solvent, a method etc. of carrying out of pressurizeing more than the boiling point of main solvent, particularly preferably in the method for carrying out of more than boiling point of main solvent pressurizeing.

The concentration of the cellulose esters in rubber cement liquid etc. can be set to the scope of meter 15 ~ 45 quality %.With regard to rubber cement liquid, in order to by the foreign matter removing in rubber cement liquid, preferably filtered further.

2) curtain coating operation

By liquid-feeding pump (such as, compression type quantitative gear pump) by rubber cement liquid liquor charging to pressurization die head.Then, from the slit of pressurization die head, by rubber cement liquid curtain coating to ad infinitum carrying out in the metal support of the annular transferred the casting position of (metal drum etc. that such as stainless steel band or carry out rotates).

The shape of slit of the mouth mould part of die head can be regulated, preferably easily make the pressurization die head of uniform film thickness.In pressurization die head, there are rack type die, T-shaped die head etc., all can preferably use.The surface of metal support becomes minute surface.In order to improve film speed, can arrange in metal support the pressurization die head of more than 2, by the flow of rubber cement liquid segmentation and overlapping.Or also by multiple rubber cement liquid being carried out the common the tape casting of curtain coating and obtain the film of stepped construction simultaneously.

3) solvent evaporation stripping process

Rubber cement liquid by curtain coating in metal support heats in metal support, makes the solvent in rubber cement liquid evaporate and obtain membranoid substance.

In order to make solvent evaporate, have the method from rubber cement liquid level cross air blow, method that the back side from supporting mass is undertaken conducting heat by liquid, carried out the method etc. of conducting heat from the table back of the body by radiation heat, the drying efficiency of rear surface liquid heat-transferring method is high, preferably.Under atmosphere preferably in the scope of 40 ~ 100 DEG C, the glue slurry dried made on supporting mass in metal support.Under maintaining the atmosphere in the scope of 40 ~ 100 DEG C, preferably make the rubber cement liquid level on the warm air contacting metal supporting mass of this temperature or heated by the means of infrared ray etc.

The membranoid substance obtained making solvent evaporate in metal support is peeled off in stripping position.From the viewpoint of face quality, moisture-penetrability, the fissility of the membranoid substance obtained, preferably within 30 ~ 120 seconds, membranoid substance is peeled off from metal support after curtain coating.The temperature of the stripping position in metal support is preferably the scope of 10 ~ 40 DEG C, is more preferably the scope of 11 ~ 30 DEG C.

The residual solvent amount of the membranoid substance in metal support during stripping can be set to the scope of such as 50 ~ 120 quality %.

The residual solvent amount of membranoid substance is defined by following formula.

Residual solvent amount (%)=(before the heating of membranoid substance quality-membranoid substance heating after quality)/(after the heating of membranoid substance quality) × 100

So-called heating when measuring residual solvent amount, represents the heating carried out at 140 DEG C 1 hour.

Stripping tension force when metal support and film are peeled off is generally in the scope of 196 ~ 245N/m, but when easily producing gauffer when peeling off, preferably peeling off with the tension force of below 190N/m, more preferably peeling off with the tension force of below 80N/m.

For the membranoid substance peeled off, can carry in drying device with multiple roller be configured with as required while make it dry.With regard to dry, the method two sides of membranoid substance being blowed to hot blast is general method, but can replace hot blast and irradiating microwaves heats.From first to last, drying is carried out in the scope of roughly 40 ~ 250 DEG C.Especially, in the scope of 40 ~ 200 DEG C, preferably make it dry.When making its drying with stenter stretching device, the baking temperature preferably scope of 30 ~ 160 DEG C, the more preferably scope of 50 ~ 150 DEG C.

As previously mentioned, in order to improve the tensile modulus of elasticity of diaphragm, preferably by above-mentioned 3) film that obtains carries out stretching and makes molecular resin orientation.Therefore, can carry out above-mentioned 3 further) film that obtains carries out the operation (stretching process) that stretches.

4) stretching process

With regard to the stretching of film obtained, can at least one party in the Width of film (TD direction), throughput direction (MD direction) or vergence direction upwards stretch.At the Width (TD direction) of film and throughput direction (MD direction), both stretches, the stretching of the Width (TD direction) of film and the stretching of throughput direction (MD direction) can successively be carried out, and also can side by side carry out.

Stretching ratio can be set to 1.01 ~ 3.0 times, preferably 1.1 ~ 2.0 times in all directions.Both stretches at the Width (TD direction) of film and throughput direction (MD direction), in all directions, be preferably finally set to 1.01 ~ 3.0 times, preferably 1.1 ~ 2.0 times.

Draft temperature is preferably Tg ~ (Tg+50) DEG C, is more preferably Tg ~ (Tg+40) DEG C.Particularly, when the potpourri of (methyl) acrylic resin/cellulose esters, draft temperature can be set to about 100 ~ 190 DEG C.

In order to the delay of film obtained after regulating stretching, or change in size is reduced, the film obtained after can making stretching is as required at throughput direction (MD direction) or Width (TD direction) is upper shrinks.In order to the film obtained after making stretching shrinks at throughput direction (MD direction), such as, the fixture held in the direction of the width can be removed and make it relax at throughput direction.

5) rolling step

The diaphragm obtained can provide with long size shape, also can with individual sheet (Mei Leaf shape) provide.With regard to the diaphragm of long size shape, usually, the coiling body of length direction (MD direction) wound into rolls can be formed in.

