JP7332786B2 - Resin composition and unstretched optical film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polycarbonate-based resin composition and an unstretched optical film containing composite tungsten oxide fine particles having high heat resistance, excellent transparency, flex resistance, moist heat resistance, and low three-dimensional retardation.

Conventionally, a polycarbonate resin (hereinafter referred to as PC-A) obtained by reacting 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A) with a carbonate precursor has transparency, heat resistance and mechanical properties. Due to its excellent properties and dimensional stability, it has been widely used as an engineering plastic in many fields. Furthermore, in recent years, by taking advantage of its transparency, it is being used as an optical material in the fields of optical discs, films, lenses, and the like.

However, polycarbonate resins have a higher photoelastic coefficient than acrylic resins, cyclic olefin resins, etc., and are a material that easily develops a retardation due to stress. There was a problem that rainbow unevenness was visible when viewed with polarized sunglasses. Head-up display devices, which are beginning to be installed in automobiles in recent years, require a dust-proof cover to prevent dust and dirt from entering from the projection port for projecting an image from the device body onto a projection part such as glass. there is When a cover made of polycarbonate resin is used, if the cover itself has a high phase difference, the projected image may be distorted, so it has been necessary to reduce the phase difference.

Therefore, various methods have been studied as countermeasures against the above problem. As one of them, it has been proposed that a copolymer of bisphenol A and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene polycarbonate can provide high heat resistance (Patent Documents 1 and 2).

In addition, a film using a polycarbonate resin composed of the 9,9-bis(4-hydroxy-3-methylphenyl)fluorene is used as a retardation film and a protective film for a polarizing plate (Patent Documents 3 and 4 , 5, 6) and film formation of a polycarbonate resin composed of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene and spiroglycol having a fluorene structure by a melt film-forming method has been proposed. (Patent Document 7).

However, the above-described polycarbonate resin composed of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene and spiroglycol has a low thermal decomposition temperature, making melt film formation difficult, and decomposition occurs during film formation. There is a problem that air bubbles and gels are generated. In addition, the strength of the film was low, and there was a problem with the bending characteristics. Further, as in Patent Document 8, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and 3,9-bis(2-hydroxy -1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane has been proposed, but it is very brittle when formed into a film and difficult to use. there were.

On the other hand, transparent materials with infrared shielding properties are effective in suppressing rises in indoor temperatures and in people's sense of temperature. be. In particular, by imparting infrared ray shielding performance to the transparent resin, it is highly effective in reducing environmental load such as reducing CO ₂ emissions from the viewpoint of weight reduction and thermal management. As a method for developing infrared shielding performance, Patent Document 9 discloses a technique of adding composite tungsten oxide fine particles to a transparent resin, but there is a problem that the infrared shielding performance deteriorates over time under moist heat conditions. . Patent Document 10 discloses a technique for improving the resistance to moist heat by limiting the particle size of composite tungsten oxide fine particles, but the effect is insufficient. Further, Patent Document 11 discloses a technique for improving the thermal stability of a resin by blending a fatty acid ester, but the effect of improving the moist heat resistance of the infrared shielding performance is not recognized. Further, Patent Document 12 discloses a technique for suppressing hydrolysis of a resin by blending an epoxy resin with a transparent resin. Therefore, it is desired to improve the infrared shielding performance of the transparent resin to which the composite tungsten oxide fine particles are added and the resistance to moist heat.

So far, we have developed an optical film made of a mixture of a polycarbonate resin containing a fluorene structure with excellent heat resistance, transparency, flex resistance, and resistance to moist heat and a low three-dimensional retardation, and a bisphenol A polycarbonate containing composite tungsten oxide fine particles. has not yet been reported regarding

Japanese Patent Application Laid-Open No. 2004-331688 JP-A-8-134199 WO 2000/026705 pamphlet WO 01/009649 pamphlet Japanese Patent Application Laid-Open No. 2001-296423 Japanese Patent Application Laid-Open No. 2001-194530 WO 2008/156186 Pamphlet International Publication No. 2017/10318 Pamphlet Japanese Patent No. 5714826 JP 2017-95686 A JP 2008-156386 A Japanese Patent Publication No. 2003-531926

An object of the present invention is to provide a polycarbonate-based resin composition and an unstretched optical film containing composite tungsten oxide fine particles, which have high heat resistance, excellent transparency, flex resistance, moist heat resistance, and low three-dimensional retardation. It is in.

As a result of extensive research, the present inventors have found that a diol having a fluorene ring in its side chain, a monomer having a specific spiro ring structure, and 2,2-bis(4-hydroxyphenyl)propane are contained in a specific ratio. The inventors have found that the above object can be achieved by adding composite tungsten oxide fine particles, an epoxy resin and a fatty acid ester to a polycarbonate composition or copolymer.

That is, according to the present invention, the following configurations are provided.

1. (A) the main repeating unit is a carbonate unit (a-1) having a fluorene ring in the side chain, the following formula (a-2)

(Wherein, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, and R is a branched or linear alkyl group having 1 to 20 carbon atoms, or having a substituent represents a cycloalkyl group having 6 to 20 carbon atoms, and u represents an integer of 0 to 3.)
including a carbonate unit (a-2) represented by and a carbonate unit (a-3) derived from 2,2-bis(4-hydroxyphenyl)propane, wherein the carbonate unit (a-1) and the carbonate unit (a -2) is 50/50 to 80/20, and the molar ratio of the sum of the carbonate unit (a-1) and the carbonate unit (a-2) to the carbonate unit (a-3) is 1 (B) general formula MxWyOz (where M is H, He, an alkali metal, an alkaline earth metal, Rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn , Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and one or more selected from I element, W is tungsten, O is oxygen, 0.001 ≤ x/y ≤ 1, 2.2 ≤ z/y ≤ 3.0) Composite tungsten oxide fine particles (B component) 0.0001 to 0 .2 parts by weight, (C) epoxy resin (C component) 0.0001 to 0.1 parts by weight, and (D) release agent (D Component) A resin composition containing 0.001 to 0.5 parts by weight.

2. Component A is a copolymerized polycarbonate resin (A1 ) and a polycarbonate resin (A2) whose main repeating unit is 2,2-bis(4-hydroxyphenyl)propane, and the carbonate unit (a-1) and the carbonate unit (a- 2) is 50/50 to 80/20, and the weight ratio of the copolymerized polycarbonate resin (A1) and the polycarbonate resin (A2) is 1:99 to 70:30. 1. The resin composition according to 1 above.

3. The carbonate unit (a-1) is represented by the following formula (a-1-1)

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms, or a halogen atom, and R ₃ and R ₄ each independently represents a hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms, m and n each independently represents an integer of 0 to 4, p and q each independently represents an integer of 0 or more indicates.)
3. The resin composition according to the preceding item 1 or 2, which is a unit represented by.

4. The preceding item, wherein the carbonate unit (a-1) is a unit derived from 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene or 9,9-bis(4-hydroxy-3-methylphenyl)fluorene 4. The resin composition according to any one of 1 to 3.

5. Carbonate unit (a-2) is a unit derived from 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane 5. The resin composition according to any one of 1 to 4 above.

6. 6. The resin composition according to any one of the preceding items 1 to 5, wherein component A has a single glass transition temperature in the range of 130°C to 160°C.

7. 7. The resin composition according to any one of the preceding items 1 to 6, wherein the particle size of component B is 1 nm to 800 nm.

8. 8. The resin composition as described in any one of the preceding items 1 to 7, wherein component D is a fatty acid ester represented by the following formula (D1) or (D2).

(In the formula, R ₁ to R ₆ are independently the same or different and are alkyl groups having 10 to 32 carbon atoms.)

(In the formula, R ₁ to R ₄ are independently the same or different and are alkyl groups having 10 to 32 carbon atoms.)
9. 9. The resin composition according to any one of the preceding items 1 to 8, which contains 0.0002 to 0.8 parts by weight of (E) a heat stabilizer (component E) per 100 parts by weight of component A.

10. The E component is at least one thermal stabilizer selected from the group consisting of a phenol stabilizer (E-1 component), a sulfur stabilizer (E-2 component) and a phosphorus stabilizer (E-3 component). 9. The resin composition according to 9 above.

