JP2014059548A - Polarizing plate and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polarizing plate having excellent durability of a polarizer in a high temperature and high humidity environment as well as in a high temperature and low humidity environment, and hardly causing degradation in display performances depending on a use environment when the polarizing plate is assembled in a liquid crystal display device, and to provide a liquid crystal display device.SOLUTION: The polarizing plate includes a first protective film, a polarizer and a second protective film, in this order. The first protective film has a thickness of 5 μm or more and 60 μm or less and comprises a cellulose acylate and a compound (A) having at least one hydrogen bond-forming hydrogen-donating group and having a ratio of (molecular weight)/(number of aromatic rings) of 190 or less. The second protective film comprises a cycloolefin polymer.

Description

  The present invention relates to a polarizing plate and a liquid crystal display device. In particular, the present invention relates to a polarizing plate and a liquid crystal display device that are excellent in polarizer durability even under both high temperature and high humidity and high temperature and low humidity environments, and that display performance is not easily deteriorated due to the use environment when incorporated in a liquid crystal display device.

Liquid crystal display devices are increasingly used year by year as space-saving image display devices with low power consumption.
The basic configuration of a liquid crystal display device is one in which polarizing plates are provided on both sides of a liquid crystal cell. The polarizing plate plays a role of allowing only light having a polarization plane in a certain direction to pass through, and the performance of the liquid crystal display device is greatly influenced by the performance of the polarizing plate. The polarizing plate generally has a configuration in which a polarizer made of a polyvinyl alcohol film or the like on which iodine or a dye is adsorbed and oriented, and a transparent protective film are bonded to both the front and back sides of the polarizer. As a polarizing plate protective film, a cellulose acylate type polarizing plate protective film typified by cellulose acetate is widely used because it has high transparency and can easily ensure adhesion with polyvinyl alcohol used in a polarizer. I came.

  In recent years, in addition to indoor applications such as televisions, as the market for outdoor applications such as mobile phones, tablet PCs, and electronic signboards has expanded, the demand for durability of liquid crystal display devices has become stricter. In addition, for the long-term use in harsh environments, suppression of polarization performance deterioration has become a major issue.

Patent Document 1 discloses a polarizing plate using a polarizing plate protective film containing a cellulose ester and a hindered phenol on one side and a polarizing plate protective film mainly containing a cycloolefin polymer on the other side.
Patent Document 2 discloses that the first polarizing plate protective film has a moisture permeability of 300 g / m ² · H or less at 60 ° C. and a relative humidity of 95%, and the second polarizing plate protective film is a cellulose acylate film. A polarizing plate is disclosed.

International Publication No. 2007/066470 JP 2008-102475 A

  When the polarizing plate described in Patent Document 1 or 2 is used for a long time in a harsh environment, a certain effect can be seen, but the deterioration in display quality when used for a long time in a high temperature and high humidity environment is still large. As a result of investigations by the inventors, it has become clear and improvements have been demanded.

  The purpose of the present invention is a polarizing plate that is excellent in polarizer durability both in a high-temperature and high-humidity environment and in a high-temperature and low-humidity environment, and is less susceptible to deterioration in display performance due to the usage environment when incorporated in a liquid crystal display device, Another object is to provide a liquid crystal display device.

  When the present inventors diligently studied for the purpose of solving the above-mentioned problems, it was found that a polarizing plate in which the polarization performance is hardly deteriorated in both a high temperature and high humidity environment and a high temperature and low humidity environment can be obtained by the following means. I found it.

  That is, the said subject is solved by the following structures.

[1]
A polarizing plate having a first protective film, a polarizer, and a second protective film in this order,
The first protective film has a thickness of 5 μm or more and 60 μm or less, has a cellulose acylate and at least one hydrogen bondable hydrogen donating group, and has a molecular weight / aromatic ring number ratio of 190 or less ( A) and
The polarizing plate in which the second protective film contains a cycloolefin polymer.
[2]
The polarizing plate according to [1], wherein the aromatic ring in the compound (A) is a hydrocarbon aromatic ring.
[3]
The polarizing plate according to [1] or [2], wherein the compound (A) is a compound represented by the following general formula (2).

In the general formula (2), R ²⁶ represents an alkyl group, an alkenyl group, or an aryl group, R ²⁷ and R ²⁸ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heteroaryl group, and R ²⁹ represents a hydrogen atom. R ²⁶ , R ²⁷ , and R ²⁸ may each independently have a substituent. However, at least one of R ²⁶ , R ²⁷ and R ²⁸ contains an aromatic ring.
[4]
The polarizing plate according to [1] or [2], wherein the compound (A) is a compound represented by the following general formula (1).

In general formula (1), R ¹ represents a substituent, R ² represents a group represented by the following general formula (1-2); n1 represents an integer of 0 to 4, and n1 is 2 or more. A plurality of R ¹ may be the same as or different from each other; n2 represents an integer of 1 to 5, and when n2 is 2 or more, a plurality of R ² may be the same or different from each other Good.

In general formula (1-2), A represents a substituted or unsubstituted aromatic ring; R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the following general formula: Represents a group represented by (1-3); R ⁵ represents a single bond or an alkylene group having 1 to 5 carbon atoms; X represents a substituted or unsubstituted aromatic ring; Represents an integer of 10, and when n3 is 2 or more, the plurality of R ⁵ and X may be the same or different from each other.

In General Formula (1-3), X ₁ represents a substituted or unsubstituted aromatic ring; R ⁶ , R ⁷ , R ⁸ , and R ⁹ each independently represent a hydrogen atom or 1 to 5 carbon atoms. N5 represents an integer of 1 to 11, and when n5 is 2 or more, a plurality of R ⁶ , R ⁷ , R ⁸ , R ⁹ and X ₁ may be the same or different from each other Good.
[5]
The polarizing plate according to [4], wherein the group represented by the general formula (1-2) is a group represented by the following general formula (1-2 ′).

In General Formula (1-2 ′), R ³ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a substituent represented by General Formula (1-3); R ⁵ represents a single bond or Represents an alkylene group having 1 to 5 carbon atoms; X represents a substituted or unsubstituted aromatic ring; n3 represents an integer of 0 to ^5, and when n3 is 2 or more, a plurality of R ⁵ and X are They may be the same or different.
[6]
The polarizing plate according to any one of [1] to [5], wherein the first protective film contains a hydrophobizing agent.
[7]
A liquid crystal display device comprising at least one polarizing plate according to any one of [1] to [6].

  According to the present invention, the polarizer has excellent durability in both high temperature and high humidity environments and high temperature and low humidity environments. Further, when incorporated in a liquid crystal display device, the polarizing plate is less susceptible to deterioration in display performance due to the use environment, and A liquid crystal display device can be provided.

It is the schematic which shows the example of the liquid crystal display device of this invention.

[Polarizer]
The polarizing plate of this invention is a polarizing plate which has a 1st protective film, a polarizer, and a 2nd protective film in this order, Comprising: The said 1st protective film is 5 micrometers or more and 60 micrometers or less in thickness. A cellulose acylate and a compound (A) having at least one hydrogen-bonding hydrogen-donating group and a molecular weight / aromatic ring number ratio of 190 or less, wherein the second protective film is a cycloolefin It is a polarizing plate containing a polymer.

In conventional polarizing plates, the content of boric acid in the polarizer decreases under high temperature and high humidity, and the complex of hydrophilic polymer (eg, polyvinyl alcohol) and dichroic dye (eg, iodine) often destabilizes. This was the cause of polarization performance degradation. On the other hand, the polarizing plate of the present invention has at least one hydrogen-bonding hydrogen-donating group in a polarizing plate protective film containing cellulose acylate, and has a molecular weight / aromatic ring number ratio of 190 or less. A) is contained in an amount of 1 part by mass or more and 20 parts by mass or less based on 100 parts by mass of cellulose acylate, thereby suppressing a decrease in boric acid content in the polarizer, and the additive can be used together with the polarizer under high temperature and high humidity. It is considered that the iodine complex is stabilized by being ubiquitous at the interface of the polarizing plate protective film.
Hereinafter, the polarizing plate of the present invention will be described in detail.

<Performance of polarizing plate>
(Orthogonal transmittance CT)
In the polarizing plate of the present invention, the orthogonal transmittance CT is preferably CT ≦ 2.0, more preferably CT ≦ 1.3, and most preferably CT ≦ 0.6 (unit is%) ).

(Orthogonal transmittance change)
Further, it is preferable that the amount of change in the orthogonal transmittance is small before and after the polarizing plate durability test.
The polarizing plate of the present invention has an orthogonal single plate transmittance change (%) of less than 0.8% when allowed to stand at 80 ° C. and 90% relative humidity for 168 hours, and at 105 ° C. in a Dry environment ( The humidity is not adjusted, and in the examples of the present invention, the change (%) in the orthogonal single plate transmittance is less than 0.04% when left in a relative humidity of 0% to 20% for 240 hours. It is preferable that
It is more preferable that the amount of change (%) in the orthogonal single plate transmittance when left to stand at 80 ° C. and 90% relative humidity for 168 hours is less than 0.4%. On the other hand, the change amount (%) of the orthogonal single plate transmittance when left standing at 105 ° C. in a Dry environment for 240 hours is more preferably less than 0.02%.

Here, the change amount of the orthogonal transmittance is calculated by the following equation.
Change in orthogonal transmittance (%) = orthogonal transmittance after durability test (%)-orthogonal transmittance before durability test (%)
If the range of the change amount of the orthogonal transmittance is satisfied, the stability of the polarizing plate can be ensured during use or storage for a long time under high temperature and high humidity and high temperature and low humidity.

In the present invention, the orthogonal transmittance CT of the polarizing plate was measured at a wavelength of 410 nm or 510 nm by the following method using an automatic polarizing film measuring device VAP-7070 manufactured by JASCO Corporation.
Two samples (5 cm × 5 cm) in which the polarizing plate of the present invention is bonded onto glass through an adhesive are prepared. At this time, the first polarizing plate protective film is attached so as to be on the side opposite to the glass (air interface) side. The orthogonal transmittance measurement is performed by setting the glass side of the sample facing the light source. Each of the two samples is measured, and the average value is defined as the orthogonal transmittance.

(Other characteristics)
Other preferable optical characteristics and the like of the polarizing plate of the present invention are described in [0238] to [0255] of JP-A-2007-086748, and it is preferable to satisfy these characteristics.

<Shape and configuration>
The shape of the polarizing plate of the present invention is not only a polarizing plate in the form of a film piece cut into a size that can be incorporated into a liquid crystal display device as it is, but also produced in a long shape by continuous production, and in a roll shape. A polarizing plate in a rolled up mode (for example, a roll length of 2500 m or longer or 3900 m or longer) is also included. In order to use for a large-screen liquid crystal display device, the width of the polarizing plate is preferably 1470 mm or more.
Hereinafter, the detail of the polarizer and polarizing plate protective film which can be used for the polarizing plate of this invention is demonstrated.

<Polarizing plate protective film>
Next, two polarizing plate protective films used for the polarizing plate of the present invention will be described.

(Thickness of polarizing plate protective film)
The polarizing plate protective film has a thickness of 5 μm to 60 μm, preferably 5 μm to 35 μm, particularly preferably 10 μm to 30 μm.

[First polarizing plate protective film]
Hereinafter, the first polarizing plate protective film (also referred to as “first protective film”) will be described in detail.
The first protective film comprises a cellulose acylate and a cellulose acylate film containing at least one hydrogen-bonding hydrogen-donating group and a compound (A) having a molecular weight / aromatic ring number ratio of 190 or less. It is.

(Cellulose acylate)
Hereinafter, the cellulose acylate that can be used in the present invention will be described in detail.
The degree of substitution of cellulose acylate means the ratio of acylation of three hydroxyl groups present in the structural unit of cellulose (glucose having a (β) 1,4-glycoside bond). The degree of substitution (acylation degree) can be calculated by measuring the amount of bound fatty acid per unit mass of cellulose. In the present invention, the substitution degree of the cellulose body is determined from the peak intensity ratio of the carbonyl carbon in the acyl group by dissolving the cellulose body in a solvent such as dimethyl sulfoxide substituted with deuterium and measuring the ¹³ C-NMR spectrum. This can be calculated. It can be determined by ¹³ C-NMR measurement after substituting the remaining hydroxyl group of cellulose acylate with another acyl group different from the acyl group of cellulose acylate itself. Details of the measurement method are described in Tezuka et al. (Carbohydrate. Res., 273 (1995) 83-91).

  The total acyl substitution degree of the cellulose acylate is preferably 2.0 to 2.97, more preferably 2.2 to 2.95, and particularly preferably 2.3 to 2.95. The compound (A) used in the present invention has a high polarizing plate durability improving effect particularly when used in combination with cellulose acylate having such a range of total acyl substitution.

  Although it does not specifically limit as an acyl group of a cellulose acylate, A C2-C20 acyl group is preferable, A C2-C10 acyl group is more preferable, A C2-C8 acyl group is still more preferable. Specifically, an acetyl group, a propionyl group, and a butyryl group are particularly preferable, and an acetyl group is most preferable.

A mixed fatty acid ester composed of two or more kinds of acyl groups can also be preferably used as the cellulose acylate in the present invention. Also in this case, the acyl group is preferably an acetyl group and an acyl group having 3 to 4 carbon atoms. Moreover, when using mixed fatty acid ester, the substitution degree of an acetyl group is preferably less than 2.5, and more preferably less than 1.9. On the other hand, the substitution degree of the acyl group having 3 to 4 carbon atoms is preferably 0.1 to 1.5, more preferably 0.2 to 1.2, and 0.5 to 1.1. It is particularly preferred.
In the present invention, two types of cellulose acylates having at least one of a substituent and a substitution degree may be used in combination, mixed, or a plurality of different cellulose acylates formed by a co-casting method described later. A film composed of layers may be formed.

  Furthermore, mixed acid esters having fatty acid acyl groups and substituted or unsubstituted aromatic acyl groups described in JP-A-2008-20896, [0023] to [0038] can also be preferably used in the present invention.

The cellulose acylate used in the present invention preferably has a number average molecular weight (Mn) of 70000 to 230,000, more preferably 75000 to 230,000, and a number average molecular weight of 78,000 to 200000. Is most preferred. The cellulose acylate used in the present invention preferably has a weight average molecular weight (Mw) of 100,000 to 500,000, more preferably 150,000 to 450,000, and a weight average molecular weight of 170000 to 400,000. Most preferably it has.
The ratio (Mw / Mn) of the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the cellulose acylate of the present invention is preferably 1.8 or more and 4.5 or less, preferably 2.0 or more and 4.0 or less, Most preferred is 2.0 or more and 3.5 or less. If Mw / Mn is 4.5 or less, the ratio of the low-molecular component does not increase, and the elastic modulus of the film tends to increase, which is preferable. On the other hand, if Mw / Mn is 1.8 or more, the additive is easily compatible with cellulose acylate, and the haze is hardly increased.

  The average molecular weight and molecular weight distribution of cellulose acylate can be measured by a known method using high performance liquid chromatography. Using this, the number average molecular weight and the weight average molecular weight can be calculated, and the ratio (Mw / Mn) can be calculated.

The measurement conditions of the average molecular weight and molecular weight distribution of cellulose acylate are as follows.
Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 23 ° C
Sample concentration: 0.1% by mass
Detector: RI (RI-71S) Shodex
Pump: DU-H7000 SYSTEM-21H (Shodex)
Flow rate: 1.0 ml / min
Injection volume: 300 μl
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 100000-500 calibration curves with 13 samples were used. The 13 samples are preferably used at approximately equal intervals.

  In the first protective film of the present invention, the content of cellulose acylate is preferably 70% by mass or more and 99% by mass or less, and more preferably 75% by mass or more and 95% by mass or less.

  The cellulose acylate used in the present invention can be synthesized using an acid anhydride or acid chloride as an acylating agent. When the acylating agent is an acid anhydride, an organic acid (for example, acetic acid) or methylene chloride is used as a reaction solvent. Further, a protic catalyst such as sulfuric acid can be used as the catalyst. When the acylating agent is an acid chloride, a basic compound can be used as a catalyst. In the most common synthetic method in the industry, cellulose is an organic acid corresponding to acetyl group and other acyl groups (acetic acid, propionic acid, butyric acid) or their acid anhydrides (acetic anhydride, propionic anhydride, butyric anhydride). A cellulose ester is synthesized by esterification with a mixed organic acid component containing.