The length of the diaphragm of long size shape can be set to the scope of 100 ~ 10000m.The width of the diaphragm of long size shape can be set to the scope of scope, the preferably 1.4 ~ 3m of 1 ~ 4m.

2. polaroid

The diaphragm that polaroid of the present invention contains polarizer and is at least simultaneously configured with at it.

For polarizer

Polarizer can be iodine system polarizing coating or the dyestuff system polarizing coating employing two look dyestuffs.With regard to iodine system polarizing coating and dyestuff system polarizing coating, usually, can be the film will obtained after polyvinyl alcohol mesentery uniaxial tension, with iodine or dichroic dye dyeing; Also can be by after polyvinyl alcohol mesentery iodine or dichroic dye dyeing, the film (preferably, implementing the film of permanance process further with boron compound) of uniaxial tension.The absorption axle of polarizer is parallel with the draw direction of film.

Polyvinyl alcohol mesentery can be the film being filmed polyvinyl alcohol water solution and obtaining.With regard to polyvinyl alcohol mesentery, from polarization property and excellent durability, look inequality waits consideration less, optimal ethylene modified PVA membrane.

In the example of dichroic dye, containing azo system pigment, 1,2-talan system pigment, pyrazolone system pigment, triphenyl methane system pigment, quinoline system pigment, piperazine system pigment, thiazine system pigment and anthraquinone system pigment etc.

With regard to the thickness of polarizer, from considerations such as the convergent forces in order to reduce polarizer, being preferably less than 30 μm, being more preferably the scope of 2 ~ 25 μm.

For diaphragm (F1 or F4)

Diaphragm is preferably diaphragm of the present invention.Preferably with the MD direction of the diaphragm mode consistent with the absorption direction of principal axis of polarizer by diaphragm of the present invention and polarizer stacked.Because with regard to the convergent force of polarizer, think that absorption direction of principal axis is maximum.

For phase retardation film (F2 or F3)

Polarizer, the face of the opposition side in the face that is configured with aforesaid diaphragm, aforesaid diaphragm can be configured further; Also configurable phase retardation film.

To phase retardation film, there is no particular restriction, can be such as cellulose ester membrane.In the example of cellulose esters contained in cellulose ester membrane, containing cellulose acetate, cellulose-acetate propionate, acetate propionate cellulose butyrate etc.

Total acyl substitution of cellulose esters is preferably more than 1.5 and less than 2.5, more preferably meets following formula (a) and (b) simultaneously.

Formula (a) 2.0≤X+Y≤2.5

Formula (b) 0≤Y≤1.5 (in formula, X represents the degree of substitution of acetyl group, and Y represents the degree of substitution of propiono or bytyry or their potpourri)

The delay of phase retardation film can set according to the kind of the liquid crystal cell of combination.Such as, phase retardation film, postpone the scope that Ro (590) can be set to 30 ~ 150nm under 23 DEG C of RH55%, in the face that measures under wavelength 590nm, the delay Rth (590) of thickness direction can be set to the scope of 70 ~ 300nm.The phase retardation film that delay is above-mentioned scope is suitable as the phase retardation film of such as VA type liquid crystal cell etc.

Polaroid can through obtaining the step of polarizer and diaphragm laminating.With regard to the laminating of diaphragm and polarizer, the polyethenol series bonding agent of fully saponified type (water paste) can be used, active energy ray-curable bonding agent carries out.Such as, when using water to stick with paste in laminating, after polarizer and diaphragm can being stuck with paste laminating via water; Make the sandwich that obtains dry and obtain polaroid.

The amount of cellulose esters contained in diaphragm is few, sometimes with water stick with paste can not fully by diaphragm and polarizer bonding.In this situation, easy adhesive linkage can be formed at diaphragm further with the binding face of polarizer.

With regard to easy adhesive linkage, after the resin combination containing the carbamate resins and crosslinking chemical with carboxyl can being coated with, making its drying and be solidified to form.Such as, with regard to the carbamate resins with carboxyl, except polyvalent alcohol and polyisocyanates, make the cahin extension agent (Lock Long drug with free carboxy further) copolymerization and obtaining.In the example of cahin extension agent with free carboxy, containing dihydroxy carboxylic acids, dihydroxysuccinic acid etc.Crosslinking chemical preferably have can with the polymkeric substance of the group of carboxyl reaction; In its example, containing having the acrylic acid series polymeric compounds of azoles quinoline base or styrene acrylic based polymer etc.

With regard to diaphragm contained in polaroid of the present invention, elongation is extended both speed and be adjusted to necessarily.Thus, when making to stick with paste the sandwich drying of diaphragm and polarizer having been fitted via water, the moisture that the water entering into diaphragm is stuck with paste moderately can be extracted out.Thus, in order to the moisture removing will remained in diaphragm, when carrying out heating and make it dry, polarizer can be suppressed deteriorated and micro-red (red-deficiency) of the polaroid of generation.

3. liquid crystal indicator

Liquid crystal indicator of the present invention contains liquid crystal cell and clamps its a pair polaroid.And, at least one of a pair polaroid can be made to be polaroid of the present invention.

Fig. 2 is the schematic diagram of an example of the basic formation representing liquid crystal indicator.As shown in Figure 2, liquid crystal indicator 10 of the present invention is containing liquid crystal cell 30, the first polaroid 50 clamped and the second polaroid 70 and backlight 90.

The transparency carrier 31 and 33 that liquid crystal cell 30 has a pair and the liquid crystal layer 35 clamped between which.