11. 11. The resin composition according to any one of the preceding items 1 to 10, which contains 0.1 to 2 parts by weight of (F) an ultraviolet absorber (component F) with respect to 100 parts by weight of component A.

12. The F component is at least one type of ultraviolet light selected from the group consisting of benzotriazole-based UV absorbers (F-1 component), triazine-based UV absorbers (F-2 component) and oxazine-based UV absorbers (F-3 component). 12. The resin composition as described in 11 above, which is an absorbent.

13. 13. An optical film having a thickness of 0.2 to 0.6 mm and formed from the resin composition according to any one of 1 to 12 above.

14. 14. The optical film as described in 13 above, which has an in-plane retardation Re of 20 nm or less and a retardation Re(40) measured from an oblique angle of 40 degrees of 80 nm or less.

15. 15. The optical film according to item 13 or item 14, wherein a hard coat is formed on at least one surface.

16. 16. A head-up display device using the optical film according to any one of 13 to 15 above.

An unstretched optical film formed from the resin composition of the present invention comprises a diol having a fluorene ring in its side chain, a monomer having a specific spiro ring structure, and 2,2-bis(4-hydroxyphenyl)propane at a specific ratio. By adding composite tungsten oxide fine particles, epoxy resin and fatty acid ester to the polycarbonate blend or copolymer contained in, high heat resistance, transparency, bending resistance, excellent moist heat resistance, three-dimensional retardation It is extremely useful as an optical film for liquid crystal display devices, organic EL display devices, head-up display devices, etc., and therefore has a remarkable industrial effect.

The present invention will be described in detail below.
<Polycarbonate resin blend or copolymer (A)>
The polycarbonate resin blend or copolymer of the present invention comprises, as main repeating units, a carbonate unit (a-1) having a fluorene ring in a side chain, and a carbonate having a spiro ring structure represented by the above formula (a-2). Unit (a-2) and carbonate unit (a-3) derived from 2,2-bis(4-hydroxyphenyl)propane, wherein carbonate unit (a-1) and carbonate unit (a-2) The molar ratio is 50/50 to 80/20, and the molar ratio of the sum of the carbonate unit (a-1) and the carbonate unit (a-2) to the carbonate unit (a-3) is 1:99 to 70: 30 polycarbonate resin blends or copolymers.

The molar ratio of carbonate units (a-1) and carbonate units (a-2) is 50/50 to 80/20, preferably 50/50 to 75/25. Within the above range, a polycarbonate resin blend or copolymer with excellent balance between heat resistance and retardation can be obtained.

Further, the molar ratio of the total of the carbonate units (a-1) and the carbonate units (a-2) to the carbonate units (a-3) is 1:99 to 70:30, preferably 10:90 to It is in the range of 50:50, more preferably in the range of 20:80 to 40:60. Within the above range, it is possible to obtain a polycarbonate resin blend or copolymer which is excellent in heat resistance, transparency, flex resistance, resistance to moist heat, and has a low three-dimensional retardation.

In particular, a copolymerized polycarbonate resin in which main repeating units are a carbonate unit (a-1) having a fluorene ring in a side chain and a carbonate unit (a-2) having a spiro ring structure represented by the above formula (a-2) (A1), and a polycarbonate resin (A2) whose main repeating unit is 2,2-bis(4-hydroxyphenyl)propane, wherein the carbonate unit (a-1) and the carbonate unit (a) in the polycarbonate resin (A1) -2) is 50/50 to 80/20, and the weight ratio of polycarbonate resin (A1) to polycarbonate resin (A2) is 1:99 to 70:30. be done.
<Copolymer polycarbonate resin (A1)>
In the copolymerized polycarbonate resin (A1) in the present invention, the main repeating units are a carbonate unit (a-1) having a fluorene ring in a side chain and a carbonate unit (a-2) represented by the above formula (a-2). It is a copolymerized polycarbonate resin (A1).

Here, the term “main” means that the total amount of carbonate units (a-1) and carbonate units (a-2) is 70 mol% or more, more preferably 75 mol% or more, based on all carbonate units, and further Preferably, it indicates that it is 80 mol % or more.
(Carbonate unit (a-1))
The carbonate unit (a-1) is a polycarbonate resin having a fluorene ring in its side chain.

Preferred structures of the carbonate unit (a-1) include the following (a-1-1) or (a-1-2). Then, more preferred structures include the following (a-1-1), and further preferred structures of (a-1-1) include the following (a-1-1-a) or (a-1-1- b), and particularly preferred structures include the following (a-1-1-a1) or (a-1-1-b1).

The carbonate unit (a-1-1) is represented by the following formula.

In the carbonate unit (a-1-1), R ₁ and R ₂ each independently represent a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms, or a halogen atom. Preferred hydrocarbon groups are alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 5 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, aralkyl groups having 7 to 10 carbon atoms, and 1 to 10 carbon atoms. is an alkenyl group of R ₃ and R ₄ each independently represent a hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms. The hydrocarbon group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and still more preferably an ethylene group. m and n are each independently an integer of 0 to 4, p and q are each independently an integer of 0 or more, preferably an integer of 0 to 20, more preferably an integer of 0 to 12; More preferably an integer of 0-8, particularly preferably an integer of 0-4, most preferably 0 and 1.

When p and q are 0, the carbonate unit (a-1-1) is represented by the following formula (a-1-1-a).

R ₁ and R ₂ in the above formula each independently represent a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms, or a halogen atom.

Preferred hydrocarbon groups are alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 5 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, aralkyl groups having 7 to 10 carbon atoms, and 1 to 10 carbon atoms. is an alkenyl group of R ₃ and R ₄ each independently represent a hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms. The hydrocarbon group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and still more preferably an ethylene group. m and n each independently represent an integer of 0 to 4;

Specific compounds of the unit (a-1-1-a) include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9- Bis(4-hydroxy-3-ethylphenyl)fluorene, 9,9-bis(4-hydroxy-3-n-propylphenyl)fluorene, 9,9-bis(4-hydroxy-3-isopropylphenyl)fluorene, 9 ,9-bis(4-hydroxy-3-n-butylphenyl)fluorene, 9,9-bis(4-hydroxy-3-sec-butylphenyl)fluorene, 9,9-bis(4-hydroxy-3-tert -propylphenyl)fluorene, 9,9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, and the like are preferred. . Compounds that induce these units (a-1-1-a) can be used alone or in combination of two or more.

Among them, 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are more preferable, and 9,9-bis(4-hydroxy-3-methylphenyl) A unit (a-1-1-a1) represented by the following formula derived from fluorene is particularly preferred.

Further, when p and q are integers of 1 or more, the carbonate unit (a-1-1) is represented by the following formula (a-1-1-b).

In the carbonate unit (a-1-1-b), R ₁ and R ₂ each independently represent a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms, or a halogen atom.

Preferred hydrocarbon groups are alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 5 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, aralkyl groups having 7 to 10 carbon atoms, and 1 to 10 carbon atoms. is an alkenyl group of R ₃ and R ₄ each independently represent a hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms. The hydrocarbon group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and still more preferably an ethylene group. m and n each independently represent an integer of 0 to 4;

Specific compounds of the carbonate unit (a-1-1-b) include 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(3-hydroxypropoxy)phenyl ] Fluorene, 9,9-bis[4-(4-hydroxybutoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[2 -(2-hydroxyethoxy)-5-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-ethylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy) )-3-propylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-isopropylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-n- Butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-isobutylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-(1-methylpropyl) phenyl]fluorene, 9,9-bis[4-(3-hydroxypropoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(4-hydroxybutoxy)-3-methylphenyl]fluorene, 9, 9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-2,5-dimethylphenyl]fluorene, 9,9- Bis[4-(2-hydroxyethoxy)-3,5-diethylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dipropylphenyl]fluorene, 9,9-bis [4-(2-hydroxyethoxy)-3,5-diisopropylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-di-n-butylphenyl]fluorene, 9,9 -bis[4-(2-hydroxyethoxy)-3,5-diisobutylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-bis(1-methylpropyl)phenyl]fluorene , 9,9-bis[4-(3-hydroxypropoxy)-3,5-dimethylphenyl]fluorene, 9,9-bis[4-(4-hydroxybutoxy)-3,5-dimethylphenyl]fluorene, 9 ,9-bis[4-(2-hydroxyethoxy)-3-cyclohexylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, 9,9-bis[4 -(2-hydroxyethoxy)-3,5-diphenylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-benzylphenyl]fluorene, 9,9-bis[4-(2- hydroxyethoxy)-3,5-dibenzylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-propenylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy) -3-Fluorophenyl]fluorenes and units derived from these 9,9-bis(hydroxyalkoxyphenyl)fluorenes are preferred. Units derived from 9,9-bis[hydroxypoly(alkyleneoxy)phenyl]fluorene and the like having p and q of 2 or more are more preferred.

