TW202118821A - Polycarbonate resin film - Google Patents

Abstract

An object of the present invention is to provide a film which absorbs specific ultraviolet and does not have roll staining or bleed out according to a polycarbonate resin containing a specific polycarbonate resin and a specific ultraviolet absorber. The present invention relates to the polycarbonate resin film made of a polycarbonate resin composition which comprises 100 parts by weight of the polycarbonate resin containing a structural unit derived from a dihydroxy compound represented by the following formula (1); and more than 0.45 parts by weight and 7 parts by weight or less of the ultraviolet absorber having a melting point of 135℃ or higher and less than 300℃ and 5% weight loss temperature of higher than 240℃ relative to 100 parts by weight of polycarbonate resin, wherein light transmittance at a wavelength of 380nm is from 0.001% or more and 15% or less, and thickness is from 5μm to 120μm.

Description

Polycarbonate resin film

The present invention relates to a polycarbonate resin film composed of a polycarbonate resin composition, a polarizer protective film using the polycarbonate resin composition, and a polycarbonate resin composition.

As a conventional method for obtaining polycarbonate resin, it has been proposed to use isosorbide (hereinafter sometimes referred to as ISB), which is a dihydroxy compound obtained from biomass resources, as a monomer component, by using an ester with a carbonic acid diester. Exchange is a method of obtaining a polycarbonate resin while distilling off the by-produced monohydroxy compound under reduced pressure (for example, refer to Patent Documents 1 to 4). In addition, the polycarbonate resin obtained from ISB is not only used as a molding material that utilizes heat resistance, but has also been studied for its superior optical properties and use in optical films (for example, refer to Patent Document 5).

Generally, the polarizer protective film is to protect the polarizer from ultraviolet rays, and an ultraviolet absorber is added. However, there are problems such as the need for a large amount of ultraviolet absorber and the seepage of the absorber. In order to eliminate these problems, a method of adding an ultraviolet absorber with high compatibility with the resin or a polymer having an ultraviolet absorbing function is known (for example, refer to Patent Document 6).

Among them, cellulose ester films generally used for polarizer protective films have high water absorption and have problems such as insufficient durability when used in large-scale televisions. In addition, although a polarizer protective film using acrylic resin is also proposed (for example, refer to Patent Literature 7) However, due to its fragility, it may break during operation, making it difficult to thin.

In addition, in the case of a display using a general polarizing plate, since the light passing through the polarizing plate is linearly polarized light, there are cases where the display is blacked out due to the angle when viewing the display through polarized sunglasses. In order to eliminate this situation, the surface layer of the polarizer protective film may be a retardation film (for example, refer to Patent Document 8). In order to protect the polarizer from ultraviolet rays, these retardation films also contain ultraviolet absorbers.

For example, in the case of using a cycloolefin polymer (hereinafter sometimes referred to as COP), in order to prevent bleeding or roll soiling, there is a technology that has two types of three layers and contains only the core layer with a UV absorber (for example, refer to Patent Literature 9).

[Prior Technical Literature]

[Patent Literature]

Patent Document 1: International Patent Publication No. 2004/111106

Patent Document 2: Japanese Patent Laid-Open No. 2006-232897

Patent Document 3: Japanese Patent Laid-Open No. 2006-28441

Patent Document 4: Japanese Patent Laid-Open No. 2008-24919

Patent Document 5: Japanese Patent Laid-Open No. 2011-021171

Patent Document 6: Japanese Patent Laid-Open No. 2002-047357

Patent Document 7: Japanese Patent Laid-Open No. 2013-83956

Patent Document 8: Japanese Patent Laid-Open No. 2011-137954

Patent Document 9: Japanese Patent Laid-Open No. 2015-31753

However, the polycarbonate resin obtained from ISB hardly absorbs violet It must contain a large amount of ultraviolet absorber when used in polarizer protective film. On the other hand, if the polycarbonate resin contains a large amount of ultraviolet absorber, the heat resistance of the film will be reduced, the film will be turbid due to the exuded material, the film foreign matter caused by the roller dirt, etc., the appearance of the film will be poor. , The uniformity of film thickness is reduced, etc. In addition, there are cases where roller contamination or the like occurs due to specific compounds.

Therefore, the object of the present invention is to provide a polycarbonate resin film to eliminate these problems by using a specific polycarbonate resin to contain a specific ultraviolet absorber without reducing the heat resistance of the film. Problems such as film turbidity caused by exuded substances, film foreign matter caused by roller dirt, and poor film appearance such as gear wear marks, have uniform film thickness and absorb specific ultraviolet rays.

The inventors of the present invention conducted intensive research to solve the above-mentioned problems and found that by using a polycarbonate resin containing structural units derived from the dihydroxy compound represented by the following formula (1) and adding a specific ultraviolet absorber, it is possible to provide There are no problems such as reduced heat resistance of the film, film turbidity caused by exuded substances, film foreign matter caused by roller dirt, gear wear marks and other film appearance defects. The high-quality film that absorbs specific ultraviolet rays has achieved the cost invention. That is, the gist of the present invention is aimed at the following [1] to [6].

[1] A polycarbonate resin film composed of a polycarbonate resin composition, the polycarbonate resin composition comprising: polycarbonate containing structural units derived from a dihydroxy compound represented by the following formula (1) 100 parts by weight of ester resin; and relative to 100 parts by weight of polycarbonate resin, more than 0.45 parts by weight and 7 parts by weight or less, the melting point is 135°C or more but less than 300°C and 5% weight reduction temperature is higher than 240°C UV absorption Agent; The polycarbonate resin film has a light transmittance of 380nm wavelength of 0.001% or more and 15% or less, and a thickness of 5μm~120μm.

[化1]

[2] The polycarbonate resin film according to [1], wherein the content of the compound represented by the following formula (3) in the polycarbonate resin is 10 wt ppm or more and 1200 wt ppm or less.

[化2]

系、苯并三唑系、喹啉酮系、苯并

唑系或吲哚系。 [3] The polycarbonate resin film according to [1] or [2], wherein the ultraviolet absorber is three

Series, benzotriazole series, quinolinone series, benzo

Azole series or indole series.

[4] The polycarbonate resin film according to any one of [1] to [3], wherein the in-plane retardation at 548 nm is 100 nm or more and 200 nm or less.

[5] A polarizer protective film using the polycarbonate resin film described in any one of [1] to [4].

[6] A polycarbonate resin composition comprising: 100 parts by weight of a polycarbonate resin containing a structural unit derived from a dihydroxy compound represented by the following formula (1); and more than 100 parts by weight of the polycarbonate resin 0.45 parts by weight and 7 parts by weight or less, a UV absorber with a melting point of 135°C or higher but less than 300°C and a 5% weight loss temperature higher than 240°C; among the above polycarbonate resins, the compound represented by the following formula (3) The content is 10 ppm by weight or more and 1200 ppm by weight or less.

[化3]

[化4]

According to the present invention, even if a large amount of ultraviolet absorber is contained, the heat resistance of the film will not be reduced when the film is manufactured, the film will be turbid due to the oozing substance, the film foreign matter caused by the roller dirt, etc., gear wear marks, etc. Problems such as poor appearance of the film show that it is an optical film that exhibits high performance as a polarizer protective film. Furthermore, since roller contamination does not occur, it is possible to drastically reduce appearance defects during molding, and improve productivity, workability, and product quality.

The embodiments of the present invention will be described in detail below. The description of the constituent elements described below is an example (representative example) of the embodiments of the present invention. The present invention is not limited to the following contents unless the gist thereof is exceeded.

The polycarbonate resin film of the present invention is composed of a polycarbonate resin composition containing a polycarbonate resin and an ultraviolet absorber.

[Polycarbonate resin]

The polycarbonate resin composition of the present invention contains: Polycarbonate resin which is the structural unit of hydroxyl compound.

[化5]

(Terminal group structure of polycarbonate resin)

The polycarbonate resin can be produced by polycondensing a dihydroxy compound, a carbonic acid diester, and a catalyst under melting. As the carbonic acid diester, those described later can be used. Among them, diphenyl carbonate is preferably used.

At this time, in the manufactured polycarbonate resin, the number (A) of the terminal groups represented by the following structural formula (2) (hereinafter sometimes referred to as "phenyl terminal") is relative to the total number of terminals (B) The ratio (A/B) is preferably in the range of 75% or more and less than 98%.

[化6]

In addition, the ratio (A/B) of the number of phenyl terminals present in the polycarbonate resin (A) to the total number of terminals (B) is more preferably in the range of 76% or more, particularly preferably in the range of 77% or more. In addition, it is more preferably a range of 96% or less, and particularly preferably a range of 95% or less.

If the ratio (A/B) of the number of phenyl terminals (A) relative to the total number of terminals (B) (A/B) is less than 75%, it is likely to occur in the appearance of so-called silver bars in the molded product during injection molding, and during extrusion molding. Of bubbles. In addition, if the ratio (A/B) of the number of phenyl terminals (A) to the total number of terminals (B) is more than 98%, there is a tendency that defects in appearance at the time of injection molding or extrusion molding are reduced. In addition, if it is desired to obtain (A/B) more than 98% polycarbonate resin, the polymerization conditions are severe, or the reaction takes a long time, resulting in polycarbonate resin Deterioration of grease and the possibility of obtaining only those with degraded color are very high.

The method of adjusting the ratio (A/B) of the number of phenyl terminals present in the polycarbonate resin to the total number of terminals (B) (A/B) is not particularly limited. For example, by adjusting the ratio of the carbonic acid diester to the total dihydroxy compound used in the reaction according to the range in which the desired high molecular weight body can be obtained, or by degassing the remaining monomers to the outside of the reaction system in the latter stage of the polymerization reaction , Or in the latter stage of the polymerization reaction to increase the stirring efficiency of the reactor to increase the reaction speed, the ratio (A/B) of the number of phenyl ends (A) relative to the total number of ends (B) (A/B) can be adjusted to the above range .

The ratio of the phenyl terminal in the polycarbonate resin can be calculated by an NMR spectrometer, using tritiated chloroform with TMS (tetramethylsilane) added as a measurement solvent, and by ^{the measurement of the 1} H-NMR spectrum.

Furthermore, the use ratio of the dihydroxy compound having the combination structure of structural formula (1), the alicyclic dihydroxy compound, and other dihydroxy compounds used as necessary is matched with the polycarbonate resin used in the present invention. The ratio of the constituent units of each dihydroxy compound is adjusted appropriately.

(The content and content control method of the compound shown in formula (3))

The polycarbonate resin of the present invention preferably contains a specific oligomer component represented by the following formula (3) in a specific amount.

[化7]

When the amount of the above compound is too small, it is made of polycarbonate resin During the manufacturing stage, excessive heat may be applied or the reaction residence time may become longer, which may cause deterioration of the color tone of the polymer. In addition, if it is too large, there will be a problem of device contamination during molding or a problem of poor appearance of the molded product. Therefore, the content of the compound represented by formula (3) in the polycarbonate resin of the present invention is preferably 10 wt ppm or more and 1200 wt ppm or less.

In addition, the content of the compound represented by the formula (3) in the polycarbonate resin of the present invention is more preferably 15 ppm by weight or more, particularly preferably 20 ppm by weight or more. In addition, it is more preferably 650 ppm by weight or less, particularly preferably 400 ppm by weight or less. If the content of the compound represented by the formula (3) in the polycarbonate resin is in the above range, there will be no dirt or odor during molding, and the molding appearance is good, which is preferable.

In order to adjust the content of the compound represented by formula (3), it is preferable to make the ratio (A/B) of the number of phenyl ends (A) relative to the total number of ends (B) (A/B) 98 in the production of polycarbonate resin. %the following.

Furthermore, by making the pressure in the final polymerization tank 1 kPa or less, or making the polymerization time at a temperature higher than 220°C less than 2 hours, the occurrence of the compound represented by the formula (3) can be suppressed. In particular, by setting the final polymerization tank as a horizontal reaction tank, the degassing efficiency can be drastically improved. In addition, the compound represented by the formula (3) can be controlled to a specific amount by using an extruder to degas through a vacuum vent, or performing water injection during degassing.

The polycarbonate resin of the present invention is usually obtained by polycondensing a dihydroxy compound, a carbonic acid diester, and a catalyst under melting as described later. In this polycondensation reaction, a monohydroxy compound is generated from the carbonic acid diester in the form of separated components.

For example, in the case of using diphenyl carbonate as the carbonic acid diester, the produced monohydroxy compound is phenol. At this time, if the content of the monohydroxy compound in the obtained polycarbonate resin is large, problems of device contamination or odor during molding may occur.

The upper limit of the content of the monohydroxy compound in the polycarbonate resin of the present invention is not particularly limited, but it is usually 1200 ppm by weight or less, preferably 650 ppm by weight or less, particularly preferably 500 ppm by weight or less. In the production of polycarbonate resin, by using an appropriate amount of a specific phosphorus compound as a catalyst deactivator as described later, and then fully performing degassing treatment, the content of the monohydroxy compound in the polycarbonate resin can be reduced. And can suppress the occurrence under heating. The details of the method for measuring the amount of the monohydroxy compound in the polycarbonate resin are described in the section of Examples.