  In the above method, cellulose such as cotton linter or wood pulp is activated with an organic acid such as acetic acid and then esterified using a mixture of organic acid components as described above in the presence of a sulfuric acid catalyst. In many cases. The organic acid anhydride component is generally used in excess relative to the amount of hydroxyl groups present in the cellulose. In this esterification treatment, in addition to the esterification reaction, a hydrolysis reaction (depolymerization reaction) of the cellulose main chain (β) 1,4-glycoside bond) proceeds. When the hydrolysis reaction of the main chain proceeds, the degree of polymerization of the cellulose ester is lowered, and the physical properties of the cellulose ester film to be produced are lowered. Therefore, the reaction conditions such as the reaction temperature are preferably determined in consideration of the degree of polymerization and molecular weight of the resulting cellulose ester.

(Polarizer durability improver)
The first protective film in the polarizing plate of the present invention has a cellulose acylate and at least one hydrogen-bonding hydrogen-donating group, and a compound (A) having a molecular weight / aromatic ring ratio of 190 or less (polarizing light Child durability improving agent). By using such an additive, the first polarizing plate protective film can improve the polarizer durability under high temperature and high humidity. Due to the effect of the hydrogen-bonding hydrogen donating group in the additive, the additive tends to be unevenly distributed at the interface between the polarizer and the first polarizing plate protective film under high temperature and high humidity, and the aromatic ring in the additive is It is considered that the diffusion of boric acid in the polarizer to the outside of the polarizing plate is suppressed.

Examples of hydrogen bonding hydrogen donating groups are described, for example, in Jeffrey, George A., et al. It is described in a book such as Introduction to Hydrogen Bonding published by Oxford UP.
In the present invention, the hydrogen bondable hydrogen donating group in the polarizer durability improving agent includes amino group, acylamino group, alkoxycarbonylamino group, aryloxycarbonyl from the viewpoint of interaction with carbonyl group in cellulose acylate. An amino group, a sulfonylamino group, a hydroxyl group, a mercapto group, a carboxyl group, a methylene group having an electron-withdrawing substituent, and a methine group having an electron-withdrawing substituent are preferable. A sulfonylamino group, an acylamino group, an amino group A methine group having a group, a hydroxyl group or an electron withdrawing substituent is more preferred, and an amino group, a hydroxyl group or a methine group having an electron withdrawing substituent is still more preferred.

The electron-withdrawing substituent of the present invention is preferably a substituent having a Hammett's σ _p value of 0 or more. Here, Hammett's substituent constant σ value will be described. Hammett's rule is a method described in 1935 by L. E. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include σp value and σm value, and these values can be found in many general books. For example, J.A. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Areas of Chemistry”, No. 122, 96-103, 1979 (Nankodo), Chem. Rev. 1991, 91, 165-195. The substituent having Hammett's substituent constant σp value of 0 or more in the present invention is an electron-withdrawing group. The σp value is preferably 0.2 or more.

Examples of the electron withdrawing group having a Hammett constant σp value of 0 or more include a halogen atom (for example, σp value of chloro atom is 0.23), CN (σp value 0.66), NO ₂ (σp value 0. 78), C (= O) R (for example, acetyl group has σp value of 0.50), C (= O) OR (for example, methoxycarbonyl group has σp value of 0.45), C (= O) NR ^a R ^b (eg, —CONH _{2 has} a σp value of 0.36), SO ₂ R (eg, —SO ₂ Me has a σp value of 0.72), or SO ₂ NR ^a R ^b is included. R, R ^a , and R ^b each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms (preferably an unsubstituted alkyl group having ₁ to ₇ carbon atoms).

The ratio of molecular weight / aromatic ring number in the polarizer durability improver is 190 or less, preferably 160 or less, more preferably 130 or less.
By setting the aromatic ring / molecular weight ratio to 190 or less, the durability of the polarizer under high temperature and high humidity can be greatly improved.
The ratio of molecular weight / aromatic ring number in the polarizer durability improving agent is preferably 90 or more, and more preferably 100 or more, from the viewpoint of improving compatibility with cellulose acylate.

  From the viewpoint of improving the durability of the polarizer, the aromatic ring in the polarizer durability improving agent of the present invention is a hydrocarbon aromatic ring (an aromatic ring containing no element other than carbon as a ring member in the ring structure). preferable.

(Molecular weight)
The molecular weight of the polarizer durability improving agent is preferably 200 to 1,000, more preferably 250 to 800, and particularly preferably 280 to 600. When the molecular weight is equal to or higher than the lower limit of the above range, disappearance due to volatilization of the polarizer durability improving agent during film formation of the first polarizing plate protective film can be suppressed, and the molecular weight is equal to or lower than the upper limit of the above range. Since the compatibility of a cellulose acylate and a polarizer durability improving agent is good and a polarizing plate film having a low haze is obtained, it is preferable.

<Compound represented by the general formula (1)>
As the polarizer durability improver, a compound represented by the following general formula (1) is preferable.

In general formula (1), R ¹ represents a substituent, R ² represents a substituent represented by the following general formula (1-2); n1 represents an integer of 0 to 4, and n1 is 2 or more. A plurality of R ¹ may be the same or different from each other; n2 represents an integer of 1 to 5, and when n2 is 2 or more, a plurality of R ² may be the same or different from each other Also good.

In general formula (1-2), A represents a substituted or unsubstituted aromatic ring; R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the following general formula: Represents a substituent represented by (1-3); R ⁵ represents a single bond or an alkylene group having 1 to 5 carbon atoms; X represents a substituted or unsubstituted aromatic ring; and n3 represents 0. Represents an integer of -10, and when n3 is 2 or more, the plurality of R ⁵ and X may be the same or different from each other.

In General Formula (1-3), X ₁ represents a substituted or unsubstituted aromatic ring; R ⁶ , R ⁷ , R ⁸ , and R ⁹ each independently represent a hydrogen atom or 1 to 5 carbon atoms. N5 represents an integer of 1 to 11, and when n5 is 2 or more, a plurality of R ⁶ , R ⁷ , R ⁸ , R ⁹ and X ₁ may be the same or different from each other Good.

R ¹ represents a substituent. Examples of the substituent are not particularly limited, and may be an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2 -Ethoxyethyl, 1-carboxymethyl, etc.), alkenyl groups (preferably alkenyl groups having 2-20 carbon atoms, such as vinyl, allyl, oleyl, etc.), alkynyl groups (preferably alkynyl groups having 2-20 carbon atoms). , For example, ethynyl, butadiynyl, phenylethynyl, etc.), a cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), an aryl group (preferably An aryl group having 6 to 26 carbon atoms, such as phenyl, -Naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl and the like), a heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms, such as 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, etc.), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), an aryloxy group (preferably carbon An aryloxy group having 6 to 26 atoms such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc., an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as Ethoxycarbonyl, 2-ethylhexyloxycar Nyl, etc.), an amino group (preferably an amino group having 0 to 20 carbon atoms, such as amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc.), a sulfonamide group (preferably Is a sulfonamide group having 0 to 20 carbon atoms, such as N, N-dimethylsulfonamide, N-phenylsulfonamide, etc., an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, such as acetyloxy, Benzoyloxy and the like), a carbamoyl group (preferably a carbamoyl group having 1 to 20 carbon atoms, such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl and the like), an acylamino group (preferably an acylamino group having 1 to 20 carbon atoms) For example, acetylamino, benzoylamino, etc.), cyano group, or halogen atom (For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.) and a hydroxyl group are mentioned.

R ¹ is preferably an alkyl group having 1 to 20 carbon atoms and a hydroxyl group, and more preferably a hydroxyl group and a methyl group. R ¹ may have one or more substituents as substituents. R ¹ may further have one or more substituents, and examples of the further substituents include the same substituents as R ¹ .

  n1 represents the integer of 0-4, and 2-4 are preferable.

  n2 represents the integer of 1-5, 1-3 are preferable and 1-2 are more preferable.

R ² represents a substituent represented by the following general formula (2).

In general formula (1-2), A represents a substituted or unsubstituted aromatic ring; R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the following general formula: Represents a substituent represented by (1-3); R ⁵ represents a single bond or an alkylene group having 1 to 5 carbon atoms; X represents a substituted or unsubstituted aromatic ring; and n3 represents 0. Represents an integer of -10, and when n3 is 2 or more, the plurality of R ⁵ and X may be the same or different from each other.

A represents a substituted or unsubstituted aromatic ring. The aromatic ring may be a heterocyclic ring containing a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom. Examples of A include benzene ring, indene ring, naphthalene ring, fluorene ring, phenanthrene ring, anthracene ring, biphenyl ring, pyrene ring, pyran ring, dioxane ring, dithiane ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring Morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring, triazine ring and the like. Further, other 6-membered rings or 5-membered rings may be condensed. A is preferably a benzene ring.
Examples of the substituent that A may have include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group, a hydroxyl group, etc., preferably an alkyl group or a hydroxyl group, A C1-C10 alkyl group or a hydroxyl group is more preferable, and a C1-C5 alkyl group or a hydroxyl group is still more preferable.

R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms and a substituent represented by the following general formula (1-3). R ³ and R ⁴ are preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a substituent represented by the general formula (1-3), and a hydrogen atom, a methyl group, or a general formula (1-3). The substituent represented is more preferred.

In General Formula (1-3), X ₁ represents a substituted or unsubstituted aromatic ring; R ⁶ , R ⁷ , R ⁸ , and R ⁹ each independently represent a hydrogen atom or 1 to 5 carbon atoms. N5 represents an integer of 1 to 11, and when n5 is 2 or more, a plurality of R ⁶ , R ⁷ , R ⁸ , R ⁹ and X ₁ may be the same or different from each other Good.

X _{1 in the} general formula (1-3) has the same meaning as X in the general formula (1-2), and the preferred range is also the same.
R ⁶ , R ⁷ , R ⁸ , and R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ⁶ , R ⁷ , R ⁸ and R ⁹ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.

  n5 represents an integer of 1 to 11, preferably 1 to 9, and more preferably 1 to 7.

  The general formula (1-3) is preferably represented by the following general formula (1-3 ′).

  The definition of each symbol of general formula (1-3 ') is synonymous with each in general formula (1-3), and its preferable range is also the same.

  The general formula (1-3) is preferably represented by the following general formula (1-3 ″).

  In general formula (1-3 ″), n4 represents an integer of 0 to 10.

  n4 represents the integer of 0-10, 0-8 are preferable and 0-6 are more preferable.

In General Formula (1-2), R ⁵ represents a single bond or an alkylene group having 1 to 5 carbon atoms, and the alkylene group having 1 to 5 carbon atoms may have a substituent. R ⁵ is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms. Examples of the substituent that R ⁵ may have include an alkyl group having 1 to 5 carbon atoms (eg, methyl, ethyl, isopropyl, t-butyl), a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine). Atoms), hydroxyl groups and the like.

  In general formula (1-2), X represents a substituted or unsubstituted aromatic ring. The aromatic ring may be a heterocyclic ring containing a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom. Examples of X include benzene ring, indene ring, naphthalene ring, fluorene ring, phenanthrene ring, anthracene ring, biphenyl ring, pyrene ring, pyran ring, dioxane ring, dithiane ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring Morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring, triazine ring and the like. Further, other 6-membered rings or 5-membered rings may be condensed. X is preferably a benzene ring. Examples of the substituent which X may have are the same as the examples given as the substituent of A.

n3 represents the integer of 0-10, 0-2 are preferable and 0-1 are more preferable. When n3 is an integer of 2 or more, a plurality of groups represented by — (R ⁵ —X) may be the same as or different from each other, and each bond to A. When n3 is 0, a group represented by — (R ⁵ —X) does not exist, and thus a group represented by — (R ⁵ —X) is not bonded to A.

  The general formula (1-2) is preferably represented by the following general formula (1-2 ').

In General Formula (1-2 ′), R ³ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a substituent represented by General Formula (1-3); R ⁵ represents a single bond. Or an alkylene group having 1 to 5 carbon atoms; X represents a substituted or unsubstituted aromatic ring; n3 represents an integer of 0 to ^5, and when n3 is 2 or more, a plurality of R ⁵ and X May be the same as or different from each other.

  The preferred range of each symbol in the general formula (1-2 ') is the same as that in the general formula (1-2).

  The general formula (1-2) is preferably represented by the following general formula (1-2 ″).

In general formula (1-2 ″), n3 represents an integer of 0 to 5.
The preferable range of n3 in the general formula (1-2 ″) is the same as the preferable range of n3 in the general formula (1-2).

In the compound represented by the general formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ² is represented by the general formula (1-2 ″), and n1 is 2 to 4 It is preferable that n2 represents an integer of 1 to 3, and n3 represents an integer of 0 to 2.

  Although the specific example of a compound represented by General formula (1) below is shown, it is not limited to the following specific examples.

  In order to allow the compound represented by the general formula (1) having a different number of hydroxyl groups to be hydrogen-bonded at multiple points, at least 2 compounds represented by the general formula (1) which are different from each other are bonded. It is good also as a mixture containing a seed. One example is a styrenated phenol in which 1 to 3 moles of styrene are alkylated with respect to phenol, a styrenated phenol in which styrene is further alkylated at the phenyl moiety of the alkylated styrene, and an oligomer of about 2 to 4 mers of styrene. Mention may be made of mixtures with styrenated phenols alkylated to phenol.

The compound represented by the general formula (1) can generally be synthesized by adding 1 equivalent or more of styrenes in the presence of an acid catalyst to 1 equivalent of phenols, and a commercially available product may be used. . Moreover, you may use the mixture obtained by the said synthesis method as it is.
As a commercial item of the compound represented by the general formula (1), “TSP” which is a styrenated phenol manufactured by Sanko Co., Ltd., “PH-25” manufactured by Nikko Paint Chemical Co., Ltd., “ Non-flex WS "etc. are mentioned.

<Compound represented by formula (2)>
As the polarizer durability improver, a compound represented by the following general formula (2) is also preferable.

In the general formula (2), R ²⁶ represents an alkyl group, an alkenyl group, or an aryl group, R ²⁷ and R ²⁸ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heteroaryl group, R ²⁹ represents a hydrogen atom. R ²⁶ , R ²⁷ and R ²⁸ may each independently have a substituent.

R ²⁶ is preferably an alkyl group having 1 to 20 carbon atoms (including a cycloalkyl group), an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and an alkyl group having 1 to 12 carbon atoms. A group (including a cycloalkyl group), an alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms (including a cycloalkyl group), It is more preferably an alkenyl group having 2 to 10 carbon atoms or an aryl group having 6 to 18 carbon atoms, an alkyl group having 1 to 8 carbon atoms (including a cycloalkyl group), an alkenyl group having 2 to 5 carbon atoms, or An aryl group having 6 to 12 carbon atoms is particularly preferable, and an alkyl group having 1 to 6 carbon atoms (including a cycloalkyl group) or an aryl group having 6 to 12 carbon atoms is most preferable. Good.
Among these, a methyl group, an ethyl group, a propyl group, a cyclohexyl group, a phenyl group or a naphthyl group is more preferable, and a methyl group, a cyclohexyl group or a phenyl group is most preferable.

R ²⁷ and R ²⁸ are each independently an alkyl group having 1 to 20 carbon atoms (including a cycloalkyl group), an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 20 carbon atoms. A C1-C12 alkyl group (including a cycloalkyl group), a C2-C20 alkenyl group, or a C6-C20 aryl group is more preferable. It is more preferable that it is a C1-C12 alkyl group (a cycloalkyl group is also included), a C2-C10 alkenyl group, or a C6-C18 aryl group, and a C1-C8 alkyl group (cycloalkyl). Group), an alkenyl group having 2 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, and an alkyl group having 1 to 6 carbon atoms (cycloalkyl group). Including), or most preferably an aryl group having 6 to 12 carbon atoms.
Among these, a methyl group, an ethyl group, a propyl group, a cyclohexyl group, a phenyl group, or a naphthyl group is most preferable, and a methyl group, an ethyl group, a cyclohexyl group, or a phenyl group is particularly preferable.

The substituent that R ²⁶ may have is not particularly limited as long as it does not contradict the gist of the present invention, but is preferably a halogen atom, an alkyl group, or an aryl group, and preferably a halogen atom, carbon number 1 It is more preferably an alkyl group having ˜6 or an aryl group having 6 to 12 carbon atoms, particularly preferably a chlorine atom, a methyl group, or a phenyl group.

The substituent which R ²⁷ and R ²⁸ may have is not particularly limited as long as it does not contradict the gist of the present invention, but is preferably an aryl group having 6 to 12 carbon atoms, and is a phenyl group. It is more preferable.