Among these, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene and the like are particularly preferred.

In particular, the following formula (a-1-1-b1)

A preferred carbonate unit (a-1-2) is represented by the following formula.

[In the formula, R ₅ and R ₆ are each independently a direct bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, an arylene group having 4 to 10 optionally substituted carbon atoms, or a substituted an optionally substituted aralkylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms which may be substituted, an arylene group having 4 to 10 carbon atoms which may be substituted and an optionally substituted A group in which two or more groups selected from the group consisting of aralkylene groups having 6 to 10 carbon atoms are linked via an oxygen atom, an optionally substituted sulfur atom, an optionally substituted nitrogen atom or a carbonyl group. and R ₇ is a direct bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, or an optionally substituted 6 carbon atoms. 1 to 10 aralkylene groups, and R ₈ to R ₉ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted aryl group having 4 to 10 carbon atoms. group, optionally substituted acyl group having 1 to 10 carbon atoms, optionally substituted alkoxy group having 1 to 10 carbon atoms, optionally substituted aryloxy group having 1 to 10 carbon atoms, substituted an optionally substituted amino group, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. r and s each independently represent an integer of 0-4, and t represents an integer of 1-5. ]
Specific examples of compounds that induce the above general formula (a-1-2) include 9,9′-di(hydroxymethyl)-9,9′-bifluorenyl and bis(9-hydroxymethylfluoren-9-yl) methane, 1,2-bis(9-hydroxymethylfluoren-9-yl)ethane, bis[9-(3-hydroxypropyl)-fluoren-9-yl]methane, bis{9-[2-(2-hydroxy ethoxy)carbonylethyl]fluoren-9-yl}methane, 9,9-bis[(9-hydroxymethylfluoren-9-yl)-methyl]fluorene, 1,2-bis[9-(3-hydroxypropyl)- fluoren-9-yl]ethane, α,α'-bis-(9-hydroxymethylfluoren-9-yl)-1,4-xylene, 1,2-bis(9-hydroxymethylfluoren-9-yl)butane , 1-bis(9-hydroxymethylfluoren-9-yl)ethane, 1,2-bis(9-hydroxyfluoren-9-yl)ethane, bis-{[4-(2-hydroxyethoxy)phenyl]fluorene- 9-yl}ethane is preferred.
(Carbonate unit (a-2))
The carbonate unit (a-2) in the present invention is derived from a diol having a spiro ring structure, as shown in formula (a-2) above. As diol compounds having a spiro ring structure, 3,9-bis(2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, 3,9-bis(2-hydroxy-1 ,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, 3,9-bis(2-hydroxy-1,1-diethylethyl)-2,4,8,10 -tetraoxaspiro(5.5)undecane, 3,9-bis(2-hydroxy-1,1-dipropylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, etc. A cyclic diol compound can be mentioned.

Preferably, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane (a-2-1 ) is used.

(composition)
In the copolymerized polycarbonate resin (A1) in the present invention, the main repeating unit contains a carbonate unit (a-1) and a carbonate unit (a-2), and the molar ratio of (a-1) to (a-2) is 50/50 to 80/20, preferably 50/50 to 75/25. Within the above range, compatibility with the aforementioned polycarbonate resin (A2), heat resistance, transparency, flex resistance, resistance to moist heat, low retardation, etc. are well balanced.

As other carbonate units, bisphenol A, 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter Bis-C), 1,1-bis(4-hydroxyphenyl)-3,3,5 A ternary composition containing trimethylcyclohexane (hereinafter BisTMC) or the like may also be used.

If the carbonate unit (a-1) of the polycarbonate resin (A1) in the present invention is lower than the lower limit, heat resistance is poor, and if (a-1) is higher than the upper limit, the resin becomes brittle. The molar fraction can be measured and calculated by proton NMR.
(Method for producing copolymerized polycarbonate resin (A1))
The copolymerized polycarbonate resin (A1) in the present invention is produced by a reaction means known per se for producing ordinary polycarbonate resins, for example, a method of reacting a diol component with a carbonate precursor such as a diester carbonate. Next, the basic means of these manufacturing methods will be briefly described.

The transesterification reaction using a carbonic acid diester as a carbonate precursor is carried out by a method in which a predetermined proportion of the diol component and the carbonic acid diester are heated and stirred under an inert gas atmosphere to distill off the resulting alcohol or phenol. Although the reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, it is usually in the range of 120 to 300°C. The reaction is completed under reduced pressure from the initial stage while the alcohol or phenols produced are distilled off. Moreover, you may add a terminal terminator, an antioxidant, etc. as needed.

Carbonic acid diesters used in the transesterification reaction include esters such as optionally substituted aryl groups and aralkyl groups having 6 to 12 carbon atoms. Specific examples include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate and m-cresyl carbonate. Among them, diphenyl carbonate is particularly preferred. The amount of diphenyl carbonate to be used is preferably 0.97-1.10 mol, more preferably 1.00-1.06 mol, per 1 mol of the total dihydroxy compound.

In the melt polymerization method, a polymerization catalyst can be used in order to increase the polymerization rate, and examples of such polymerization catalysts include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and metal compounds.

As such compounds, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, quaternary ammonium hydroxides, etc. of alkali metals and alkaline earth metals are preferably used, and these compounds are They can be used singly or in combination.

Alkali metal compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, Sodium Stearate, Potassium Stearate, Cesium Stearate, Lithium Stearate, Sodium Borohydride, Sodium Benzoate, Potassium Benzoate, Cesium Benzoate, Lithium Benzoate, Disodium Hydrogen Phosphate, Dipotassium Hydrogen Phosphate, Phosphorus Dilithium oxyhydrogen, disodium phenylphosphate, disodium salt, dipotassium salt, dicesium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt, lithium salt of phenol and the like are exemplified.

Alkaline earth metal compounds include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, diacetic acid. Barium, barium stearate and the like are exemplified.

Examples of nitrogen-containing compounds include quaternary ammonium hydroxides having an alkyl or aryl group such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. mentioned. Also included are tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine, and imidazoles such as 2-methylimidazole, 2-phenylimidazole and benzimidazole. Bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate are also exemplified.

Examples of metal compounds include zinc aluminum compounds, germanium compounds, organic tin compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds and the like. These compounds may be used alone or in combination of two or more.

The amount of these polymerization catalysts used is preferably 1×10 ^-9 to 1×10 ^-2 equivalents, preferably 1×10 ^-8 to 1×10 -5 equivalents, more preferably 1×10 ^-5 equivalents, per 1 mol of the diol component. It is selected in the range of 10 ^-7 to 1×10 ^-3 equivalent.

Also, a catalyst deactivator can be added in the latter stage of the reaction. As the catalyst deactivator to be used, known catalyst deactivators are effectively used, and among these, ammonium salts and phosphonium salts of sulfonic acid are preferable. Further preferred are salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium dodecylbenzenesulfonate and salts of p-toluenesulfonic acid such as tetrabutylammonium p-toluenesulfonate.

Examples of sulfonic acid esters include methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, Octyl p-toluenesulfonate, phenyl p-toluenesulfonate and the like are preferably used. Among them, dodecylbenzenesulfonic acid tetrabutylphosphonium salt is most preferably used.