In addition, there is no particular limitation on the lower limit, but it is usually 0.1 wt ppm or more, preferably 1 wt ppm or more, particularly preferably 10 wt ppm or more. If these are too small, excessive heat must be applied in the refining stage, or the reaction residence time must be increased, and the color tone of the polymer may deteriorate. Therefore, the above range is preferable.

[Manufacturing method of polycarbonate resin]

The method for producing the polycarbonate resin of the present invention will be described in detail below.

<raw materials>

(Dihydroxy compound)

The polycarbonate resin of the present invention contains a polycarbonate resin derived from a structural unit of a dihydroxy compound represented by the following formula (1).

[化8]

In the present invention, in addition to the structural unit derived from the dihydroxy compound represented by the above formula (1), the polycarbonate resin preferably contains one derived from the following formula (4) if necessary. The dihydroxy compound shown in the following formula (5), the dihydroxy compound shown in the following formula (6), the dihydroxy compound shown in the following formula (7) and the dihydroxy compound shown in the following formula (8) The structural unit of more than one dihydroxy compound that forms a group.

[化9]

HO-R ⁵ -OH (5)

(In the above formula (5), R ⁵ represents a substituted or unsubstituted cycloalkylene group with 4 to 20 carbon atoms.)

HO-CH ₂ -R ⁶ -CH ₂ -OH (6)

(In the above formula (6), R ⁶ represents a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms.)

H-(OR ⁷ ) _p -OH (7)

(In the above formula (7), R ⁷ represents a substituted or unsubstituted alkylene group with 2 to 10 carbon atoms, and p is an integer of 2 to 100.)

HO-R ⁸ -OH (8)

(In the above formula (8), R ⁸ represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms.)

In addition, in the following, the carbon number of various groups refers to the case where the group has a substituent, and means the total carbon number including the carbon number of the substituent.

(Dihydroxy compound represented by formula (1))

The polycarbonate resin of the present invention contains structural units derived from the dihydroxy compound represented by the above formula (1).

As the dihydroxy compound represented by the above formula (1), for example, isosorbide, isomannitol, isoidide, etc., which belong to the relationship of stereoisomers, can be mentioned. Water sugar alcohol. These can be used individually by 1 type, and can also be used in combination of 2 or more types. Among these dihydroxy compounds, in terms of ease of acquisition and manufacture, optical properties, and moldability, the best is the isoform obtained by dehydrating and condensing sorbitol produced from various starches that are abundant in resources and readily available. Sorbitol.

When the polycarbonate resin also contains structural units other than the structural units of the dihydroxy compound represented by the above formula (1), the ratio is not particularly limited, and can be appropriately set according to the required performance of the corresponding polycarbonate resin. can.

(Dihydroxy compound shown in formula (4)~(8))

In the present invention, the polycarbonate resin may contain a dihydroxy compound selected from the above formula (4), a dihydroxy compound represented by the above formula (5), a dihydroxy compound represented by the above formula (6), and the above formula if necessary. (7) The structural unit of more than one dihydroxy compound in the group consisting of the dihydroxy compound and the dihydroxy compound shown in the above formula (8).

[Dihydroxy compound represented by formula (4)]

The dihydroxy compound represented by the above formula (4) is a compound having a cyclic ether structure in the molecule, so-called spiroglycerin.

[Dihydroxy compound represented by formula (5)]

Formula (5) based dihydroxy compound having a carbon number in R ⁵ 4 ~ 20, preferably 4 to 18 carbon atoms of a substituted or unsubstituted alicyclic of extending dihydroxy compound cycloalkyl. Here, when R ⁵ has a substituent, examples of the substituent include a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. When the alkyl group has a substituent, examples of the substituent include an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group, and an aryl group such as a phenyl group and a naphthyl group.

Since this dihydroxy compound has a ring structure, it can improve the toughness of the molded product when the obtained polycarbonate resin is formed, and especially the toughness when it is formed into a film.

The ^{cycloalkylene group of R 5} is not particularly limited as long as it is a hydrocarbon group having a ring structure, and it may have a bridge structure having a carbon atom at the head of the bridge. From the viewpoint that the dihydroxy compound is easy to manufacture and can reduce the amount of impurities, the dihydroxy compound represented by the above formula (5) is preferably a compound containing a 5-membered ring structure or a 6-membered ring structure, that is, R ⁵ is substituted or Unsubstituted cyclopentyl or substituted or unsubstituted cyclohexylene dihydroxy compounds. In the case of such a dihydroxy compound, by including a 5-membered ring structure or a 6-membered ring structure, the heat resistance of the obtained polycarbonate resin can be improved. The 6-membered ring structure can also be fixed into a chair shape or a boat shape by co-bonding.

Among them, the dihydroxy compound represented by the above formula (5) preferably R ⁵ is various isomers represented by the following formula (9). Here, in the formula (9), R ¹¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. When R ¹¹ is a substituted alkyl group having 1 to 12 carbon atoms, examples of the substituent include alkoxy groups such as methoxy, ethoxy, and propoxy, and phenyl, naphthyl, etc. Aryl etc.

[化10]

As the dihydroxy compound represented by the above formula (5), more specifically, for example, tetramethylcyclobutanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2- Cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4- Cyclohexanediol, tricyclodecanediols, pentacyclic diols, etc. are not limited to these.

These may be used individually by 1 type, and may use 2 or more types together.

[Dihydroxy compound represented by formula (6)]

The dihydroxy compound represented by the above formula (6) is an alicyclic dihydroxy compound having a substituted or unsubstituted cycloalkylene having 4 to 20 carbon atoms, preferably 3 to 18 carbon atoms ^{in R 6.} Here, when R ⁶ has a substituent, examples of the substituent include a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. When the alkyl group has a substituent, examples of the substituent include an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group, and an aryl group such as a phenyl group and a naphthyl group.

Since this dihydroxy compound has a ring structure, it can improve the toughness of the molded product when the obtained polycarbonate resin is formed, and especially the toughness when it is formed into a film.

The ^{cycloalkylene group of R 6} is not particularly limited as long as it is a hydrocarbon group having a ring structure, and it may have a bridge structure having a carbon atom at the head of the bridge. From the viewpoint that the dihydroxy compound is easy to manufacture and can reduce the amount of impurities, the dihydroxy compound represented by the above formula (6) is preferably a compound containing a 5-membered ring structure or a 6-membered ring structure, that is, R ⁶ is substituted or Unsubstituted cyclopentyl or substituted or unsubstituted cyclohexylene dihydroxy compounds.

In the case of such a dihydroxy compound, by including a 5-membered ring structure or a 6-membered ring structure, the heat resistance of the obtained polycarbonate resin can be improved. The 6-member ring can also be fixed in the shape of a chair or a boat by co-bonding. Among the dihydroxy compounds represented by the above formula (6), R ⁶ is preferably various isomers represented by the above formula (9).

As the dihydroxy compound represented by the above formula (6), more specifically, for example, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 3,8 -Bis(hydroxymethyl) tricyclo[5.2.1.0 ^2.6 ]decane, 3,9-bis(hydroxymethyl)tricyclo[5.2.1.0 ^2.6 ]decane, 4,8-bis(hydroxymethyl)tri Cyclo[5.2.1.0 ^2.6 ]decane, 4,9-bis(hydroxymethyl)tricyclo[5.2.1.0 ^2.6 ]decane, etc. are not limited to these.

These may be used individually by 1 type, and may use 2 or more types together. That is, these dihydroxy compounds may be obtained in the form of a mixture of isomers for manufacturing reasons, and in this case, the mixture of isomers can be used directly.

For example, 3,8-bis(hydroxymethyl)tricyclo[5.2.1.0 ^2.6 ]decane, 3,9-bis(hydroxymethyl)tricyclo[5.2.1.0 ^2.6 ]decane, 4,8-bis (Hydroxymethyl)tricyclo[5.2.1.0 ^2.6 ]decane and 4,9-bis(hydroxymethyl)tricyclo[5.2.1.0 ^2.6 ]decane, etc.

Among the specific examples of the dihydroxy compound represented by the above formula (6), cyclohexane dimethanol is particularly preferred, and from the viewpoint of easy acquisition and easy handling, 1,4-cyclohexane dimethanol, 1 ,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol.

[Dihydroxy compound represented by formula (7)]

The dihydroxy compound represented by the above formula (7) is a compound having a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms ^{in R 7.} p is an integer of 2-100, preferably an integer of 6-50, more preferably an integer of 12-40.

As the dihydroxy compound represented by the above formula (7), more specifically, for example, diethylene glycol, triethylene glycol, polyethylene glycol (molecular weight 150 to 4000), etc., but it is not limited to these. As the dihydroxy compound represented by the above formula (7), polyethylene glycol with a molecular weight of 300 to 2000 is preferred, and polyethylene glycol with a molecular number of 600 to 1500 is more preferred.

These may be used individually by 1 type, and may use 2 or more types together.

[Dihydroxy compound represented by formula (8)]

The dihydroxy compound represented by the above formula (8) is a substituted or unsubstituted alkylene having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms ^{in R 8.} When ^{the alkylene group of R 8} has a substituent, examples of the substituent include an alkyl group having 1 to 5 carbon atoms.

In the dihydroxy compound represented by the above formula (8), as the dihydroxy compound in which R ⁸ is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, specific examples include ethylene glycol, propylene glycol, and 1,4-butane. Diol, 1,6-hexanediol, etc., but not limited to these.

Among these dihydroxy compounds, 1,3-propanediol and 1,6-hexanediol are preferred from the viewpoints of easy availability, easy handling, high reactivity during polymerization, and the hue of the obtained polycarbonate resin. Moreover, from the viewpoint of heat resistance, spiroglycerol having an acetal ring is preferred. These are combined with the required performance of polycarbonate resin and can be used alone or in combination of two or more.

Furthermore, in the present invention, the polycarbonate resin is derived from the structural unit of the dihydroxy compound represented by the above formula (4), from the structural unit of the dihydroxy compound represented by the above formula (5), and from the structural unit represented by the above formula (6) Among the structural unit of the dihydroxy compound, the structural unit derived from the dihydroxy compound represented by the above formula (7) and the structural unit derived from the dihydroxy compound represented by the above formula (8), it is preferable to contain the structural unit derived from the above formula (6) The structural unit of the dihydroxy compound and/or the structural unit derived from the dihydroxy compound represented by the above formula (7). In addition, due to reactivity, heat resistance, and less decomposition during heat retention, it is more preferable to contain a structural unit derived from the dihydroxy compound represented by the above formula (6).

(Other dihydroxy compounds)

In the present invention, the polycarbonate resin system may optionally substitute the structural unit derived from the dihydroxy compound represented by the above formulas (4) to (8) with the structural unit derived from other dihydroxy compounds.

Examples of other dihydroxy compounds include bisphenols or ethylene oxide (EO) additions of bisphenols, and stilbene compounds.

<Bisphenols>

Examples of bisphenols include 2,2-bis(4-hydroxyphenyl)propane (=bisphenol A), 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2- Bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane, bis(4-hydroxy Phenyl) methane, bis(4-hydroxy-5-nitrophenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane, 1 ,1-Bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl) sulfide, 2,4'-dihydroxydiphenyl sulfide, bis(4-hydroxyphenyl)sulfide, 4, 4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 4,4'-dihydroxy-2,5-diethoxydiphenyl ether Wait.

<Ethylene oxide (EO) addition of bisphenols>

Examples of the ethylene oxide (EO) additions of bisphenols include those in which ethylene oxide (EO) is added to the above-mentioned bisphenol compounds.

<Fructus compound>

As the pyridium compound, for example, 9,9-bis(4-hydroxyphenyl)pyridium, 9,9-bis(4-hydroxy-3-methylphenyl)pyridium, 9,9-bis(4-hydroxy- 3-ethylphenyl) quince, 9,9-bis(4-hydroxy-3-n-propylphenyl) quince, 9,9-bis(4-hydroxy-3-isopropylphenyl) quince, 9 ,9-bis(4-hydroxy-3-n-butylphenyl) pyridium, 9,9-bis(4-hydroxy-3-second butylphenyl) pyridium, 9,9-bis(4-hydroxy- 3-tertiary butylphenyl) quince, 9,9-bis(4-hydroxy-3-cyclohexylphenyl) quince, 9,9-bis(4-hydroxy-3-phenylphenyl) quince, 9 ,9-bis(4-(2-hydroxyethoxy)phenyl)pyridium, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)pyridium, 9,9- Bis(4-(2-hydroxyethoxy)-3-isopropylphenyl) 茀, 9,9-bis(4-(2-hydroxyethoxy)-3-isobutylphenyl) 茀, 9,9-bis(4-(2-hydroxyethoxy)-3-third Butylphenyl) pyridium, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl) pyridium, 9,9-bis(4-(2-hydroxyethoxy)- 3-phenylphenyl) quince, 9,9-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl) quince, 9,9-bis(4-(2-hydroxy Ethoxy)-3-tert-butyl-6-methylphenyl)pyridium, 9,9-bis(4-(3-hydroxy2,2-dimethylpropoxy)phenyl)pyridium and the like.

These may be used individually by 1 type, and may use 2 or more types together. Among them, the dihydroxy compound having an aromatic ring in the structure other than the one represented by the above formula (1) may have an adverse effect on the optical properties, so the structural unit derived from the dihydroxy compound is relative to the polycarbonate The total amount of structural units derived from the dihydroxy compound in the resin is preferably 50 mol% or less, more preferably 20 mol% or less, and still more preferably 5 mol% or less. The particularly preferred polycarbonate resin does not contain a structural unit derived from a dihydroxy compound having an aromatic ring in the structure other than the one represented by the above formula (1).