  As the compound represented by the general formula (2), a compound represented by the following general formula (2-a) can be used. The compound represented by the general formula (2-a) is preferable from the viewpoint of suppressing volatilization during film formation.

In the general formula (2-a), L ^{1 to} L ³ each independently represents a single bond or an alkylene group. Ar ^{1 to} Ar ³ each independently represents an aryl group having 6 to 20 carbon atoms.

In the general formula (2-a), L ^{1 to} L ³ each independently represents a single bond or an alkylene group. L ^{1 to} L ³ are more preferably a single bond or an alkylene group having 1 to 6 carbon atoms, more preferably a single bond, a methylene group or an ethylene group, and particularly preferably a single bond or a methylene group. preferable. The divalent linking group may have a substituent, and the substituent is synonymous with a substituent that Ar ¹ , Ar ² , and Ar ³ described later may have.

In the general formula (2-a), Ar ^{1 to} Ar ³ each independently represents an aryl group having 6 to 20 carbon atoms, preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. Ar ¹ to Ar ³ may have a substituent, the substituent has the same meaning as the substituent which may have is ^Ar 1, Ar ^2, and Ar ^3, which will be described later. Ar ^{1 to} Ar ³ do not have a substituent, or when it has a substituent, the substituent preferably has no ring structure.

Ar ¹ , Ar ² , and Ar ³ may have a substituent. The substituent is not particularly limited, and may be an alkyl group (preferably having 1 to 10 carbon atoms such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl and the like), alkenyl groups (preferably having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl and the like), alkynyl groups (preferably having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl and the like) ), A cycloalkyl group (preferably having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), an aryl group (preferably having 6 to 26 carbon atoms, such as phenyl, 1-naphthyl, etc. 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), Terocyclic group (preferably a heterocyclic group having 0 to 20 carbon atoms, wherein the ring-forming heteroatom is preferably an oxygen atom, a nitrogen atom or a sulfur atom, and is a 5- or 6-membered ring fused with a benzene ring or a heterocyclic ring. The ring may be a saturated ring, an unsaturated ring, or an aromatic ring. For example, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, etc.), alkoxy Group (preferably having 1 to 20 carbon atoms, for example, methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), aryloxy group (preferably having 6 to 26 carbon atoms, for example, phenoxy, 1-naphthyloxy, 3-methyl Phenoxy, 4-methoxyphenoxy, etc.),

An alkylthio group (preferably having 1 to 20 carbon atoms, such as methylthio, ethylthio, isopropylthio, benzylthio, etc.), an arylthio group (preferably having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylthio, 3-methylphenylthio, etc. , 4-methoxyphenylthio, etc.), acyl groups (including alkylcarbonyl groups, alkenylcarbonyl groups, arylcarbonyl groups, and heterocyclic carbonyl groups, preferably having 20 or less carbon atoms, such as acetyl, pivaloyl, acryloyl, metachloroyl, benzoyl , Nicotinoyl, etc.), aryloylalkyl group, alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), aryloxycarbonyl group (preferably having 7 to 7 carbon atoms). 0, for example, phenyloxycarbonyl, naphthyloxycarbonyl, etc.), an amino group (including amino group, alkylamino group, arylamino group, heterocyclic amino group, preferably 0-20 carbon atoms, for example, amino, N , N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, 1-pyrrolidinyl, piperidino, morphonyl, etc.), sulfonamide group (preferably having 0 to 20 carbon atoms, for example, N, N-dimethylsulfone, for example) Amide, N-phenylsulfonamide and the like), sulfamoyl group (preferably having 0 to 20 carbon atoms, for example, N, N-dimethylsulfamoyl, N-phenylsulfamoyl etc.), acyloxy group (preferably having 1 carbon atom) -20, for example, acetyloxy, benzoyloxy, etc.), carbamoyl group (preferably Has 1 to 20 carbon atoms, for example, N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), acylamino group (preferably 1 to 20 carbon atoms, for example, acetylamino, acryloylamino, benzoylamino, nicotinamide, etc. ), Cyano group, hydroxyl group, mercapto group or halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.).

The substituent that Ar ¹ , Ar ² , and Ar ³ may have may further have the substituent.

Here, among the above substituents that each of Ar ¹ , Ar ² , and Ar ³ may have, an alkyl group, an aryl group, an alkoxy group, and an acyl group are preferable.

The molecular weight of the compound represented by the general formula (2) or (2-a) is preferably 250 to 1200, and more preferably 300 to 800.
If the molecular weight is 250 or more, volatilization from the film is suppressed, and if it is 1200 or less, the compatibility with the cellulose acylate is excellent, and thus the transparency of the film is good.

  Specific examples of the compound represented by the general formula (2) or (2-a) are shown below, but the present invention is not limited thereto. In the following exemplary compounds, Me represents a methyl group.

It is known that the compound represented by the general formula (2) can be synthesized by using a barbituric acid synthesis method in which a urea derivative and a malonic acid derivative are condensed. Barbituric acid having two substituents on N can be obtained by heating N, N 'disubstituted urea and malonic acid chloride or by combining malonic acid and an activating agent such as acetic anhydride. For example, Journal of the American Chemical Society 61, 1015 (1939), Journal of Medicinal Chemistry, 54, 2409 (2011), Tetrahedron Letters 99, 40, The method described in WO2007 / 150011 and the like can be preferably used.
In addition, the malonic acid used for the condensation may be unsubstituted or substituted, and if malonic acid having a substituent corresponding to R ⁵ is used, a barbituric acid is constructed to construct the general formula of the present invention. The compound represented by (2) can be synthesized. Further, when an unsubstituted malonic acid and a urea derivative are condensed, a 5-position unsubstituted barbituric acid is obtained. By modifying this, a compound represented by the general formula (2) of the present invention is synthesized. May be.
In addition, the synthesis | combining method of the compound represented by General formula (2) used for this invention is not limited above.

  The compound represented by the general formula (2) may be obtained commercially or synthesized by a known method.

(Content of polarizer durability improver)
The content of the polarizer durability improving agent in the first polarizing plate protective film is preferably 1 part by mass or more and 20 parts by mass with respect to 100 parts by mass of cellulose acylate. If it is 1 part by mass or more, the effect of improving the durability of the polarizer can be easily obtained, and if it is 20 parts by mass or less, bleeding out and bleeding are less likely to occur when a polarizing plate protective film is formed.
As for content of the said polarizer durability improving agent, it is more preferable that it is 1-15 mass parts with respect to 100 mass parts of cellulose acylates, and it is especially preferable that it is 1-10 mass parts.

(Hydrophobicizing agent)
The first polarizing plate protective film of the present invention preferably contains a carbohydrate derivative as a hydrophobizing agent.

(Carbohydrate derivative plasticizer)
The hydrophobizing agent is preferably a monosaccharide or a carbohydrate derivative containing 2 to 10 monosaccharide units (hereinafter referred to as a carbohydrate derivative plasticizer).

The monosaccharide or polysaccharide preferably constituting the carbohydrate derivative plasticizer is characterized in that a substitutable group in the molecule (for example, hydroxyl group, carboxyl group, amino group, mercapto group, etc.) is substituted. Examples of structures formed by substitution include an ether structure formed by replacing the hydroxyl group with an alkyl group, an ester structure formed by replacing the hydroxyl group with an acyl group, and an amino group substituted with an acyl group. An amide structure or an imide structure formed by
Examples of the monosaccharide or carbohydrate containing 2 to 10 monosaccharide units include, for example, erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, fructose, mannose, gulose, idose, galactose , Talose, trehalose, isotrehalose, neotrehalose, trehalosamine, caudibiose, nigerose, maltose, maltitol, isomaltose, sophorose, laminaribiose, cellobiose, gentiobiose, lactose, lactosamine, lactitol, lactulose, melibiose, primebelloose, rutiose , Sucrose, sucralose, turanose, vicyanose, cellotriose, cacotriose, gentianose, isomal Triose, isopanose, maltotriose, manninotriose, melezitose, panose, planteose, raffinose, solatriose, umbelliferose, lycotetraose, maltotetraose, stachyose, maltopentaose, bellbassose, maltohexaose, Examples include α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, xylitol, sorbitol and the like.

  Preferably, ribose, arabinose, xylose, lyxose, glucose, fructose, mannose, galactose, trehalose, maltose, cellobiose, lactose, sucrose, sucralose, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin Xylitol, sorbitol, more preferably arabinose, xylose, glucose, fructose, mannose, galactose, maltose, cellobiose, sucrose, β-cyclodextrin, γ-cyclodextrin, particularly preferably xylose, glucose, fructose , Mannose, galactose, maltose, cellobiose, sucrose, xylitol, sorbitol.

Examples of the substituent of the carbohydrate derivative plasticizer include an alkyl group (preferably an alkyl group having 1 to 22 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms, for example, Methyl group, ethyl group, propyl group, hydroxyethyl group, hydroxypropyl group, 2-cyanoethyl group, benzyl group, etc.), aryl group (preferably having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 6 carbon atoms). 12 aryl groups such as phenyl and naphthyl groups, acyl groups (preferably having 1 to 22 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as acetyl groups, (Propionyl, butyryl, pentanoyl, hexanoyl, octanoyl, benzoyl, toluyl, phthalyl, naphthal, etc.) It can be mentioned. Further, as a preferred structure formed by substitution with an amino group, an amide structure (preferably an amide having 1 to 22 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as formamide, acetamide, etc. And imide structure (preferably having 4 to 22 carbon atoms, more preferably 4 to 12 carbon atoms, and particularly preferably 4 to 8 carbon atoms, such as succinimide and phthalimide).
Among these, an alkyl group, an aryl group or an acyl group is more preferable, and an acyl group is particularly preferable.

Preferable examples of the carbohydrate derivative plasticizer include the following. However, the carbohydrate derivative plasticizer that can be used in the present invention is not limited to these.
Xylose tetraacetate, glucose pentaacetate, fructose pentaacetate, mannose pentaacetate, galactose pentaacetate, maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, xylitol pentaacetate, sorbitol hexaacetate, xylose tetrapropionate, glucose pentapropioate , Fructose pentapropionate, mannose pentapropionate, galactose pentapropionate, maltose octapropionate, cellobiose octapropionate, sucrose octapropionate, xylitol pentapropionate, sorbitol hexapropionate, Xylose tetrabutyrate, glucose pentab Rate, fructose pentabylate, mannose pentabylate, galactose pentabylate, maltose octabutyrate, cellobiose octabutyrate, sucrose octabutyrate, xylitol pentabylate, sorbitol hexabutyrate, xylose tetrabenzoate, glucose pentabenzoate, Fructose pentabenzoate, mannose pentabenzoate, galactose pentabenzoate, maltose octabenzoate, cellobiose octabenzoate, sucrose benzoate, xylitol pentabenzoate, sorbitol hexabenzoate and the like are preferable. Xylose tetraacetate, glucose pentaacetate, fructose pentaacetate, mannose pentaacetate, galactose pentaacetate, maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, xylitol pentaacetate, sorbitol hexaacetate, xylose tetrapropionate, glucose pentapropioate , Fructose pentapropionate, mannose pentapropionate, galactose pentapropionate, maltose octapropionate, cellobiose octapropionate, sucrose octapropionate, xylitol pentapropionate, sorbitol hexapropionate, Xylose tetrabenzoate, glucose penta Nzoeto, fructose pentabenzoate, mannose pentabenzoate, galactose pentabenzoate, maltose octabenzoate, cellobiose octabenzoate, sucrose benzoate, xylitol pentabenzoate, sorbitol hexabenzoate is more preferable. Maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, xylose tetrapropionate, glucose pentapropionate, fructose pentapropionate, mannose pentapropionate, galactose pentapropionate, maltose octapropionate, cellobiose octane Propionate, sucrose octapropionate, xylose tetrabenzoate, glucose pentabenzoate, fructose pentabenzoate, mannose pentabenzoate, galactose pentabenzoate, maltose octabenzoate, cellobiose octabenzoate, sucrose benzoate, xylitol pentabenzoate, sorbitol hexabenzoate, etc. Especially preferred .
The carbohydrate derivative hydrophobizing agent preferably has a pyranose structure or a furanose structure. The molecular weight is preferably from 300 to 1,000, and more preferably from 350 to 800. Further, the ratio of substituent introduction to the total hydroxyl groups is preferably 0.2 or more and 1.0 or less, and more preferably 0.2 or more and 0.8 or less.

  As the carbohydrate derivative used in the present invention, the following compounds are particularly preferred. However, the carbohydrate derivatives that can be used in the present invention are not limited to these. In the following structural formulas, R each independently represents an arbitrary substituent, and a plurality of R may be the same or different. In the following structure, each of the substituents 1 and 2 represents an arbitrary R. The degree of substitution represents the number of R represented by the substituent. “None” represents that R is a hydrogen atom.

(how to get)
As a method for obtaining the carbohydrate derivative, it can be obtained as a commercial product from Tokyo Kasei Co., Ltd., Aldrich, etc., or known ester derivatization methods for commercially available carbohydrates (for example, JP-A-8-245678). Can be synthesized by carrying out the method described in the publication.

  The carbohydrate derivative-based plasticizer can be obtained as a commercially available product from Tokyo Kasei Co., Ltd., Aldrich, etc., or known ester derivatization methods for commercially available carbohydrates (for example, JP-A-8 The method can be synthesized by the method described in JP-A-245678.

  The carbohydrate derivative plasticizer is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the cellulose acylate constituting the first polarizing plate protective film. If it is 1 part by mass or more, the effect of improving the durability of the polarizer can be easily obtained, and if it is 30 parts by mass or less, bleeding out and bleeding are less likely to occur when the first polarizing plate protective film is formed. . The content of the hydrophobizing agent is more preferably 5 to 20 parts by mass, and particularly preferably 5 to 15 parts by mass.

(Aromatic terminal ester compounds)
A compound represented by the following general formula (4) (hereinafter referred to as “aromatic terminal ester compound”) can also be preferably used as the hydrophobizing agent for the first polarizing plate protective film of the present invention.

General formula (4) B- (GA) n-GB
(In the formula, B independently represents a benzene monocarboxylic acid residue. G independently represents an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or 4 carbon atoms. Represents an oxyalkylene glycol residue having ˜12, A represents an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 0 or more.)

The aromatic terminal ester compound represented by the general formula (4) includes a benzene monocarboxylic acid residue represented by B, an alkylene glycol residue, and an oxyalkylene glycol residue represented by G in the general formula (4). Or an aryl glycol residue and an alkylene dicarboxylic acid residue or aryl dicarboxylic acid residue represented by A, and can be obtained by a reaction similar to that of a normal polyester (polycondensation ester).
In the present specification, the “residue” is a partial structure of the aromatic terminal ester compound represented by the general formula (4) and has the characteristics of the monomer forming the compound (polymer). Represents a partial structure. For example, the monocarboxylic acid residue formed from monocarboxylic acid R—COOH is R—CO—.

Examples of the benzene monocarboxylic acid in the benzene monocarboxylic acid residue include benzoic acid, paratertiary butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, normal propylbenzoic acid, amino There exist benzoic acid, acetoxybenzoic acid, etc., These can be used as a 1 type, or 2 or more types of mixture, respectively.
Of these, benzoic acid, orthotoluic acid, metatoluic acid, and p-toluic acid are preferable, and benzoic acid, orthotoluic acid, and metatoluic acid are more preferable.

The alkylene glycol in the alkylene glycol residue is an alkylene glycol having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms.
Examples of the alkylene glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl 1,3-propanediol, 1, 4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane) ), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol 1,6-hexanediol, 2,2,4- Trimethyl 1,3-pentanediol, 2-ethyl 1,3-hexanediol, 2-methyl 1,8-octanediol, 1 9-nonanediol, 1,10-decanediol, there are 1,12-octadecane diol, these glycols may be used alone or in combination.
Among these, 1,4-butanediol, ethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol are preferable, and ethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol are preferable. It is more preferable.

The oxyalkylene glycol in the oxyalkylene glycol residue is an oxyalkylene glycol having 4 to 12 carbon atoms, and the carbon number is preferably 4 to 8 and more preferably 4 to 6.
Examples of the oxyalkylene glycol include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and the like, and these glycols can be used as one kind or a mixture of two or more kinds.
Of these, diethylene glycol and dipropylene glycol are preferable, and more preferable.