Transparency carrier 31 and 33 is preferably glass substrate.From in order to liquid crystal indicator is carried out the considerations such as slimming, the thickness of glass substrate be preferably certain below, be preferably more than 0.3mm and less than 0.7mm, be more preferably 0.3 ~ 0.5mm.

The display mode of liquid crystal cell 30 can be the various display mode of such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS etc., in order to obtain high contrast, is preferably VA (MVA, PVA) pattern.

Such as, in the liquid crystal cell of VA mode, with regard to the transparency carrier of a side, be configured for and alive pixel electrode is executed to liquid crystal molecule.Opposite electrode is configurable in the transparency carrier of (being configured with pixel electrode) one side, also configurable in the transparency carrier of the opposing party.

Liquid crystal layer contains the liquid crystal molecule of the dielectric constant anisotropy with negative or positive.With regard to liquid crystal molecule, the orientation control force of the alignment films arranged by the face of the liquid crystal layer side at transparency carrier, when not applying voltage (when not producing electric field between pixel electrode and opposite electrode), the major axis of liquid crystal molecule is relative to the surface generally perpendicularly orientation of transparency carrier.

In the liquid crystal cell of the VA mode formed like this, by applying picture signal (voltage) to pixel electrode, make to produce electric field between pixel electrode and opposite electrode.Thus, the liquid crystal molecule relative to the surface vertically initial stage orientation of transparency carrier is made to become the mode orientation of horizontal direction relative to real estate with its major axis.Like this, drive liquid crystal layer, make transmissivity and the reflectivity change of each secondary pixel, carry out image display.

With regard to the first polaroid 50, can be configured on the glass substrate 31 of liquid crystal cell 30 via adhesive phase (not shown).The diaphragm 55 (F2) that first polaroid 50 comprises the first polariscope 51, the diaphragm 53 (F1) be configured with in the face of the visible side of the first polariscope 51 and is configured with in the face of the liquid crystal cell side of the first polariscope 51.

With regard to the second polaroid 70, can be configured on the glass substrate 33 of liquid crystal cell 30 via adhesive phase (not shown).The diaphragm 75 (F4) that second polaroid 70 comprises the second polarizer 71, the diaphragm 73 (F3) be configured with in the face of the liquid crystal cell side of the second polarizer 71 and is configured with in the face of the backlight side of the second polarizer 71.

The thickness of adhesive phase can be set to about 1 ~ 30 μm.

And, can make at least one of the first polaroid 50 and the second polaroid 70 or both be polaroid of the present invention.That is, at least one of diaphragm 53 (F1) and diaphragm 75 (F4) can be made to be diaphragm of the present invention.The MD direction of preferred diaphragm 53 (F1) is consistent with the absorption direction of principal axis of the first polariscope 51.The MD direction of preferred diaphragm 75 (F4) is consistent with the absorption direction of principal axis of the second polarizer 71.

As previously mentioned, with regard to diaphragm of the present invention, the elongation speed of extending is adjusted to certain below.Thus, with regard to diaphragm of the present invention, although have high tensile modulus of elasticity, the change in size of (make its from when changing under high temperature low humidity hot and humid) diaphragm is little; That is, there is high physical strength and alleviate by moisture caused convergent force.Thus, the panel bending easily produced when the glass substrate of liquid crystal cell can be suppressed thin.

Embodiment

Below, enumerate embodiment and the present invention is specifically described, but the present invention is not limited to these.

1. the material of diaphragm

(1) resinous principle

A1 ~ A9: (methyl) acrylic resin shown in following table 2

U1: the carbamate carbamide resin synthesized by following method

(synthesis of carbamate carbamide resin U1)

1) synthesis of aromatic polyester polyol (a2-1)

2 are loaded in the four-hole boiling flask of internal volume 3 liters possessing thermometer, stirrer and reflux cooler, 6-naphthalene dicarboxylic acids dimethyl ester 659.4g, dimethyl terephthalate (DMT) 58.3g, 1,2-propylene glycol 684.8g and the zinc acetate 2 hydrate 0.084g as esterification catalyst, stir on one side periodically heating direct on one side under nitrogen flowing and, to becoming 210 DEG C, add up to reaction 13 hours.After reaction, unreacted 1,2-PD decompression removing is obtained aromatic polyester polyol (the a2-1) (acid number: 0.08, hydroxyl value: 213, number-average molecular weight: 590) of normal temperature solid at 160 DEG C.

2) synthesis of carbamate carbamide resin U1

In the four-hole boiling flask of 5 liters possessing thermometer, stirrer, non-active gas introducing port and reflux cooler, load polycarbonate polyol (a1-1) (UC-100, hydroxyl value that space portion emerging product (strain) makes: 116.4mgKOH/g) 300 mass parts containing aliphatics ring structures and above-mentioned aromatic polyester polyol (a2-1) 75 mass parts of having synthesized, add 4,4 '-dicyclohexyl methyl hydride diisocyanate (c-1) 238.0 mass parts, toluene 330.1 mass parts, suppress heat release to be reacted 3 hours at 80 DEG C.Thus, the toluene solution in molecular end with the carbamate prepolymer of isocyanate group is obtained.

Then, after 205.9 mass parts mixing of above-mentioned toluene solution, N, 1235.6 mass parts of dinethylformamide (b-1), 287.7 mass parts of toluene and sec-butyl alcohol, be cooled to 40 DEG C, mix with 73.4 mass parts of isophorone diamine, react 3 hours at 70 DEG C, obtain carbamate carbamide resin U1 (weight-average molecular weight: 147000, non-volatile content: 25 quality %).