[Containing ratio of structural units from dihydroxy compounds]

In the present invention, the content ratio of the structural unit derived from the dihydroxy compound represented by the above formula (1) contained in the polycarbonate resin is preferably 20% by weight or more with respect to the total of the structural unit derived from the dihydroxy compound. More preferably, it is 25% by weight or more, and still more preferably 30% by weight or more. Moreover, it is 95 weight% or less normally, Preferably it is 90 weight% or less.

If the content ratio of the structural unit is too small, the heat resistance may be low and the surface hardness may deteriorate. In addition, if the content ratio of the structural unit is too high, the glass transition temperature of the polycarbonate resin may be too high, and molding may be difficult, or the water absorption rate may deteriorate.

In addition, the polycarbonate resin contains a dihydroxy compound selected from the group consisting of the dihydroxy compound represented by the above formula (4), the dihydroxy compound represented by the above formula (5), the dihydroxy compound represented by the above formula (6), and the It is composed of a dihydroxy compound and the dihydroxy compound shown in the above formula (8) In the case of one or more structural units of dihydroxy compounds in the group, the content ratio is relative to the total of structural units derived from dihydroxy compounds contained in the polycarbonate resin, preferably 0.1% by weight or more and less than 20% by weight, more It is preferably 0.1% by weight or more and 18% by weight or less, and still more preferably 0.2% by weight or more and 15% by weight or less.

Since the polycarbonate resin contains structural units derived from the dihydroxy compounds represented by the above formulas (4) to (8) above the above lower limit, when the polycarbonate resin is melt-molded, it can be prevented from being caused by heat. Cause foreign matter or air bubbles, or prevent the coloration of polycarbonate resin. Among them, if there are too many structural units, the light resistance tends to decrease when forming a molded product.

All dihydroxy compounds used in the production of the polycarbonate resin of the present invention may also contain stabilizers such as reducing agents, antioxidants, deoxidizers, light stabilizers, antacids, pH stabilizers or heat stabilizers. In particular, since the specific dihydroxy compound of the present invention is easily deteriorated under acidic conditions, it is preferable to contain an alkaline stabilizer.

Examples of alkaline stabilizers include hydroxides, carbonates, phosphates, phosphites, and hypophosphites of Group 1 or Group 2 metals in the long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). , Borate and fatty acid salt, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, trimethyl ethyl ammonium hydroxide, trimethyl benzyl hydrogen Ammonium oxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributyl Alkaline ammonium compounds such as phenyl ammonium hydroxide, tetraphenyl ammonium hydroxide, benzyl triphenyl ammonium hydroxide, methyl triphenyl ammonium hydroxide and butyl triphenyl ammonium hydroxide, diethyl Amine, dibutylamine, triethylamine, formaldehyde, N-methylformaldehyde, pyrrolidine, piperidine, 3-amino-1-propanol, ethylenediamine, N-methyldiethanolamine, diethyl Ethanolamine, 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methyl Amine compounds such as oxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole and aminoquinoline, and bis-(tertiary butyl) Hindered amine compounds such as amine and 2,2,6,6-tetramethylpiperidine. Among these stabilizers, tetramethylammonium hydroxide, imidazole, or hindered amine compounds are preferred in terms of stabilization effect.

The content of these alkaline stabilizers in all dihydroxy compounds used in the present invention is not particularly limited. Since the specific dihydroxy compounds used in the present invention are unstable in an acidic state, it is preferable to add stabilizers The pH of the aqueous solution of the specific dihydroxy compound containing the above-mentioned stabilizer is set to around 7.

If the amount of the alkaline stabilizer is too small, there is a possibility that the effect of preventing the deterioration of the specific dihydroxy compound may not be obtained; if it is too large, it may cause the modification of the specific dihydroxy compound. Therefore, compared with the various dihydroxy compounds used in the present invention, the alkaline stabilizer is preferably 0.0001% by weight to 1% by weight, more preferably 0.001% by weight to 0.1% by weight.

If these alkaline stabilizers are contained in the dihydroxy compound used in the present invention and directly used as a raw material for the production of polycarbonate resin, the alkaline stabilizer itself becomes a polymerization catalyst, not only the polymerization rate or quality control becomes Difficulty, which also leads to the deterioration of the resin hue.

Therefore, regarding specific dihydroxy compounds or other dihydroxy compounds containing alkaline stabilizers, it is preferable to remove the alkaline stabilizers by ion exchange resin or distillation before using as a raw material for the production of polycarbonate resins. Agent.

In addition, the specific dihydroxy compound used in the present invention is likely to be slowly oxidized by oxygen. Therefore, in order to prevent oxygen from being caused during storage or manufacturing operations, It is preferable to decompose by preventing moisture from being mixed in, or using a deoxidizer, or under a nitrogen environment.

(Carbon diester)

The polycarbonate resin of the present invention is obtained by polycondensing the above-mentioned specific dihydroxy compound-containing dihydroxy compound and carbonic acid diester as raw materials, and polycondensing it by transesterification reaction. As the carbonic acid diester to be used, those represented by the following formula (10) can usually be exemplified. These carbonic acid diesters may be used individually by 1 type, and may mix and use 2 or more types.

[化11]

In the above formula (10), A ¹ and A ² are substituted or unsubstituted aliphatic hydrocarbon groups with 1 to 18 carbons, or substituted or unsubstituted aromatic hydrocarbon groups. A ¹ and A ² may be the same or different . Preferably, A ¹ and A ² are substituted or unsubstituted aromatic hydrocarbon groups, more preferably unsubstituted aromatic hydrocarbon groups.

Examples of the carbonic acid diester represented by the above formula (10) include substituted diphenyl carbonates such as diphenyl carbonate (DPC) and tricresyl carbonate, dimethyl carbonate, and diethyl carbonate And di-tert-butyl carbonate and so on. Among them, diphenyl carbonate or substituted diphenyl carbonate is preferred, and diphenyl carbonate is particularly preferred.

In addition, carbonic acid diesters may contain impurities such as chloride ions, and impurities may hinder the polymerization reaction or deteriorate the hue of the obtained polycarbonate resin. Therefore, if necessary, it is better to use refined products such as distillation. .

<Transesterification reaction catalyst>

The polycarbonate resin of the present invention is produced by transesterifying the above-mentioned dihydroxy compound and carbonic acid diester. In more detail, it is obtained by subjecting it to transesterification to remove the by-produced monohydroxy compound etc. out of the system.

In the above-mentioned transesterification reaction, polycondensation is carried out in the presence of a transesterification reaction catalyst. The transesterification reaction catalyst that can be used in the production of the polycarbonate resin of the present invention (hereinafter sometimes referred to as a catalyst or a polymerization catalyst) , Can have a great influence on the reaction speed or the quality of the polycarbonate resin obtained by polycondensation.

The catalyst used is not limited as long as it satisfies the transparency, hue, heat resistance, weather resistance, and mechanical strength of the manufactured polycarbonate resin. Examples include metal compounds of Group 1 or Group 2 (hereinafter referred to as "Group 1" and "Group 2") in the long-period periodic table, as well as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amines. Basic compounds such as chemical compounds. Preferably, a Group 1 metal compound and/or a Group 2 metal compound are used.

Examples of the above-mentioned group 1 metal compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, and lithium carbonate. , Cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, boron hydride Cesium, sodium phenyl boron, potassium phenyl boron, lithium phenyl boron, cesium phenyl boron, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate , Dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenyl phosphate, dipotassium phenyl phosphate, dilithium phenyl phosphate, dicesium phenyl phosphate, sodium, potassium, lithium, cesium alcoholate, phenolate, double Disodium salt, dipotassium salt, dilithium salt and dicesium salt of phenol A. Among them, from the viewpoint of polymerization activity and the hue of the obtained polycarbonate resin, a lithium compound is preferred.

Examples of the above-mentioned group 2 metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, and magnesium carbonate. , Strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate and strontium stearate.

Among them, a magnesium compound, a calcium compound, or a barium compound is preferred. From the viewpoint of polymerization activity and the hue of the obtained polycarbonate resin, a magnesium compound and/or a calcium compound are more preferred, and a calcium compound is most preferred.

Furthermore, basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may also be used in combination with the above-mentioned Group 1 metal compounds and/or Group 2 metal compounds, but are particularly preferred Only Group 1 metal compounds and/or Group 2 metal compounds are used.

Examples of the above-mentioned basic boron compounds include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, and trimethylphenylboron. , Triethyl methyl boron, triethyl benzyl boron, triethyl phenyl boron, tributyl benzyl boron, tributyl phenyl boron, tetraphenyl boron, benzyl triphenyl boron, methyl Sodium salt, potassium salt, lithium salt, calcium salt, barium salt, magnesium salt or strontium salt of triphenyl boron, butyl triphenyl boron, etc.

As said basic phosphorus compound, triethylphosphine, tri-n-propyl phosphine, triisopropyl phosphine, tri-n-butyl phosphine, triphenyl phosphine, tributyl phosphine, a quaternary phosphonium salt, etc. are mentioned, for example.

As the above-mentioned basic ammonium compound, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylammonium hydroxide, Benzyl ammonium hydroxide, trimethyl phenyl ammonium hydroxide, triethyl methyl ammonium hydroxide, triethyl benzyl ammonium hydroxide, triethyl phenyl ammonium hydroxide, tributyl benzyl ammonium hydroxide , Tributyl phenyl ammonium hydroxide, tetraphenyl ammonium hydroxide, benzyl triphenyl Base ammonium hydroxide, methyl triphenyl ammonium hydroxide and butyl triphenyl ammonium hydroxide, etc.

Examples of the above-mentioned amine compounds include 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2 -Methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and guanidine, etc.

The usage amount of the above-mentioned polymerization catalyst is per 1 mol of the total dihydroxy compound used in the polymerization, preferably 0.1 μmol~300 μmol, more preferably 0.5 μmol~100 μmol, particularly preferably 1 μmol~50 μmol.

Among them, when a compound containing at least one metal selected from the group consisting of Group 2 in the long-period periodic table and lithium is used, especially when a magnesium compound and/or a calcium compound is used, the amount of metal is the same as the above-mentioned total two Per 1 mol of the hydroxy compound, it is preferably 0.1 μmol or more, more preferably 0.3 μmol or more, and particularly preferably 0.5 μmol or more. Furthermore, as the upper limit, it is preferably 20 μmol or less, more preferably 10 μmol or less, still more preferably 5 μmol or less, particularly preferably 3 μmol or less.

If the amount of the catalyst is too small, the polymerization rate will slow down, so there are cases where the polymerization temperature has to be increased in order to obtain a polycarbonate resin with a desired molecular weight. Therefore, the hue of the obtained polycarbonate resin is highly likely to deteriorate, or unreacted raw materials volatilize during the polymerization and the molar ratio of the dihydroxy compound to the carbonic acid diester is unbalanced, and the desired molecular weight may not be reached. On the other hand, if the amount of the polymerization catalyst used is too large, undesirable side reactions will occur, which may result in deterioration of the hue of the obtained polycarbonate resin or coloration of the resin during molding.

Among them, among the Group 1 metals, if a large amount of sodium, potassium, or cesium is contained in the polycarbonate resin, there is a possibility of adversely affecting the hue. Moreover, these metals are not only derived from the catalyst used, but also mixed in from raw materials or reaction equipment. Do not Regarding the source, the total amount of these metal compounds in the polycarbonate resin is preferably 1 wt ppm or less, more preferably 0.5 wt ppm or less based on the amount of metal.

<Manufacturing method of polycarbonate resin>

The polycarbonate resin of the present invention is obtained by polycondensation of a dihydroxy compound containing a specific dihydroxy compound and a carbonic acid diester by transesterification reaction.

The dihydroxy compound and the carbonic acid diester, which are raw materials, are preferably uniformly mixed before the transesterification reaction. The mixing temperature is usually 80°C or higher, preferably 90°C or higher. In addition, the upper limit is usually 250°C or lower, preferably 200°C or lower, and more preferably 150°C or lower. Among them, it is preferably 100°C or higher and 120°C or lower.

If the mixing temperature is too low, there is the possibility of slow dissolution rate and insufficient dissolution, which will often lead to undesirable situations such as curing; if the mixing temperature is too high, it may cause thermal degradation of the dihydroxy compound, resulting in damage to the obtained polycarbonate Possibility of adverse effects caused by the hue or thermal stability of the ester resin.

The operation of mixing the dihydroxy compound containing the specific dihydroxy compound and the carbonic acid diester, which is the raw material of the polycarbonate resin of the present invention, is preferably at an oxygen concentration of 10 vol% or less, more preferably 0.0001 vol% to 10 vol%, and more It should be carried out in an environment of 0.0001vol%~5vol%, especially 0.0001vol%~1vol%. By being in the above range, the hue can be prevented from deteriorating.

In order to obtain the polycarbonate resin of the present invention, relative to the total dihydroxy compounds containing specific dihydroxy compounds used in the reaction, it is preferable to use a carbonic acid diester at a molar ratio of 0.94 to 1.04, more preferably 0.98 to 1.02, and even more A molar ratio of 1.00~1.01 is preferred. If the molar ratio is small, the terminal phenyl group of the manufactured polycarbonate resin will be reduced, and poor appearance during molding is likely to occur.

