JP7186642B2 - organic-inorganic composite - Google Patents

Description

Application of Article 30, Paragraph 2 of the Patent Law 2018 Research Group on Fundamental Polymer Properties, Research Group on Polymer Computer Science, Research Group on Polymer Nanotechnology, pp. 50-51 Published by: Public Interest Incorporated Association The Society for Molecular Science Publication date: December 19, 2018 [Publications] 2018 Research Group on Basic Polymer Physics, Research Group on Polymer Computer Science, Research Group on Polymer Nanotechnology Date: December 20, 2018 Day

The present disclosure relates to an organic-inorganic composite material containing a polycarbonate resin and inorganic fine particles.

In recent years, the development of optical materials has been actively carried out. For example, in the field of optical lenses, optical materials with high refractive index, high Abbe's number, heat resistance and excellent transparency are required. Conventionally used glass can realize various required optical properties and is excellent in environmental resistance, but has a problem of poor workability. In contrast, resin materials, which are less expensive than glass materials and have excellent workability, have been used for optical components. However, resin materials generally have a lower refractive index than glass. For example, in order to reduce the thickness of an optical component made of a resin material, it is required to increase the refractive index of the resin material.

As a method of increasing the refractive index of a resin material, for example, there is a method of dispersing fine particles of an inorganic oxide such as titanium oxide or zirconium oxide in a resin. However, since such fine particles have a large surface energy and are difficult to disperse in a matrix resin, various studies have been made so far.

As a technique for dispersing fine particles in a resin, there is a technique for chemically modifying the fine particle surface with a surface modifier. For example, in Patent Document 1, particles modified with a specific chemical structure are mixed with a resin or the like to prepare a masterbatch, and then the masterbatch and a thermoplastic resin are melt-kneaded to form a transparent resin composition. It describes how to get it.

Another approach is to use polymers with polar functional groups. For example, Patent Document 2 and Non-Patent Document 1 describe a method of dispersing inorganic fine particles using a polymer containing a carboxyl group. Further, Patent Document 3 describes a method of dispersing inorganic fine particles using a polar functional group-containing graft polymer.

Patent Documents 4 and 5 describe that an inorganic filler or the like can be blended with a polycarbonate resin. Patent Document 6 describes polycarbonate resin pellets with a reduced amount of miscut and a method for producing the same.

Japanese Unexamined Patent Application Publication No. 2011-38012 JP 2018-138624 A JP 2006-307199 A WO2004/111106 WO2011/021720 Japanese Patent Application Laid-Open No. 2003-200421

"FUJIFILM RESEARCH & DEVELOPMENT", 2013, Vol. 58, p. 48-51.

Since the resin composition obtained by the method described in Patent Document 1 contains a small amount of inorganic fine particles, it has been difficult to sufficiently increase the refractive index of the resin material.

When the methods described in Patent Document 2 and Non-Patent Document 1 are applied to a polymer obtained by a polycondensation reaction such as polycarbonate, the carboxyl groups react during polymerization, so a large amount of carboxyl groups are introduced into the polymer. Can not. Therefore, it has been difficult to sufficiently disperse the inorganic fine particles in the polycarbonate resin material.

In the method described in Patent Document 3, since a graft chain having a polar functional group is introduced by radical polymerization, the side chain linking chain length connecting the main chain and the polar functional group cannot be controlled, resulting in an organic-inorganic composite material. In this case, the fluidity, the dispersion stability of the inorganic fine particles, etc. may be affected.

An object of the present disclosure is to provide an organic-inorganic composite material with improved dispersibility of inorganic fine particles in a polycarbonate resin.

式１中、
Ｒ^１及びＲ^２は、それぞれ独立に、アルキレン基、アラルキレン基、アリーレン基、及びシクロアルキレン基からなる群から選ばれる基を表し、Ｒ^２の水素原子はカルボキシル基で置換されてもよい。
〈態様２〉
前記ポリカーボネート樹脂が、下記式２で表される構造単位を含む、態様１に記載の有機無機複合材料：