(3) other adjuvant

Adjuvant 1: ア Network ト Off ロ-UT1001 (combine and grind chemical society system, acrylic acid series low-molecular weight, terminal hydroxyl)

Adjuvant 2: polyester-urethane system plastifier (polyester-urethane of the mean molecular weight 7300 being made the dihydroxy polyester of the mean molecular weight 2125 formed by hexane diacid and ethylene glycol and toluene diisocyanate react and obtain by conventional method)

Plastifier 1:ARUFONUP1170 (East Asia synthesis society system, acrylic acid series plastifier, without official's energy)

Plastifier 2: dioctyl phthalate (DOP)

UV absorbing agent: ア デ カ ス タ Block LA31RG (ア デ カ society system, ア デ カ ス タ Block 2,2 '-di-2-ethylhexylphosphine oxide [6-(2H-benzotriazole-2-base)-4-(1,1,3,3-tetramethyl butyl) phenol])

2. the making of diaphragm

(embodiment 1)

Rubber cement is prepared in following compositions mixing.

(composition of rubber cement)

(methyl) acrylic acid series resinoid A2:95 mass parts

Adjuvant 1 (ア Network ト Off ロ-UT1001): 5 mass parts

Methylene chloride: 213.9 mass parts

Ethanol: 67.6 mass parts

Use band casting device by the rubber cement that obtains at temperature 30 DEG C, with the wide curtain coating equably of 2m to stainless steel band supporting mass.Stainless steel band supporting mass make the solvent in rubber cement evaporate until residual solvent amount becomes 70%.Then, the membranoid substance obtained is peeled off from stainless steel band supporting mass.

Then, the membranoid substance peeled off is made after further drying, to carry out conveying with multiple roller the dry section of 110 DEG C, 140 DEG C for the film obtained while make it dry, obtain the film of thickness 40 μm at 45 DEG C.

Under the condition of 100W, corona treatment is implemented to the surface of the film obtained.Then, the film by corona treatment hangs in removable flask, is loaded as the pyridine (medicine pure with light) of catalyzer, 3H-tetrafluoro propionyl chloride (medicine pure with light) as modifier, reaction 24 hours under decompression at 60 DEG C.Thus the surface fluorination of film is obtained film 101.

(embodiment 2)

Except being changed into except the mass parts of (methyl) acrylic resin A6/ cellulose esters E=90 mass parts/10 by film composition, obtain the film 102 of thickness 40 μm similarly to Example 1.

(embodiment 3)

Except being changed into except the mass parts of (methyl) acrylic resin A1/ cellulose esters E=90 mass parts/10 by film composition, obtain the film 103 of thickness 40 μm similarly to Example 1.

(comparative example 1)

Except film composition is changed into except general PMMA, after obtaining pellet similarly to Example 1, carry out melt extruding and be shaped and obtain the film of thickness 40 μm.This film is coated with following vinylidene chloride solution and becomes 5 μm to make dry thickness, obtain film 104.

(vinylidene chloride solution)

Polymkeric substance (Asahi Chemical Industry ラ イ Off & リ PVC Application グ (strain) サ ラ processed Application レ ジ Application R204) containing chlorine: 12 mass parts

Tetrahydrofuran: 63 mass parts

(comparative example 2)

Except being changed into except the mass parts of (methyl) acrylic resin A1/ cellulose esters I=90 mass parts/10 by film composition, obtain the film 105 of thickness 40 μm similarly to Example 1.

(comparative example 3)

Except film composition being changed into general PMMA/CAP482 (cellulose-acetate propionate of degree of substitution with acetyl group 0.19, propiono degree of substitution 2.56, total degree of substitution 2.75)=65 mass parts/35 mass parts, obtain the film 106 of thickness 40 μm similarly to Example 1.

(embodiment 4)

Rubber cement 1 is prepared in following compositions mixing.

(rubber cement 1)

Carbamate carbamide resin U1:100 mass parts

Adjuvant 2 (polyester-polyurethane): 10 mass parts

Methyl ethyl ketone: 500 mass parts

Use band casting device, at temperature 30 DEG C, with 2m wide by the rubber cement 1 that obtains equably curtain coating to stainless steel band supporting mass.Stainless steel band supporting mass make the solvent in rubber cement evaporate until residual solvent amount becomes 70%.Then, the membranoid substance obtained is peeled off from stainless steel band supporting mass.The membranoid substance obtained is made after drying, at 110 DEG C, 140 DEG C, to make it dry further, obtain the film 107 of thickness 40 μm at 45 DEG C.

(embodiment 5)

Except film composition being changed into (methyl) acrylic resin A391.4 mass parts, plastifier 1 (East Asia synthesis society ARUFONUP1170) 5 mass parts, plastifier 2 (dioctyl phthalate) 2 mass parts, UV absorbing agent (ア デ カ society LA31RG) 1.6 mass parts, obtain the film 108 of thickness 40 μm similarly to Example 1.

(embodiment 6)

Except being changed into except the mass parts of (methyl) acrylic resin A6/ cellulose esters A=90 mass parts/10 by film composition, obtain the film 109 of thickness 40 μm similarly to Example 1.

(comparative example 4)

As tri cellulose acetate membrane, prepare 4UA (コ ニ カ ミ ノ Le タ society system, thickness 40 μm).The hard masking liquid 1 of the following composition recorded in the coated on one side Japanese Unexamined Patent Publication 2008-158483 publication of this film becomes 5 μm to make dry thickness, obtains film 110.