The aryl glycol in the aryl glycol residue is an aryl glycol having 6 to 12 carbon atoms, and the carbon number is preferably 6 to 8.
Examples of the aryl glycol include hydroquinone, resorcin, bisphenol A, bisphenol F, and bisphenol, and these glycols can be used as one kind or a mixture of two or more kinds.
Of these, hydroquinone and resorcin are preferable, and hydroquinone is more preferable.

The alkylene dicarboxylic acid in the alkylene dicarboxylic acid residue is an alkylene dicarboxylic acid having 4 to 12 carbon atoms, and the carbon number is preferably 4 to 10 and more preferably 4 to 8.
Examples of the alkylenedicarboxylic acid include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid, and these are used as one kind or a mixture of two or more kinds, respectively. can do.
Of these, succinic acid and maleic acid are preferable, and succinic acid is more preferable.

The aryl dicarboxylic acid in the aryl dicarboxylic acid residue is an alkylene dicarboxylic acid having 8 to 12 carbon atoms.
Examples of the aryl dicarboxylic acid include phthalic acid, terephthalic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and the like. These can be used as one kind or a mixture of two or more kinds, respectively.
Of these, 1,5-naphthalenedicarboxylic acid, phthalic acid, and terephthalic acid are preferable, and phthalic acid and terephthalic acid are more preferable.

  In General formula (4), 0-4 are preferable, as for n, 1-3 are more preferable, and 1-2 are still more preferable.

  The aromatic terminal ester compound of the present invention has a number average molecular weight of preferably 300 to 2000, more preferably 500 to 1500. The acid value is preferably 0.5 mgKOH / g or less, the hydroxyl value is 25 mgKOH / g or less, more preferably the acid value is 0.3 mgKOH / g or less, and the hydroxyl value is 15 mgKOH / g or less.

(Acid value and hydroxyl value of aromatic terminal ester compounds)
Here, the acid value means the number of milligrams of potassium hydroxide necessary for neutralizing the acid (carboxyl group present at the molecular end) contained in 1 g of the sample.
The hydroxyl value refers to the number of milligrams of potassium hydroxide required to neutralize acetic acid bonded to OH groups contained in 1 g of a sample.
The acid value and the hydroxyl value are measured according to JIS K0070.

  Hereinafter, the synthesis example of the aromatic terminal ester plasticizer which concerns on this invention is shown.

<Sample No. 1 (Aromatic terminal ester sample)>
Into a reaction vessel, 820 parts (5 moles) of phthalic acid, 608 parts (8 moles) of 1,2-propylene glycol, 610 parts (5 moles) of benzoic acid and 0.30 parts of tetraisopropyl titanate as a catalyst are charged all at once. While stirring in an air stream, a reflux condenser was attached to reflux excess monohydric alcohol, and heating was continued at 130 to 250 ° C. until the acid value became 2 or less, and water produced was continuously removed. Next, the distillate is removed under reduced pressure of 6.65 × 10 ³ Pa to 4 × 10 ² Pa or less at 200 to 230 ° C., followed by filtration to obtain an aromatic terminal ester having the following properties. It was.

Viscosity (25 ° C., mPa · s): 19815
Acid value: 0.4

<Sample No. 2 (Aromatic terminal ester sample)>
A sample was used except that 500 parts (3.5 moles) of adipic acid, 305 parts (2.5 moles) of benzoic acid, 583 parts (5.5 moles) of diethylene glycol and 0.45 parts of tetraisopropyl titanate as a catalyst were used in the reaction vessel. No. In the same manner as in No. 1, an aromatic terminal ester having the following properties was obtained.

Viscosity (25 ° C., mPa · s): 90
Acid value: 0.05

<Sample No. 3 (Aromatic terminal ester sample)>
Sample No. except that 410 parts (2.5 moles) of phthalic acid, 610 parts (5 moles) of benzoic acid, 737 parts (5.5 moles) of dipropylene glycol and 0.40 parts of tetraisopropyl titanate as the catalyst were used in the reaction vessel. . In the same manner as in No. 1, an aromatic terminal ester plasticizer having the following properties was obtained.

Viscosity (25 ° C., mPa · s): 43400
Acid value: 0.2

  Although the specific compound of the aromatic terminal ester plasticizer which concerns on this invention below is shown, this invention is not limited to this.

The content of the compound represented by the general formula (4) used in the present invention is preferably 2 to 20 parts by mass with respect to 100 parts by mass of cellulose acylate in the first protective film, and 5 to 15 It is more preferable to contain by mass part.
In the first protective film, two or more compounds represented by the general formula (4) may be contained from the viewpoint of reducing haze of the film. As for the content when two or more kinds are used, the total amount is preferably in the above range. When using 2 or more types, it is especially preferable from a viewpoint of the haze reduction of a film to mix the compound from which n in the said structure differs.

<The manufacturing method of a 1st protective film>
The cellulose acylate film which is the first protective film can be produced by a solvent cast method. Hereinafter, the production method of the first polarizing plate protective film will be described by taking an example in which cellulose acylate is used as the main component resin, but the same applies to the case where other resins are used. ) Including the first polarizing plate protective film.
In the solvent cast method, a film is produced using a solution (dope) in which cellulose acylate is dissolved in an organic solvent.

The organic solvent is selected from ethers having 3 to 12 carbon atoms, ketones having 3 to 12 carbon atoms, esters having 3 to 12 carbon atoms, and halogenated hydrocarbons having 1 to 6 carbon atoms. It is preferable to include a solvent.
The ether, ketone and ester may have a cyclic structure. A compound having two or more functional groups of the ether, ketone, and ester (that is, —O—, —CO—, and —COO—) can also be used as the organic solvent. The organic solvent may have other functional groups such as alcoholic hydroxyl groups. In the case of an organic solvent having two or more kinds of functional groups, the number of carbon atoms is preferably within the above-described preferable range of carbon atoms of the solvent having any functional group.

Examples of the ether having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phenetole.
Examples of the ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexanone.
Examples of the esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate.
Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

The number of carbon atoms of the halogenated hydrocarbon having 1 to 6 carbon atoms is preferably 1 or 2, and most preferably 1. The halogen of the halogenated hydrocarbon is preferably chlorine. The proportion of halogen atoms substituted by halogen in the halogenated hydrocarbon is preferably 25 to 75 mol%, more preferably 30 to 70 mol%, and more preferably 35 to 65 mol%. More preferably, it is most preferable that it is 40-60 mol%. Methylene chloride is a representative halogenated hydrocarbon.
Two or more kinds of organic solvents may be mixed and used.

  The cellulose acylate solution (dope) can be prepared by a general method comprising processing at a temperature of 0 ° C. or higher (ordinary temperature or high temperature). The cellulose acylate solution can be prepared using a dope preparation method and apparatus in a normal solvent cast method. In the case of a general method, it is preferable to use a halogenated hydrocarbon (particularly methylene chloride) as the organic solvent.

  The amount of cellulose acylate in the cellulose acylate solution is preferably adjusted so that it is contained in an amount of 10 to 40% by mass in the resulting solution. The amount of cellulose acylate is more preferably 10 to 30% by mass. Arbitrary additives described later may be added to the organic solvent (main solvent).

  The cellulose acylate solution can be prepared by stirring the cellulose acylate and the organic solvent at room temperature (0 to 40 ° C.). High concentration solutions may be stirred under pressure and heating conditions. Specifically, cellulose acylate and an organic solvent are placed in a pressure vessel and sealed, and stirred while heating to a temperature not lower than the boiling point of the solvent at normal temperature and in a range where the solvent does not boil. The heating temperature is usually 40 ° C. or higher, preferably 60 to 200 ° C., and more preferably 80 to 110 ° C.

  Each component may be coarsely mixed in advance and then placed in a container. Moreover, you may put into a container sequentially. The container must be configured to allow stirring. The container can be pressurized by injecting an inert gas such as nitrogen gas. Moreover, you may utilize the raise of the vapor pressure of the solvent by heating. Or after sealing a container, you may add each component under pressure.

  When heating, it is preferable to heat from the outside of the container. For example, a jacket type heating device can be used. The entire container can also be heated by providing a plate heater outside the container and piping to circulate the liquid.

  Stirring is preferably performed using a stirring blade provided inside the container. The stirring blade preferably has a length that reaches the vicinity of the wall of the container. A scraping blade is preferably provided at the end of the stirring blade in order to renew the liquid film on the vessel wall.

  Instruments such as a pressure gauge and a thermometer may be installed in the container. Each component is dissolved in a solvent in a container. The prepared dope is taken out of the container after cooling, or taken out and then cooled using a heat exchanger or the like.

  A cellulose acylate solution can also be prepared by a cooling dissolution method. As for the details of the cooling dissolution method, the techniques described in [0115] to [0122] of JP-A-2007-86748 can be used.

  A cellulose acylate film is produced from the prepared cellulose acylate solution (dope) by a solvent cast method. It is preferable to add a retardation developer to the dope. The dope is cast on a drum or band and the solvent is evaporated to form a film. The concentration of the dope before casting is preferably adjusted so that the solid content is 18 to 35%. The surface of the drum or band is preferably finished in a mirror state. The dope is preferably cast on a drum or band having a surface temperature of 10 ° C. or less.

  Regarding the drying method in the solvent cast method, U.S. Pat. Nos. 2,336,310, 2,367,603, 2,492,078, 2,492,977, 2,492,978 Nos. 2,607,704, 2,739,069 and 2,739,070, British Patent Nos. 640731 and 736892, and Japanese Examined Patent Publication No. 45-4554. 49-5614, JP-A-60-176834, JP-A-60-203430 and JP-A-62-115035. Drying on the band or drum can be performed by blowing an inert gas such as air or nitrogen.

  Further, the obtained film can be peeled off from the drum or band and further dried with high-temperature air whose temperature is successively changed from 100 ° C. to 160 ° C. to evaporate the residual solvent. The above method is described in Japanese Patent Publication No. 5-17844. According to this method, it is possible to shorten the time from casting to stripping. In order to carry out this method, the dope is preferably gelled at the surface temperature of the drum or band during casting.

  Using the prepared cellulose acylate solution (dope), two or more layers can be cast to form a film. In this case, it is preferable to produce a cellulose acylate film by a solvent cast method. The dope is cast on a drum or band and the solvent is evaporated to form a film. It is preferable to adjust the concentration of the dope before casting so that the solid content is in the range of 10 to 40% by mass. The surface of the drum or band is preferably finished in a mirror state.

  When casting a plurality of cellulose acylate solutions of two or more layers, it is possible to cast a plurality of cellulose acylate solutions, and a plurality of casting ports provided at intervals in the traveling direction of the support Alternatively, a film may be produced while casting and laminating solutions containing cellulose acylate. For example, the methods described in JP-A-61-158414, JP-A-1-122419, and JP-A-11-198285 can be used. Also, a film can be formed by casting a cellulose acylate solution from two casting ports. For example, JP-B-60-27562, JP-A-61-94724, JP-A-61-947245, JP-A-61-104413, JP-A-61-158413, and JP-A-6-158413. The method described in each publication of No. 134933 can be used. Further, a flow of a cellulose acylate film in which a flow of a high-viscosity cellulose acylate solution described in JP-A-56-162617 is wrapped with a low-viscosity cellulose acylate solution and the high-low viscosity cellulose acylate solution is simultaneously extruded. A rolling method can also be used.

  Also, using two casting ports, the film formed on the support by the first casting port is peeled off, and the second casting is performed on the side in contact with the support surface to produce a film. You can also For example, the method described in Japanese Patent Publication No. 44-20235 can be mentioned.

  As the cellulose acylate solution to be cast, the same solution may be used, or two or more different cellulose acylate solutions may be used. In order to give a function to a plurality of cellulose acylate layers, a cellulose acylate solution corresponding to the function may be extruded from each casting port. Furthermore, the cellulose acylate solution in the present invention can be cast simultaneously with other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, an ultraviolet absorbing layer, a polarizing layer, etc.).

(Addition of polarizer durability improver)
The timing for adding the polarizer durability improver to the cellulose acylate solution that is a resin raw material for the first polarizing plate protective film is not particularly limited as long as it is added at the time of film formation. For example, it may be added at the time of cellulose acylate synthesis, or may be mixed with cellulose acylate during dope preparation.

(Addition of hydrophobizing agents)
The timing for adding the hydrophobizing agent to the cellulose acylate solution is not particularly limited as long as it is added at the time of film formation. For example, it may be added at the time of cellulose acylate synthesis, or may be mixed with cellulose acylate during dope preparation.

(Addition of UV absorber)
In the present invention, an ultraviolet absorber may be added to the cellulose acylate solution from the viewpoint of preventing deterioration of the polarizing plate or the liquid crystal. As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties. Specific examples of ultraviolet absorbers preferably used in the present invention include, for example, hindered phenol compounds, hydroxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds Etc. Examples of hindered phenol compounds include 2,6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert) -Butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate and the like. Examples of benzotriazole compounds include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6 (2H-benzotriazol-2-yl) phenol), (2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5- Triazine, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-tert-butyl-4- Hydroxy-hydrocinnamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, (2 (2'-hydroxy-3', 5'-di-tert-amylphenyl) -5-chloro And benzotriazole, 2,6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like. The addition amount of the ultraviolet light inhibitor is preferably 0.1 parts by mass to 10.0 parts by mass with respect to 100 parts by mass of the first protective film.

(Addition of other additives)
A degradation inhibitor (for example, an antioxidant, a peroxide decomposer, a radical inhibitor, a metal deactivator, an acid scavenger, an amine, etc.) may be added to the first polarizing plate protective film. The deterioration preventing agents are described in JP-A-3-199201, JP-A-51907073, JP-A-5-194789, JP-A-5-271471, and JP-A-6-107854. Moreover, it is preferable that the addition amount of the said deterioration inhibitor is 0.01-1 mass% of the solution (dope) to prepare, and it is further more preferable that it is 0.01-0.2 mass%. If the addition amount is 0.01% by mass or more, the effect of the deterioration inhibitor is sufficiently exhibited, and if the addition amount is 1% by mass or less, the deterioration inhibitor bleeds out to the film surface (bleeding). And the like are less likely to occur. Examples of particularly preferred deterioration inhibitors include butylated hydroxytoluene (BHT) and tribenzylamine (TBA).

  Moreover, it is preferable to add fine particles as a matting agent to the first polarizing plate protective film. The fine particles used in the present invention include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and Mention may be made of calcium phosphate. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable. The silicon dioxide fine particles preferably have a primary average particle size of 20 nm or less and an apparent specific gravity of 70 g / liter or more. The apparent specific gravity is preferably 90 to 200 g / liter or more, and more preferably 100 to 200 g / liter or more. A larger apparent specific gravity is preferable because a high-concentration dispersion can be produced, and haze and aggregates are improved.

  These fine particles usually form secondary particles having an average particle diameter of 0.1 to 3.0 μm, and these fine particles are present as aggregates of primary particles in the film, and 0.1 to 0.1 μm on the film surface. An unevenness of 3.0 μm is formed. The secondary average particle diameter is preferably 0.2 μm to 1.5 μm, more preferably 0.4 μm to 1.2 μm, and most preferably 0.6 μm to 1.1 μm. The primary and secondary particle sizes were determined by observing the particles in the film with a scanning electron microscope and determining the diameter of a circle circumscribing the particles as the particle size. In addition, 200 particles were observed at different locations, and the average value was taken as the average particle size.

  As fine particles of silicon dioxide, for example, commercially available products such as Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.) can be used. Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.

  Among these, Aerosil 200V and Aerosil R972V are fine particles of silicon dioxide having a primary average particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more, and while maintaining low turbidity of the optical film, friction This is particularly preferable because the effect of reducing the coefficient is great.

In order to obtain the 1st polarizing plate protective film which has a particle | grain with a small secondary average particle diameter in this invention, several methods can be considered when preparing the dispersion liquid of microparticles | fine-particles. For example, a fine particle dispersion prepared by stirring and mixing a solvent and fine particles is prepared in advance, and the fine particle dispersion is added to a separately prepared small amount of cellulose acylate solution and dissolved by stirring. Further, a main cellulose acylate solution (dope solution) and There is a way to mix. This method is a preferred preparation method in that the dispersibility of the silicon dioxide fine particles is good and the silicon dioxide fine particles are more difficult to reaggregate. In addition, after adding a small amount of cellulose ester to the solvent and dissolving with stirring, add the fine particles to this and disperse with a disperser, and use this as a fine particle additive solution. There is also a method of mixing. The present invention is not limited to these methods, but the concentration of silicon dioxide when the silicon dioxide fine particles are mixed and dispersed with a solvent or the like is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and 15 to 20%. Mass% is most preferred. A higher dispersion concentration is preferable because the liquid turbidity with respect to the added amount is lowered, and haze and aggregates are improved. The addition amount of the matting agent fine particles in the final cellulose acylate dope solution is preferably 0.01 to 1.0 g, more preferably 0.03 to 0.3 g, more preferably 0.08 to 0.16 g per m ^3. Is most preferred.
The solvent used is preferably lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. Although it does not specifically limit as solvents other than a lower alcohol, It is preferable to use the solvent used at the time of film forming of a cellulose ester.