式２中、
Ｒ^３及びＲ^４は、前記式１で表される基を表し、
ａ及びｂは、それぞれ独立に、ａ＋ｂ≧１を満たす０～４の整数であり、
Ｒ^５及びＲ^６は、それぞれ独立に、ハロゲン原子、アルキル基、アルコキシ基、シクロアルキル基、シクロアルコキシ基、アルケニル基、アリール基、アリールオキシ基、アラルキル基、アラルキルオキシ基、ニトロ基、アルデヒド基、及びシアノ基からなる群から選ばれる基を表し、
ｃ及びｄは、それぞれ独立に、ｃ≦４－ａ及びｄ≦４－ｂを満たす０～４の整数であり、
Ｘは、単結合、アルキレン基、アラルキレン基、アリーレン基、シクロアルキレン基、硫黄原子、又は酸素原子を表す。
〈態様３〉
前記無機微粒子の表面が、表面修飾剤により修飾されている、態様１又は２に記載の有機無機複合材料。
〈態様４〉
前記表面修飾剤が、酸性官能基を有する、態様３に記載の有機無機複合材料。
〈態様５〉
前記酸性官能基が、スルホン酸基、ホスホン酸基、ホスフィン酸基、及びカルボン酸基からなる群より選ばれる少なくとも１つの酸性官能基である、態様４に記載の有機無機複合材料。
〈態様６〉
前記無機微粒子の表面が、前記無機微粒子に対して１～３０質量％の前記表面修飾剤により修飾されている、態様３～５のいずれかに記載の有機無機複合材料。
〈態様７〉
前記無機微粒子の平均粒子径が、１～２０ｎｍである、態様１～６のいずれかに記載の有機無機複合材料。
〈態様８〉
前記無機微粒子の含有量が、前記ポリカーボネート樹脂に対して１～９５質量％である、態様１～７のいずれかに記載の有機無機複合材料。
〈態様９〉
前記無機微粒子が、酸化ジルコニウム、酸化チタン、酸化スズ、酸化ケイ素、及び酸化アルミニウムからなる群より選ばれる少なくとも一種である、態様１～８のいずれかに記載の有機無機複合材料。
〈態様１０〉
態様１～９のいずれかに記載の有機無機複合材料を用いて得られる成形品。
〈態様１１〉
炭素－炭素二重結合を有するポリカーボネート樹脂、及びカルボキシル基を有するチオール化合物を反応させて、前記式１で表される基を有するポリカーボネート樹脂を調製することと、
前記式１で表される基を有するポリカーボネート樹脂、及び無機微粒子を混合することと
を含む、態様１～９のいずれかに記載の有機無機複合材料の製造方法。 <Aspect 1>
An organic-inorganic composite material comprising a polycarbonate resin having a group represented by the following formula 1 and inorganic fine particles:

In formula 1,
R ¹ and R ² each independently represent a group selected from the group consisting of an alkylene group, an aralkylene group, an arylene group and a cycloalkylene group, and the hydrogen atom of R ² may be substituted with a carboxyl group.
<Aspect 2>
The organic-inorganic composite material according to aspect 1, wherein the polycarbonate resin comprises a structural unit represented by the following formula 2:

In formula 2,
R ³ and R ⁴ represent a group represented by the formula 1,
a and b are each independently an integer of 0 to 4 that satisfies a+b≧1;
^R5 and ^R6 each independently represent a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an alkenyl group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a nitro group, an aldehyde group; , and represents a group selected from the group consisting of a cyano group,
c and d are each independently an integer of 0 to 4 that satisfies c ≤ 4-a and d ≤ 4-b;
X represents a single bond, an alkylene group, an aralkylene group, an arylene group, a cycloalkylene group, a sulfur atom, or an oxygen atom.
<Aspect 3>
The organic-inorganic composite material according to aspect 1 or 2, wherein the surfaces of the inorganic fine particles are modified with a surface modifier.
<Aspect 4>
The organic-inorganic composite material according to aspect 3, wherein the surface modifier has an acidic functional group.
<Aspect 5>
The organic-inorganic composite material according to aspect 4, wherein the acidic functional group is at least one acidic functional group selected from the group consisting of a sulfonic acid group, a phosphonic acid group, a phosphinic acid group, and a carboxylic acid group.
<Aspect 6>
The organic-inorganic composite material according to any one of aspects 3 to 5, wherein the surfaces of the inorganic fine particles are modified with 1 to 30% by mass of the surface modifier with respect to the inorganic fine particles.
<Aspect 7>
The organic-inorganic composite material according to any one of aspects 1 to 6, wherein the inorganic fine particles have an average particle size of 1 to 20 nm.
<Aspect 8>
The organic-inorganic composite material according to any one of aspects 1 to 7, wherein the content of the inorganic fine particles is 1 to 95% by mass with respect to the polycarbonate resin.
<Aspect 9>
The organic-inorganic composite material according to any one of aspects 1 to 8, wherein the inorganic fine particles are at least one selected from the group consisting of zirconium oxide, titanium oxide, tin oxide, silicon oxide, and aluminum oxide.
<Aspect 10>
A molded article obtained using the organic-inorganic composite material according to any one of aspects 1 to 9.
<Aspect 11>
reacting a polycarbonate resin having a carbon-carbon double bond and a thiol compound having a carboxyl group to prepare a polycarbonate resin having a group represented by the formula 1;
The method for producing an organic-inorganic composite material according to any one of aspects 1 to 9, which comprises mixing a polycarbonate resin having a group represented by Formula 1 and inorganic fine particles.