(hard masking liquid 1)

PET-30 (potpourri [Japanese chemical drug (strain) system] of pentaerythritol triacrylate, tetramethylol methane tetraacrylate): 40.0g

DPHA (potpourri [Japanese chemical drug (strain) system] of Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate): 10.0g

イルガキュア184：2.0g

SX-350 (crosslinked polystyrene particle, mean grain size 3.5 μm, refractive index 1.60, combine grind chemistry (strain) system, 30% toluene dispersion liquid): 2.0g

Crosslink propylene acids-styrene particles (mean grain size 3.5 μm, refractive index 1.55, combine grind chemistry (strain) system, 30% toluene dispersion liquid): 13.0g

FP-13 (the fluorine system surface modifier of following formula): 0.06g

Sol solutions a:11.0g

Toluene: 38.5g

[chemical formula 3]

(embodiment 7)

Except being changed into except the mass parts of (methyl) acrylic resin A6/ cellulose esters E=65 mass parts/35 by film composition, obtain the film 111 of thickness 40 μm similarly to Example 1.

(embodiment 8)

The film obtained similarly to Example 7 is stretched at draft temperature 170 DEG C after 1.7 times, thermal treatment 24 hours and obtain the film 112 of thickness 40 μm at 120 DEG C further.

(comparative example 5)

Except not carrying out the coating of corona treatment and vinylidene chloride solution, obtain the film 113 of thickness 40 μm in the same manner as comparative example 1.

(comparative example 6,8 ~ 9)

Prepare the film 114,116 ~ 117 shown in table 4.In table 4,4UA represents cellulose ester membrane 4UA (コ ニ カ ミ ノ Le タ society system, thickness 40 μm); COP represents cyclic olefin resin film (Japanese ゼ オ Application society system, thickness 68 μm); Pet sheet shows polyethylene terephthalate film (thickness 100 μm).

(comparative example 7)

Except being changed into except the mass parts of general PMMA/CAP482=70 mass parts/30 by film composition, obtain the film 115 of thickness 40 μm in the same manner as comparative example 2.

(embodiment 9 ~ 12, comparative example 10)

Except as shown in table 5 change like that cellulose esters containing except ratio, obtain the film 118 ~ 122 of thickness 40 μm similarly to Example 2.

(embodiment 13 ~ 19)

Except the kind changing cellulose esters like that as shown in table 6, obtain the film 123 ~ 129 of thickness 40 μm similarly to Example 2.

(embodiment 20 ~ 25)

Except the kind changing (methyl) acrylic resin like that as shown in table 7, obtain the film 130 ~ 135 of thickness 40 μm similarly to Example 13.

The tensile modulus of elasticity of the film obtained, elongation speed and elongation is determined by following method.

(tensile modulus of elasticity)

The film obtained is cut out the size of 100mm (MD direction) × 10mm (TD direction), obtain sample film.By this sample film according to JISK7127, use オ リ エ ンテック society テ Application シ ロ Application RTC-1225A, make chuck spacing be 50mm, the tensile modulus of elasticity in MD direction of carrying out in MD direction stretching, determine.Carry out under being determined at 23 DEG C of 55%RH.

(elongation elongation speed)

Film (the thickness 40 μm) damping more than 12 hours will obtained under the condition of 23 ± 1 DEG C of 55%RH.Then, use Hitachi ハイテク society TMA/SS7100 by be provided with the film immersion of water retting accessory in the pure water of 23 ± 1 DEG C, taking-up and determine the elongation of film.With regard to the mensuration of elongation, determine the MD direction of film.Then, obtain " elongation (%) " of the film from dipping after 30 minutes.

For the determination data obtained, make dip time (minute) as transverse axis, the elongation (%) of film is drawn as the longitudinal axis, obtains curve.Calculate the curve obtained, from dipping to the slope (slope relative to the elongation of dip time) after 2 minutes, obtain " extending speed (%/minute) ".

In addition, for a part of film, have rated the cementability with polarizer.

(cementability)

First, make polyvinyl alcohol film impregnated in aqueous solution 100 mass parts containing iodine 1 mass parts, boric acid 4 mass parts, the stretching ratio 6 with throughput direction at 50 DEG C doubly stretches, and prepares the polarizer of thick 25 μm.

1) cementability of saponification process is utilized

After alkali saponified process has been carried out under the following conditions to the film obtained in embodiment or comparative example, washing, neutralization and washing are carried out.

The film drying obtained is made at 80 DEG C.

After fully saponified type polyvinyl alcohol (PVA) 5% aqueous solution being made as bonding agent the above-mentioned alkali saponified film processed fit in the one side of the above-mentioned polarizer made, make it dry, obtain sandwich.Measure the cementability at the interface of the polaroid protective film of the polaroid protective film of the sandwich obtained when 180 ° of directions have been peeled off and polarizer, evaluate based on following standard.

Zero: polaroid protective film ftractures, and does not peel off in the interface of polaroid protective film and polarizer

△: find some strippings at the interface of polaroid protective film and polarizer

×: at the interface peel of polaroid protective film and polarizer

2) cementability of easy adhesive linkage is utilized

Relative to water system carbamate resins (the first industrial pharmaceutical system, trade name: ス ー パ ー Off レ ッ Network ス 210, the solid constituent: 33%) 100g with carboxyl, add crosslinking chemical (Japanese catalyst system, trade name: エ Port Network ロ ス WS700, solid constituent: 25%) 20g, stir 3 minutes, obtain easy adhesive composite.