In addition, if the molar ratio increases, the speed of the transesterification reaction may decrease, or it may be difficult to produce a polycarbonate resin with a desired molecular weight. The decrease in the transesterification reaction rate increases the heat history during the polymerization reaction, and as a result, there is a possibility that the hue or weather resistance of the obtained polycarbonate resin may deteriorate.

Furthermore, relative to the total dihydroxy compounds containing specific dihydroxy compounds, if the molar ratio of the carbonic acid diester increases, the amount of residual carbonic acid diester in the obtained polycarbonate resin or the formula (3) The increase of the compound causes the problems of dirt, odor, and poor appearance during molding.

In the present invention, the method of polycondensing a dihydroxy compound and a carbonic acid diester is carried out in multiple stages in the presence of the above-mentioned catalyst, usually using a plurality of reactors. The form of the reaction may be any one of batch type, continuous type, or a combination of batch type and continuous type, preferably a continuous type that can obtain polycarbonate resin with less heat history and is excellent in productivity.

Preferably, in the early stage of polymerization, the prepolymer is obtained at a relatively low temperature and low vacuum, and in the late stage of the polymerization, the molecular weight is increased to a predetermined value with a relatively high temperature and high vacuum. In addition, from the viewpoint of the control of the polymerization rate or the quality of the obtained polycarbonate resin, it is important to appropriately select the jacket temperature and internal temperature of each molecular weight stage, and the pressure in the reaction system.

For example, if one of the temperature and pressure is changed earlier before the polymerization reaction reaches a predetermined value, the unreacted monomer will distill out and the molar ratio of the dihydroxy compound and the carbonic acid diester will be unbalanced, resulting in a decrease in the polymerization rate. Or it may not be possible to obtain a polymer with a predetermined molecular weight or terminal group, and as a result, it may not be possible to achieve the purpose of the invention.

Furthermore, in order to suppress the amount of distilled monomers, it is effective to use a reflux cooler in the polymerization reactor, especially in the early stage of polymerization when there are more unreacted monomer components. The response system has a greater effect. The temperature of the refrigerant introduced into the reflux cooler can be appropriately selected according to the monomer used. Generally, the temperature of the refrigerant introduced into the reflux cooler is 45~180℃, preferably 80~ at the inlet of the reflux cooler. 150°C, especially 100~130°C.

If the temperature of the refrigerant is too high, the amount of reflux will decrease and its effect will decrease. On the contrary, if the temperature of the refrigerant is too low, the distillation efficiency of the monohydroxy compound to be distilled off tends to decrease. As the refrigerant, temperature, steam, heating medium oil, etc. are used, and steam and heating medium oil are preferred.

It is important to select the type and amount of the above-mentioned catalyst in order not to impair the hue of the final polycarbonate resin under the proper maintenance of the polymerization rate and suppression of monomer distillation. The polycarbonate resin of the present invention is preferably produced by using a catalyst and polymerizing it in multiple stages using a plurality of reactors.

The reason for carrying out the polymerization in plural reactors is that in the early stage of the polymerization reaction, since the reaction solution contains more monomers, it is important to maintain the necessary polymerization rate and suppress the volatilization of the monomers; in the late stage of the polymerization reaction, for To shift the balance to the polymerization side, it is important to fully distill off the by-produced monohydroxy compound. In this way, when setting different polymerization reaction conditions, from the viewpoint of production efficiency, it is preferable to use a plurality of polymerization reactors arranged in series.

The reactor used for the production of the polycarbonate resin of the present invention is as described above, and it may be at least two. From the viewpoint of production efficiency, etc., 3 or more are preferable, 3 to 5 are more preferable, and 4 are particularly preferable. In the present invention, if there are two or more reactors, it is also possible to further have a plurality of reaction stages with different conditions, and continuously change the temperature and pressure.

In the present invention, the polymerization catalyst can be added to the raw material preparation tank and the raw material storage tank, or directly added to the polymerization tank. From the viewpoint of supply stability and aggregation control In other words, it is preferable to provide a catalyst supply line in the middle of the raw material line before the polymerization tank, and it is preferable to supply it as an aqueous solution.

If the polymerization temperature is too low, there is a possibility that the productivity will decrease or the thermal history of the product will increase; if it is too high, it will not only cause the monomer to volatilize, but also promote the decomposition or coloring of the polycarbonate resin. . Specifically, in the first-stage reaction, the temperature as the internal temperature of the polymerization reactor is 130 to 210°C, preferably 150 to 205°C, and more preferably 170 to 200°C.

In addition, the reaction system has a pressure (absolute pressure) of 1 to 110 kPa, preferably 5 to 70 kPa, more preferably 7 to 30 kPa (absolute pressure), and the reaction time is 0.1 to 10 hours, preferably 0.5 to 3 hours, It is carried out while distilling the produced monohydroxy compound to the outside of the reaction system.

After the second stage, the pressure of the reaction system is slowly decreased from the pressure of the first stage, and then the produced monohydroxy compound is removed to the outside of the reaction system. Especially in order to control the amount of the compound represented by the above formula (3), after the second stage, it is set to 15kPa or less, and finally the pressure (absolute pressure) of the reaction system is set to 600kPa or less, and the maximum temperature according to the internal temperature is 190~240 ℃, preferably 195~235℃, usually 0.1~5 hours, preferably 0.1~4 hours, particularly preferably 0.5~3 hours.

In order to obtain a polycarbonate resin of a predetermined molecular weight, if the polymerization temperature is too high and the polymerization time is too long, the color tone tends to deteriorate. In particular, in order to suppress the coloration or thermal deterioration of the polycarbonate resin, and obtain a polycarbonate resin with a good hue and a low content of the compound represented by the above formula (3), it is preferable that the highest temperature of the internal temperature in all reaction stages is less than 240°C, especially 210~235°C.

In addition, if the internal temperature in all reaction stages is 210°C or higher and the reaction time when the reaction time is less than 240°C is less than 3 hours, the effect of polycarbonate resin can be suppressed. The color or heat is deteriorated to obtain a polycarbonate resin with a good hue, and the amount of the compound represented by the above formula (3) is suppressed, so it is preferable, and it is particularly preferably within 2.5 hours.

Furthermore, in order to suppress the decrease of the polymerization rate in the second half of the polymerization reaction and to minimize the deterioration caused by the thermal history, it is preferable to use the plug flow and interface renewability in the final stage of the polymerization, as shown in the above formula (3). Shows a horizontal reactor with superior compound control.

From the viewpoint of effective utilization of resources, the by-produced monohydroxy compound is preferably purified as necessary and then reused as a raw material for diphenyl carbonate, bisphenol A, and the like.

The polycarbonate resin of the present invention is polycondensed as described above, usually cooled and solidified, and pelletized by a rotary cutter or the like. The method of granulation is not limited. For example, it can be extracted from the final polymerization reactor in a molten state, and cooled and solidified in the form of strands to be granulated; and the resin is supplied to the uniaxial from the final polymerization reactor in the molten state. Or a twin-screw extruder is a method in which after melt extrusion, it is cooled and solidified and pelletized. Or it is extracted from the final polymerization reactor according to the molten state, cooled and solidified according to the strand shape, and temporarily pelletized, and then the resin is supplied to a uniaxial or biaxial extruder, and after melt extrusion, it is cooled and solidified to form pellets. The method of transformation and so on.

In the case of using an extruder, in the extruder, the residual monomers can also be degassed under reduced pressure, or the commonly known heat stabilizers, neutralizers, ultraviolet absorbers, light stabilizers, and mold release can be added and kneaded. Agents, coloring agents, antistatic agents, lubricants, lubricants, plasticizers, compatibilizers, flame retardants, etc.

The melt-kneading temperature in the extruder depends on the glass transition temperature or molecular weight of the polycarbonate resin, and is usually 200-300°C, preferably 210-280°C, more preferably 220-270°C. If the melt-kneading temperature is lower than 200℃, the polycarbonate resin The melt viscosity is high, the load on the extruder increases, and the productivity decreases. If the melt-kneading temperature is higher than 300°C, the thermal deterioration of the polycarbonate resin will be intense, resulting in a decrease in the mechanical strength or coloration due to a decrease in molecular weight, and the generation of bubbles due to gas generation during film formation.

The molecular weight of the polycarbonate resin of the present invention thus obtained can be represented by reduced viscosity. The reduction viscosity is usually 0.30 dL/g or more, preferably 0.35 dL/g or more. In addition, the upper limit of the reduction viscosity is usually 1.20 dL/g or less, preferably 1.00 dL/g or less, and more preferably 0.80 dL/g or less.

If the reduced viscosity of the polycarbonate resin is too low, there is a possibility that the mechanical strength of the molded product will be low. In addition, if the reduction viscosity is too large, the fluidity during molding decreases, and productivity or moldability tends to decrease. In addition, the reduced viscosity of the polycarbonate resin was measured using a Ubbelohde viscosity tube at a temperature of 20.0°C±0.1°C using dichloromethane as a solvent, and the concentration of the polycarbonate resin was precisely adjusted to 0.6 g/dL. The details of the method for measuring reduction viscosity are described in the example items.

[Additives for polycarbonate resins]

<Phosphorus Compounds>

The polycarbonate resin of the present invention preferably contains a phosphorus compound added to deactivate the polymerization catalyst and further suppress the coloration of the polycarbonate resin at high temperatures.

As this phosphorus compound, it is preferable to use at least one selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, phosphonic acid, phosphonate, acidic phosphate, and aliphatic cyclic phosphite. Among the above, phosphorous acid, phosphonic acid, and phosphonate are the ones with superior effects of catalyst deactivation and coloration inhibition, and phosphonate is particularly preferred.

Examples of phosphonic acid include phosphonic acid (phosphorous acid), methylphosphonic acid, and ethyl Phosphonic acid, vinylphosphonic acid, decylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, aminomethylphosphonic acid, methylene diphosphonic acid, 1-hydroxyethane-1, 1-diphosphonic acid , 4-Methoxyphenylphosphonic acid, nitrogen-based ginseng (methylene phosphonic acid), propyl phosphonic anhydride, etc.

Examples of phosphonates include dimethyl phosphonate, diethyl phosphonate, bis(2-ethylhexyl) phosphonate, dilauryl phosphonate, dioleyl phosphonate, and phosphonic acid. Diphenyl ester, dibenzyl phosphonate, dimethyl methyl phosphonate, diphenyl methyl phosphonate, diethyl ethyl phosphonate, diethyl benzyl phosphonate, phenyl Dimethyl phosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, diethyl (methoxymethyl)phosphonate, diethyl vinylphosphonate, hydroxymethyl Diethyl phosphonate, dimethyl (2-hydroxyethyl) phosphonate, diethyl p-methylbenzyl phosphonate, diethyl phosphonate, ethyl diethyl phosphonate Ester, tert-butyl diethylphosphinyl acetate, (4-chlorobenzyl) diethyl phosphonate, diethyl cyanophosphonate, diethyl cyanomethylphosphonate, 3, 5-Di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester, diethylphosphinoacetaldehyde diethyl acetal, (methylthiomethyl)phosphonic acid diethyl ester, etc.

Examples of acidic phosphates include dimethyl phosphate, diethyl phosphate, divinyl phosphate, dipropyl phosphate, dibutyl phosphate, bis(butoxyethyl) phosphate, phosphoric acid Phosphoric diesters such as bis(2-ethylhexyl) ester, diisododecyl phosphate, dioleyl phosphate, distearyl phosphate, diphenyl phosphate, dibenzyl phosphate, etc., or two A mixture of esters and monoesters, diethyl chlorophosphate, stearyl zinc phosphate, etc.

Aliphatic cyclic phosphite is defined as a phosphite compound that does not contain an aromatic group in a cyclic structure containing a phosphorus atom. For example, bis(decyl)pentaerythritol diphosphite, bis(dodecyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis(2,6-tertiary butylphenyl) pentaerythritol Diphosphite, bis(nonane Phenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol Diphosphite, hydrogenated bisphenol A‧ pentaerythritol phosphite polymer and other polymer-type compounds composed of dihydroxy compounds and pentaerythritol diphosphorous acid.

These can be used individually by 1 type, and can also mix and use 2 or more types by arbitrary combinations and ratios.

If the content of the above-mentioned phosphorus compound is too small, the effect of catalyst deactivation or coloring inhibition is insufficient. In addition, if the content of the above-mentioned phosphorus compound is too large, the polycarbonate resin may be colored or colored under moist heat conditions. Therefore, the content of the phosphorus-based compound is not particularly limited, and based on the content of phosphorus atoms in the polycarbonate resin, it is preferably 0.02 wt ppm or more and 0.7 wt ppm or less, more preferably 0.05 wt ppm or more and 0.65 wt ppm or less, It is particularly preferably 0.07 wt ppm or more and 0.60 wt ppm or less.

The above-mentioned phosphorus-based compounds usually use phosphorus trichloride as the starting material, so there may be cases where chlorine-containing components from unreacted or desorbed hydrochloric acid remain. Preferably, the amount of chlorine atoms contained in the above-mentioned phosphorus-based compounds It is 5% by weight or less. If the residual amount of chlorine atoms is large, it may corrode the metal parts of the manufacturing equipment where the above-mentioned phosphorus compounds are added, or reduce the thermal stability of the polycarbonate resin, or promote coloring or reduce the molecular weight due to thermal degradation. Yu.