According to the present disclosure, it is possible to provide an organic-inorganic composite material with improved dispersibility of inorganic fine particles in a polycarbonate resin.

Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments, and various modifications can be made within the scope of the spirit of the invention.

式１中、Ｒ^１及びＲ^２は、それぞれ独立に、アルキレン基、アラルキレン基、アリーレン基、及びシクロアルキレン基からなる群から選ばれる基を表し、Ｒ^２の水素原子はカルボキシル基で置換されてもよい。 An organic-inorganic composite material of one embodiment is an organic-inorganic composite material containing a polycarbonate resin having a group represented by the following formula 1 and inorganic fine particles:

In Formula 1, R ¹ and R ² each independently represent a group selected from the group consisting of an alkylene group, an aralkylene group, an arylene group, and a cycloalkylene group, and the hydrogen atom of R ² is substituted with a carboxyl group. good too.

The organic-inorganic composite material of the present disclosure is excellent in dispersibility of inorganic fine particles in polycarbonate resin, especially under high-temperature conditions. Although not limited by the principle, the working principle of the organic-inorganic composite material of the present disclosure is believed to be as follows.

The polycarbonate resin in the organic-inorganic composite material of the present disclosure does not introduce carboxyl groups into the polycarbonate resin in parallel with the formation of the polycarbonate resin during the polycondensation reaction, as described in Patent Document 2. After the polycarbonate resin is produced by the reaction, a group represented by the above formula 1 containing a carboxyl group is introduced into the polycarbonate resin by an addition reaction such as an enethiol reaction. As a result, it is possible to avoid the problem related to the reaction of the carboxyl group during the polymerization of the polycarbonate resin as in Patent Document 2, and the carboxyl group can be quantitatively introduced into the polycarbonate resin, so that the dispersion of the inorganic fine particles is higher than before. It is considered that the quality can be improved.

In addition, the group represented by Formula 1 above contains a sulfur atom, and is considered to have improved heat resistance compared to a system containing no sulfur atom. As a result, it is believed that the organic-inorganic composite material of the present disclosure can improve the dispersibility of the inorganic fine particles in a high-temperature environment, for example, during thermoforming.

《Organic-inorganic composite materials》
Since the organic-inorganic composite material of the present disclosure has excellent dispersibility of inorganic fine particles, it can exhibit the following performances, for example.

<transparency>
The organic-inorganic composite material of the present disclosure can exhibit excellent transparency. For example, when using a 100 μm thick film obtained from an organic-inorganic composite, the transmittance in such a sheet can be 80% or more, 83% or more, or 85% or more. This upper limit is not particularly limited, but can be, for example, 99% or less, 97% or less, or 95% or less. Transmittance in the present disclosure means light transmittance at a wavelength of 589 nm measured at 25° C. using a spectrophotometer. The film obtained from the organic-inorganic composite material of the present disclosure is not particularly limited in its manufacturing method, and can be obtained, for example, by known methods such as a melt extrusion method and a solution casting method (casting method).

<Refractive index>
The organic-inorganic composite material of the present disclosure can exhibit a high refractive index. For example, when using a 100 μm thick film obtained from an organic-inorganic composite, the refractive index in such a sheet can be 1.585 or greater, 1.590 or greater, or 1.595 or greater. This upper limit is not particularly limited, but can be, for example, 1.900 or less, 1.850 or less, or 1.800 or less. A refractive index in the present disclosure means a value measured at 25° C. and a wavelength of 589 nm using an Abbe refractometer according to ASTM D542.

<Polycarbonate resin>
The polycarbonate resin used in the organic-inorganic composite material of the present disclosure has a group represented by Formula 1 below:

In Formula 1, R ¹ and R ² may be the same or different and are each independently selected from the group consisting of an alkylene group (alkanediyl group), an aralkylene group, an arylene group, and a cycloalkylene group. represents a group A hydrogen atom of ^R2 may be substituted with a carboxyl group.