  These steps from casting to post-drying may be performed in an air atmosphere or an inert gas atmosphere such as nitrogen gas. The winder used for the production of the first polarizing plate protective film in the present invention may be one generally used, and a constant tension method, a constant torque method, a taper tension method, a program tension control method with a constant internal stress. It can be wound by a winding method such as

(Extension process)
The first polarizing plate protective film can be stretched. A desired retardation can be imparted to the first polarizing plate protective film by the stretching treatment. The stretching direction of the cellulose acylate film is preferably either the width direction or the longitudinal direction.
Methods for stretching in the width direction are described in, for example, JP-A-62-115035, JP-A-4-152125, JP-A-2842211, JP-A-298310, and JP-A-11-48271. Yes.

  The film is stretched under heating conditions. The film can be stretched by a treatment during drying, and is particularly effective when the solvent remains. In the case of stretching in the longitudinal direction, for example, the film is stretched by adjusting the speed of the film transport roller so that the film winding speed is higher than the film peeling speed. In the case of stretching in the width direction, the film can also be stretched by conveying while holding the width of the film with a tenter and gradually widening the width of the tenter. After the film is dried, it can be stretched using a stretching machine (preferably uniaxial stretching using a long stretching machine).

The cellulose acylate film is preferably stretched at a temperature of (Tg−5 ° C.) to (Tg + 40 ° C.), using the glass transition temperature Tg of the first polarizing plate protective film, and Tg to (Tg + 35 ° C.). ) Is more preferable, and (Tg + 10 ° C.) to (Tg + 30 ° C.) is particularly preferable. In the case of a dry film, 130 ° C to 200 ° C is preferable.
Moreover, when extending | stretching in the state in which the dope solvent remained after casting, it becomes possible to extend | stretch at temperature lower than a dry film, In this case, 100 to 170 degreeC is preferable.

The stretch ratio of the cellulose acylate film (elongation relative to the film before stretching) is preferably 1% to 200%, more preferably 5% to 150%. In particular, stretching in the width direction is preferably 1% to 200%, more preferably 5% to 150%, and particularly preferably 10 to 45%.
The stretching speed is preferably 1% / min to 300% / min, more preferably 10% / min to 300% / min, and most preferably 30% / min to 300% / min.

  In addition, the cellulose acylate film is manufactured through a step (hereinafter sometimes referred to as a “relaxation step”) that is stretched to the maximum draw ratio and then held for a certain period of time at a draw ratio lower than the maximum draw ratio. It is preferable. The stretching ratio in the relaxation step is preferably 50% to 99% of the maximum stretching ratio, more preferably 70% to 97%, and most preferably 90% to 95%. In addition, the relaxation step time is preferably 1 second to 120 seconds, and more preferably 5 seconds to 100 seconds.

Furthermore, the said cellulose acylate film can be preferably manufactured by including the shrinkage | contraction process shrink | contracted, holding a film in the width direction.
In the manufacturing method characterized by including a stretching step of stretching in the width direction of the film and a shrinking step of contracting in the film transport direction (longitudinal direction), the film width is held by a pantograph type or linear motor type tenter. The film can be shrunk by gradually narrowing the interval between the clips in the conveying direction while stretching in the direction.

  In the method described above, it can be said that at least a part of the stretching step and the shrinking step are performed simultaneously.

  In addition, Ichikin Kogyo Co., Ltd. is a stretching apparatus that specifically performs a stretching process that stretches either the longitudinal direction or the width direction of the film as described above, simultaneously shrinks the other, and simultaneously increases the film thickness of the film. A company-made FITZ machine or the like can be desirably used. This apparatus is described in Japanese Patent Laid-Open No. 2001-38802.

The stretching ratio in the stretching step and the shrinkage rate in the shrinking step can be arbitrarily selected depending on the target in-plane retardation Re and the thickness direction retardation Rth. It is preferable that the draw ratio is 10% or more and the shrinkage rate in the shrinking step is 5% or more.
In particular, it preferably includes a stretching step of stretching 10% or more in the width direction of the film and a shrinking step of contracting the transport direction of the film by 5% or more while holding the film in the width direction of the film.
In addition, the shrinkage rate as used in the field of this invention means the ratio of the contracted length of the film after contraction with respect to the length of the film before contraction in the contraction direction.
The shrinkage rate is preferably 5 to 40%, particularly preferably 10 to 30%.

[Method of forming cellulose acylate film using peelable laminate film]
The cellulose acylate film of the present invention can also be produced by peeling the cellulose acylate film from the peelable laminated film. The peelable laminate film has a laminate of an A layer containing cellulose acylate and a B layer containing a resin capable of forming a solution different from the cellulose acylate, and the adhesion between the A layer and the B layer is 5 N / It is preferable that it is cm or less.
Hereinafter, the preferable aspect of a peelable laminated film is demonstrated.

<Layer structure of peelable laminated film>
(A layer thickness)
The laminate of the peelable laminate film has an A layer containing cellulose acylate and a B layer containing a resin capable of forming a solution different from cellulose acylate, and the adhesion between the A layer and the B layer is 5N. The laminate is preferably / cm or less. With such a configuration, the peelable laminated film has characteristics that each layer is suitable as a thin film under the thick film production conditions. Further, the adhesion between the A layer and the B layer is preferably 0.1 N / cm or more and 2.0 N / cm or less, more preferably 0.1 N / cm or more and 1.8 N / cm or less, and 0.2 N / cm or more and 1.0 N. / Cm or less is more preferable, and 0.2 N / cm or more and 0.7 N / cm or less is particularly preferable. If the interlayer adhesion is too small, the film is peeled off during conveyance of the film forming process, causing manufacturing trouble. On the other hand, if it is too high, the surface condition such as peeling unevenness is deteriorated, which is not preferable.
The total thickness of the laminate including the A layer and the B layer is preferably 20 μm or more and 200 μm or less, more preferably 20 μm or more and 180 μm or less, and particularly preferably 30 μm or more and 150 μm or less. Most preferably, it is 40 μm or more and 100 μm or less. If it is too thin, there is a concern about deterioration of the surface condition from the viewpoint of film forming suitability, and if it is too thick, there is a concern about deterioration of handling properties. When the total film thickness of the laminate is 40 μm or more and 100 μm or less, it is close to the thickness currently distributed as a cellulosic film, so that it is very easy to divert and introduce various technologies and devices such as conveyance and processing. preferable.
The thickness of the A layer alone can be set to a desired thickness, but is preferably 5 μm or more and 60 μm or less, more preferably 8 μm or more and 50 μm or less, and further 8 μm or more and 30 μm or less, 10 μm. The thickness is particularly preferably 25 μm or less.

(B layer thickness)
The film thickness of the B layer alone can be set to a desired thickness as with the A layer.
However, when the B layer is produced as a carrier for transportation, the B layer needs to have an appropriate mechanical performance in order to support and assist the other layers, and therefore preferably has a certain thickness.

(Lamination mode)
In addition to the A layer and the B layer, the peelable laminated film may further include a C layer containing a resin capable of forming a solution different from the A layer and the B layer, and each of the A layer, the B layer, and the C layer may include a plurality of layers. It can also be an alternating layer structure.

<B layer>
In the peelable laminated film, the B layer contains a resin capable of forming a solution different from the cellulose acylate. In the present specification, resins capable of forming a solution different from cellulose acylate include (meth) acrylic resins (also referred to as “(meth) acrylic resins” and “(meth) acrylic acid resins”), polycarbonate-based resins. Examples thereof include resins, polystyrene resins, cycloolefin resins, and the like, and these resins and mixed resins of these plural types of resins can be selected.

Further, the B layer is preferably laminated so that the adhesiveness with the A layer has a peelability of 5 N / cm or less.
In order to impart releasability, it is preferable that the composition of the A layer and the B layer is not compatible, and an SP value (solubility parameter) can be used as an index thereof. Thus, the B layer can be formed.
In order to impart releasability in the present invention, it can be adjusted by selecting materials used for each layer so that the difference in SP value between the A layer and the B layer is 0.2 or more. Note that the SP value of the layer substantially corresponds to the SP value of the resin used for the layer. Therefore, in this invention, it is preferable that the difference of SP value of resin (cellulose acylate) used for A layer and resin used for B layer is 0.2 or more. A more preferable difference in SP value is 0.5 or more and 3.5 or less, a further preferable difference in SP value is 1.0 or more and 3.5 or less, and most preferably 1.5 or more and 3.5 or less. Solubility parameters are described in, for example, J. Brandrup, E.I. “Polymer Handbook (4th. Edition)” such as H and the like described in VII / 671 to VII / 714.

  The (meth) acrylic resin is a concept including both a methacrylic resin and an acrylic resin. The (meth) acrylic resin also includes acrylate / methacrylate derivatives, particularly acrylate / methacrylate (co) polymers.

((Meth) acrylic resin)
The repeating structural unit of the (meth) acrylic acid resin is not particularly limited. The (meth) acrylic resin preferably has a repeating structural unit derived from a (meth) acrylic acid ester monomer as a repeating structural unit.

The (meth) acrylic acid ester is not particularly limited, and examples thereof include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, and benzyl acrylate. Acrylic acid esters; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, methacrylic acid esters such as benzyl methacrylate; These may be used alone or in combination of two or more. Among these, methyl methacrylate is particularly preferable from the viewpoint of excellent heat resistance and transparency.
When using the said (meth) acrylic acid ester, the content rate in the monomer component with which it uses for a superposition | polymerization process becomes like this. Preferably it is 10-100 mass%, More preferably, in order to fully demonstrate the effect of this invention. -100 mass%, More preferably, it is 40-100 mass%, Most preferably, it is 50-100 mass%.

The monomer component may form a lactone ring after polymerization. In that case, it is preferable to polymerize the monomer component to obtain a polymer having a hydroxyl group and an ester group in the molecular chain.
The polymerization reaction form for polymerizing the monomer components to obtain a polymer having a hydroxyl group and an ester group in the molecular chain is preferably a polymerization form using a solvent, and solution polymerization is particularly preferred. preferable.

  As the (meth) acrylic resin, a (meth) acrylic resin containing an alicyclic alkyl group as a copolymerization component or having a cyclic structure formed in the molecular main chain by intramolecular cyclization can also be used. As an example of the (meth) acrylic resin in which a cyclic structure is formed in the molecular main chain, as one preferred embodiment, a (meth) acrylic thermoplastic resin containing a lactone ring-containing polymer can be mentioned. Preferred resin composition and synthesis The method is described in JP-A-2006-171464. Another preferred embodiment is a resin containing glutaric anhydride as a copolymerization component, and the copolymerization component and a specific synthesis method are described in JP-A-2004-070296.

  There is no limitation on the combination of the weight average molecular weight of the resin forming the B layer (sometimes referred to as a mass average molecular weight) and the weight average molecular weight of the A layer, but the weight average is appropriately adjusted so as to be optimal in the process of film formation. The molecular weight can be selected.

Here, a (meth) acrylic resin having a molecular weight of about 100,000 is generally used for film formation. Specifically, it is impossible in the first place to form a high molecular weight (meth) acrylic resin film by melt film formation. In addition, the (meth) acrylic resin film can be formed by solution casting, but in that case, it is necessary to prepare a dope having a viscosity that facilitates solution casting. If it is a (meth) acrylic resin having a molecular weight of 300,000 or more, it is easy to prepare a dope having high casting suitability, and such a (meth) acrylic resin has been conventionally used for film formation.
On the other hand, the peelable laminated film is preferably formed using a (meth) acrylic resin having a larger weight average molecular weight in order to realize co-casting with the cellulose acylate A layer. That is, the resin for forming the B layer used in the peelable laminated film of the present invention is preferably 600,000 to 4,000,000 in terms of weight average molecular weight (Mw), particularly from the viewpoint of brittleness as an optical film and self-film-forming properties. More preferably, it is 800,000-2 million, more preferably in the range of more than 1 million to 2 million or less, and particularly preferably in the range of more than 1 million to 1.8 million or less. When a (meth) acrylic resin is used, the polymerization average molecular weight of the (meth) acrylic resin as the main component is preferably 600,000 to 4,000,000, more preferably 800,000 to 2,000,000. In addition, a main component means the component with most content (mass%) in the component which comprises a layer.
The weight average molecular weight of the resin forming the B layer can be measured by gel permeation chromatography.
The resin forming the B layer is particularly preferably a (meth) acrylic resin having a weight average molecular weight of 800,000 to 2,000,000 and having 50% by mass or more of methyl methacrylate units in the molecule.

  The resin forming the B layer has a glass transition temperature (Tg) of preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and still more preferably 110 ° C. or higher.

  The peel strength of the A layer and the B layer is preferably adjusted by appropriately adding an additive described later to the B layer, and added to the balance of hydrophilicity / hydrophobicity of the main polymer resin of the A layer and the B layer. The peeling force is controlled by controlling the hydrophilicity / hydrophobicity of the agent. Moreover, it can adjust suitably by changing the solvent composition of the solvent to be used.

(Polycarbonate resin)
The layer B in the present invention can be used by adding an additive to a commercially available polycarbonate resin to appropriately control the peeling force and toughness.

(Polystyrene resin)
The layer B in the present invention can be used by adding an additive to a commercially available polystyrene resin to appropriately control the peeling force and toughness.

(Cyclic polyolefin resin)
In the present invention, a cyclic polyolefin resin can be used for the B layer. Here, the cyclic polyolefin resin (also referred to as cyclic polyolefin or cyclic polyolefin polymer) represents a polymer resin having a cyclic olefin structure.
Examples of the polymer resin having a cyclic olefin structure used in the present invention include (1) a norbornene polymer, (2) a monocyclic olefin polymer, (3) a cyclic conjugated diene polymer, (4) There are vinyl alicyclic hydrocarbon polymers and hydrides of (1) to (4).

(Other thermoplastic resins that may be included in layer B)
The B layer in the present invention may contain a thermoplastic resin other than the above resin. Other thermoplastic resins are not particularly limited as long as they do not contradict the gist of the present invention, but thermoplastic resins that are thermodynamically compatible are preferred in terms of improving mechanical strength and desired physical properties.

  Examples of the other thermoplastic resins include olefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, and poly (4-methyl-1-pentene); halogen-containing polymers such as vinyl chloride and chlorinated vinyl resins. Polymer; Acrylic polymer such as polymethyl methacrylate; Styrene polymer such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer; polyethylene terephthalate, polybutylene Polyesters such as terephthalate and polyethylene naphthalate; polyamides such as nylon 6, nylon 66, nylon 610; polyacetal; polycarbonate; polyphenylene oxide; polyphenylene sulfide; Polyetheretherketone; polysulfone; polyether sulfone; polyoxyethylene benzylidene alkylene; polyamideimide; polybutadiene rubber, rubber-like polymer such as ABS resin or ASA resin containing an acrylic rubber; and the like. The rubbery polymer preferably has a graph collar portion having a composition compatible with the lactone ring polymer of the present invention on the surface, and the average particle diameter of the rubbery polymer is transparency when formed into a film. From the viewpoint of improvement, it is preferably 100 nm or less, and more preferably 70 nm or less.

  Examples of the thermoplastic resin thermodynamically compatible with the resin forming the B layer include a copolymer containing a vinyl cyanide monomer unit and an aromatic vinyl monomer unit, specifically acrylonitrile- A polymer containing 50% by mass or more of a styrene copolymer, a polyvinyl chloride resin, or a methacrylic acid ester may be used. Among them, when an acrylonitrile-styrene copolymer is used, the B layer having a glass transition temperature of 120 ° C. or more, a phase difference per 100 μm in the plane direction of 20 nm or less, and a total light transmittance of 85% or more can be easily obtained. Can be obtained.