The above-mentioned phosphorus-based compound is as described above, and it is preferable to use an extruder to add and knead the polycarbonate resin. Especially after the polycarbonate resin is polymerized, it is directly supplied to the extruder in a molten state, and the above-mentioned phosphorus-based compound is added to the resin immediately is the most effective. Furthermore, if the degassing treatment is carried out with a vacuum exhaust port through an extruder in a state in which the catalyst is inactivated, the low-molecular components can be efficiently degassed and removed.

<Hindered Phenolic Compounds>

The polycarbonate resin of the present invention contains a hindered phenol compound in addition to the above-mentioned phosphorus compound, and further improvement of the color tone of the polycarbonate resin can be expected.

Specific examples of hindered phenol compounds include 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4-methoxyphenol, and 2-tert-butylphenol. Butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,5-di Tributylhydroquinone, n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 2-tert-butyl-6-(3'- Tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylpropyl acrylate, 2,2'-methylene-bis-(4-methyl-6-tert-butyl) Phenol), 2,2'-methylene-bis-(6-cyclohexyl-4-methylphenol), 2,2'-ethylene-bis-(2,4-di-tert-butylphenol) ), Si-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate]-methane, n-octadecyl-3-(3',5 '-Di-tert-butyl-4'-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-gin-(3,5-di-tert-butyl-4- Hydroxybenzyl)benzene, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentanediol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid Esters] etc.

These can be used individually by 1 type, and 2 or more types can also be mixed and used by arbitrary combinations and ratios.

The content of the hindered phenol compound in the polycarbonate resin of the present invention is based on 100 parts by weight of the polycarbonate resin, preferably 0.001 part by weight to 1 part by weight, more preferably 0.005 part by weight to 0.5 part by weight, and more More preferably, it is 0.01 part by weight to 0.3 part by weight.

In addition, as for the hindered phenol compound or the following antioxidants, it is preferable to add and knead the polycarbonate resin using an extruder similarly to the phosphorus compound.

<Antioxidant>

In the polycarbonate resin of the present invention, for the purpose of anti-oxidation, commonly known antioxidants can also be added.

Specific examples of antioxidants include triphenyl phosphite, ginseng (nonylphenyl) phosphite, ginseng (2,4-di-tert-butylphenyl) phosphite, and tridecyl phosphite. , Trioctyl phosphite, tris(octadecyl) phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, Monobutyl diphenyl phosphate, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylene bis (4,6-di-tertiary butyl benzene) phosphite Base) octyl phosphite, ginseng (2,4-di-tert-butylphenyl) phosphate, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphosphate Phenyl mono-ortho-biphenyl ester, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4'-biphenyl diphosphonic acid (2,4-di-third butyl) Phenyl) ester, pentaerythritol 4 (3-mercaptopropionate), pentaerythritol 4 (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, N,N-hexamethylene Bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamate), ginseng (3,5-di-tert-butyl-4-hydroxybenzyl) trimeric isocyanate, 4,4'-extension Biphenyl diphosphonate (2,4-di-tertiary butyl phenyl) ester, 3,9-bis{1,1-dimethyl-2-[β-(3-tertiary butyl-4) -Hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxspiro(5,5)undecane and the like.

These antioxidants may be used individually by 1 type, and may use 2 or more types together.

The blending amount of these antioxidants is when the polycarbonate resin is set to 100 parts by weight, preferably 0.0001 parts by weight to 0.1 parts by weight, more preferably 0.0005 parts by weight to 0.08 parts by weight, still more preferably 0.001 parts by weight to 0.05 parts by weight Parts by weight.

<Blue Dye>

The polycarbonate resin of the present invention may also contain a blue dye.

The blue dye used in the present invention is appropriately selected from the blue dye used in the usual polycarbonate resin composition, and can be used by adjusting the blending amount, and multiple blue dyes may also be used.

The content of the blue dye in the polycarbonate resin is usually 100 parts by weight of the polycarbonate resin (A), preferably 0.1×10 ^-4 to 10.0×10 ^-4 parts by weight, more preferably 0.3× 10 ^-4 to 5.0×10 ^-4 parts by weight, particularly preferably 0.3×10 ^-4 to 2.0×10 ^-4 parts by weight.

If the content of the blue dye is 0.1×10 ^-4 parts by weight or more, it is easy to set the YI value before and after the accelerated light resistance test of the polycarbonate resin sheet of the present invention into a specific range, or it is easy to make the b* value 3 or less. So better. On the other hand, if the content of the blue dye is 10.0×10 ^-4 parts by weight or less, since the lightness does not decrease, it is easy to make the L* value 90 or more, which is preferable.

As the blue dye used in the present invention, a polycarbonate resin composition is suitable for users. From the viewpoint of absorption wavelength, it is preferable to use a dye with a maximum absorption wavelength of 520 to 600 nm, more preferably 540 to 580 nm.

Specific examples of anthraquinone blue dyes that can be preferably used in the present invention include: general name Solvent Violet 13 [CA. No (color index No) 60725; brand name "Macrolex Violet B" manufactured by LANXESS Corporation, Mitsubishi Chemical "Diaresin Blue G" manufactured by Sumitomo Chemical Industries, Ltd., "Sumiplast Violet B" manufactured by Sumitomo Chemical Industries Co., Ltd.], Solvent Violet 14, generic name Solvent Violet 31 [CA.No 68210; brand name "Diaresin Violet" manufactured by Mitsubishi Chemical D"], Solvent Violet 33 [CA.No 60725; brand name "Diaresin Blue J" manufactured by Mitsubishi Chemical Co., Ltd.], Solvent Violet 36 [CA.No 68210; brand name "Macrolex Violet 3R" manufactured by LANXESS], Solvent Blue 45[CA.No 61110; brand name "Tetrazole Blue" manufactured by Sandoz RLS"], general name Solvent Blue 94 [CA.No 61500; brand name "Diaresin Blue N" manufactured by Mitsubishi Chemical Co., Ltd.], general name Solvent Blue 97 [manufactured by LANXESS "Macrolex Blue RR"], general name Solvent Blue 45. The general name is Solvent Blue 87 and the general name is Disperse Violet 28.

Among these, the general name Solvent Violet 13 [LANXESS company "Macrolex Violet B"], the general name Solvent Violet 36 [LANXESS company "Macrolex Violet 3R"], and the general name Solvent Blue 97 [LANXESS company "" Macrolex Blue RR"], more preferably the general name Solvent Violet 13 ["Macrolex Violet B" made by LANXESS].

Among them, the dye with the structure shown in the following formula (11) is preferred, that is, the general name Solvent Violet 13 [CA. No (color index No) 60725; the brand name "Macrolex Violet B" manufactured by LANXESS Corporation and Mitsubishi Chemical (stocks) ) "Diaresin Blue G" and "Sumiplast Violet B" manufactured by Sumitomo Chemical Industry Co., Ltd.

[化12]

In addition, as a blue dye in the present invention, a pigment with a maximum absorption wavelength of preferably 520 to 600 nm, more preferably 540 to 580 nm can be used, and the above-mentioned dyes and pigments can also be used in combination.

In the present invention, one type of blue dye can be used alone, or two or more types can be used in combination. However, the amount of blue dye is preferably less, and the type of blue dye used is also preferably less.

In the present invention, the above-mentioned blue dye formulated in polycarbonate resin (A) The preparation period and method of preparation are not particularly limited. As the preparation time, for example: the method of adding together with the raw materials before the polymerization reaction and directly performing polymerization; the method of preparing the mixture by pipe or extruder at the end of the polymerization reaction; and the method of mixing the polycarbonate resin with other preparation agents. The method of blending during melt kneading, etc. After the polymerization reaction is completed, it is preferable to perform melt kneading and blending, since the blue dye can be well dispersed and the adjustment of b* value and L* value can be easily achieved. In particular, the method of directly introducing into an extruder in a molten state after the completion of the polycondensation reaction, blending a blue dye, and performing melt kneading is preferable because the influence of heat history or oxygen mixing can be suppressed to a minimum.

<Ultraviolet Absorber>

The ultraviolet absorber used in the present invention has the specific physical properties of the present invention, and is not limited as long as it absorbs light in the ultraviolet wavelength region.

The melting point of the ultraviolet absorber used in the present invention is 135°C or higher. Furthermore, it is preferably 140°C or higher, more preferably 145°C or higher.

In addition, the melting point of the ultraviolet absorber used in the present invention is less than 300°C. Furthermore, it is preferably 290°C or lower, more preferably 280°C or lower.

With the melting point within this range, roll fouling or adhesion to the T-die can be reduced during extrusion film formation, and the film has a good appearance. At the same time, when the ultraviolet absorber is kneaded by the extrusion kneader, since the particles of the ultraviolet absorber are completely melted and uniformly dispersed, the appearance of the film from the ultraviolet absorber particles can be prevented from being bad.

The 5% weight reduction temperature of the ultraviolet absorber used in the present invention is higher than 240°C. Furthermore, it is preferably higher than 245°C, more preferably higher than 250°C. With this range, the ultraviolet absorber can be prevented from decomposing during melt kneading. In this way, not only can the ability of the ultraviolet absorber be fully utilized, but it can also prevent the decomposition products from accumulating in the discharge outlet of the extrusion. It prevents continuous operation, or decomposes accumulation in T-shaped molds or rolls, and damages the appearance of the film.

In the present invention, the ultraviolet absorber system contains more than 0.45 parts by weight with respect to 100 parts by weight of the polycarbonate resin. Moreover, it is preferable to contain more than 0.47 part by weight, and more preferably to contain more than 0.5 part by weight.

With this range, the target penetration rate in the ultraviolet region can be maintained, and the desired effect can be obtained.

In addition, the ultraviolet absorber is contained at 7 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin. Moreover, it is preferable to contain 5 parts by weight or less, and it is more preferable to contain 3 parts by weight or less. With this range, not only can the appearance of the film due to roll contamination be prevented, but also the increase of foreign matter caused by the aggregation of the ultraviolet absorber can be prevented.

If the ultraviolet absorber is attached to the roller, the unevenness is transferred to the film using the attached matter as a starting point, and the uniformity of the film thickness cannot be maintained, resulting in uneven thickness or uneven retardation of the resulting film. As for the thickness accuracy of the film, the preferable thickness accuracy in the width direction varies depending on the physical properties required by various applications, and is usually within ±10%, preferably within ±5%, and particularly preferably within ±3%.

In addition, when the melting point of the ultraviolet absorber is within the above-mentioned range or the addition amount is within the above-mentioned range, the glass transition temperature of the polycarbonate resin composition is not significantly lowered after the addition of the ultraviolet absorber, and heat resistance can be maintained. The glass transition temperature of the composition is within 7°C, preferably within 5°C, and more preferably within 3°C relative to the glass transition temperature of polycarbonate resin without UV absorber.

系、二苯基酮系、苯并三唑系、喹啉酮系、苯甲酸酯系、氰基丙烯酸酯系、苯并

唑系等。 As a preferable ultraviolet absorber, for example, three

Series, benzophenone series, benzotriazole series, quinolinone series, benzoate series, cyanoacrylate series, benzotriazole series

Azole series and so on.

系紫外線吸收劑) (three

(UV absorber)

系紫外線吸收劑，可舉例如2,4-二苯基-6-(2-羥基-4-甲氧基苯基)-1,3,5-三

、2,4-二苯基-6-(2-羥基-4-乙氧基苯基)-1,3,5-三

、2,4-二苯基-(2-羥基-4-丙氧基苯基)-1,3,5-三

、2,4-二苯基-(2-羥基-4-丁氧基苯基)-1,3,5-三

、2,4-二苯基-6-(2-羥基-4-丁氧基苯基)-1,3,5-三

、2,6-二苯基-4-(2-羥基-4-己氧基苯基)-1,3,5-三

、2,4-二苯基-6-(2-羥基-4-辛氧基苯基)-1,3,5-三

、2,4-二苯基-6-(2-羥基-4-癸氧基苯基)-1,3,5-三

、2,4-二苯基-6-(2-羥基-4-苄氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-4-丙氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-4-丁氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-4-丁氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-4-己氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-4-辛氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-4-十二烷氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-4-苄氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-4-乙氧基乙氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-4-丁氧基乙氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-4-丙氧基乙氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-4-甲氧基羰基丙氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-4-乙氧基羰基乙氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-4-(1-(2-乙氧基己氧基)-1-側氧丙烷-2-基氧基)苯基)-1,3,5-三

、2,4,6-參(2-羥基-3-甲基-4-乙氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-3-甲基-4-丙氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-3-甲基-4-丁氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-3-甲基-4-丁氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-3-甲基-4-己氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-3-甲基-4-辛氧基苯基)-1,3,5- 三

、2,4,6-參(2-羥基-3-甲基-4-十二烷氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-3-甲基-4-苄氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-3-甲基-4-乙氧基乙氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-3-甲基-4-丁氧基乙氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-3-甲基-4-丙氧基乙氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-3-甲基-4-甲氧基羰基丙氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-3-甲基-4-乙氧基羰基乙氧基苯基)-1,3,5-三