From the viewpoint of dispersibility of inorganic fine particles, R ¹ and R ² are preferably an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or an aralkylene group having 7 to 20 carbon atoms. and more preferably an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 10 carbon atoms, or an aralkylene group having 7 to 12 carbon atoms.

From the viewpoint of the dispersibility of the inorganic fine particles, the polycarbonate resin preferably contains a structural unit represented by the following formula 2:

In Formula 2, R ³ and R ⁴ represent groups represented by Formula 1, a and b are each independently an integer of 0 to 4 satisfying a+b≧1, and R ⁵ and R ⁶ are which may be the same or different and are each independently a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an alkenyl group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, represents a group selected from the group consisting of a nitro group, an aldehyde group, and a cyano group, c and d are each independently an integer of 0 to 4 satisfying c≦4-a and d≦4-b, and X is , a single bond, an alkylene group (alkanediyl group), an aralkylene group, an arylene group, a cycloalkylene group, a sulfur atom, or an oxygen atom.

From the viewpoint of the dispersibility of inorganic fine particles, R ⁵ and R ⁶ are each independently preferably a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 5 carbon atoms. -20 cycloalkyl group, 6-20 carbon cycloalkoxy group, 2-10 carbon alkenyl group, 6-10 carbon aryl group, 6-10 carbon aryloxy group, carbon It is an aralkyl group having 7 to 20 atoms or an aralkyloxy group having 7 to 20 carbon atoms. More preferably, R ⁵ and R ⁶ are each independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

Preferably, a and b in Formula 2 are each independently an integer of 0 to 2, more preferably an integer of 1, provided that a+b≧1.

Preferably, c and d in formula 2 are each independently an integer of 0 to 2, more preferably each of 0 to 1, provided that c ≤ 4-a and d ≤ 4-b is an integer.

Preferably, X in Formula 2 is a single bond, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or an aralkylene group having 7 to 20 carbon atoms, a sulfur atom, or an oxygen is an atom, more preferably a single bond, an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 10 carbon atoms, or an aralkylene group having 7 to 12 carbon atoms.

The polycarbonate resin can have the following carboxyl group content and various performances.

(Carboxyl group amount)
The amount of carboxyl groups in the polycarbonate resin is, for example, 1 eq/ton-polycarbonate (hereinafter also referred to as "eq/ton") in consideration of the dispersibility of inorganic fine particles, the performance (eg, mechanical performance) of the resulting molded product, and the like. above, 50eq/ton or more, 100eq/ton or more, or 150eq/ton or more, and 2,000eq/ton or less, 1,700eq/ton or less, 1,500eq/ton or less, or 1,000eq/ton /ton or less.

The amount of carboxyl groups can be calculated, for example, by dissolving a polycarbonate resin in benzyl alcohol under a nitrogen atmosphere, titrating with a benzyl alcohol solution of sodium hydroxide using phenol red as an indicator, and calculating the amount of the solution dropped.

(Glass transition temperature: Tg)
The glass transition temperature of the polycarbonate resin is, for example, preferably 90 to 160°C, more preferably 100 to 150°C, from the viewpoint of heat resistance stability, moldability, and the like.

The glass transition temperature is determined using a differential scanning calorimetry (DSC) device under the conditions of a nitrogen atmosphere (nitrogen flow rate: 40 mL/min) and a heating rate of 20°C/min in accordance with JIS K7121. can do.

(Viscosity average molecular weight: Mv)
The viscosity-average molecular weight (Mv) of the polycarbonate resin is preferably 15,000 to 40,000, more preferably 16,000 to 35, more preferably 16,000 to 35, from the viewpoint of, for example, impact resistance, melt fluidity, molding processability, and the like. 000, more preferably 18,000 to 30,000.

The viscosity-average molecular weight of the polycarbonate resin is, for example, the specific viscosity (η _SP ) and can be calculated from Equations 4 and 5 below:
Specific viscosity (η _SP )=(tt ₀ )/t ₀ Equation 3
η _SP /c=[η]+0.45×[η] ² c Equation 4
[η]=1.23×10 ⁻⁴ Mv ^0.83 Equation 5
Here, in formula 3, t ₀ is the number of seconds for methylene chloride to fall, t is the number of seconds for the sample solution to fall, and [η] in formulas 4 and 5 is the limiting viscosity, c is 0.7.

<Method for Producing Polycarbonate Resin Having Group Represented by Formula 1>
The method for producing a polycarbonate resin having a group represented by the formula 1 is not particularly limited, and for example, step i for producing a polycarbonate resin having a carbon-carbon double bond, and the polycarbonate resin obtained in step i and a step ii of reacting a thiol compound having a carboxyl group.