When at least one polymerization catalyst selected from alkali metal compounds and/or alkaline earth metal compounds is used, the amount of these catalyst deactivators used is preferably per mol of the metal element contained in the catalyst. It can be used in a proportion of 0.5 to 50 mol, more preferably in a proportion of 0.5 to 10 mol, still more preferably in a proportion of 0.8 to 5 mol.
<Polycarbonate resin (A2)>
The polycarbonate resin (A2) in the present invention is a polycarbonate whose main repeating unit is 2,2-bis(4-hydroxyphenyl)propane (bisphenol A).

Here, "mainly" means that the carbonate containing bisphenol A accounts for 70 mol% or more, more preferably 75 mol% or more, and still more preferably 80 mol% or more, based on all carbonate units.
(Specific viscosity: η _SP )
The specific viscosity (η _SP ) of the copolymerized polycarbonate resin (A1) and polycarbonate resin (A2) is preferably in the range of 0.2 to 1.5. When the specific viscosity is in the range of 0.2 to 1.5, the strength and moldability of molded articles such as films are improved. It is more preferably 0.20 to 1.2, still more preferably 0.20 to 1.0, and particularly preferably 0.20 to 0.5.

The specific viscosity referred to in the present invention is obtained from a solution of 0.7 g of a polycarbonate resin dissolved in 100 ml of methylene chloride at 20° C. using an Ostwald viscometer.
Specific viscosity (η _SP ) = (tt ₀ )/t ₀
[t ₀ is the number of seconds the methylene chloride falls, t is the number of seconds the sample solution falls]
In addition, as a specific measurement of specific viscosity, for example, it can be performed in the following manner. First, the polycarbonate resin is dissolved in 20 to 30 times its weight of methylene chloride, and the soluble matter is collected by celite filtration, then the solution is removed and sufficiently dried to obtain a methylene chloride soluble solid matter. The specific viscosity at 20° C. of a solution obtained by dissolving 0.7 g of this solid in 100 ml of methylene chloride is determined using an Ostwald viscometer.
(Method for Producing Polycarbonate Resin Blend Containing Copolycarbonate Resin (A1) and Polycarbonate Resin (A2))
The resin composition of the present invention is preferably obtained by blending the copolymerized polycarbonate resin (A) and the polycarbonate resin (B) in a molten state. As a method for blending in a molten state, an extruder is generally used, and kneading and pelletizing are carried out at a molten resin temperature of 200 to 320°C, preferably 220 to 300°C, more preferably 230 to 290°C. As a result, resin blend pellets in which both resins are uniformly blended are obtained. The structure of the extruder, the structure of the screw, etc. are not particularly limited. If the molten resin temperature in the extruder exceeds 320°C, the resin may be colored or thermally decomposed. On the other hand, if the resin temperature is lower than the lower limit, the resin viscosity is too high and the extruder may be overloaded.
(Composition ratio of copolymerized polycarbonate resin (A1) and polycarbonate resin (A2))
The weight ratio of the copolymerized polycarbonate resin (A1) to the PC-A resin (A2) is preferably in the range of 1:99 to 70:30. It is more preferably in the range of 10:90 to 50:50 (weight ratio), still more preferably in the range of 20:80 to 40:60 (weight ratio). Within the above range, it is possible to obtain a polycarbonate resin blend having high heat resistance, excellent transparency, flex resistance and moist heat resistance, and low three-dimensional retardation. If the content of the copolymerized polycarbonate resin component is more than the upper limit, cracking becomes a problem.
(Glass transition temperature: Tg)
The polycarbonate resin blend of the present invention preferably has a single glass transition temperature (Tg), preferably 130-160°C, more preferably 135-150°C. When the Tg is within the above range, the heat resistance and moldability are good, which is preferable.

The glass transition temperature (Tg) is measured using a Model 2910 DSC manufactured by TA Instruments Japan Co., Ltd. at a heating rate of 20°C/min. In the present invention, a single glass transition temperature (Tg) means that the glass transition temperature is measured using a differential scanning calorimeter (DSC) at a heating rate of 20° C./min according to JIS K7121. Only one inflection point indicating the glass transition temperature appears.

In general, the fact that the polymer blend has a single glass transition temperature means that the resins to be mixed are in a compatible state at the nanometer order (molecular level), and it is recognized as a compatible system. be able to.
(Component B: Composite Tungsten Oxide Fine Particles)
Composite tungsten oxide fine particles (component B) are represented by the general formula MxWyOz. In the formula, M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Represents one or more elements selected from Hf, Os, Bi and I, and one or more elements selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba and more preferably K, Rb, or Cs. Further, W represents tungsten and O represents oxygen.

x, y, and z are numbers satisfying the expressions of 0.001≦x/y≦1 and 2.2≦z/y≦3.0. Furthermore, the ranges of x/y and z/y are preferably 0.01 ≤ x/y ≤ 0.5, 2.7 ≤ z/y ≤ 3.0, and 0.2 ≤ x/y ≤ 0.4. , 2.8≦z/y≦3.0.

The particle size of the composite tungsten oxide fine particles (component B) is preferably 1 nm to 800 nm, more preferably 1 nm to 600 nm, and even more preferably 1 nm to 300 nm. If the particle size is smaller than 1 nm, the aggregation effect increases, and thus poor dispersibility tends to occur.

The composite tungsten oxide fine particles (component B) can be obtained by heat-treating a tungsten compound as a starting material in an inert gas atmosphere or a reducing gas atmosphere. The composite tungsten oxide fine particles obtained through the heat treatment have sufficient near-infrared shielding power, and have desirable properties as infrared shielding fine particles.

The starting material for the composite tungsten oxide fine particles (component B) is a tungsten compound containing the element M in the form of a single element or a compound. Specifically, tungsten trioxide powder, tungsten dioxide powder, tungsten oxide hydrate, tungsten hexachloride powder, ammonium tungstate powder, and tungsten hexachloride containing the element M in the form of a single element or a compound. Tungsten oxide hydrate powder obtained by dissolving in alcohol and then drying; It is preferably one or more selected from the group consisting of hydrate powder, tungsten compound powder obtained by drying an ammonium tungstate aqueous solution, and metallic tungsten powder. If the starting material is a solution, it is more preferable to use an ammonium tungstate aqueous solution or a tungsten hexachloride solution from the viewpoint that each element can be uniformly mixed easily. By using these raw materials and heat-treating them in an inert gas atmosphere or a reducing gas atmosphere, the composite tungsten oxide fine particles described above can be obtained.

Here, in order to produce a tungsten compound, which is a starting material in which each component is uniformly mixed at the molecular level, it is preferable to mix each raw material in a solution, and the tungsten compound containing the element M is dissolved in water, an organic solvent, or the like. It is preferably soluble in a solvent. Examples include, but are not limited to, tungstates, chloride salts, nitrates, sulfates, oxalates, oxides, carbonates, and hydroxides containing the element M, and those that form a solution. It is preferable if

The raw material for producing the composite tungsten oxide fine particles (component B) will be described in detail again below.

As a starting material for obtaining the composite tungsten oxide fine particles (component B) represented by the general formula MxWyOz, a powder obtained by mixing the tungsten oxide powder and the M element powder can be used. As the tungsten oxide powder, tungsten trioxide powder, tungsten dioxide powder, tungsten oxide hydrate, tungsten hexachloride powder, ammonium tungstate powder, and tungsten hexachloride are dissolved in alcohol and then dried. Tungsten oxide hydrate powder obtained by dissolving tungsten hexachloride in alcohol and then adding water to precipitate and drying the precipitate. and tungsten compound powders and metal tungsten powders obtained by Further, as the M element-based powder, a single substance or compound powder containing the M element can be used. Furthermore, when the tungsten compound, which is the starting material for obtaining composite tungsten oxide fine particles (component B), is a solution or a dispersion liquid, each element can be easily and uniformly mixed. From this point of view, the starting material of the composite tungsten oxide fine particles (component B) is a powder obtained by mixing an alcohol solution of tungsten hexachloride or an aqueous solution of ammonium tungstate with a solution of a compound containing the element M, and then drying. It is even more preferable to have Similarly, the starting materials for the fine particles of composite tungsten oxide (component B) are a dispersion obtained by dissolving tungsten hexachloride in alcohol and then adding water to form a precipitate, and a single substance containing the M element. Alternatively, a powder obtained by mixing a powder of the compound or a solution of the compound containing the element M and then drying is also preferable.