、2,4,6-參(2-羥基-3-甲基-4-(1-(2-乙氧基己氧基)-1-側氧丙烷-2-基氧基)苯基)-1,3,5-三

、2,4-雙(2,4-二甲基苯基)-6-(2-羥基-4-N-辛氧基苯基)-1,3,5-三

、2-(4,6-二苯基-1,3,5-三

-2-基)-5-(2-(2-乙基己醯氧基)乙氧基)酚等。 As three

UV absorbers, such as 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-tri

, 2,4-Diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3,5-tri

, 2,4-Diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-tri

, 2,4-Diphenyl-(2-hydroxy-4-butoxyphenyl)-1,3,5-tri

, 2,4-Diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-tri

, 2,6-Diphenyl-4-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-tri

, 2,4-Diphenyl-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-tri

, 2,4-Diphenyl-6-(2-hydroxy-4-decyloxyphenyl)-1,3,5-tri

, 2,4-Diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-tri

, 2,4,6-Shen (2-hydroxy-4-propoxyphenyl)-1,3,5-tri

, 2,4,6-Shen (2-hydroxy-4-butoxyphenyl)-1,3,5-tri

, 2,4,6-Shen (2-hydroxy-4-butoxyphenyl)-1,3,5-tri

, 2,4,6-Shen (2-hydroxy-4-hexyloxyphenyl)-1,3,5-tri

, 2,4,6-Shen (2-hydroxy-4-octyloxyphenyl)-1,3,5-tri

, 2,4,6-Gins (2-hydroxy-4-dodecyloxyphenyl)-1,3,5-tri

, 2,4,6-Shen (2-hydroxy-4-benzyloxyphenyl)-1,3,5-tri

, 2,4,6-Ginseng (2-hydroxy-4-ethoxyethoxyphenyl)-1,3,5-tri

, 2,4,6-Shen (2-hydroxy-4-butoxyethoxyphenyl)-1,3,5-tri

, 2,4,6-Gins (2-hydroxy-4-propoxyethoxyphenyl)-1,3,5-tri

, 2,4,6-Ginseng (2-hydroxy-4-methoxycarbonylpropoxyphenyl)-1,3,5-tri

, 2,4,6-Ginseng (2-hydroxy-4-ethoxycarbonylethoxyphenyl)-1,3,5-tri

, 2,4,6-Shen (2-hydroxy-4-(1-(2-ethoxyhexyloxy)-1-oxopropan-2-yloxy)phenyl)-1,3,5 -three

, 2,4,6-Shen (2-hydroxy-3-methyl-4-ethoxyphenyl)-1,3,5-tri

, 2,4,6-Shen (2-hydroxy-3-methyl-4-propoxyphenyl)-1,3,5-tri

, 2,4,6-Ginseng (2-hydroxy-3-methyl-4-butoxyphenyl)-1,3,5-tri

, 2,4,6-Ginseng (2-hydroxy-3-methyl-4-butoxyphenyl)-1,3,5-tri

, 2,4,6-Shen (2-hydroxy-3-methyl-4-hexyloxyphenyl)-1,3,5-tri

, 2,4,6-Ginseng (2-hydroxy-3-methyl-4-octyloxyphenyl)-1,3,5-tri

, 2,4,6-Gins (2-hydroxy-3-methyl-4-dodecyloxyphenyl)-1,3,5-tri

, 2,4,6-Shen (2-hydroxy-3-methyl-4-benzyloxyphenyl)-1,3,5-tri

, 2,4,6-Shen (2-hydroxy-3-methyl-4-ethoxyethoxyphenyl)-1,3,5-tri

, 2,4,6-Shen (2-hydroxy-3-methyl-4-butoxyethoxyphenyl)-1,3,5-tri

, 2,4,6-Ginseng (2-hydroxy-3-methyl-4-propoxyethoxyphenyl)-1,3,5-tri

, 2,4,6-Shen (2-hydroxy-3-methyl-4-methoxycarbonylpropoxyphenyl)-1,3,5-tri

, 2,4,6-Shen (2-hydroxy-3-methyl-4-ethoxycarbonylethoxyphenyl)-1,3,5-tri

, 2,4,6-Shen (2-hydroxy-3-methyl-4-(1-(2-ethoxyhexyloxy)-1-oxopropan-2-yloxy)phenyl)- 1,3,5-Three

, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-N-octyloxyphenyl)-1,3,5-tri

, 2-(4,6-diphenyl-1,3,5-tri

-2-yl)-5-(2-(2-ethylhexyloxy)ethoxy)phenol and the like.

(CHEMIPRO化成(股)製「Kemisorb 102」)、2,4,6-參(2-羥基-3-甲基-4-己氧基苯基)-1,3,5-三

(ADEKA(股)製「ADK STAB LA-F70」)、2-(4,6-二苯基-1,3,5-三

-2-基)-5-(2-(2-乙基己醯氧基)乙氧基)酚(ADEKA(股)製「ADK STAB LA-46」)、2,4-二苯基-6-(2-羥基-4-己氧基苯基)-1,3,5-三

(BASF JAPAN(股)製「TINUVIN 1577」)。 Among them, as a commercially available product, for example, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-N-octyloxyphenyl)-1,3,5 -three

(Kemisorb 102 manufactured by CHEMIPRO Chemicals Co., Ltd.), 2,4,6-ginseng (2-hydroxy-3-methyl-4-hexyloxyphenyl)-1,3,5-tri

(ADK STAB LA-F70 manufactured by ADEKA Co., Ltd.), 2-(4,6-diphenyl-1,3,5-tri

-2-yl)-5-(2-(2-ethylhexyloxy)ethoxy)phenol (ADK STAB LA-46 manufactured by ADEKA Co., Ltd.), 2,4-diphenyl-6 -(2-Hydroxy-4-hexyloxyphenyl)-1,3,5-tri

(BASF JAPAN (stock) system "TINUVIN 1577").

(Diphenylketone UV absorber)

Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-octyloxydiphenyl ketone. Ketone, 2-hydroxy-4-benzyloxy diphenyl ketone, 2-hydroxy-4-methoxy-5-sulfonyl diphenyl ketone, 2-hydroxy-4-methoxy-5-sulfonyl ketone Diphenyl ketone trihydrate, 2-hydroxy-4-dodecyloxy-diphenyl ketone, 2-hydroxy-4-octadecyloxy-diphenyl ketone, 2,2'-dihydroxy -4-Methoxydiphenyl Ketone, 2,2',4,4'-tetrahydroxydiphenyl ketone, 2,2'-dihydroxy-4,4'-dimethoxydiphenyl ketone, 2,2'-dihydroxy-4 , 4'-Dimethoxy-5-sulfonyl diphenyl ketone sodium, bis(5-benzyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-n Dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 4,4'-bis(diethylamino)benzophenone, etc.

Among them, examples of commercially available products include 2,2',4,4'-tetrahydroxydiphenyl ketone (Shipro Chemicals Co., Ltd. "Seesorb 106", BASF Japan (Stock) "Uvinul 3050"), 2 ,2'-Dihydroxy-4,4'-Dimethoxybenzophenone (Shipro Chemicals Co., Ltd. "Seesorb 107", BASF Japan Co., Ltd. "Uvinul 3049").

(Benzotriazole-based ultraviolet absorber)

Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-3',2-(2' -Hydroxy-3'-tertiary butyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 5'-bis( α,α-Dimethylbenzyl)phenyl)-benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole, 2-( 2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylbenzene Yl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-third pentyl)-benzotriazole, 2-(2'-hydroxy-3',5' -Ditertiary pentylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-(3",4",5",6"-tetrahydrophthaliminomethyl )-5'-methylphenyl)benzotriazole, 2-(2-hydroxy-3,5-ditertiary amylphenyl), 2-(2'-hydroxy-5'-tertiary octyl) Phenyl)benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl) Phenol] etc.

Among them, as a commercially available product, for example, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2- Phenol) (ADK STAB LA-31 manufactured by ADEKA Co., Ltd., Kemisorb 279 manufactured by CHEMIPRO Chemical Co., Ltd.), 2-(2'-hydroxy-5'-tertiary octylphenyl) benzo Triazole (Seesorb 709, manufactured by SHIPRO Chemical Co., Ltd.).

(Indole UV absorber)

As the indole-based ultraviolet absorber, a compound represented by the following formula (12) can be used, for example, 2-[(1-methyl-2-phenyl-1H-indol-3-yl)methylene] Propane dinitrile (“BONASORB UA-3901” manufactured by ORIENT Chemical Industry Co., Ltd.), etc.

[化13]

In the above formula (12), R ₁ to R ₃ represent optional substituents. Wherein, R ₂ and R ₃ may be substituted at one or a plurality of positions. In the case of substitution at a plurality of positions, each substituent may be the same or different.

(Quinolinone UV absorber)

As the quinolinone-based ultraviolet absorber, a compound represented by the following formula (13) can be used, for example 4-hydroxy-3-[(phenylimino)methyl]-2(1H)-quinoline Ketone ("BONASORB UA-3701" manufactured by ORIENT Chemical Industry Co., Ltd.), etc.

[化14]

In the above formula (13), R ₄ to R ₆ represent optional substituents. Wherein, R ₅ and R ₆ may be substituted at one place or plural places. In the case of substitution at plural places, each substituent may be the same or different.

(Benzoic acid ester-based ultraviolet absorber)

Examples of benzoate-based ultraviolet absorbers include 2,4-di-tert-butylphenyl-3',5'-di-tert-butyl-4'-hydroxybenzoate, 2,6- Di-tert-butylphenyl-3',5'-di-tert-butyl-4'-hydroxybenzoic acid ester, n-hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoic acid Esters, n-octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc. These benzoate-based ultraviolet absorbers can be used as ultraviolet absorbers.

(Cyanoacrylate-based ultraviolet absorber)

Examples of cyanoacrylate-based ultraviolet absorbers include 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3-(3',4 '-Methylenedioxyphenyl)-acrylate and the like. These cyanoacrylate-based ultraviolet absorbers can be used as ultraviolet absorbers.

In the present invention, the ultraviolet absorber may be used singly or in combination of two or more kinds.

系、苯并三唑系、喹啉酮系、吲哚系。 Among them, from the viewpoint of thermal stability or less coloration to the resin, three

Series, benzotriazole series, quinolinone series, indole series.

(Other UV absorbers)

唑系之2,5-雙(5-第三丁基-2-苯并

唑基)噻吩(BASF Japan(股)「TINOPAL OB」)、4,4'-雙(2-苯并

唑基)二苯乙烯等。其中，較佳為苯并

唑系。 In addition to the above-mentioned ultraviolet absorbers, fluorescent whitening agents may also be used as ultraviolet absorbers. For example, 7-(dimethylamino)-4-methylcoumarin, or belongs to benzo

The 2,5-bis(5-tert-butyl-2-benzo

Azolyl)thiophene (BASF Japan (Stock) ``TINOPAL OB''), 4,4'-bis(2-benzo

Azolyl) stilbene and the like. Among them, benzo

Azole series.

[Polycarbonate resin composition]

The polycarbonate resin composition of the present invention can also be combined with, for example, aromatic polycarbonate resin, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, ABS One or two or more of synthetic resins such as, AS, biodegradable resins such as polylactic acid, polytetramethylene succinate, and rubber are kneaded to form a polymer blend for use.

Furthermore, the polycarbonate resin used in the present invention can also be added with these other resin components together with nucleating agents, flame retardants, flame retardant additives, inorganic fillers, impact modifiers, etc. commonly used in resin compositions. Hydrolysis inhibitors, foaming agents, dyes and pigments are used to make polycarbonate resin compositions.

[Manufacturing method of polycarbonate resin extrusion molded product]

<Manufacturing method>

The polycarbonate resin film of the present invention is a film obtained by molding a resin composition containing the polycarbonate resin used in the present invention, an ultraviolet absorber, and other additives as necessary, according to a conventional method. The manufacturing method of the polycarbonate resin film is preferably a melt extrusion molding method such as a T-die molding method or an inflation molding method, and particularly preferably a T-die molding method.

When the polycarbonate resin film of the present invention is located on the front or back of the image display device, the displayed image must not be damaged due to defects, strains, etc. and cannot be recognized. Therefore, it is required that when filming by the melt extrusion molding method, there are few defects of foreign matter from the resin such as gels, bubbles, black spots, and uniform thickness in the width direction without optical strain such as local retardation.

The resin temperature during melt extrusion molding is usually in the range of 150 to 265°C, preferably 200 to 260°C, particularly preferably 210 to 250°C. When the temperature is lower than the above-mentioned temperature, the melt viscosity is too high and the extrusion load tends to be high. On the other hand, if it is higher than the above temperature When the temperature is higher, at least the polycarbonate resin in the resin composition starts to thermally decompose, and deterioration such as coloration or viscosity reduction occurs.

In addition to controlling the resin temperature to a melt viscosity suitable for molding, the resin extrusion can be rectified by feedback control of the discharge amount of the raw material feeder, the number of screw rotations of the extruder, and the amount of liquid delivered by the gear pump. Improve the accuracy of film thickness. The preferred thickness accuracy in the width direction varies depending on the physical properties required for each application, and is usually within ±10%, preferably within ±5%, particularly preferably within ±3%.