By rod coaters (#6), the easy adhesive composite obtained is coated the Corona discharge Treatment face of the film implementing Corona discharge Treatment.The film obtained is put into air drier (140 DEG C), make easy adhesive composite drying about 5 minutes, define easy adhesive linkage (0.2 ~ 0.4 μm).Then, the easy adhesive linkage obtained and the above-mentioned polarizer made after fitting via fully saponified type polyvinyl alcohol (PVA) 5% aqueous solution, are made it dry, obtain sandwich.In the same manner as aforementioned, the cementability of the sandwich obtained is evaluated.

The evaluation result of embodiment 1 ~ 8 and comparative example 1 ~ 9 is shown in table 4; The evaluation result of embodiment 9 ~ 12 and comparative example 10 is shown in table 5; The evaluation result of embodiment 13 ~ 19 is shown in table 6; The evaluation result of embodiment 20 ~ 25 is shown in table 7.

As shown in table 4 ~ 7, learn: with regard to the film of embodiment 1 ~ 25, elongation elongation speed is all moderately low and tensile modulus of elasticity is all moderately high.And learn: with regard to comparative example 1 ~ 10, all can not take into account the elongation of appropriateness, elongation speed and tensile modulus of elasticity.

Particularly, learn: the film of comparative example 1 and 8 ~ 9 is films of low moisture permeability in the past; Or have the film of low soak layer, speed of at least extending is too small.On the other hand, learn: with regard to the film of comparative example 4,6 and 10, due to containing cellulose ester membrane, speed of therefore at least extending is excessive.Learn: with regard to comparative example 3 and 7, owing to containing the low cellulose esters of certain above LogP value, speed of therefore extending is excessive.Learn: with regard to the film of comparative example 5, tensile modulus of elasticity is low.

And as shown in table 5, learn: the content of the cellulose esters that moisture permeability is higher is more, the elongation speed of extending of film more becomes large.As shown in table 6, learn: because the hydrophobicity of cellulose esters is higher, the compatibility of film and water gets over step-down, therefore elongation speed of extending all diminishes.As shown in table 7, learn: because the hydrophobicity of (methyl) acrylic resin is higher, the compatibility of film and water is lower, therefore the elongation of film speed of extending diminishes.

3. the making of polaroid

(embodiment 26)

1) making of polarizer

By the long size rolled polyvinyl alcohol film immersion of thick 120 μm in aqueous solution 100 mass parts containing iodine 1 mass parts, boric acid 4 mass parts, stretch with the stretching ratio 6 times of throughput direction at 50 DEG C, obtain the polarizer of thick 25 μm.

2) making of phase retardation film RT1

After following compositions dissolver is uniformly mixed 50 minutes, obtain particle dispersion liquid 1 with the dispersion of マ Application ト ン ゴ ー リ Application.

(particle dispersion liquid 1)

Particulate (ア エ ロ ジ Le R812 Japan ア エ ロ ジ Le (strain) system): 11 mass parts

Ethanol: 89 mass parts

Then, the dissolving tank that methylene chloride is housed fully to be stirred, while the particle dispersion liquid 1 obtained is added lentamente, and then make it disperse to make the particle diameter of offspring to become the size of regulation with masher.The solution the obtained Off ァ イ Application メ ッ ト NF that Japanese smart line (strain) is made is filtered, obtains particulate annex solution 1.

(particulate annex solution 1)

Methylene chloride: 99 mass parts

Particle dispersion liquid 1:5 mass parts

Prepare the main rubber cement liquid of following composition.First, in dissolved under pressure tank, methylene chloride and ethanol is added.Stir in the dissolved under pressure tank that solvent is housed while drop into the cellulose acetate of degree of substitution with acetyl group 2.00, saccharide ester compound and particulate annex solution 1, heat and stir, fully make it dissolve.The peace using the long-pending filter paper (strain) of peace to make is amassed filter paper No.244 and is filtered, and prepares main rubber cement liquid.By the main dissolution kettle 1 having put into airtight above, stir and dissolve, prepare rubber cement liquid.

(main rubber cement liquid)

Methylene chloride: 340 mass parts

Ethanol: 64 mass parts

Cellulose acetate (degree of substitution with acetyl group 2.00): 100 mass parts

Saccharide ester compound: the benzyl sucrose of average substitution degree 5.5: 12 mass parts

Particulate annex solution 1:1 mass parts

By after aforesaid rubber cement liquid curtain coating (casting) on stainless steel band supporting mass, solvent is evaporated until residual solvent amount becomes 75%, obtains net.The net obtained peeled off from stainless steel band supporting mass to peel off tension force 130N/m, the heat applying 170 DEG C uses stenter to stretch 37% in the direction of the width.The residual solvent of the net stretched when starting is 15%.

Then, carry in dry section with multiple roller, while complete drying.Baking temperature is 130 DEG C, and conveyance tension is set to 100N/m.As described above, the phase retardation film RT1 of dry film thickness 25 μm is obtained.

The making of polaroid

As shown in the following, after alkali saponified process has been carried out to the above-mentioned film made, washing, neutralization and washing has been carried out.

Then, at 80 DEG C, make the polaroid protective film drying obtained.Similarly, alkali saponified process has also been carried out to the above-mentioned phase retardation film RT1 made.