Examples of the compound containing the M element include, but are not limited to, tungstates, chloride salts, nitrates, sulfates, oxalates, oxides, carbonates, and hydroxides of the M element. , so long as it becomes a solution. Furthermore, in the case of industrially producing composite tungsten oxide fine particles (component B), if a tungsten oxide hydrate powder or tungsten trioxide and an element M carbonate or hydroxide are used, heat treatment or the like is required. This is a preferred production method because no harmful gas is generated at the stage of .

Here, 650° C. or higher is preferable as the heat treatment condition for the composite tungsten oxide fine particles (component B) in an inert atmosphere. A starting material heat-treated at 650° C. or higher has a sufficient near-infrared shielding power and is efficient as an infrared shielding fine particle. Inert gases such as Ar and N ₂ are preferably used as the inert gas.

In addition, as the heat treatment conditions in a reducing atmosphere, the starting material is first heat treated at 100 ° C. or higher and 850 ° C. or lower in a reducing gas atmosphere, and then in an inert gas atmosphere at a temperature of 650 ° C. or higher and 1,200 ° C. or lower. It is preferable to heat-treat at Although the reducing gas at this time is not particularly limited, H ₂ is preferable. When H ₂ is used as the reducing gas, the composition of the reducing atmosphere is preferably 0.1% or more by volume, _more preferably 2% or more. If the H ₂ content is 0.1% or more by volume, the reduction can proceed efficiently.

From the viewpoint of improving weather resistance, the surfaces of the composite tungsten oxide fine particles (component B) are preferably coated with an oxide containing one or more metals selected from Si, Ti, Zr, and Al. The coating method is not particularly limited, but the surface of the composite tungsten oxide fine particles (component B) is coated by adding the alkoxide of the above metal to the solution in which the composite tungsten oxide fine particles (component B) are dispersed. Is possible.

Also, the composite tungsten oxide fine particles (component B) are preferably coated with a dispersant. Dispersants include polycarbonate, polysulfone, polyacrylonitrile, polyarylate, polyethylene, polyvinyl chloride, polyvinylidene chloride, fluororesin, polyvinyl butyral, polyvinyl alcohol, polystyrene, silicone resins and derivatives thereof. Coating with these improves the dispersibility when added to the resin, and has the effect of preventing deterioration of mechanical properties. As a method of coating with a dispersant, composite tungsten oxide fine particles (component B) and a dispersant are dissolved in a solvent such as toluene and stirred to prepare a dispersion, and then the solvent is removed by a treatment such as vacuum drying to form a composite. A method of coating tungsten oxide microparticles (component B) can be used.

Further, as a method of adding the B component to the polycarbonate blend or copolymer (A component), a method of directly adding composite tungsten oxide fine particles (B component) or coated composite tungsten oxide fine particles (B component). Alternatively, a method of adding after diluting with a polycarbonate blend or copolymer (component A) of 1 to 100 times.

The content of component B is 0.0001 to 0.2 parts by weight, preferably 0.001 to 0.1 parts by weight, more preferably 0.002 to 0.05 parts by weight, relative to 100 parts by weight of component A. preferable. If the content of the B component is less than 0.0001 parts by weight, the infrared shielding ability cannot be sufficiently exhibited, and if it is more than 0.2 parts by weight, the moist heat resistance is deteriorated and the total light transmittance is very small. put away.
(C component: epoxy resin)
The resin composition of the present invention contains an epoxy resin as a C component for the purpose of maintaining high transparency and having good moist heat resistance and infrared shielding performance. The epoxy resin used is preferably an epoxy polymer containing a glycidyl group, more preferably an epoxy polymer containing glycidyl methacrylate in the copolymer, and polystyrene is suitable for the other component of the copolymer. used for Among them, polyglycidyl methacrylate-polystyrene copolymer is preferably used. When an epoxy polymer containing no glycidyl group is used, compatibility with component A may be poor and transparency may be poor. Monomer components of polymers containing glycidyl groups include allyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, Examples include epoxy succinic acid and the like, and examples of the polymer include terminal epoxy-modified polydimethylsiloxane and side-chain epoxy-modified polydimethylsiloxane.

The content of component C is 0.0001 to 0.1 parts by weight, preferably 0.001 to 0.05 parts by weight, more preferably 0.001 to 0.05 parts by weight, per 100 parts by weight of component A. 03 parts by weight. If the content is less than 0.0001 parts by weight, sufficient moist heat resistance is not exhibited, and if it exceeds 0.1 parts by weight, the hue deteriorates and the transparency is impaired.
(Component D: release agent)
The resin composition of the present invention is intended to have infrared shielding performance with good moisture and heat resistance while maintaining high transparency. Contains a templating agent.

Such fatty acids preferably have 3 to 32 carbon atoms, and particularly preferably fatty acids having 10 to 32 carbon atoms. Examples of the fatty acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanic acid, behenic acid, icosanoic acid, and saturated aliphatic carboxylic acids such as docosanoic acid, and unsaturated fatty acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetoleic acid. Among the above fatty acids, those having 14 to 20 carbon atoms are preferred. Among them, saturated fatty acids are preferred. Stearic acid and palmitic acid are particularly preferred.

The above fatty acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal oils and fats such as beef tallow and lard and vegetable oils and fats such as palm oil and sunflower oil. The fatty acids of are usually mixtures containing other carboxylic acid components with different numbers of carbon atoms. Therefore, in the production of the fatty acid ester of the present invention, fatty acids, particularly stearic acid and palmitic acid, which are produced from such natural fats and oils and which are in the form of mixtures containing other carboxylic acid components, are preferably used.

Such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol-hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Pentaerythritol and dipentaerythritol are preferred in the fatty acid ester of the present invention.

The fatty acid esters of the present invention are full esters. When a partial ester is used, sufficient moist heat resistance is not exhibited. The acid value of the fatty acid ester of the present invention is preferably 20 or less, more preferably in the range of 4-20, still more preferably in the range of 4-12, from the viewpoint of thermal stability. Incidentally, the acid value can be substantially zero. Further, the hydroxyl value of the fatty acid ester is preferably in the range of 0.1-30. Furthermore, the iodine value is preferably 10 or less. Incidentally, the iodine value can be substantially zero. These properties can be obtained by the method specified in JIS K 0070.

In view of the above, component D is preferably a fatty acid ester represented by formula (D1) or formula (D2) below.

(In the formula, R ₁ to R ₆ are independently the same or different and are alkyl groups having 10 to 32 carbon atoms.)

(In the formula, R ₁ to R ₄ are independently the same or different and are alkyl groups having 10 to 32 carbon atoms.)
The content of component D is 0.001 to 0.5 parts by weight, preferably 0.01 to 0.4 parts by weight, more preferably 0.05 to 0.5 parts by weight per 100 parts by weight of component A. 3 parts by weight. If the content is less than 0.001 parts by weight, sufficient moist heat resistance is not exhibited, and if it exceeds 0.5 parts by weight, the molecular weight of the polycarbonate resin composition decreases during molding.
(E component: heat stabilizer)
The resin composition of the present invention preferably contains a heat stabilizer as the E component. As the heat stabilizer, at least one heat stabilizer selected from the group consisting of a phenol stabilizer (component E-1), a sulfur stabilizer (component E-2) and a phosphorus stabilizer (component E-3). is preferred. The content of component E is preferably 0.0002 to 0.8 parts by weight, more preferably 0.001 to 0.7 parts by weight, and 0.01 to 0.0 parts by weight with respect to 100 parts by weight of component A. .1 part by weight is more preferred. If the content is less than 0.0002 parts by weight, the effect of thermal stability may not be exhibited. may not be possible.
(E-1 component: phenolic stabilizer)
Phenolic stabilizers include, for example, α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β-(4′-hydroxy-3′,5′-di-tert-butylfer) propionate, 2-tert-butyl-6-(3′-tert-butyl-5′-methyl-2′-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N -dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis( 4-ethyl-6-tert-butylphenol), 4,4′-methylenebis(2,6-di-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-cyclohexylphenol), 2,2′ -dimethylene-bis(6-α-methyl-benzyl-p-cresol) 2,2′-ethylidene-bis(4,6-di-tert-butylphenol), 2,2′-butylidene-bis(4-methyl- 6-tert-butylphenol), 4,4′-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl ) propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl 6-(3-tert -butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1 ,-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4′-thiobis(6-tert-butyl-m-cresol), 4,4′-thiobis(3 -methyl-6-tert-butylphenol), 2,2′-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, 4,4 '-di-thiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylenebis-[3-(3 ,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3′,5′-di-tert-butylanilino)-1, 3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di- tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4, 6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert -butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris-2[3( 3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate and tetrakis[methylene-3-(3′,5′-di-tert-butyl-4-hydroxyphenyl)propionate]methane etc. are exemplified. All of these are readily available. The above phenolic stabilizers may be used alone or in combination of two or more.
(E-2 component: sulfur stabilizer)
Sulfur compounds include dilauryl thiodipropionate, ditridecylthiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), pentaerythritol tetrakis ( 3-dodecylthiopropionate), pentaerythritol tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol tetrakis (3-stearylthiopropionate), etc. be done. These may be used alone or in combination of two or more.
(E-3 component: phosphorus stabilizer)
Phosphorus-based stabilizers are already widely known as heat stabilizers for aromatic polycarbonates. In the present invention, the phosphorus-based stabilizer enhances the thermal stability of the resin composition to the extent that it can withstand extremely severe thermal loads. Phosphite compounds and phosphonites are mainly used as phosphorus-based stabilizers.