The thickness measurement in the width direction is in the case of a horizontal continuous thickness measuring machine in a continuous film production line, and evaluation is performed at each point of the measurement. In the case of off-line measurement by cutting the film, it is evaluated by using a dial thickness gauge equal to the measurement point at an interval of 50 mm in the width direction. Here, the both ends of the extruded film became thick due to necking or the like, so it was cut and the wide-direction range where the discarded part was removed was evaluated.

The temperature of the cooling roll is relative to the glass transition temperature (Tg) of the polycarbonate resin composition, preferably Tg-100°C~Tg+50°C, more preferably Tg-80°C~Tg+40°C, particularly preferably Tg-60 ℃~Tg+30℃. More specifically, the temperature of the cooling roll is preferably 20 to 170°C, more preferably 40 to 160°C, particularly preferably 60 to 150°C.

When the temperature of the cooling roll is lower than the above temperature, gear wear marks on the surface of the film or localized optical strain unevenness become significant. On the other hand, when the temperature is higher than the above-mentioned temperature, the extruded film is not easily peeled off by the cooling roll, and there is a tendency for peeling marks to occur or to contaminate the roll.

In addition, the polycarbonate resin film of the present invention may be a stretched film, or may be used as a retardation film by stretching in at least one direction.

The extension method can use various extension methods such as free end extension, fixed end extension, free end contraction, fixed end contraction, etc., and can also be used simultaneously or successively. Also, about The stretching method can be performed in various directions or dimensions such as the horizontal direction, the vertical direction, the thickness direction, and the diagonal direction, and is not particularly limited. Preferably, for example, the horizontal uniaxial stretching direction, the vertical and horizontal simultaneous biaxial stretching method, the vertical and horizontal sequential biaxial stretching direction, etc. are mentioned.

As the stretching means, a tenter stretching machine, a biaxial stretching machine, or any appropriate stretching machine can be used.

The extension temperature depends on the purpose, and an appropriate and suitable value can be selected. Preferably, it is based on the glass transition temperature (Tg) relative to the original film (that is, the polycarbonate or resin composition of the present invention, which is the film-forming material of the original film), at Tg-20°C~Tg+30°C, Preferably, the range of Tg-10°C~Tg+20°C, more preferably Tg-5°C~Tg+10°C is extended. By selecting such conditions, the retardation value can be made uniform, and the film is not easy to become cloudy. Specifically, the stretching temperature is 90°C to 210°C, preferably 100°C to 200°C, particularly preferably 100°C to 180°C.

The stretching magnification is appropriately selected depending on the purpose. When it is not stretched, it is set to 1 time, preferably 1.1 times or more and 6 times or less, more preferably 1.5 times or more and 4 times or less, and more preferably 1.8 times or more and 3 times or less , Especially good 2 times or more and 2.5 times or less.

If the stretch magnification is too large, not only may it cause breakage during stretching, but also may reduce the effect of inhibiting changes in optical characteristics caused by long-term use under high temperature conditions; if it is too low, it may be below the required thickness The possibility of not being able to impart the optical properties of the target.

The extension speed is also selected appropriately according to the purpose. The strain speed shown in the following formula is usually 50%~2000%, preferably 100%~1500%, more preferably 200%~1000%, particularly preferably 250%~500%. If the extension speed is too high, it may cause breakage during extension, or large changes in optical characteristics caused by long-term use under high temperature conditions. In addition, if the extension speed is too low, not only the productivity will be reduced, but also in order to obtain the required phase difference. When the extension ratio must be increased excessively.

Strain speed (%/min)=(extension speed (mm/min)/length of original film (mm))×100

In addition, after stretching, a heating furnace can be used for heat fixation, or the width of the tenter can be controlled, or the roll peripheral speed can be adjusted to perform a relaxation step.

With this treatment, it is possible to suppress changes in optical characteristics caused by long-term use under high temperature conditions.

The film of the present invention can be produced by appropriately selecting and adjusting the processing conditions in this stretching step.

The upper limit of the thickness of the film of the present invention is 120 μm or less. It is preferably 50 μm or less, more preferably 30 μm or less. With the upper limit of the film thickness being within this range, it is more efficient because it is possible to produce a thin film of the same area with less film-forming materials. Furthermore, the thickness of the product using the film can be maintained to be relatively thin, while the uniformity can be controlled, and it can be used for machines that require precision, thinness, and homogeneity.

On the other hand, the lower limit of the thickness of the film of the present invention is 5 μm or more. It is preferably 10 μm or more. If the film thickness is too thin, film handling becomes extremely difficult, wrinkles may occur during production, or it may be difficult to adhere to other films or sheets such as protective films. This problem can be solved by setting the lower limit of the thickness of the film of the present invention within this range.

The film of the present invention can be used as a polarizer protective film, and can also be subjected to hard coating or anti-reflection treatment, or treatment for the purpose of anti-sticking, non-diffusion or anti-glare, or corona discharge treatment before bonding, Ultraviolet irradiation treatment or the like is used as surface treatment.

The lower limit of the light transmittance at a wavelength of 380 nm of the film of the present invention is 0.001% or more. Preferably 0.005% or more, more preferably 0.008% or more, still more preferably 0.01% the above. If the transmittance is too low, the content of the ultraviolet absorber will inevitably increase, which may cause poor film appearance.

In addition, the upper limit of the light transmittance at a wavelength of 380 nm of the film of the present invention is 15% or less. It is preferably 8% or less, more preferably 1% or less, still more preferably 0.1% or less. If the transmittance is too high, when used in a polarizer protective film, the polarizer may be degraded by ultraviolet rays.

When the film of the present invention is used as a retardation film, the in-plane retardation at 548 nm is preferably 100 nm or more, more preferably 110 nm or more, and still more preferably 120 nm or more.

Furthermore, it is preferably 200 nm or less, more preferably 180 nm or less, and still more preferably 160 nm or less. With the in-plane phase difference within this range, the image quality of the polarizing plate or image display device obtained by using the present invention is extremely clear and good. Specifically, if the polarizing plate or the image display device obtained by using the present invention is observed through polarized sunglasses, rainbow patterns caused by changes in the visual angle are also less likely to occur.

<Foreign body of film>

The occurrence of film foreign matter not only impairs the quality of the film, but also is not good from the viewpoint of film productivity. In order to reduce film foreign matter, as described above, it is particularly effective to reduce the content of specific compounds in the resin composition, to prevent the occurrence of unmelted materials during melt kneading or the occurrence of film forming roll contamination caused by bleeding during film formation.

Regarding the foreign matter in the film, it is evaluated by the method described below, preferably 15 pieces/m ² or less, more preferably 10 pieces/m ² or less, even more preferably 5 pieces/m ² or less, particularly ^{preferably 3 pieces/m 2} or less . In the case of foreign matter exceeding this value, it will not only damage the appearance of the film, but also significantly affect the optical properties of the film.

[Example]

Hereinafter, the present invention will be explained in more detail with examples. However, the present invention is not limited to the following examples without exceeding its gist.

[Evaluation method]

Hereinafter, the physical properties or characteristics of the polycarbonate resin were evaluated by the following methods.

(1) Determination of reduction viscosity

A sample of polycarbonate resin was dissolved in dichloromethane to prepare a polycarbonate resin solution with a concentration of 0.6 g/dL. The Ubbelohde viscosity tube manufactured by Moriyu Physics and Chemical Industry Co., Ltd. is used for measurement at a temperature of 20.0℃±0.1℃. The _{relative viscosity η rel is obtained from the passage time t 0 of the} solvent and the passage time t of the solution by the following formula (i), and the relative viscosity η _rel uses the following formula (ii) to obtain the viscosity ratio η _sp .

η _rel = t/t ₀ ... (i)

η _sp =(η-η ₀ )/η ₀ =η _rel -1...(ii)

Divide the specific viscosity η _sp by the concentration c (g/dL) to obtain the reduced viscosity η _sp /c. The higher the value, the greater the molecular weight. The greater the reduction viscosity value, the better the mechanical strength of the film can be obtained.

(2) Ultraviolet transmittance of 380nm

The light transmittance at a wavelength of 380nm is measured in accordance with JISK0115 (2004) (General Rules for Absorbance Analysis), using an ultraviolet-visible spectrophotometer (U2900 manufactured by High-Technologies, Japan).

(3) 5% weight reduction temperature

Using TG-DTA6300 (manufactured by Seiko) under nitrogen (flow 200ml/min), Approximately 10 mg of the sample was heated from room temperature to 500°C at 10°C/min, and the measurement was performed to determine the 5% weight loss temperature.

(4) Melting point

The measurement was performed using a differential scanning calorimeter (DSC6220 manufactured by SII Nano Technology). Put about 10 mg of the sample into an aluminum pan made by the same company and seal it. Under a nitrogen flow of 50 mL/min, the temperature is raised from room temperature to 400°C at a heating rate of 10°C/min. The apex temperature of the melting peak is obtained as the melting point.

(5) Glass transition temperature (Tg) of polycarbonate resin

The glass transition temperature of the polycarbonate resin was measured using a differential scanning calorimeter (DSC6220 manufactured by SII Nano Technology). Put about 10 mg of the polycarbonate resin sample into an aluminum pan made by the same company and seal it. Under a nitrogen flow of 50 mL/min, the temperature is raised from room temperature to 250°C at a temperature rise rate of 20°C/min. After keeping the temperature for 3 minutes, cool to 0°C at a rate of 20°C/min. Keep it at 0°C for 3 minutes, and then increase the temperature to 200°C at a rate of 20°C/min. Based on the DSC data obtained from the second temperature increase, the start temperature of the extrapolation glass transition is used.

(6) Determination of the content of phenol and the compound represented by formula (3)

After weighing approximately 1 g of the polycarbonate resin sample and dissolving it in 5 mL of dichloromethane to make a solution, acetone was added to make the total amount to 25 mL, and the reprecipitation treatment was performed. Next, the treatment liquid was filtered with a 0.2 μm disc filter and quantified by liquid chromatography.

[化15]

(7) Film forming and roll fouling evaluation

2kg/Hr in the gel counter FSA film inspection line made by OCS Company (roller setting temperature: 240℃, T-shaped mold (width 150mm, setting temperature: 240℃), cooling roller (setting temperature: 105℃)) The thickness of the film is formed, and the presence or absence of roller contamination is judged based on the following criteria.

Dirty rollers can be visually confirmed for more than 0 minutes but less than 15 minutes: ××

It can be visually confirmed that the roller is dirty in more than 15 minutes but less than 30 minutes: ×

Dirty rollers can be visually confirmed in more than 30 minutes but less than 60 minutes: △-

Dirty rollers can be visually confirmed for more than 60 minutes but less than 90 minutes: △

Dirty rollers can be visually confirmed for more than 90 minutes but less than 120 minutes: ○-

Dirty rollers can be visually confirmed for more than 120 minutes but less than 150 minutes: ○

Dirty rollers can be visually confirmed for more than 150 minutes but less than 180 minutes: ◎

(8) Film thickness and thickness accuracy

In the part about 10m from the beginning of the film, a contact thickness meter (manufactured by Ono Sokki Co., Ltd., product name "Digital Linear Gauge DG-933") is used for a range of 30 mm in the width direction from the center of the film at 10 mm intervals in the TD direction. ") Measure the thickness of the film. Here, the term "film thickness" in the present invention refers to the calculation of the total average of the above-mentioned measured values. In addition, the value obtained from the following formula is regarded as the "thickness accuracy" of the present invention.

Thickness accuracy (%)={(Maximum deviation from film thickness)/(film thickness)}×100

(The "maximum deviation from the film thickness" in the formula refers to the maximum value of the difference between the above-mentioned measured values and the average value (film thickness).)

The smaller the value of the thickness accuracy, the more uniform the thickness of the film.

(9) Film foreign body

For a sample with a width of 50 mm and a length of 200 mm cut out from the obtained film, the number of foreign objects with a diameter (in the case of an ellipse circle, the long diameter) 150 μm or more in the sample was visually calculated. The smaller the number of foreign substances, the more advantageous the film is when it is used in, for example, an optical film.

[Used raw materials]

The abbreviations and manufacturers of the compounds used in the following Examples and Comparative Examples are as follows.

<Dihydroxy compound>

‧ISB: Isosorbide [manufactured by Roquette Frères]

‧CHDM: 1,4-Cyclohexane dimethanol [manufactured by SK Chemical]

‧TCDDM: Tricyclodecane dimethanol [manufactured by OXEA]

<Carbon Diester>

‧DPC: Diphenyl carbonate [manufactured by Mitsubishi Chemical Corporation]

<Hindered Phenolic Compounds>

‧Irganox 1010: Pentaerythritol 4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] [manufactured by BASF Japan]

<Phosphorus Compounds>

‧Phosphorous acid [Taiping Chemical Industry Co., Ltd.] (Molecular weight 82.0)

‧AS2112: ginseng (2,4-di-tert-butylphenyl) phosphite [manufactured by ADEKA (stock)] (molecular weight 646.9)

<Ultraviolet Absorber>

‧UVA-1: LA-31 [ADEKA (share) system]

‧UVA-2: LA-36 [ADEKA (share) system]

‧UVA-3: LA-F70 [ADEKA (share) system]

‧UVA-4: BONASORB UA-3701 [Orient Chemical Industry Co., Ltd.]