  When the said B layer contains the said other thermoplastic resin, the content rate of resin which forms the said B layer, and another thermoformable resin becomes like this. Preferably it is 60-99: 1-40 mass%, More preferably, it is 70. -97: 3-30 mass%, More preferably, it is 80-95: 5-20 mass%. However, when the layer B is also used as an optical film, from the viewpoint of the polymer blend, it is preferable not to contain the other thermoplastic resin unless the compatibility is very high.

(Residual solvent amount)
The peelable laminated film is preferably formed by lamination by co-casting or sequential casting. Thus, by forming the B layer containing a resin capable of forming a solution different from cellulose acylate by solution casting, a layer containing a resin capable of forming a solution different from cellulose acylate is melted. The surface shape of the A layer can be improved as compared with the case where it is formed by film formation.

<Additives>
In the peelable laminate film, in each of the B layer and the A layer, an additive such as a plasticizer, a brittleness improving agent, an A layer and a B together with one or more thermoplastic resins as main raw materials. Layer delamination accelerators, antistatic agents, fillers, ultraviolet absorbers, free acids, radical trapping agents, particles, and the like may be included as long as they do not contradict the spirit of the present invention.

(Film thickness)
The film thickness of the cellulose acylate film as the first protective film is preferably 5 μm or more and 60 μm or less, more preferably 5 μm or more and 45 μm or less, and further preferably 5 μm or more and 35 μm or less.

(Saponification treatment)
The cellulose acylate film can be used as a first polarizing plate protective film by being subjected to alkali saponification treatment to impart adhesion to a polarizer material such as polyvinyl alcohol.
As for the saponification method, the methods described in JP02-86748, [0211] and [0212] can be used.

  For example, the alkali saponification treatment for the cellulose acylate film is preferably performed in a cycle in which the film surface is immersed in an alkali solution, neutralized with an acidic solution, washed with water and dried. Examples of the alkaline solution include a potassium hydroxide solution and a sodium hydroxide solution, and the concentration of hydroxide ions is preferably in the range of 0.1 to 5.0 mol / L, and 0.5 to 4.0 mol / L. More preferably, it is in the range of L. The alkaline solution temperature is preferably in the range of room temperature to 90 ° C, more preferably in the range of 40 to 70 ° C.

  Instead of the alkali saponification treatment, easy adhesion processing as described in JP-A-6-94915 and JP-A-6-118232 may be performed.

<Second polarizing plate protective film>
Next, the second polarizing plate protective film (also referred to as “second protective film”) of the present invention will be described in detail.
The 2nd polarizing plate protective film of this invention contains a cycloolefin type polymer. The second polarizing plate protective film preferably contains a cycloolefin polymer as a main component. A main component is a component with the largest containing mass ratio among the components contained in a 2nd polarizing plate protective film. In the second protective film, the content of the cycloolefin-based polymer is preferably 70% by mass or more and 100% by mass or less, and more preferably 75% by mass or more and 100% by mass or less.

(Cycloolefin polymer film)
The cycloolefin polymer film preferably used in the present invention will be described.

  The cycloolefin-based polymer used in the present invention is composed of a polymer polymer containing an alicyclic structure.

  A preferred cycloolefin-based polymer is a polymer obtained by polymerizing or copolymerizing a cyclic olefin. Examples of the cyclic olefin include norbornene, dicyclopentadiene, tetracyclododecene, ethyltetracyclododecene, ethylidenetetracyclododecene, tetracyclo [7.4.0.110, 13.02,7] trideca-2,4. Unsaturated hydrocarbons of polycyclic structures such as 6,11-tetraene and derivatives thereof; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclo Examples thereof include monocyclic unsaturated hydrocarbons such as octene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, cycloheptene, cyclopentadiene, cyclohexadiene, and derivatives thereof. These cyclic olefins may have a polar group as a substituent. Examples of the polar group include a hydroxyl group, a carboxyl group, an alkoxyl group, an epoxy group, a glycidyl group, an oxycarbonyl group, a carbonyl group, an amino group, an ester group, and a carboxylic acid anhydride group. Or a carboxylic anhydride group is preferred.

  Preferred cycloolefin polymers may be those obtained by addition copolymerization of monomers other than cyclic olefins. Addition copolymerizable monomers include ethylene, propylene, 1-butene, 1-pentene and other ethylene or α-olefins; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl- Examples include dienes such as 1,4-hexadiene and 1,7-octadiene.

The cyclic olefin is obtained by an addition polymerization reaction or a metathesis ring-opening polymerization reaction. The polymerization is carried out in the presence of a catalyst. Examples of the addition polymerization catalyst include a polymerization catalyst composed of a vanadium compound and an organoaluminum compound. As a catalyst for ring-opening polymerization, a polymerization catalyst comprising a metal halide such as ruthenium, rhodium, palladium, osmium, iridium, platinum, nitrate or acetylacetone compound, and a reducing agent; or titanium, vanadium, zirconium, tungsten, molybdenum Examples thereof include a polymerization catalyst comprising a metal halide such as acetylacetone compound and an organoaluminum compound. The polymerization temperature, pressure and the like are not particularly limited, but the polymerization is usually carried out at a polymerization temperature of −50 ° C. to 100 ° C. and a polymerization pressure of 0 to 490 N / cm ² .

  The cycloolefin-based polymer used in the present invention is preferably a polymer obtained by polymerizing or copolymerizing a cyclic olefin, followed by a hydrogenation reaction to change the unsaturated bond in the molecule to a saturated bond. The hydrogenation reaction is performed by blowing hydrogen in the presence of a known hydrogenation catalyst. Examples of hydrogenation catalysts include cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, transition metal compounds such as titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium / alkyl. Homogeneous catalyst consisting of a combination of metal compounds; heterogeneous metal catalyst such as nickel, palladium, platinum; nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth And a heterogeneous solid-supported catalyst in which a metal catalyst such as palladium / alumina is supported on a carrier.

  Or the following norbornene-type polymer is also mentioned as a cycloolefin type polymer. The norbornene-based polymer preferably has a norbornene skeleton as a repeating unit. Specific examples thereof include JP-A-62-252406, JP-A-62-2252407, and JP-A-2-133413. JP-A-63-145324, JP-A-63-264626, JP-A-1-240517, JP-B-57-8815, JP-A-5-39403, JP-A-5-43663 JP-A-5-43834, JP-A-5-70655, JP-A-5-279554, JP-A-6-206985, JP-A-7-62028, JP-A-8-176411, Although what was described in the Kaihei 9-241484 gazette etc. can be utilized preferably, it is not limited to these. Moreover, these may be used individually by 1 type and may use 2 or more types together.

  In the present invention, among the norbornene-based polymers, those having a repeating unit represented by any of the following structural formulas (I) to (IV) are preferable.

  In the structural formulas (I) to (III), A, B, C and D each independently represent a hydrogen atom or a monovalent organic group.

  Among the norbornene-based polymers, a polymer obtained by metathesis polymerization of at least one compound represented by the following structural formula (V) or (VI) and an unsaturated cyclic compound copolymerizable therewith. A hydrogenated polymer obtained by hydrogenating is also preferred.

  In the structural formula, A, B, C and D each independently represent a hydrogen atom or a monovalent organic group.

  Here, A, B, C and D are not particularly limited, but preferably an organic group may be linked through a hydrogen atom, a halogen atom, a monovalent organic group, or at least a divalent linking group. These may be the same or different. A or B and C or D may form a monocyclic or polycyclic structure. Here, the at least divalent linking group includes a hetero atom typified by an oxygen atom, a sulfur atom, and a nitrogen atom, and examples thereof include ether, ester, carbonyl, urethane, amide, thioether, and the like. It is not limited. Further, the organic group may be further substituted via the linking group.

  Examples of other monomers copolymerizable with the norbornene-based monomer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, C2-C20 alpha olefins, such as 1-hexadecene, 1-octadecene, 1-eicocene, and derivatives thereof; cyclobutene, cyclopentene, cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7 -Cycloolefins such as methano-1H-indene, and derivatives thereof; non 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, etc. Conjugated dienes; and the like are used. Among these, an α-olefin, particularly ethylene is preferable.

  These other monomers copolymerizable with the norbornene-based monomer can be used alone or in combination of two or more. In the case of addition copolymerization of a norbornene monomer and another monomer copolymerizable therewith, the ratio of the structural unit derived from the norbornene monomer and the structural unit derived from the other monomer copolymerizable in the addition copolymer However, it is appropriately selected so that the mass ratio is usually 30:70 to 99: 1, preferably 50:50 to 97: 3, more preferably 70:30 to 95: 5.

  When the unsaturated bond remaining in the molecular chain of the synthesized polymer is saturated by a hydrogenation reaction, the hydrogenation rate is 90% or more, preferably 95% or more, particularly from the viewpoint of light resistance deterioration, weather resistance deterioration, etc. Preferably it is 99% or more.

  In addition, examples of the cycloolefin-based polymer used in the present invention include thermoplastic saturated norbornene-based polymers described in paragraphs [0014] to [0019] of JP-A No. 5-2108 and paragraph numbers of JP-A No. 2001-277430. [0015] to [0031] thermoplastic norbornene polymers, JP 2003-14901 paragraph Nos. [0008] to [0045] thermoplastic norbornene polymers, JP 2003-139950 paragraph No. [0014] To [0028] norbornene-based polymer composition, Japanese Patent Application Laid-Open No. 2003-161832, paragraph numbers [0029] to [0037], norbornene-based polymer, Japanese Patent Application Laid-Open No. 2003-195268, paragraph numbers [0027] to [0036] The described norbornene-based polymer, special No. 2003-211589 Paragraph Nos. [0009] to [0023] alicyclic structure-containing polymer polymer, norbornene polymer polymer or vinyl alicyclic ring described in JP-A No. 2003-111588 Paragraph Nos. [0008] to [0024] Formula hydrocarbon polymer polymer and the like.

  Specifically, ZEONEX, ZEONOR manufactured by Nippon Zeon Co., Ltd., Arton manufactured by JSR Corporation, APPEL manufactured by Mitsui Chemicals, Inc. (APL8008T, APL6509T, APL6013T, APL5014DP, APL6015T) and the like are preferably used.

  The molecular weight of the cycloolefin polymer used in the present invention is appropriately selected according to the purpose of use, but measured by gel permeation chromatography method of cyclohexane solution (toluene solution when polymer polymer is not dissolved). When the polyisoprene or polystyrene-equivalent weight average molecular weight is usually in the range of 5,000 to 500,000, preferably 8,000 to 200,000, more preferably 10,000 to 100,000, the mechanical strength and molding processability of the molded article are Highly balanced and suitable.

  The cycloolefin-based polymer film may contain an additive that can be generally blended into a plastic film, if necessary. Examples of such additives include antioxidants, heat stabilizers, light-resistant stabilizers, ultraviolet absorbers, antistatic agents, lubricants, plasticizers, fillers, and the like, the content of which is the object of the present invention. It can be selected within a range that does not damage.

  The method for forming the cycloolefin-based polymer film is not particularly limited, and either a heat-melt molding method or a solution casting method can be used. The heat-melt molding method can be further classified into an extrusion molding method, a press molding method, an inflation molding method, an injection molding method, a blow molding method, a stretch molding method, etc. Among these methods, mechanical strength, surface accuracy are included. In order to obtain an excellent film, an extrusion molding method, an inflation molding method, and a press molding method are preferable, and an extrusion molding method is most preferable. The molding conditions are appropriately selected depending on the purpose of use and the molding method. In the case of the hot melt molding method, the cylinder temperature is usually in the range of 150 to 400 ° C, preferably 200 to 350 ° C, more preferably 230 to 330 ° C. Is set as appropriate. If the polymer temperature is too low, fluidity will deteriorate, causing shrinkage and distortion in the film. If the polymer temperature is too high, voids and silver streaks will occur due to thermal decomposition of the polymer, and the film will turn yellow. Defects may occur. The thickness of the film is usually in the range of 5 to 300 μm, preferably 10 to 200 μm, more preferably 20 to 100 μm. When the thickness is too thin, handling at the time of lamination becomes difficult, and when it is too thick, the drying time after the lamination becomes long and the productivity is lowered.

  The wetting tension of the surface of the cycloolefin-based polymer film is preferably 40 mN / m or more, more preferably 50 mN / m or more, and further preferably 55 mN / m or more. When the surface wetting tension is in the above range, the adhesive strength between the film and the polarizer is improved. In order to adjust the surface wetting tension, for example, corona discharge treatment, ozone spraying, ultraviolet irradiation, flame treatment, chemical treatment, and other known surface treatments can be performed.

  When stretching a cycloolefin-based polymer film, the thickness of the unstretched film is preferably about 50 to 500 μm, and the thickness unevenness is preferably as small as possible, within ± 8%, preferably within ± 6% over the entire surface. More preferably, it is within ± 4%.

  The draw ratio is preferably 1.1 to 10 times, more preferably 1.3 to 8 times, and a desired retardation may be set within this range.

  In the film thus obtained, the molecules are oriented by stretching, and a retardation having a desired size can be obtained. In the present invention, the in-plane retardation value Ro at 589 nm is preferably 0 to 20 nm, and more preferably 0 to 10 nm. Further, the thickness direction retardation value Rth is preferably -20 to 50 nm, and more preferably -10 to 20 nm.

  The retardation can be controlled by the retardation of the film before stretching, the stretching ratio, the stretching temperature, and the thickness of the stretched oriented film. When the film before stretching has a certain thickness, the absolute value of the retardation tends to increase as the stretching ratio of the film increases. Therefore, it is possible to obtain a stretched oriented film having a desired retardation by changing the stretching ratio. I can do it.

  The variation in retardation is preferably as small as possible, and the cycloolefin polymer film according to the present invention has a retardation variation within a wavelength of 589 nm usually within ± 50 nm, preferably ± 30 nm or less, more preferably ± 20 nm or less.

  The in-plane variation of the retardation and thickness unevenness can be reduced by using these small unstretched films and by applying a uniform stress to the film during stretching. For this purpose, it is desirable to stretch in a controlled temperature environment under a uniform temperature distribution, preferably within ± 5 ° C., more preferably within ± 2 ° C., particularly preferably within ± 0.5 ° C.

<Polarizer>
First, the polarizer used for the polarizing plate of this invention is demonstrated.
The polarizer that can be used in the polarizing plate of the present invention is preferably composed of polyvinyl alcohol (PVA) and a dichroic molecule. However, as described in JP-A No. 11-248937, PVA and poly (polyethylene) are used. A polyvinylene polarizer in which a polyene structure is produced by dehydrating and dechlorinating vinyl chloride and then oriented can also be used.

(PVA)
The PVA is preferably a polymer material obtained by saponifying polyvinyl acetate, but may contain a component copolymerizable with vinyl acetate such as unsaturated carboxylic acid, unsaturated sulfonic acid, olefins, and vinyl ethers. I do not care. In addition, modified PVA containing an acetoacetyl group, a sulfonic acid group, a carboxyl group, an oxyalkylene group, or the like can also be used.

In addition, the polarizing plate of the present invention includes a PVA film having a 1,2-glycol bond amount of 1.5 mol% or less described in Japanese Patent No. 3021494, and Japanese Patent Application Laid-Open No. 2001-316492. A PVA film having 500 or less optical foreign matters of 5 μm or more per 100 cm ² , and a PVA film having a hot-water cutting temperature spot in the TD direction of 1.5 ° C. or less of the film described in JP-A No. 2002-030163 Further, a solution prepared by mixing 1 to 100% by mass of a tri- to hexavalent polyhydric alcohol such as glycerin or a solution prepared by mixing 15% by mass or more of a plasticizer described in JP-A-06-289225 is manufactured. A filmed PVA film can be preferably used.

(Dichroic molecule)
Dichroic molecule I ₃ ^- or I ₅ ^- can be preferably used an iodine ion or a dichroic dye higher such.
In the present invention, higher-order iodine ions are particularly preferably used. Higher-order iodine ions can be found in “Applications of Polarizing Plates” by Ryo Nagata, CMC Publishing and Industrial Materials, Vol. 28, No. 7, p. 39-p. As described in 45, PVA can be produced by immersing PVA in a solution obtained by dissolving iodine in an aqueous potassium iodide solution and / or an aqueous boric acid solution and adsorbing and orienting the PVA.
When a dichroic dye is used as the dichroic molecule, an azo dye is preferable, and a bisazo dye and a trisazo dye are particularly preferable. The dichroic dye is preferably a water-soluble dye. For this reason, a hydrophilic substituent such as a sulfonic acid group, an amino group, or a hydroxyl group is introduced into the dichroic molecule, and a free acid, or an alkali metal salt, ammonium salt, or amine is introduced. It is preferably used as a salt. Specific examples of such dichroic dyes include those described in JP-A-2007-086748.