Examples of phosphite compounds include triphenylphosphite, tris(nonylphenyl)phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, and dioctylmonophenylphosphite. , diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, tris(diethylphenyl ) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6- Di-tert-butylphenyl)phosphite, distearylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4 -methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite Examples include phosphite, dicyclohexylpentaerythritol diphosphite, and the like.

Furthermore, as other phosphite compounds, those having a cyclic structure which react with dihydric phenols can also be used. For example, 2,2′-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2′-methylenebis(4,6-di-tert- butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2′-methylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite , 2,2′-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite and the like.

Phosphonite compounds include, for example, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenyl diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite night, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6- Di-n-butylphenyl)-3-phenyl-phenylphosphonite, Bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, Bis(2,6-di-tert-butylphenyl) )-3-phenyl-phenylphosphonite and the like, preferably tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite, bis(di-tert-butylphenyl)-phenyl-phenylphosphonite, tetrakis(2 ,4-di-tert-butylphenyl)-biphenylenediphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite are more preferred. Such a phosphonite compound can preferably be used in combination with a phosphite compound having an aryl group substituted with two or more alkyl groups.
(F component: UV absorber)
The resin composition of the present invention may be used without coating or the like. In such a case, it is preferable to blend an ultraviolet absorber because good light resistance may be required.

As the ultraviolet absorber, at least one selected from the group consisting of benzotriazole-based ultraviolet absorbers (component F-1), triazine-based ultraviolet absorbers (component F-2), and oxazine-based ultraviolet absorbers (component F-3). is preferred. The content of component F is preferably 0.1 to 2 parts by weight, more preferably 0.12 to 1.5 parts by weight, and still more preferably 0.15 to 1 part by weight with respect to 100 parts by weight of component A. be. When the content of the F component is less than 0.1 parts by weight, sufficient light resistance may not be exhibited, and when it is more than 2 parts by weight, appearance defects and deterioration of physical properties may occur due to gas generation.
(F-1 component: benzotriazole-based UV absorber)
Benzotriazole-based UV absorbers include, for example, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2- hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2′-methylenebis[4-(1 , 1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2 -(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2 -hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2 , 2′-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis(1,3-benzoxazin-4-one), and 2-[2-hydroxy-3-( 3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole and 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole can be copolymerized with said monomers 2- Polymers having a hydroxyphenyl-2H-benzotriazole skeleton are exemplified.
(F-2 component: triazine-based UV absorber)
Examples of triazine-based UV absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3 ,5-triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol, 2-(4,6 -diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-butyloxyphenol etc. are exemplified. Furthermore, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol, etc., in which the phenyl group of the above-exemplified compounds is 2,4-dimethylphenyl A compound having a phenyl group is exemplified.
(F-3 component: oxazine-based ultraviolet absorber)
Examples of oxazine-based ultraviolet absorbers include 2,2′-p-phenylenebis(3,1-benzoxazin-4-one), 2,2′-m-phenylenebis(3,1-benzoxazin-4 -one), 2,2′-p,p′-diphenylenebis(3,1-benzoxazin-4-one) and the like.
(other additives)
In addition, the polycarbonate resin blend or copolymer of the present invention may contain a plasticizer, a light stabilizer, a polymerized metal deactivator, a flame retardant, a lubricant, an antistatic agent, a surfactant, an antibacterial Additives known per se, such as agents, colorants, impact modifiers, etc., can be included.
(Method for producing optical film)
Examples of the method for producing the optical film include known methods such as a solution casting method, a melt extrusion method, a hot press method, and a calendering method. As the method for producing the film of the present invention, a melt extrusion method is preferable from the viewpoint of productivity.

In the melt extrusion method, a method of extruding the resin using a T-die and feeding it to cooling rolls is preferably used. At this time, by compressing the molten resin before it cools and solidifies with a roll or belt, it is possible to improve the surface appearance of the film, or reduce the phase difference by relieving the orientation and stress strain of the polymer. For example, the elastic metal roll includes a shaft roll and a cylindrical metal thin film arranged to cover the outer peripheral surface of the shaft roll and in contact with the molten resin. Examples include those in which a temperature-controlled fluid such as water or oil is sealed between them, and those in which a metal belt is wound on the surface of a rubber roll. The melt extrusion temperature is determined by the molecular weight, Tg, melt flow characteristics, etc. of the resin composition, and is preferably in the range of 180 to 350°C, more preferably in the range of 200 to 320°C. If it is lower than the lower limit, the viscosity becomes high, and polymer orientation and stress strain tend to remain. On the other hand, when the thickness is higher than the upper limit, problems such as thermal deterioration, coloring, and die lines (streaks) from the T-die tend to occur. In particular, a polycarbonate resin blend or copolymer is melt-extruded into a film from a T-die of an extruder, the film-like material is sandwiched and held under pressure by metal elastic rolls, cooled by a plurality of cooling rolls, and then a plurality of A production method in which an optical film is obtained by transferring the optical film by transfer rolls is preferably adopted.
(Phase difference)
The in-plane retardation Re of the optical film using the polycarbonate resin composition used in the present invention at a wavelength of 589 nm is preferably Re≦50 nm, more preferably Re≦20 nm. The front retardation Re is defined by the following formula, and is the difference between the vibration of the light transmitted from the direction perpendicular to the film surface, that is, the incident angle being 0 degrees, and the vibration of the light passing through the film surface in the X direction and the Y direction. This is a characteristic that expresses a phase delay.

Re=(nx−ny)×d×10 ³
However, nx is the refractive index in the slow axis direction in the film plane, ny is the refractive index in the film plane in the direction perpendicular to the slow axis direction, and d is the film thickness (unit: μm).

The oblique retardation Re(40) indicates the retardation when the incident angle is 40 degrees with respect to the film plane. By measuring the oblique retardation Re(40), the refractive index nz in the thickness direction of the film can be measured, which is used when calculating the so-called three-dimensional refractive indices nx, ny, and nz. The oblique retardation Re(40) is preferably Re(40)≦80 nm, more preferably Re(40)≦50 nm.

The retardation of the optical film is measured using KOBRA-WFD manufactured by Oji Scientific Instruments Co., Ltd.