(Step i)
A polycarbonate resin having a carbon-carbon double bond can be produced by using a diol compound having at least one carbon-carbon double bond in a known reaction for producing a normal polycarbonate resin.

Reaction methods include, for example, interfacial polycondensation, melt transesterification, and solid phase transesterification of carbonate prepolymers. Here, in the case of interfacial polycondensation, a terminal terminator of a monohydric phenol compound is usually used.

A polycarbonate resin having a carbon-carbon double bond may be, for example, a copolymerized polycarbonate obtained by further copolymerizing an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid and/or a vinyl monomer. A polycarbonate resin having a carbon-carbon double bond may be, for example, a branched polycarbonate resin obtained by copolymerizing a trifunctional component.

Examples of diol compounds having a carbon-carbon double bond include 2,2-bis(3-allyl-4-hydroxyphenyl)propane and 2,2-bis(3-allyl-4-hydroxy-5-methylphenyl) propane, 2-(3-allyl-4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2,2-bis(3,5-diallyl-4-hydroxyphenyl)propane and the like. These may be used alone or in combination of two or more.

In the production of a polycarbonate resin having a carbon-carbon double bond, various diol compounds other than the diol compound having a carbon-carbon double bond can be used in combination. Examples of such diol compounds include aromatic diol compounds, aliphatic diol compounds, and alicyclic diol compounds. Specific examples include diol compounds described in Patent Documents 4 and 5, and oxyalkylene glycol compounds such as diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol. These may be used alone or in combination of two or more. Typical specific examples of such diol compounds are shown below, but are not limited thereto.

Specific examples of aromatic diol compounds include 4,4′-biphenol, 3,3′,5,5′-tetrafluoro-4,4′-biphenol, α,α′-bis(4- hydroxyphenyl)-o-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene (usually referred to as "bisphenol M"), α,α'-bis(4-hydroxyphenyl )-p-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-m-bis(1,1,1,3,3,3-hexafluoroisopropyl)benzene, 1,1-bis(4- hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, 1,1-bis(3 -cyclohexyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(3-fluoro-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy phenyl) perfluorocyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4 '-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'- Diphenyl sulfide, 4,4'-dihydroxy-3,3'-diphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyl sulfone, 1,1-bis(4-hydroxyphenyl)methane (usually "bisphenol F ), 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (usually referred to as “bisphenol A”), 1,1- Bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane (usually referred to as "bisphenol C"), 2,2-bis(4- hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxy-3 -phenylphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 4,4-bis(4- hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)decane, 1,1-bis(3-methyl-4-hydroxyphenyl)decane, 1, 1-bis(2,3-dimethyl-4-hydroxyphenyl)decane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4 -hydroxyphenyl)-4-isopropylcyclohexane, 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (commonly referred to as “bisphenol AF”). ), 6,6′-dihydroxy-3,3,3′,3′-tetramethyl-1,1′-spirobiindane, 7,7′-dimethyl-6,6′-dihydroxy-3,3,3′, 3′-tetramethyl-1,1′-spirobiindane, 7,7′-diphenyl-6,6′-dihydroxy-3,3,3′,3′-tetramethyl-1,1′-spirobiindane, 2,2 -bis(4-hydroxy-3-methylphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)-1,1 , 1,3,3,3-hexafluoropropane, 2,2-bis(3-fluoro-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2, 2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl) ) propane, and 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene.

Among the above, bisphenol M, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 3,3′-dimethyl-4, 4'-dihydroxydiphenyl sulfide, bisphenol A, bisphenol C, bisphenol AF, 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane, 9,9-bis(4 -(2-hydroxyethoxy)phenyl)fluorene and 1,1-bis(4-hydroxyphenyl)decane are preferred. Bisphenol A is particularly preferred as it is inexpensively available.

Examples of aliphatic diol compounds include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, and 1,9-nonanediol. , 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-n-butyl-2-ethyl -1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexane glycol, 1,2-octane glycol, 2- ethyl-1,3-hexanediol, 2,2-diisobutyl-1,3-propanediol, 2,2-diisoamyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, etc. is mentioned.

Examples of alicyclic diol compounds include cyclohexanedimethanol, tricyclodecanedimethanol, adamantanediol, pentacyclopentadecanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, isosorbide (1 , 4; 3,6-dianhydro-D-sorbitol) and the like.

In the production of polycarbonate resin, a method using a carbonate precursor can be adopted.

In reactions using, for example, phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent.