‧UVA-5: Uvinul 3049 [BASF Japan (share) system]

‧UVA-6: Uvinul 3050 [BASF Japan (share) system]

‧UVA-7: Seesorb 709 [SHIPRO Chemical (Stock) System]

‧UVA-8: Tinuvin 234 [BASF Japan (share) system]

‧UVA-9: TINOPAL OB[BASF Japan (share) system]

‧UVA-10: Cyasorb UV-5411 [manufactured by Cytec Industries, Japan]

The physical properties of the ultraviolet absorber are collectively shown in Table 1 below.

[Table 1]

Manufacturing method of polycarbonate resin

[Manufacturing Example 1]

The polycarbonate resin was polymerized using a continuous polymerization equipment composed of 3 vertical agitated reactors, 1 horizontal agitated reactor, and a biaxial extruder. The ISB, CHDM, and DPC were melted separately in the tank, and ISB/CHDM/DPC=0.700/0.300/1.010 was continuously supplied to the first vertical stirred reactor. At the same time, an aqueous solution of calcium acetate monohydrate as a catalyst was supplied to the first vertical stirred reactor so that it became 1.5 μmol with respect to 1 mol of the total dihydroxy compound. The liquid level was kept constant while controlling the opening of the valve of the transfer pipe provided at the bottom of the reactor so that the average residence time in the first vertical stirred reactor became 90 minutes. The reaction liquid discharged from the bottom of the reactor is continuously supplied to the second vertical stirred reactor, the third vertical stirred reactor, and the fourth horizontal stirred reactor [Hitachi Plant Techonology Co., Ltd. double shaft Glasses-shaped wings]. The first vertical agitated reactor and the second vertical agitated reactor are equipped with reflux coolers, and by adjusting the reflux ratio, the distillation of unreacted dihydroxy compound and DPC is suppressed.

The reaction temperature, internal pressure, and residence time of each reactor were set to the first vertical stirred reactor: 190°C, 25kPa, 90 minutes; the second vertical stirred reactor: 195°C, 10kPa, 45 minutes; 3 vertical stirred reactor: 210°C, 3kPa, 45 minutes; 4th horizontal stirred reactor: 230°C, 0.5kPa, 90 minutes. According to the reduction viscosity of the obtained polycarbonate resin from 0.61 dL/g to 0.64 dL/g, the operation was performed while finely adjusting the internal pressure of the fourth horizontal stirred reactor.

The polycarbonate resin is continuously extracted from the fourth horizontal agitated reactor, and then the resin is directly supplied to the twin-screw extruder in a molten state [manufactured by Nippon Steel Co., Ltd. TEX30α]. The extruder has 3 vacuum exhaust ports to degas and remove residual low-molecular components in the resin. Supply phosphorous acid-coated masterbatch from the front of the first exhaust port, add 0.65 ppm of phosphorous acid (0.2 ppm based on the amount of phosphorus atoms) to the polycarbonate resin, and apply the resin before the second exhaust port Add 2000 ppm by weight of water, perform water injection and degassing, and supply 500 ppm of AS2112 and 1000 ppm of Irganox 1010 in front of the third exhaust port. The extruder (10 rollers in total) was set to a cylinder temperature of 220°C and a screw rotation number of 230 rpm. The resin temperature at the exit of the extruder is 262°C.

The polycarbonate resin that has passed through the extruder is then passed through a filter in a molten state to filter foreign matter, then discharged from the mold in a strand shape, water-cooled and solidified, and then pelletized by a rotary cutter. The glass transition temperature of the particles is 122°C. The obtained polycarbonate resin is referred to as PC1.

[Manufacturing Example 2]

Except that the permole ratio ISB/CHDM/DPC=0.700/0.300/1.012 was continuously supplied to the first vertical stirred reactor, the same procedure was carried out as in Example 1, and a polycarbonate resin was obtained. The glass transition temperature of the particles is 122°C. The obtained polycarbonate resin is referred to as PC2.

[Manufacturing Example 3]

Except for the permolar ratio ISB/CHDM/DPC=0.700/0.300/1.000, the aqueous solution of calcium acetate monohydrate as a catalyst is continuously supplied to the first vertical stirring in such a way that it becomes 1.25 μmol relative to 1 mol of the total dihydroxy compound. Reactor, and set the reaction temperature, internal pressure and residence time of each reactor to the first vertical stirred reactor: 188°C, 24.2kPa, 90 minutes; the second vertical stirred reactor: 194°C, 19.9 kPa, 60 Minutes; the third vertical stirred reactor: 214°C, 9.9kPa, 60 minutes; the fourth horizontal stirred reactor: 225°C, 0.1kPa, 120 minutes. The temperature of the cylinder in the extruder is set in the first half of the four rollers. It was 240°C, the last six rollers were set to 195°C, and the number of screw rotations was set to 225 rpm, and the rest was performed in the same manner as in Example 1. The glass transition temperature of the particles is 122°C. The obtained polycarbonate resin is referred to as PC3.

[Manufacturing Example 4]

Polymerization of polycarbonate resin is carried out using batch type polymerization equipment consisting of a vertical agitated reactor and a twin-screw extruder. The ISB, CHDM, and DPC are melted separately in a tank, and ISB/CHDM/DPC=0.700/0.300/1.000 is supplied to the first vertical stirred reactor. At the same time, an aqueous solution of cesium carbonate as a catalyst was supplied to the first vertical stirred reactor so that it became 1.25 μmol with respect to 1 mol of cesium carbonate of the total dihydroxy compound. As the first step of the reaction, the temperature of the heating tank is heated to 150°C, the raw materials are dissolved under stirring for 15 minutes, the pressure is reduced from normal pressure to 13.3 kPa for 40 minutes, and the temperature of the heating tank is increased for 40 minutes At 190°C, extract the generated phenol to the outside of the reaction vessel. After maintaining the entire reaction vessel at 190°C for 15 minutes, as the second step, the temperature of the heating bath was increased to 240°C in 30 minutes. After 10 minutes from the start of the temperature rise, the pressure in the reaction vessel was reduced to 0.200 kPa or less in 30 minutes to distill the produced phenol. After 120 minutes, after reaching the predetermined stirring torque, the reaction was stopped, and the polycarbonate resin was continuously drawn out from the reactor, and then the resin was directly supplied to the twin-screw extruder [TEX30α manufactured by Nippon Steel Works Co., Ltd.] in a molten state. The extruder has 3 vacuum exhaust ports to degas and remove the remaining low-molecular components in the resin. The phosphorous acid-coated masterbatch is supplied from the front of the first exhaust port, and 0.65 ppm of phosphorous acid (0.2 ppm in terms of the amount of phosphorus atoms) is added to the polycarbonate resin. Add 2000 ppm by weight of water to the resin, perform water injection and degassing, and supply 500 ppm of AS2112 and 1000 ppm of Irganox 1010 in front of the third exhaust port. The extruder (10 rollers in total) was set to a cylinder temperature of 220°C and a screw rotation number of 230 rpm. The resin temperature at the exit of the extruder is 261°C.

The polycarbonate resin that has passed through the extruder is then passed through a filter in a molten state to filter foreign matter, then discharged from the mold in a strand shape, water-cooled and solidified, and then pelletized by a rotary cutter. The glass transition temperature of the particles is 122°C. The obtained polycarbonate resin is referred to as PC4.

The amounts of the phenol and the compound represented by formula (3) contained in the polycarbonate resin are collectively shown in Table 2 below.

[Table 2]

[Example 1]

100 parts by weight of the polycarbonate resin (PC1) described in Production Example 1 and 1.5 parts by weight of UVA-1 were supplied to a twin-screw extruder with an exhaust port (TEX30α manufactured by Japan Steel Works Co., Ltd.) using a quantitative feeder , Cylinder set temperature: 240℃), after filtering the foreign matter through the filter, it is discharged from the mold in a strand shape, and after water cooling and solidification, it is granulated by a rotary cutter.

After that, the polycarbonate resin composition was subjected to a gel counter FSA film inspection line manufactured by OCS Corporation at 2 kg/Hr (set temperature of the roller: 240°C, T-shaped mold (width 150mm, set temperature: 240°C), cooling roll ( Setting temperature: 105°C)), extruded into a film with a thickness of 40 μm. The results are shown in Table 3 below.

[Examples 2 to 13, Comparative Examples 1 to 5]

As shown in Table 3 below, except that the film thickness, the type of ultraviolet absorber, and the amount of ultraviolet absorber were changed, the same procedure as in Example 1 was carried out.

The numerical values of the film thickness accuracy of Examples 1 to 13 are all extremely small, and they are films with uniform thickness, and meanwhile, the amount of foreign matter per unit area of the film is also small, which is a particularly superior film.

On the other hand, in Comparative Examples 1 to 5, the heat resistance of the resin composition was reduced due to the type and amount of the ultraviolet absorber used, or the film thickness was considered to be caused by roll dirt caused by bleed-out Accuracy has deteriorated, or the amount of foreign objects has increased.

In addition, in Comparative Example 4 and Comparative Example 5, most of the entire film was confirmed to be agglomerated because the ultraviolet absorber was not melted, and was not 150 μm or more fine foreign matter.

[table 3]

[Examples 14~16]

As shown in Table 4 below, the polycarbonate resin used was changed from PC1 to any one of PC2, PC3, and PC4, and the rest was carried out in the same manner as in Example 4.

The numerical values of the film thickness accuracy of Examples 14-16 are all extremely small, and they are films with uniform thickness, and meanwhile, the amount of foreign matter per unit area of the film is also small, which is a particularly superior film.

[Table 4]

[Examples 17-19]

As shown in Table 5 below, the polycarbonate resin used was changed from PC1 to any one of PC2, PC3, and PC4, and the rest was carried out in the same manner as in Example 6.

The numerical values of the film thickness accuracy of Examples 17-19 are all extremely small, and they are films with uniform thickness, and meanwhile, the amount of foreign matter per unit area of the film is also small, which is a particularly superior film.

[table 5]

[Example 20]

100 parts by weight of the polycarbonate resin (PC1) described in Production Example 1 and 1.2 parts by weight of UVA-3 were supplied to a twin-screw extruder with an exhaust port (TEX30α manufactured by Japan Steel Works Co., Ltd.) using a quantitative feeder , Cylinder set temperature: 240℃), after filtering the foreign matter through the filter, it is discharged from the mold in a strand shape, and after water cooling and solidification, it is granulated by a rotary cutter.

After that, the polycarbonate resin composition was subjected to a gel counter FSA film inspection line manufactured by OCS Corporation at 2 kg/Hr (set temperature of the roller: 240°C, T-shaped mold (width 150mm, set temperature: 240°C), cooling roll ( Setting temperature: 105°C)), extruded into a film with a thickness of 50 μm. An unstretched film with a length of 125 mm and a width of 50 mm was cut out from the film. A batch-type biaxial stretching device (manufactured by Island Industrial Co., Ltd.) was used to perform a fixed-end sheet with a strain rate of 5 mm/min, a stretching temperature of 134°C, and a stretching ratio of 1.8 times. Axis extension. Cut out the stretched transparent film into a sample with a width of 4 cm and a length of 4 cm. Using a phase difference measuring device (manufactured by Oji Measuring Instruments Co., Ltd., product name "KOBRA WRXY2020"), measure the in-plane at a wavelength of 548 nm in a room at 23°C Phase difference R548, the result is 139nm. The results are summarized in Table 6 below.

[Table 6]

The polycarbonate resin film produced in Example 20 was attached to the surface layer of a display that displays linearly polarized images as a retardation film. When viewing the display through polarized sunglasses, there was no black display and no rainbow pattern was confirmed. For good results.

Although the present invention has been described using a specific aspect, those skilled in the art of the present invention should know that various changes and modifications can be made without departing from the intent and scope of the present invention. In addition, this application is based on a Japanese patent application (Japanese Patent Application 2015-086969) filed on April 21, 2015, and the entire content is incorporated herein by reference.

(Industrial availability)

According to the present invention, it is possible to provide problems such as reduced heat resistance without film, film turbidity due to exuded substances, film foreign matter caused by roller dirt, and poor film appearance such as gear wear marks. The appearance quality is superior, and the film thickness is excellent. Polycarbonate resin film with excellent uniformity.

Therefore, it contributes to the reduction of loss in the manufacturing process of the polarizing plate using it, and the thinning of the structure of the image display device.

Claims (4)

A polycarbonate resin film composed of a polycarbonate resin composition, the polycarbonate resin composition comprising: a polycarbonate resin 100 containing a structural unit derived from a dihydroxy compound represented by the following formula (1) Parts by weight; with respect to 100 parts by weight of polycarbonate resin, more than 0.45 parts by weight and 7 parts by weight or less of a UV absorber with a melting point of 135°C or higher but less than 300°C and a 5% weight reduction temperature higher than 240°C; The polycarbonate resin film has a light transmittance of 0.001% or more and 15% or less with a wavelength of 380nm, and a thickness of 5μm~120μm; the content of the compound represented by the following formula (3) in the above polycarbonate resin is 10 wtppm Above and below 1200 ppm by weight;

The polycarbonate resin film of claim 1, wherein the above-mentioned ultraviolet absorbers are three

Series, benzotriazole series, quinolinone series, benzo

Azole series or indole series. The polycarbonate resin film of claim 1 or 2, wherein the in-plane phase difference at 548 nm is 100 nm or more and 200 nm or less. A polarizer protective film made of the polycarbonate resin film of any one of claims 1 to 3.