Then, using fully saponified type polyvinyl alcohol (PVA) 5% aqueous solution as bonding agent, the alkali saponified aforesaid film 101 processed is fitted in the one side of the polarizer of above-mentioned making.Similarly, using fully saponified type polyvinyl alcohol (PVA) 5% aqueous solution as bonding agent, the alkali saponified phase retardation film RT1 processed is fitted in the another side of polarizer.With regard to laminating, carry out in the mode parallel with slow axis in the face of film 101 through axle of polarizer.By dry at 60 DEG C for the sandwich of having fitted, obtain polaroid 201.

(embodiment 27 ~ 50, comparative example 11 ~ 20)

Except change the kind of diaphragm as shown in table 8 ~ 11 except, obtain polaroid 202 ~ 235 similarly to Example 26.

Wherein, as shown in table 5, with regard to cellulose esters content less than 5% film 118 with regard to, due to few to the cellulose amount of saponification bonding performance function, even if therefore implement alkali saponified process, if water stick with paste, not bonding yet.Therefore, for film 118, prepare the easy adhesive composite of following composition, define easy adhesive linkage.

(preparation of easy adhesive composite)

Relative to water system carbamate resins (the first industrial pharmaceutical system, trade name: ス ー パ ー Off レ ッ Network ス 210, the solid constituent: 33%) 100g with carboxyl, add crosslinking chemical (Japanese catalyst system, trade name: エ Port Network ロ ス WS700, solid constituent: 25%) 20g, stir 3 minutes, obtain easy adhesive composite.

By rod coaters (#6), the easy adhesive composite obtained is applied to the Corona discharge Treatment face of the diaphragm implementing Corona discharge Treatment.Then, diaphragm is put in air drier (140 DEG C), make the easy adhesive composite drying that is coated with about 5 minutes, define easy adhesive linkage (0.2 ~ 0.4 μm).

Then, the easy adhesive linkage obtained and polarizer are stuck with paste via water and fitted, obtains polaroid 218.

By following method, the micro-red of the polaroid obtained and panel bending are evaluated.

(micro-red)

The polaroid obtained is loaded in the thermostat of 20 DEG C of 95%RH, preserve 200h.After preservation, whether visualization there occurs and results from the defect (micro-red) of redness of deterioration of polarizer in the polaroid obtained, and evaluates based on following standard.

◎: do not find red defect in polaroid completely

Zero: the defect finding some redness in polaroid, but the level being substantially no problem

×: in polaroid, find red defect

(panel bending)

Prepare the glass plate (A4 size) of thick 0.5mm.On this glass plate, via bonding agent, the above-mentioned polaroid made fitted and obtain panel.With regard to laminating, the mode becoming glass plate side with the phase retardation film of polaroid is carried out.With regard to bonding agent, employ the double-sided belt (without substrate tape MO-3005C) of thick 25 μm of リ ンテック society.

After the panel obtained is left standstill half under the room temperature state of 23 DEG C 55%, load in the thermostat of 40 DEG C of 90%RH, preserve 24 hours.Then, panel is taken out, loads 40 DEG C of dry thermostats, dry 2 hours.The amount of warpage of the panel obtained after measuring drying at once.With regard to the amount of warpage of panel, measure the height of the distance surface level of panel corner, get their mean value.

◎ ◎: the amount of warpage of panel is less than 1.0mm

◎: the amount of warpage of panel is more than 1.0mm and less than 2.0mm

Zero: the amount of warpage of panel is more than 2.0mm and less than 3.5mm

△: the amount of warpage of panel is more than 3.5mm and less than 5.0mm

×: the amount of warpage of panel is more than 5mm

The evaluation result of embodiment 26 ~ 33 and comparative example 11 ~ 19 is shown in table 8; The evaluation result of embodiment 34 ~ 37 and comparative example 20 is shown in table 9; The evaluation result of embodiment 38 ~ 44 is shown in table 10; The evaluation result of embodiment 45 ~ 50 is shown in table 11.

As shown in table 8 ~ 11, learn: with regard to the polaroid of embodiment 26 ~ 50, micro-red and both panel bending all do not occur.Learn on the other hand: with regard to the polaroid of comparative example 11 ~ 20, micro-at least one that is red or panel bending occurs.

Particularly, learn: with regard to the polaroid at least extending the too small comparative example 11,18 and 19 of speed of diaphragm, there is no generating plane plate benging, but occur micro-red.Learn on the other hand: with regard to the polaroid of the elongation of diaphragm and the excessive comparative example 12 ~ 14,16 and 17 of at least one of the speed of elongation, do not occur micro-red, but generating plane plate benging.With regard to the polaroid of comparative example 12, think because the LogP value of cellulose esters is too high, cellulose esters and polymethylmethacrylate compatible, the raising effect that can not get the tensile modulus of elasticity produced by the interpolation of cellulose esters deficiently.

And then, as shown in table 9, learn: if the elongation of film extends speed moderately greatly, then easily make the micro-red of polaroid alleviate.As shown in table 10 and 11, learn: if the elongation elongation speed of film is moderately little, then easily make panel bending alleviate.

4. the making of liquid crystal indicator

(embodiment 51)

As liquid crystal cell, prepare the liquid crystal cell of the VA mode with the two sheet glass substrates that thickness is 0.5mm and the liquid crystal layer be configured with between which.Then, on the two sides of the above-mentioned liquid crystal cell prepared, the double-sided belt (without substrate tape MO-3005C) of thick 25 μm via リ ンテック society makes the above-mentioned polaroid 201 made fit respectively, obtains display panels.With regard to laminating, carry out in the mode that the phase retardation film RT1 of polaroid 201 connects with liquid crystal cell.