Examples of acid binders include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine. Examples of the solvent include halogenated hydrocarbons such as methylene chloride and chlorobenzene. Catalysts such as, for example, tertiary amines or quaternary ammonium salts can also be used to accelerate the reaction.

The reaction temperature is generally 0 to 40° C., and the reaction time is generally 1 minute to 5 hours.

The transesterification reaction using, for example, a carbonic acid diester as a carbonate precursor is carried out by stirring a predetermined ratio of a diol compound with a carbonic acid diester under an inert gas atmosphere while heating to distill off the resulting alcohol or phenol compound. will be

The reaction temperature varies depending on the boiling point of the alcohol or phenol compound to be produced, but is usually in the range of 120 to 300°C. The reaction is completed under reduced pressure from the initial stage while the alcohol or phenol compound produced is distilled off. In order to accelerate the reaction, the usual catalysts used for transesterification reactions can also be used.

Carbonic acid diesters used in transesterification include, for example, diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Among these, diphenyl carbonate is particularly preferred.

A terminal terminator can be used in the production of the polycarbonate resin. A monofunctional phenol compound, for example, can be used as the terminal terminator. In the case of reactions using phosgene as the carbonate precursor, monofunctional phenolic compounds are commonly used as end-capping agents for molecular weight control. The polycarbonate resin obtained in this way is end-blocked with a group derived from a monofunctional phenol compound, so that the thermal stability can be further improved.

Specific examples of monofunctional phenol compounds include phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, Examples include p-cumylphenol, isooctylphenol, p-long-chain alkylphenol and the like.

The polycarbonate resin of the present disclosure can optionally be copolymerized with a fatty acid. Examples of such fatty acids include adipic acid (hexanedioic acid), dodecanedioic acid, isophthalic acid (1,3-benzenedicarboxylic acid), terephthalic acid (1,4-benzenedicarboxylic acid), and 2,6-naphthalene. Dicarboxylic acids, 3-hydroxybenzoic acid, and 4-hydroxybenzoic acid are included.

Polycarbonate resins of the present disclosure can include polyester carbonate resins copolymerized with aromatic or aliphatic (including cycloaliphatic) dicarboxylic acids. Aliphatic dicarboxylic acids are preferably α,ω-dicarboxylic acids. More specifically, aliphatic dicarboxylic acids include straight diacids such as adipic acid (hexanedioic acid), sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosanedioic acid. Chain saturated aliphatic dicarboxylic acids and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid are preferred. Preferred aromatic dicarboxylic acids include isophthalic acid (1,3-benzenedicarboxylic acid), terephthalic acid (1,4-benzenedicarboxylic acid), and 2,6-naphthalenedicarboxylic acid.

The polycarbonate resin of the present disclosure may optionally be copolymerized with structural units containing polyorganosiloxane units.

The polycarbonate resin of the present disclosure can also be made into a branched polycarbonate resin by copolymerizing a structural unit containing a trifunctional or higher polyfunctional aromatic compound, if necessary. Trifunctional or higher polyfunctional aromatic compounds used in branched polycarbonate resins include, for example, 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-2,2,4 ,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, and 4-{4-[1 ,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol and the like are preferred examples. Among them, 1,1,1-tris(4-hydroxyphenyl)ethane is preferred.

The ratio of structural units derived from polyfunctional aromatic compounds (hereinafter also referred to as "branched structural units") is preferably, for example, based on the total 100 mol% of structural units from other divalent components. is 0.03 to 1.5 mol %, more preferably 0.1 to 1.2 mol %, particularly preferably 0.2 to 1.0 mol %. The proportion of branched structural units can be calculated, for example, by ¹ H-NMR measurement.

The branched structural unit is not only derived from a polyfunctional aromatic compound, but also derived without using a polyfunctional aromatic compound. can be anything.

(Step ii)
A polycarbonate resin having a group represented by the above formula 1 is produced by reacting a polycarbonate resin having a carbon-carbon double bond produced in step i with a thiol compound having a carboxyl group (for example, an enthiol reaction). can do.

The enthiol reaction is a reaction in which a carbon-carbon double bond and a thiol group are added in a one-to-one ratio. That is, when a thiol is exposed to light or a radical generator is added, a thiyl radical is easily generated and added to a carbon-carbon double bond. The resulting carbon radical abstracts hydrogen from the thiol group to form a one-to-one adduct. Since the thiol group withdrawn hydrogen becomes a thiyl radical, a chain reaction proceeds. Thus, by using the enethiol reaction, a polycarbonate resin having a group represented by Formula 1 can be produced quantitatively and in high yield.