(Boric acid)
The polarizing plate of the present invention preferably contains boric acid as a crosslinking agent in the polarizer. By crosslinking the polarizer with boric acid, the stability of the complex formed from the dichroic molecule and PVA can be improved, and polarization performance deterioration under high temperature and high humidity conditions can be suppressed. The content of boric acid in the polarizer of the polarizing plate of the present invention is preferably 1 part by mass or more and 100 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polarizer. By controlling the content of boric acid within the above range, a polarizer with a well-balanced color can be produced.
The polarizing plate of the present invention preferably has a reduction rate of boric acid in the polarizer of about 50% or less at 60 ° C., a relative humidity of 95% and before and after 1000 hours. The reduction rate of boric acid is preferably 40% or less, and more preferably 30% or less.

(Polarizer film thickness)
Although the film thickness before extending | stretching of a polarizer is not specifically limited, From a viewpoint of stability of film holding | maintenance and the uniformity of extending | stretching, 1 micrometer-1 mm are preferable, and 10-200 micrometers is especially preferable. Further, as described in JP-A-2002-236212, a thin PVA film may be used in which the stress generated when stretching 4 to 6 times in water is 10 N or less.
The thickness of the polarizer of the present invention after stretching is preferably 3 μm or more and 25 μm or less. It is more preferably 3 μm or more and 15 μm or less, and most preferably 3 μm or more and 10 μm or less. By setting the polarizer to the above thickness, warpage and distortion of the liquid crystal panel due to environmental humidity can be reduced.

(Thickness of polarizing plate)
The thickness of the polarizing plate of the present invention is preferably 15 μm or more and 150 μm or less. More preferably, they are 15 micrometers or more and 120 micrometers or less, and 15 micrometers or more and 90 micrometers or less are still more preferable. By setting the polarizing plate to the above thickness, warpage and distortion of the liquid crystal panel due to environmental humidity can be reduced.

<Method for producing polarizer>
Although there is no restriction | limiting in particular as the manufacturing method of the said polarizer, For example, after forming the said PVA into a film, it is preferable to introduce | transduce a dichroic molecule and to comprise a polarizer. The production of the PVA film is carried out according to the method described in [0213] to [0237] of JP-A-2007-86748, Japanese Patent Registration No. 3342516, JP-A-09-328593, JP-A-2001-302817, This can be done with reference to Japanese Patent Application Laid-Open No. 2002-144401.

  Specifically, the manufacturing method of the polarizer may be sequentially performed in the order described in the preparation process of the PVA resin solution, the casting process, the swelling process, the dyeing process, the hardening process, the stretching process, and the drying process. Particularly preferred. Further, an on-line surface inspection process may be provided during or after the aforementioned process.

(Preparation of PVA resin solution)
In the step of preparing the PVA resin solution, it is preferable to prepare a stock solution in which the PVA resin is dissolved in water or an organic solvent. The concentration of the polyvinyl alcohol resin in the stock solution is preferably 5 to 20% by mass. For example, a method of putting a wet cake of PVA in a dissolution tank, adding a plasticizer and water as necessary, and stirring while blowing water vapor from the bottom of the tank is preferable. The internal resin temperature is preferably heated to 50 to 150 ° C., and the inside of the system may be pressurized.
Moreover, it is not necessary to add an acid to the polarizer, but it may be added, but when added, it is preferably added in this step. In addition, when adding an acid in a polarizer, you may use the same thing as the said compound (A) contained in a said 1st polarizing plate protective film.

(Casting)
In the casting step, a method of casting the PVA resin solution stock solution prepared above to form a film is generally preferably used. The casting method is not particularly limited, but the heated PVA-based resin solution stock solution is supplied to a biaxial extruder and is supported by a gear pump from discharge means (preferably a die, more preferably a T-type slit die). It is preferable to form a film by flowing upward. Moreover, there is no restriction | limiting in particular about the temperature of the resin solution discharged | emitted from die | dye.
The support is preferably a cast drum, and the drum diameter, width, rotation speed, and surface temperature are not particularly limited.
Thereafter, it is preferable to perform drying while alternately passing the back and front surfaces of the obtained roll through the drying roll.

(Swelling)
The swelling step is preferably performed only with water. However, as described in JP-A-10-153709, the optical performance is stabilized and wrinkle generation of the polarizing plate substrate on the production line is avoided. In addition, the degree of swelling of the polarizing plate substrate can be controlled by swelling the polarizing plate substrate with an aqueous boric acid solution.
Moreover, although the temperature and time of a swelling process can be defined arbitrarily, 10 to 60 degreeC and 5 to 2000 second are preferable.
In addition, you may extend slightly at the time of a swelling process, for example, the aspect extended about 1.3 times is preferable.

(staining)
For the dyeing step, the method described in JP-A-2002-86554 can be used. Further, as a dyeing method, not only immersion but any means such as application or spraying of iodine or a dye solution can be used. Further, as described in JP-A-2002-290025, a method of dyeing while stirring the iodine concentration, the dyeing bath temperature, the draw ratio in the bath, and the bath liquid in the bath may be used.
When high-order iodine ions are used as the dichroic molecule, in order to obtain a high-contrast polarizing plate, it is preferable to use a solution in which iodine is dissolved in an aqueous potassium iodide solution in order to obtain a high-contrast polarizing plate. In this case, with respect to the mass ratio of iodine and potassium iodide in the iodine-potassium iodide aqueous solution, an embodiment described in JP-A-2007-086748 can be used.
Further, as described in Japanese Patent No. 3145747, boron compounds such as boric acid and borax may be added to the dyeing solution.

(Dura mater)
In the hardening step, it is preferable to immerse in the crosslinking agent solution or apply the solution to contain the crosslinking agent. Further, as described in JP-A-11-52130, the hardening process can be performed in several steps.
As the crosslinking agent, those described in US Pat. No. 2,328,977 can be used, and as described in Japanese Patent No. 3357109, a polyhydric aldehyde is used as a crosslinking agent in order to improve dimensional stability. However, boric acids are most preferably used. When boric acid is used as the crosslinking agent used in the hardening step, metal ions may be added to the boric acid-potassium iodide aqueous solution. Zinc chloride is preferable as the metal ion. However, as described in JP-A No. 2000-35512, zinc halide such as zinc iodide, zinc sulfate such as zinc acetate is used instead of zinc chloride. It can also be used.
Alternatively, a boric acid-potassium iodide aqueous solution to which zinc chloride has been added may be prepared, and the PVA film may be immersed to perform hardening, and the method described in JP-A-2007-086748 can be used.

  Here, as a method for improving the durability under a high temperature environment, a dipping treatment using a known acidic solution may or may not be performed. Examples of the treatment with the acidic solution include methods described in JP-A-2001-83329, JP-A-6-254958, and International Publication WO2006 / 095815.

(Stretching)
The stretching step preferably uses a longitudinal uniaxial stretching method as described in US Pat. No. 2,454,515 or the like, or a tenter method as described in JP-A-2002-86554. Can do. A preferable draw ratio is 2 to 12 times, and more preferably 3 to 10 times. Moreover, the relationship between the draw ratio, the thickness of the original fabric, and the thickness of the polarizer is described in JP-A No. 2002-040256 (film thickness of the polarizer after bonding of the protective film / raw film thickness) × (all (Stretch ratio)> 0.17, or the relationship between the width of the polarizer when leaving the final bath and the width of the polarizer when bonding the protective film is 0.80 ≦ described in JP-A-2002-040247 (Polarizer width at the time of bonding the protective film / polarizer width when leaving the final bath) ≦ 0.95 can also be preferably performed.

(Dry)
As the drying step, a method known in JP-A-2002-86554 can be used, but a preferable temperature range is 30 ° C. to 100 ° C., and a preferable drying time is 30 seconds to 60 minutes. In addition, as described in Japanese Patent No. 3148513, heat treatment is performed so that the fading temperature in water is 50 ° C. or higher, or described in JP-A-07-325215 and JP-A-07-325218. As described above, aging in an atmosphere in which the temperature and humidity are controlled can be preferably performed.

  It is preferable to manufacture a polarizer having a thickness of 10 to 200 μm by such a process. In addition, control of a film thickness can be controlled by a well-known method, for example, it can control by setting the die slit width in the said casting process, and extending | stretching conditions to an appropriate value.

<Functionalization of polarizing plate>
The polarizing plate of the present invention is a function that is combined with an optical film having functional layers such as an antireflection film, a brightness enhancement film, a hard coat layer, a forward scattering layer, and an antiglare (antiglare) layer for improving the visibility of the display. It is also preferably used as a polarizing plate. The antireflection film, brightness enhancement film, other functional optical film, hard coat layer, forward scattering layer, and antiglare layer for functionalization are described in [0257] to [0276] of JP-A-2007-86748. Thus, a functionalized polarizing plate can be created based on these descriptions.

[Liquid Crystal Display]
Next, the liquid crystal display device of the present invention will be described.
The liquid crystal display device of the present invention includes at least one polarizing plate of the present invention.

  FIG. 1 is a schematic view showing an example of the liquid crystal display device of the present invention. In FIG. 1, a liquid crystal display device 10 includes a liquid crystal cell having a liquid crystal layer 5 and a liquid crystal cell upper electrode substrate 3 and a liquid crystal cell lower electrode substrate 6 disposed above and below, and upper polarizing plates disposed on both sides of the liquid crystal cell. 1 and the lower polarizing plate 8. A color filter may be disposed between the liquid crystal cell and each polarizing plate. When the liquid crystal display device 10 is used as a transmission type, a cold cathode or hot cathode fluorescent tube, or a backlight having a light emitting diode, a field emission element, or an electroluminescent element as a light source is disposed on the back surface.

The upper polarizing plate 1 and the lower polarizing plate 8 each have a structure in which a polarizer is sandwiched between two polarizing plate protective films, and the liquid crystal display device 10 of the present invention includes at least one polarizing plate. Is preferably the polarizing plate of the present invention. The liquid crystal display device 10 of the present invention is preferably laminated in the order of the first protective film, the polarizer, and the second protective film from the outside of the device (the side far from the liquid crystal cell).
The liquid crystal display device 10 includes an image direct view type, an image projection type, and a light modulation type. The present invention is effective for an active matrix liquid crystal display device using a three-terminal or two-terminal semiconductor element such as TFT or MIM. Of course, it is also effective in a passive matrix liquid crystal display device typified by STN mode called time-division driving.
The driving mode of the liquid crystal display device is effective in any of the known driving modes such as the TN mode and the IPS mode. In particular, the VA mode liquid crystal display device described in paragraphs 0245 to 0260 of JP2012-82235A is the present mode. It can be preferably used as the liquid crystal display device of the invention.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, amounts and ratios of substances, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

[Reference Example 101]
(1) Production of cellulose acylate film <Preparation of cellulose acylate>
A cellulose acylate having an acetyl substitution degree of 2.87 was prepared. This was carried out by adding sulfuric acid (7.8 parts by mass with respect to 100 parts by mass of cellulose) as a catalyst, adding carboxylic acid as a raw material for the acyl substituent, and carrying out an acylation reaction at 40 ° C. In addition, aging was performed at 40 ° C. after acylation. Further, the low molecular weight component of the cellulose acylate was removed by washing with acetone.

[Preparation of polarizing plate protective film]
<Preparation of dope 101 solution for air side surface layer>
(Preparation of cellulose acylate solution)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acylate solution 1.
―――――――――――――――――――――――――――――――――――
Composition of Cellulose Acylate Solution 1 ――――――――――――――――――――――――――――――――――――
-Cellulose acetate with acetyl substitution degree 2.87 and polymerization degree 370
100.0 parts by mass-Sucrose benzoate with an average degree of benzoyl substitution of 4.5
11.0 parts by mass-Polarizer durability improving agent (2-3) 4.0 parts by mass-Methylene chloride (first solvent) 353.9 parts by mass-Methanol (second solvent) 89.6 parts by mass-n- Butanol (3rd solvent) 4.5 parts by mass ―――――――――――――――――――――――――――――――――――

(Preparation of matting agent solution 2)
The following composition was charged into a disperser and stirred to dissolve each component to prepare a matting agent solution 2.
―――――――――――――――――――――――――――――――――――
Composition of Matte Solution 2 ―――――――――――――――――――――――――――――――――――
-Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.)
2.0 parts by mass-Methylene chloride (first solvent) 69.3 parts by mass-Methanol (second solvent) 17.5 parts by mass-N-butanol (third solvent) 0.9 parts by mass-The cellulose acylate solution 1 0.9 parts by mass ―――――――――――――――――――――――――――――――――――

  1.3 parts by weight of the matting agent solution 2 and 98.7 parts by weight of the cellulose acylate solution 1 were added and mixed using an in-line mixer to prepare an air side surface dope 101.

<Preparation of base layer dope 101>
(Preparation of cellulose acylate solution)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a base layer dope 101.
―――――――――――――――――――――――――――――――――――
Composition of base layer dope 101 (cellulose acylate solution 2) ―――――――――――――――――――――――――――――――――――
-Cellulose acetate with acetyl substitution degree 2.87 and polymerization degree 370
100.0 parts by mass-Sucrose benzoate with an average degree of benzoyl substitution of 4.5
11.0 parts by mass-Polarizer durability improver (2-3) 4.0 parts by mass-UV absorber C 2.0 parts by mass below-Methylene chloride (first solvent) 297.7 parts by mass-Methanol (No. 1) 2 solvent) 75.4 parts by mass ・ n-butanol (third solvent) 3.8 parts by mass ―――――――――――――――――――――――――――― ―――――――
UV absorber C

<Preparation of dope 101 solution for support surface layer>
1.3 parts by mass of the matting agent solution 2 prepared in the air layer side surface dope 101 solution and 99.3 parts by mass of the cellulose acylate solution 1 were mixed using an in-line mixer, and the support side surface dope 101 was mixed. Was prepared.

(Casting)
Using a drum casting apparatus, three layers of the prepared dope (base layer dope 101) and the surface layer dope on both sides of the dope are cast into a stainless steel casting support (support temperature -9 ° C.) from the casting port. Cast uniformly. Stripped in a state where the amount of residual solvent in the dope of each layer is about 70% by mass, fixed both ends in the width direction of the film with a pin tenter, and 1.28 in the lateral direction in a state of residual solvent amount of 3-5% by mass. The film was dried while being stretched twice. Then, it dried further by conveying between the rolls of the heat treatment apparatus, and the cellulose acylate film of Reference Example 101 was obtained. The obtained cellulose acylate film had a thickness of 30 μm (air-side surface layer 3 μm, base layer 24 μm, support-side surface layer 3 μm), and a width of 1480 mm.

[Reference Examples 102 to 118, 201 to 207]
In the production of the cellulose acylate film of Reference Example 101, the types and addition amounts of the polarizer durability improver and the film thickness were changed in the same manner as described in Table 1 below. 207 cellulose acylate films were produced. In addition, the kind and addition amount (mass part with respect to 100 mass parts of cellulose acylates) of the polarizer durability improver were all made the same in the three layers of the air side surface layer, the base layer, and the support side surface layer.

[Reference Example 301]
(Preparation of cellulose acylate solution 301)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acylate solution 301.
―――――――――――――――――――――――――――――――――――
Composition of Cellulose Acylate Solution 301 ――――――――――――――――――――――――――――――――――――
-Cellulose acetate with an acetyl substitution degree of 2.88 and a polymerization degree of 370
100.0 parts by mass-Hydrophobizing agent 1 (AA-1) 6.5 parts by mass-Hydrophobizing agent 2 (B-1) 4.0 parts by mass-UV absorber D 1.5 parts by mass-Methylene chloride (1 solvent) 412.2 parts by mass ・ Ethanol (second solvent) 35.8 parts by mass ―――――――――――――――――――――――――――――― ―――――

UV absorber D

(Preparation of matting agent solution 302)
The following composition was charged into a disperser and stirred to dissolve each component to prepare a matting agent solution 302.
―――――――――――――――――――――――――――――――――――
Composition of the matting agent solution 302 ―――――――――――――――――――――――――――――――――――
-Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.)
2.0 parts by mass-79.9 parts by mass of methylene chloride (first solvent)-6.9 parts by mass of ethanol (second solvent)-0.9 parts by mass of the cellulose acylate solution 301 ―――――――― ―――――――――――――――――――――――――――

(Preparation of polarizer durability improver solution 303)
The following composition was put into a mixing tank, stirred while heating to dissolve each component, and a polarizer durability improving agent solution 303 was prepared.