The optical film having retardation is preferably an unstretched optical film.
(thickness)
The thickness of the optical film of the invention is preferably 0.2 to 0.6 mm, more preferably 0.25 to 0.5 mm. If the thickness exceeds the upper limit, there is a problem that the thickness of the polarizing plate, for which there is a strong demand for a thinner film in display applications, becomes thicker. becomes more likely to occur. If the thickness is less than the lower limit, the film loses its rigidity, which tends to cause problems in the film processing process and in actual use.
(Haze)
The haze value of the optical film in the invention is preferably 5% or less, more preferably 3% or less, even more preferably 2% or less, and particularly preferably 1% or less. Visibility is excellent and it is preferable that haze is in the said range.
(surface treatment)
Various surface treatments can be applied to the optical film of the present invention. Surface treatment here refers to deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. It is to be formed, and a commonly used method can be applied. Specific examples of the surface treatment include hard coating, water-repellent/oil-repellent coating, ultraviolet-absorbing coating, infrared-absorbing coating, and various surface treatments such as metallizing (vapor deposition, etc.). The hard coat is a surface treatment that is particularly preferred and required, such as acrylic or silicone.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto. In addition, "parts" in the examples means "parts by weight". The resins used in the examples and the evaluation methods are as follows.
1. Composition ratio (NMR) of copolymerized polycarbonate resin (A1)
Each repeating unit was measured by proton NMR of JNM-ECZ400S/L1 manufactured by JEOL Ltd., and the composition ratio (molar ratio) of the copolymerized polycarbonate resin was calculated.
2. Glass transition temperature (Tg) of blend of copolymerized polycarbonate resin (A1) and polycarbonate resin (A2)
Using a thermal analysis system DSC-2910 manufactured by TA Instruments Co., Ltd. using 8 mg of a blend resin of a copolymer polycarbonate resin (A1) and a polycarbonate resin (A2), JIS K7121 compliant The temperature was measured under the conditions of a nitrogen atmosphere (nitrogen flow rate: 40 ml/min) and a temperature increase rate of 20°C/min.
3. Specific viscosity (η _SP ) of copolymerized polycarbonate resin (A1) and polycarbonate resin (A2)
The specific viscosity (η _SP ) of the copolymerized polycarbonate resin (A1) and polycarbonate resin (A2) was determined from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20° C. using an Ostwald viscometer.

Specific viscosity (η _SP ) = (tt ₀ )/t ₀
[t ₀ is the number of seconds the methylene chloride falls, t is the number of seconds the sample solution falls]
4. Unstretched film thickness (d)
The thickness (d) (unit: mm) of the central portion of the unstretched film obtained in the example was measured with an electronic micro film thickness gauge manufactured by Anritsu Corporation.
5. Front phase difference (Re)/Oblique phase difference Re (40)
A test piece having a length of 50 mm and a width of 40 mm was cut out from the unstretched film obtained in the example, and measured using KOBRA-WFD manufactured by Oji Keisoku Co., Ltd.
6. Total light transmittance, haze Using a spectroscopic haze meter SH-7000 manufactured by Nippon Denshoku Industries Co., Ltd., the total light transmittance of a blend of a copolymerized polycarbonate resin (A1) and a polycarbonate resin (A2) conforming to JIS K7136 and haze were measured.
7. Flexibility When the unstretched film obtained in the example was bent once by hand, the film that did not break was rated as "○", and the film that was broken was rated as "x".
8. Humidity and heat resistance test Humidity and heat resistance was evaluated by the film hue Δb ^* value before and after the film was treated for 500 hours with a humidity and heat tester at 85°C and 85% RH. A Δb ^* value <0.5 was indicated as “◯”, and a Δb ^* value≧0.5 was indicated as “×”.
[Copolymerized Polycarbonate Resin (A1)]
Copolymer PC1: Structural unit derived from 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (hereinafter abbreviated as BPEF)/3,9-bis(2-hydroxy-1,1-dimethylethyl) Structural unit derived from -2,4,8,10-tetraoxaspiro(5,5)undecane (hereinafter abbreviated as SPG) = 60/40 (mol%), specific viscosity (η _SP ) 0.23
Copolymer PC2: structural unit derived from BPEF/structural unit derived from SPG/structural unit derived from 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter abbreviated as BisTMC) = 52/24/24 (mol%), specific viscosity (η _SP ) 0.23
Copolymerized PC3: structural unit derived from 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter abbreviated as BCF)/structural unit derived from SPG = 35/65 (mol%), specific viscosity ( η _SP ) 0.31
[Polycarbonate resin (A2)]
PC-A resin: bisphenol A polycarbonate resin, specific viscosity (η _SP ) 0.34
[Composite Tungsten Oxide Fine Particles (B)]
Heat absorbing agent (YMDS-874R manufactured by Sumitomo Metal Mining Co., Ltd.) consisting of about 23% by weight of Cs _0.33 WO ₃ and an organic dispersion resin
[Component C]
Epoxy resin (manufactured by NOF Corporation: G-0250SP)
[Component D]
D1: Fatty acid full ester (having a structure represented by the above formula (D1) (R ₁ to R ₆ are alkyl groups with 17 carbon atoms)) (Riken Vitamin Co., Ltd.: L-8483)
D2: Fatty acid full ester (having a structure represented by the above formula (D2) (R ₁ to R ₄ are alkyl groups having 17 carbon atoms)) (manufactured by NOF Corporation: H-476S)
[Example 1]
<Production of copolymer PC1>
105.24 parts of BPEF, 48.7 parts of SPG, 89.11 parts of diphenyl carbonate (hereinafter abbreviated as DPC), and 1.68×10 ⁻⁴ parts of sodium hydrogen carbonate as a catalyst were heated to 180° C. in a nitrogen atmosphere and melted. Thereafter, the pressure was reduced to 20 kPa over 20 minutes, and the temperature of the jacket was increased to 260° C. at a rate of 60° C./hr to carry out the transesterification reaction. While maintaining the jacket at 260° C., the pressure was reduced to 0.13 kPa over 80 minutes, and the polymerization reaction was carried out for 30 minutes under conditions of 260° C. and 0.13 kPa or less. After completion of the reaction, the produced polycarbonate resin was extracted while being pelletized to obtain polycarbonate resin pellets. The composition ratio was measured by specific viscosity NMR. (Copolymerization PC1)
<Production of resin composition>
Copolymerized PC1 and PC-A resins were used, and each resin was dried at 80° C. for 12 hours or more, mixed in a weight ratio of 10:90, and then added to 100 parts by weight of component A, After blending to 0.14 parts by weight of B component, 0.02 parts by weight of C component, and 0.1 parts by weight of D1 component, a vented twin-screw extruder [KZW15-25MG manufactured by Technobell Co., Ltd.] was used to produce a cylinder. and a die to melt-knead at 260° C. to obtain pellets of a blend of copolymer PC1 and PC-A resin. The Tg of the obtained pellets was measured by DSC.
<Manufacture of optical film>
Next, the obtained pellets were dried at 90° C. for 12 hours with a hot air circulation dryer. A T-die having a width of 150 mm and a lip width of 500 μm and a film take-up device were attached to a 15 mmφ twin-screw extruder manufactured by Technobell Co., Ltd. The obtained pellets were formed into a film at 260° C. to obtain a transparent unstretched film. The thickness, retardation, total light transmittance, haze, moist heat resistance test, and flexibility of this unstretched film were measured. The results are shown in Table 1.
[Example 2]
Except for changing the blend weight ratio to copolymerized PC1/PC-A resin=20/80, the same operation as in Example 1 was performed and the same evaluation was performed. The results are shown in Table 1.
[Example 3]
Except for changing the blend weight ratio to copolymerized PC1/PC-A resin=30/70, the same operation as in Example 1 was performed and the same evaluation was performed. The results are shown in Table 1.
[Example 4]
<Production of copolymer PC2>
91.21 parts of BPEF, 29.22 parts of SPG, 29.80 parts of BisTMC, 89.11 parts of DPC, and 1.68×10 ⁻⁴ parts of sodium hydrogen carbonate as a catalyst were heated to 180° C. in a nitrogen atmosphere and melted. Thereafter, the pressure was reduced to 20 kPa over 20 minutes, and the temperature of the jacket was increased to 260° C. at a rate of 60° C./hr to carry out the transesterification reaction. While maintaining the jacket at 260° C., the pressure was reduced to 0.13 kPa over 80 minutes, and the polymerization reaction was carried out for 30 minutes under conditions of 260° C. and 0.13 kPa or less. After completion of the reaction, the produced polycarbonate resin was extracted while being pelletized to obtain polycarbonate resin pellets. The composition ratio was measured by NMR. (Copolymerization PC2)
Except for changing the blend weight ratio to copolymerized PC2/PC-A resin=30/70, the same operation as in Example 1 was performed, and the same evaluation was performed. The results are shown in Table 1.
[Example 5]
Except for changing the blend weight ratio to copolymerized PC2/PC-A resin=50/50, the same operation as in Example 4 was performed and the same evaluation was performed. The results are shown in Table 1.
[Example 6]
Except for changing the blend weight ratio to copolymerized PC2/PC-A resin=70/30, the same operation as in Example 4 was performed and the same evaluation was performed. The results are shown in Table 1.
[Example 7]
Exactly the same operation as in Example 6 was performed except that the B component was changed to 0.04 parts by weight, the C component was changed to 0.08 parts by weight, and the D component was changed to 0.3 parts by weight, and the same evaluation was performed. The results are shown in Table 1.
[Example 8]
Exactly the same operation as in Example 5 was performed, except that D1 component was changed to D2 component, and the same evaluation was performed. The results are shown in Table 1.
[Comparative Example 1]
51.41 parts of BCF, 80.26 parts of SPG, 89.29 parts of DPC, and 1.8×10 ⁻² parts of tetramethylammonium hydroxide and 1.6×10 ⁻⁴ parts of sodium hydroxide as catalysts were heated to 180° C. under a nitrogen atmosphere. It was heated and melted. After that, the degree of pressure reduction was adjusted to 13.4 kPa over 30 minutes. After that, the temperature was raised to 260° C. at a rate of 20° C./hr, the temperature was maintained for 10 minutes, and the degree of pressure reduction was reduced to 133 Pa or less over 1 hour. The reaction was carried out under stirring for a total of 6 hours.