Examples of thiol compounds having a carboxyl group include 3-mercaptopropanoic acid, 3-mercapto-2-methylpropanoic acid, mercaptosuccinic acid, 2-mercaptobenzoic acid, 1-(mercaptomethyl)cyclopropaneacetic acid and the like. .

In the enthiol reaction, it is preferable to use a radical generator. The enethiol reaction may be a radical reaction by irradiation with light (eg, ultraviolet rays). Examples of radical generators include azo compounds and organic peroxides, and those that generate radicals by heat and those that generate radicals by light irradiation can be preferably used. Examples of azo compounds include azobisisobutyronitrile (AIBN), 1,1'-azobis(cyclohexanecarbonitrile) (ABCN), and the like. Examples of organic peroxides include di-tert-butyl peroxide, benzoyl peroxide, and the like.

More specifically, the enethiol reaction involves dissolving a polycarbonate resin having a carbon-carbon double bond, a thiol compound having a carboxyl group, and a radical generator in an organic solvent and maintaining the conditions under which radicals are generated. It can be done by Although the reaction temperature is not particularly limited, it is preferably 50 to 120°C. The enethiol reaction may be performed in an inert gas atmosphere such as nitrogen gas or argon gas.

Examples of organic solvents include alcohols (alkyl alcohols such as ethanol, propanol and isopropanol; glycols such as ethylene glycol and propylene glycol); hydrocarbons (aliphatic hydrocarbons such as hexane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as toluene and xylene), halogenated hydrocarbons (methylene chloride, chloroform, etc.), ethers (chain ethers such as dimethyl ether and diethyl ether, cyclic ethers such as dioxane and tetrahydrofuran), esters (methyl acetate , ethyl acetate, butyl acetate, ethyl lactate, ethyl butyrate, etc.), ketones (acetone, ethyl methyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.) , carbitol (methyl carbitol, ethyl carbitol, butyl carbitol, etc.), propylene glycol monoalkyl ether (propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, etc.), glycol ether ester (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, etc.), amides (N,N-dimethylformamide, N,N-dimethylacetamide, etc.), sulfoxides (dimethylsulfoxide, etc.), nitriles (acetonitrile, benzonitrile, etc.), N-methylpyrrolidone and organic solvents such as The organic solvents may be used alone or in combination of two or more.

<Inorganic fine particles>
_The inorganic _fine particles used in the organic-inorganic _composite material of the _present disclosure are not particularly limited. Al ₂ O ₃ (aluminum oxide) and the like can be mentioned. Among them, inorganic fine particles having a refractive index of 1.80 or more or 2.00 or more are preferable, ZrO ₂ and TiO ₂ are more preferable, and ZrO ₂ is particularly preferable, from the viewpoint of utilization as an optical member or optical component. The inorganic fine particles may be used alone or in combination of two or more.

The average particle size of the inorganic fine particles is not particularly limited, and is preferably in the range of 1 to 20 nm, more preferably in the range of 1 to 10 nm, from the viewpoint of refractive index, transparency, and the like. The average particle size of inorganic fine particles can be measured, for example, by a dynamic light scattering method (DLS).

The content of the inorganic fine particles in the organic-inorganic composite material of the present disclosure may be appropriately adjusted depending on the intended use, and is not particularly limited. With respect to the resin, it can be 1% by mass or more, 3% by mass or more, 5% by mass or more, or 10% by mass or more, and 95% by mass or less, 65% by mass or less, 45% by mass or less, 35% by mass % or less, or 30% by mass or less.

(Surface modifier)
The surface of the inorganic fine particles may be modified with a surface modifier in order to further improve dispersibility. Surface modifiers can be used alone or in combination of two or more. As for the surface modifier, it is desirable to appropriately select and use a surface modifier that tends to improve the affinity with the polycarbonate resin to be used.

The surface modifier is not particularly limited as long as it can ensure the dispersibility of the inorganic fine particles in the composite polycarbonate resin. For example, a surface modifier having an acidic functional group can be used. Among them, a surface modifier having at least one acidic functional group selected from the group consisting of a sulfonic acid group, a phosphonic acid group, a phosphinic acid group and a carboxylic acid group is preferred. Such a surface modifier can further improve the dispersibility or refractive index of the inorganic fine particles.