―――――――――――――――――――――――――――――――――――
Composition of polarizer durability improver solution 303 --------------
・ Polarizer durability improver (1-11) 20.0 parts by mass ・ Methylene chloride (first solvent) 73.6 parts by mass ・ Ethanol (second solvent) 6.4 parts by mass ―――――――― ―――――――――――――――――――――――――――

<Casting>
1.3 parts by weight of the matting agent solution 302 and 3.4 parts by weight of the polarizer durability improving agent solution 303 are mixed using an in-line mixer after filtration, and further 95.3 parts by weight of the cellulose acylate solution 301. Part of the mixture was added and mixed using an in-line mixer. Using the band casting apparatus, the prepared dope was cast on a stainless steel casting support (support temperature 22 ° C.). The dope is peeled off in a state where the amount of residual solvent in the dope is approximately 20% by mass, both ends in the width direction of the film are held by a tenter, and the amount of residual solvent is 5 to 10% by mass in the width direction at a temperature of 120 ° C. To 1.10 times (10%). Then, it dried further by conveying between the rolls of the heat processing apparatus, and the cellulose acylate film of Reference Example 301 was obtained. The obtained cellulose acylate film had a thickness of 20 μm and a width of 1480 mm.

[Reference Examples 302 to 310 and 401 to 404]
In the production of the cellulose acylate film of Reference Example 301, the types and addition amounts of the polarizer durability improver, and the film thickness were changed in the same manner as described in Table 2 below. A 404 cellulose acylate film was produced.

[Reference Example 501]
(Preparation of acrylic solution 501)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare an acrylic solution 501.
―――――――――――――――――――――――――――――――――――
Composition of acrylic solution 501 ―――――――――――――――――――――――――――――――――――
-Mitsubishi Rayon Co., Ltd. Dianal BR88 (solvent type thermoplastic acrylic resin)
100.0 parts by mass-Sucrose benzoate with an average degree of benzoyl substitution of 5.0
11.0 parts by mass-UV absorber C 2.0 parts by mass-Polarizer durability improver (1-13) 6.0 parts by mass-Methylene chloride (first solvent) 393.0 parts by mass-Methanol (second Solvent) 59.0 parts by mass ―――――――――――――――――――――――――――――――――――

(Preparation of cellulose acylate solution 502)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acylate solution 502.
―――――――――――――――――――――――――――――――――――
Composition of Cellulose Acylate Solution 502 ――――――――――――――――――――――――――――――――――――
-Cellulose acetate with an acetyl substitution degree of 2.86 and a polymerization degree of 350
100.0 parts by mass-Sucrose benzoate with an average degree of benzoyl substitution of 5.0
5.0 parts by mass UV absorber C 2.0 parts by mass Polarizer durability improver (1-13) 8.0 parts by mass Methylene chloride (first solvent) 414.0 parts by mass Methanol (second Solvent) 62.0 parts by mass ―――――――――――――――――――――――――――――――――――

<Preparation of laminated film>
Acrylic layer / cellulose acylate layer / acrylic layer = 30 μm / 10 μm / from the side closer to the metal support using the acrylic solution 501 and the cellulose acylate solution 502 through a casting Giuser capable of co-casting with three layers. The film was cast so as to have a layer structure of 30 μm. While on the metal support, the dope was dried with a drying air at 40 ° C. to form a film, and then peeled off. Both ends of the film were fixed with pins, and 5 ° Dried for minutes. After removing the pin, the film was further dried at 130 ° C. for 20 minutes and wound up in the state of a laminated film.
A cellulose acylate film having a thickness of 10 μm was obtained by peeling off and removing the upper and lower acrylic films from the laminated film thus produced.

[Reference Examples 502 to 504]
The polarizing plate protective films of Reference Examples 502 to 504 were produced in the same manner except that the thickness of the polarizing plate protective film of Reference Example 501 was changed to the values shown in Table 3 below.

[Reference Example 601]
A cycloolefin polymer film (trade name “Arton Film FEKV150D0” manufactured by JSR) was uniaxially stretched 3.8 times in the width direction to produce a cycloolefin polymer polarizing plate protective film 601 having a thickness of 40 μm.

[Reference Example 602]
A cycloolefin polymer film (trade name “ZEONOR FILM ZB14-55 / 135” manufactured by ZEON Corporation) is uniaxially stretched 3.5 times in the width direction to produce a cycloolefin polymer polarizing plate protective film 602 having a thickness of 20 μm. did.

[Reference Example 603]
A cycloolefin polymer-based polarizing plate protective film 603 having a thickness of 29 μm was produced by uniaxially stretching a cycloolefin polymer-based film (trade name “Arton Film FEKV150D0” manufactured by JSR) 5.2 times in the width direction.

<Production of Polarizer A>
After applying an aqueous solution prepared by dissolving PVA powder having an average polymerization degree of 2400 and a saponification degree of 99.9% or more in pure water to 10% by mass on a polyester film and drying at 40 ° C. for 3 hours. Further, drying was performed at 110 ° C. for 60 minutes to obtain a PVA film having a thickness of 50 μm. The obtained film was swollen with warm water at 30 ° C. for 1 minute, immersed in an aqueous solution of potassium iodide / iodine (mass ratio 10: 1) at 30 ° C., and stretched uniaxially 1.5 times. The concentration of the aqueous solution of potassium iodide / iodine (mass ratio 10: 1) was set to an iodine concentration of 0.38% by mass. Next, in a 4.25% by mass boric acid aqueous solution at 50 ° C., the film is uniaxially stretched so that the total draw ratio is 7 times, immersed in a 30 ° C. water bath, washed with water, and dried at 50 ° C. for 4 minutes. A polarizer A having a thickness of 12.5 μm was obtained.

<Preparation of Polarizer B>
An aqueous solution prepared by dissolving a PVA powder having an average degree of polymerization of 2400 and a degree of saponification of 99.9% or more in pure water to 12% by mass is applied onto a polyester film and dried at 40 ° C. for 3 hours. Further, drying was performed at 110 ° C. for 60 minutes to obtain a PVA film having a thickness of 50 μm. The obtained film was swollen with warm water at 30 ° C. for 1 minute, immersed in an aqueous solution of potassium iodide / iodine (mass ratio 10: 1) at 30 ° C., and stretched uniaxially twice. The concentration of the aqueous solution of potassium iodide / iodine (mass ratio 10: 1) was set to an iodine concentration of 0.38% by mass. Next, in a 50 ° C. aqueous solution of boric acid 4.25% by mass, the film was uniaxially stretched so that the total draw ratio was 6.5 times, immersed in a 30 ° C. water bath, washed with water, and dried at 50 ° C. for 4 minutes. Thus, a polarizer B having a thickness of 16 μm was obtained.

<Production of Polarizer C>
A polarizer C was produced in the same manner as the polarizer A except that the original film thickness was 32 μm. The thickness of the polarizer C was 8 μm.

<Production of Polarizer D>
A polarizer D was produced in the same manner as the polarizer A except that the original film thickness was 16 μm. The thickness of the polarizer D was 4 μm.

<Production of Polarizer E>
A polarizer E was produced in the same manner as the polarizer A, except that the original film thickness was 77 μm. The thickness of the polarizer E was 19 μm.

[Saponification treatment of polarizing plate protective film]
The produced polarizing plate protective film of Reference Example 101 was immersed in a 2.3 mol / L sodium hydroxide aqueous solution at 55 ° C. for 3 minutes. It wash | cleaned in the room temperature water-washing bath, and neutralized using 0.05 mol / L sulfuric acid at 30 degreeC. Again, it was washed in a water bath at room temperature and further dried with hot air at 100 ° C. Thus, the surface of the polarizing plate protective film of Reference Example 101 was saponified.

(Preparation of adhesive)
Polyvinyl alcohol resin having an acetoacetyl group (average polymerization degree 1200, saponification degree 98.5% mol%, acetoacetyl group modification degree 5 mol%) 100 parts by mass, 50 parts by mass of methylol melamine at 30 ° C. It melt | dissolved in the pure water under temperature conditions, and prepared the aqueous solution with a solid content density | concentration of 3.7 mass%. A metal colloid-containing adhesive aqueous solution was prepared by adding 18 parts by mass of an aqueous solution containing a positively charged alumina colloid (average particle diameter of 15 nm) at a solid content concentration of 10% by mass to 100 parts by mass of this aqueous solution. The viscosity of the adhesive solution was 9.6 mPa · s, the pH was in the range of 4 to 4.5, and the blending amount of the alumina colloid was 74 parts by mass with respect to 100 parts by mass of the polyvinyl alcohol resin. The average particle diameter of the alumina colloid is measured by a dynamic light scattering method (light correlation method) using a particle size distribution meter (manufactured by Nikkiso, product name “Nanotrack UAP150”).

<Preparation of polarizing plate>
[Example A-101]
What applied the said adhesive agent to the single side | surface (air side surface layer side) of the said polarizing plate protective film 101, and the single side | surface of the said polarizing plate protective film 601 so that the adhesive bond layer thickness after drying might be set to 80 nm, It is bonded to one side of the polarizer A using a roll machine through an adhesive layer, dried at 70 ° C. for 6 minutes, and a polarizing plate with a polarizing plate protective film 101 and the polarizer sandwiched on one side of the polarizer. A polarizing plate A-101 having a polarizing plate protective film 601 on the side opposite to the protective film 101 was prepared. Under the present circumstances, it arrange | positioned so that the transmission axis of a polarizer and the width direction of a polarizing plate protective film may become parallel.

[Examples A-102 to A-135, B-101, C-101, D-101, E-101, and Comparative Examples A-201 to 213]
In Example A-101, the polarizing plate of the example and the polarizing plate of the comparative example were the same as in Example A-101 except that the polarizing plate protective film and the type of the polarizer were changed to those shown in Table 4. Was made.

(Evaluation of polarizing plate durability)
For each of the polarizing plates of Examples and Comparative Examples prepared above, the orthogonal transmittances of two polarizers at wavelengths of 410 nm and 510 nm were measured by the following method.
The orthogonal transmittance CT of the polarizing plate was measured at a wavelength of 410 nm or 510 nm by the following method using an automatic polarizing film measuring device VAP-7070 manufactured by JASCO Corporation.
Two samples (5 cm × 5 cm) in which a polarizing plate was attached on glass via an adhesive were prepared. At this time, the first polarizing plate protective film (cellulose acylate film) was attached so as to be on the side opposite to the glass (air interface) side. The orthogonal transmittance was measured by setting the glass side of the sample facing the light source. Two samples were measured respectively, and the average value was defined as the orthogonal transmittance.
Thereafter, the orthogonal transmittance was measured in the same manner after one sheet was stored for 168 hours in an environment of 80 ° C. and 90% relative humidity. The remaining one sheet was stored at 105 ° C. in an environment without humidity control for 240 hours, and then the orthogonal transmittance was measured by the same method. The amount of change in the orthogonal transmittance before and after aging was determined and evaluated according to the following criteria, and the results are shown in Table 4 below as the polarizer durability.

When stored for 168 hours in an environment of 80 ° C. and relative humidity 90% A: Change in orthogonal transmittance at wavelength 410 nm is less than 0.4% B: Change in orthogonal transmittance at wavelength 410 nm is 0.4% or more and 0.8% Less than C: Orthogonal transmittance change at wavelength 410 nm is 0.8% or more and less than 1.6% D: Orthogonal transmittance change at wavelength 410 nm is 1.6% or more

When stored for 240 hours in an environment of 105 ° C and no humidity control (relative humidity 20% or less)
A: Change in orthogonal transmittance at wavelength 510 nm is less than 0.02% B: Change in orthogonal transmittance at wavelength 510 nm is 0.02% or more and less than 0.04% C: Change in orthogonal transmittance at wavelength 510nm is 0.04% or more Less than 0.1% D: Change in orthogonal transmittance at a wavelength of 510 nm is 0.1% or more

  From the results of Table 4, the polarizing plate using the polarizing plate protective film having the polarizer durability improving agent of the present invention is 80 ° C., relative humidity 90%, before and after aging for 168 hours with respect to the polarizing plate of the comparative example. It was found that both the change in cross transmittance at 410 nm and the change in cross transmittance at 510 nm after a lapse of 240 hours without humidity adjustment at 105 ° C. were preferable.

[Production of liquid crystal display device]
Peel off the two polarizing plates of a commercially available liquid crystal television (BRAVIA J5000 from Sony Corporation) so that the polarizing plate protective film described in Table 4 of the present invention is on the liquid crystal cell side on the viewer side and the backlight side. A single sheet was attached to the observer side and the backlight side. The crossed Nicols were arranged so that the transmission axis of the polarizing plate on the viewer side was in the vertical direction and the transmission axis of the polarizing plate on the backlight side was in the horizontal direction.
Similarly, the other polarizing plates in Table 4 were attached to the observer side and the backlight side one by one so that the polarizing plate protective film described in Table 4 was on the liquid crystal cell side.
The liquid crystal display device incorporating the polarizing plate of the present invention is preferable because the display performance is hardly deteriorated both when stored for a long time in a high temperature and high humidity environment and when stored for a long time in a high temperature and low humidity environment. I understood.

DESCRIPTION OF SYMBOLS 1 Upper polarizing plate 2 Upper polarizing plate Absorption axis direction 3 Liquid crystal cell upper electrode substrate 4 Upper substrate alignment control direction 5 Liquid crystal layer 6 Liquid crystal cell lower electrode substrate 7 Lower substrate alignment control direction 8 Lower polarizing plate 9 Lower polarization Direction of plate absorption axis 10 Liquid crystal display device

Claims (7)

A polarizing plate having a first protective film, a polarizer, and a second protective film in this order,
The first protective film has a thickness of 5 μm or more and 60 μm or less, has a cellulose acylate and at least one hydrogen bondable hydrogen donating group, and has a molecular weight / aromatic ring number ratio of 190 or less ( A) and
The polarizing plate in which the second protective film contains a cycloolefin polymer.   The polarizing plate according to claim 1, wherein the aromatic ring in the compound (A) is a hydrocarbon aromatic ring. The polarizing plate according to claim 1 or 2, wherein the compound (A) is a compound represented by the following general formula (2).

In the general formula (2), R ²⁶ represents an alkyl group, an alkenyl group, or an aryl group, R ²⁷ and R ²⁸ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heteroaryl group, and R ²⁹ represents a hydrogen atom. R ²⁶ , R ²⁷ , and R ²⁸ may each independently have a substituent. However, at least one of R ²⁶ , R ²⁷ and R ²⁸ contains an aromatic ring. The polarizing plate according to claim 1, wherein the compound (A) is a compound represented by the following general formula (1).

In general formula (1), R ¹ represents a substituent, R ² represents a group represented by the following general formula (1-2); n1 represents an integer of 0 to 4, and n1 is 2 or more. A plurality of R ¹ may be the same as or different from each other; n2 represents an integer of 1 to 5, and when n2 is 2 or more, a plurality of R ² may be the same or different from each other Good.

In general formula (1-2), A represents a substituted or unsubstituted aromatic ring; R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the following general formula: Represents a group represented by (1-3); R ⁵ represents a single bond or an alkylene group having 1 to 5 carbon atoms; X represents a substituted or unsubstituted aromatic ring; Represents an integer of 10, and when n3 is 2 or more, the plurality of R ⁵ and X may be the same or different from each other.

In General Formula (1-3), X ₁ represents a substituted or unsubstituted aromatic ring; R ⁶ , R ⁷ , R ⁸ , and R ⁹ each independently represent a hydrogen atom or 1 to 5 carbon atoms. N5 represents an integer of 1 to 11, and when n5 is 2 or more, a plurality of R ⁶ , R ⁷ , R ⁸ , R ⁹ and X ₁ may be the same or different from each other Good. The polarizing plate according to claim 4, wherein the group represented by the general formula (1-2) is a group represented by the following general formula (1-2 ′).

In General Formula (1-2 ′), R ³ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a substituent represented by General Formula (1-3); R ⁵ represents a single bond or Represents an alkylene group having 1 to 5 carbon atoms; X represents a substituted or unsubstituted aromatic ring; n3 represents an integer of 0 to ^5, and when n3 is 2 or more, a plurality of R ⁵ and X are They may be the same or different.   The polarizing plate as described in any one of Claims 1-5 which contains a hydrophobizing agent in a said 1st protective film.   A liquid crystal display device comprising at least one polarizing plate according to claim 1.

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