After completion of the reaction, the nitrogen was discharged from the bottom of the reactor under pressure, and while cooling in a water tank, pellets were obtained by cutting with a pelletizer. The composition ratio was measured by NMR. (Copolymerized PC3)
An unstretched film was obtained by carrying out exactly the same operation as in Example 1 except that the blend weight ratio was extruded at a copolymerized PC3/PC-A resin = 30/70 to obtain blend pellets, but it lacked transparency. It was cloudy and incompatible. The results are listed in Table 2.
[Comparative Example 2]
Exactly the same operation as in Example 1 was performed except that the composition was changed to copolymer PC1 alone without blending, and the C component and D component were not added, and the same evaluation was performed. The results are shown in Table 2. Although the retardation was low, it was very brittle and easily broken when bent by hand, and the wet heat resistance test was also unsatisfactory.
[Comparative Example 3]
Exactly the same operation as in Example 4 was performed except that only the copolymer PC2 was used without blending, and the same evaluation was performed. The results are shown in Table 2. Although the retardation was low, it was very brittle and easily broken when bent by hand.
[Comparative Example 4]
Exactly the same operation as in Example 1 was performed except for changing to a composition in which only the PC-A resin was used without blending, and the B component, C component, and D component were not added, and the same evaluation was performed. The results are shown in Table 2. The retardation Re(40) was higher than that of Examples, and the wet heat resistance test was also poor.
[Comparative Example 5]
Exactly the same operation as in Example 4 was performed except that the composition was changed to one in which the C component and the D component were not added, and the same evaluation was performed. The results are shown in Table 2. The wet heat resistance test was also poorer than that of the examples.

The optical film of the present invention is excellent in heat resistance, transparency, flex resistance, and resistance to moist heat, and has a low phase difference, so it is extremely useful as an optical film for liquid crystal display devices, organic EL display devices, head-up display devices, and the like. be.

Claims (14)

(A) the main repeating unit is the following formula (a-1-1)
(wherein R ₁ and R ₂ each independently represent a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms, or a halogen atom, and R ₃ and R ₄ each independently represents a hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms, m and n each independently represent an integer of 0 to 4, and p and q each independently represent an integer of 0 to 4. indicates an integer.)
A carbonate unit (a-1-1) having a fluorene ring in the side chain represented by the following formula (a-2)
(Wherein, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, and R is a branched or linear alkyl group having 1 to 20 carbon atoms, or having a substituent represents a cycloalkyl group having 6 to 20 carbon atoms, and u represents an integer of 0 to 3.)
including a carbonate unit (a-2) represented by and a carbonate unit (a-3) derived from 2,2-bis(4-hydroxyphenyl)propane, a carbonate unit ( a-1-1 ) and a carbonate unit (a-2) is a molar ratio of 50/50 to 80/20, and the total of the carbonate unit ( a-1-1 ) and the carbonate unit (a-2) and the carbonate unit (a-3) Per 100 parts by weight of a polycarbonate resin blend or copolymer (component A) having a molar ratio of 1:99 to 70:30, (B) general formula MxWyOz (where M is H, He, alkali metal, alkali Earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si , Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I One or more elements, W for tungsten, O for oxygen, 0.001 ≤ x/y ≤ 1, 2.2 ≤ z/y ≤ 3.0), the particle size coated with the dispersant is 0.0001 to 0.2 parts by weight of composite tungsten oxide fine particles of 1 to 800 nm (component B); A resin composition containing 0.001 to 0.5 parts by weight of (D) a release agent (component D) which is a fatty acid ester mainly composed of a full ester composed of a fatty acid and a polyhydric alcohol. In component A, the main repeating unit is a carbonate unit (a-1-1) having a fluorene ring in the side chain represented by the formula (a-1-1) and the formula (a-2). A copolymer polycarbonate resin (A1) that is a carbonate unit (a-2) and a polycarbonate resin (A2) that is a main repeating unit of 2,2-bis(4-hydroxyphenyl)propane, and the copolymer polycarbonate resin (A1 ) has a molar ratio of the carbonate unit ( a-1-1 ) and the carbonate unit (a-2) of 50/50 to 80/20, and the weight of the copolymerized polycarbonate resin (A1) and the polycarbonate resin (A2) The resin composition according to claim 1, which is a polycarbonate resin blend with a ratio of 1:99 to 70:30. The carbonate unit (a-1-1) having a fluorene ring in its side chain is 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene or 9,9-bis(4-hydroxy-3-methylphenyl) 3. The resin composition according to claim 1, which is a unit derived from fluorene. Carbonate unit (a-2) is a unit derived from 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane The resin composition according to any one of claims 1 to 3. The resin composition according to any one of claims 1 to 4, wherein component A has a single glass transition temperature in the range of 130°C to 160°C. 6. The resin composition according to any one of claims 1 to 5, wherein component D is a fatty acid ester represented by the following formula (D1) or (D2).
(In the formula, R ₁ to R ₆ are independently the same or different and are alkyl groups having 10 to 32 carbon atoms.)
(In the formula, R ₁ to R ₄ are independently the same or different and are alkyl groups having 10 to 32 carbon atoms.) The resin composition according to any one of claims 1 to 6, which contains 0.0002 to 0.8 parts by weight of (E) a heat stabilizer (component E) per 100 parts by weight of component A. The E component is at least one thermal stabilizer selected from the group consisting of a phenol stabilizer (E-1 component), a sulfur stabilizer (E-2 component) and a phosphorus stabilizer (E-3 component). The resin composition according to claim 7. The resin composition according to any one of claims 1 to 8, wherein (F) an ultraviolet absorber (component F) is contained in an amount of 0.1 to 2 parts by weight with respect to 100 parts by weight of component A. The F component is at least one type of ultraviolet light selected from the group consisting of benzotriazole-based UV absorbers (F-1 component), triazine-based UV absorbers (F-2 component) and oxazine-based UV absorbers (F-3 component). The resin composition according to claim 9, which is an absorbent. An optical film having a thickness of 0.2 to 0.6 mm and formed from the resin composition according to any one of claims 1 to 10. 12. The optical film according to claim 11, wherein the in-plane retardation Re is 20 nm or less, and the retardation Re(40) measured at an oblique angle of 40 degrees is 80 nm or less. 13. The optical film according to claim 11 or 12, wherein a hard coat is formed on at least one surface. A head-up display device using the optical film according to any one of claims 11 to 13.