Then, after display panels (sandwich of polaroid/liquid crystal cell/polaroid) being pulled down from SONY system 40 escope BRAVIAKLV-40J3000 (VA mode), configure the above-mentioned display panels made, obtain liquid crystal indicator 301 (1).With regard to the display panels installed, make the slow axis of phase retardation film RT1 parallel with the slow axis of the polaroid pasted in advance.

Except the thickness of the two sheet glass substrates making formation liquid crystal cell is respectively except 0.2mm, 0.7mm, similarly make liquid crystal indicator 301 (2) and 301 (3).

(embodiment 52 ~ 76, comparative example 21 ~ 30)

Except changing into except polaroid 202 ~ 235 successively by polaroid 201, obtain liquid crystal indicator 302 ~ 335 in the same manner as embodiment 51.

The bending inequality of the liquid crystal indicator obtained is determined by following method.

(bending uneven)

The above-mentioned liquid crystal indicator made be placed 24 hours under the environment of 40 DEG C of 95%RH.Then, under 40 DEG C of dry environment under the state of black display that made liquid crystal indicator carry out, the difference (image of central part and periphery is uneven) of the brightness near 4 summits of visualization display frame and the brightness near display frame central portion.Then, based on following standard evaluation.

Zero: do not find that image is uneven

×: find that image is uneven

The evaluation result of embodiment 51 ~ 58 and comparative example 21 ~ 29 is shown in table 12; The evaluation result of embodiment 59 ~ 62 and comparative example 30 is shown in table 13; The evaluation result of embodiment 62 ~ 68 is shown in table 14; The evaluation result of embodiment 69 ~ 74 is shown in table 15.

As shown in table 12 ~ 15, when being 0.5mm when making the thickness of glass substrate, with regard to employ the evaluation result of panel bending be △ or × polaroid liquid crystal indicator with regard to, there occurs panel bending practicality becoming problem uneven; And on the other hand, being with regard to the liquid crystal indicator of the polaroid of more than zero with regard to employing the evaluation result of panel bending, all not finding bending inequality practicality becoming problem.

Learn in addition: even do not bend uneven polaroid when the thickness of glass substrate is 0.5mm, also bend when being 0.2mm when making the thickness of glass substrate inequality sometimes.Learn: even with its uneven polaroid that bends when the thickness of glass substrate is 0.5mm on the contrary, do not bend when being 0.7mm when making the thickness of glass substrate inequality sometimes yet.From these: diaphragm of the present invention can suppress the thickness of particularly glass substrate to be more than 0.3mm and less than bending inequality during 0.7mm well.

The application requires right of priority based on the Japanese Patent Application 2013-156705 applied on July 29th, 2013.The content be recorded in this application instructions and accompanying drawing is all quoted in present specification.

Utilizability in industry

According to the present invention, even if the polaroid that the deterioration of the thickness of polarizer polarizer that is thin, that caused by the moisture of moisture-inhibiting can be provided also little.

The explanation of symbol

10 liquid crystal indicators

30 liquid crystal cells

50 first polaroids

51 the first polariscopes

53 diaphragms (F1)

55 diaphragms (F2)

70 second polaroids

71 second polarizers

73 diaphragms (F3)

75 diaphragms (F4)

90 backlights

Claims (9)

1. a polaroid protective film, wherein, 23 DEG C, tensile modulus of elasticity under 55%RH is more than 3GPa,

23 ± 1 DEG C, under 55%RH after damping more than 12 hours, in the water that impregnated in 23 ± 1 DEG C time, the elongation speed at initial stage of film is 0.03 ~ 0.1%/minute, and be less than 0.4% by the elongation of the film of film immersion in water after 30 minutes.

2. polaroid protective film according to claim 1, it contains (methyl) acrylic resin.

3. polaroid protective film according to claim 2, wherein, the water-octanol partition coefficient of described (methyl) acrylic resin is more than 1.2.

4. polaroid protective film according to claim 1, it is also containing the cellulose esters relative to described film being 5 ~ 25 quality %.

5. polaroid protective film according to claim 4, wherein, the water-octanol partition coefficient of described cellulose esters is more than 0.

6. polaroid protective film according to claim 1, its contain water-octanol partition coefficient be more than 1.2 (methyl) acrylic resin and water-octanol partition coefficient be the cellulose esters of more than 0.

7. polaroid protective film according to claim 1, wherein, the thickness of described polaroid protective film is 10 ~ 50 μm.

8. a polaroid, it contains polarizer and polaroid protective film according to claim 1.

9. a liquid crystal indicator, it contains:

Containing thick more than 0.3mm and less than first glass substrate of 0.7mm and the second glass substrate and the liquid crystal cell of liquid crystal layer that is configured with between described first glass substrate and described second glass substrate;

The first polaroid that described first glass substrate of described liquid crystal cell is configured with; With

The second polaroid that described second glass substrate of described liquid crystal cell is configured with,

Described first polaroid contains the first polariscope, at the diaphragm F1 be configured with the face of the opposition side of described liquid crystal cell of described the first polariscope and the diaphragm F2 be configured with in the face of the described liquid crystal cell side of described the first polariscope,

Described second polaroid contains the second polarizer, the diaphragm F3 be configured with in the face of the described liquid crystal cell side of described second polarizer and the diaphragm F4 be configured with the face of described liquid crystal cell opposition side at described second polarizer,

The one or both of described diaphragm F1 and described diaphragm F4 is polaroid protective film according to claim 1.