Examples of surface modifiers having a sulfonic acid group include alkylsulfonic acids such as butanesulfonic acid, hexanesulfonic acid and dodecanesulfonic acid, and arylsulfonic acids such as benzenesulfonic acid, methylbenzenesulfonic acid and dodecylbenzenesulfonic acid. mentioned. Among them, arylsulfonic acid is preferable from the viewpoint of the dispersibility in polycarbonate resin and the effect of improving the refractive index.

Examples of surface modifiers having a phosphonic acid group include alkylphosphonic acids such as propanephosphonic acid and arylphosphonic acids such as benzenephosphonic acid. Among them, arylphosphonic acid is preferable from the viewpoint of dispersibility in polycarbonate resin and the effect of improving the refractive index.

Examples of surface modifiers having a phosphinic acid group include alkylphosphinic acids such as dimethylphosphinic acid, diethylphosphinic acid and di(2-ethylhexyl)phosphinic acid, and arylphosphinic acids such as phenylphosphinic acid and diphenylphosphinic acid. are mentioned. By using thiophosphinic acid or dithiophosphinic acid in which an oxygen atom constituting a phosphinic acid group is substituted with a sulfur atom, inorganic fine particles having a higher refractive index can be obtained. Among them, arylphosphinic acid is preferable, phenylphosphinic acid and diphenylphosphinic acid are more preferable, and diphenylphosphinic acid is particularly preferable, from the viewpoint of dispersibility in polycarbonate resin and effect of improving the refractive index.

Examples of surface modifiers having a carboxylic acid group include alkylcarboxylic acids such as butanoic acid, isobutanoic acid, methacrylic acid, hexanoic acid, octanoic acid, oleic acid, linoleic acid, and lauric acid, as well as benzoic acid, hydroxybenzoic acid, Arylcarboxylic acids such as phenoxybenzoic acid can be mentioned. By using a thiocarboxylic acid or a dithiocarboxylic acid in which an oxygen atom constituting a carboxyl group is substituted with a sulfur atom, inorganic fine particles having a higher refractive index can be obtained. Among these, arylcarboxylic acids are preferable, phenoxybenzoic acids having a phenoxy group at the ortho-, meta- or para-position are more preferable, and para-phenoxybenzoic acid is particularly preferable, from the viewpoint of dispersibility in polycarbonate resins and the effect of improving the refractive index.

The method of surface modification of the inorganic fine particles is not particularly limited, but it is carried out, for example, by the following methods.

A surface modifier is added to a mixture of methanol mixed with an aqueous dispersion of hydrophilic inorganic fine particles, then water and methanol are removed by azeotropic operation, and the solvent is replaced with toluene or methylene chloride. can prepare a dispersion in which surface-modified inorganic fine particles are dispersed. Optionally, surface-modified inorganic microparticles can be obtained by further solvent evaporation thereafter.

The amount of the surface modifier used is not particularly limited, but for example, from the viewpoint of the dispersibility in polycarbonate resin and the effect of improving the refractive index, it is preferably 1 to 30% by mass relative to the inorganic fine particles. , more preferably 3 to 25% by mass, particularly preferably 5 to 20% by mass.

<Optional component>
The organic-inorganic composite material of the present disclosure has known functions such as release agents, heat stabilizers, antioxidants, ultraviolet absorbers, flow modifiers, and antistatic agents within a range that does not impair the effects of the present disclosure. may contain a sexual additive. These can be used alone or in combination of two or more. Although some optional ingredients are described in detail below, optional ingredients that can be added are not limited to these.

(Release agent)
Release agents include, for example, fatty acid esters, polyolefin waxes (polyethylene waxes, 1-alkene polymers, etc., including those modified with functional group-containing compounds such as acid modification), fluorine compounds (polyfluoroalkyl ethers, etc. fluorine oil, etc.), paraffin wax, beeswax, and the like. Among these, fatty acid esters are preferred from the viewpoints of ease of availability, releasability and transparency. The amount of the release agent is preferably 0.005 to 0.5 parts by mass, more preferably 0.007 to 0.4 parts by mass, and still more preferably 0.01 to 0 parts by mass with respect to 100 parts by mass of the polycarbonate resin. .3 parts by mass. When the blending amount is above the lower limit of the above range, the effect of improving releasability is clearly exhibited, and when it is below the upper limit, adverse effects such as mold contamination during molding can be reduced.

Among the above, the fatty acid ester used as the preferred release agent will be further described in detail. Fatty acid esters are esters of fatty alcohols and fatty carboxylic acids. The aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. The number of carbon atoms in the aliphatic alcohol is preferably 3-32, more preferably 5-30. Monohydric alcohols include, for example, dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol. Polyhydric alcohols include, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. More preferably, the fatty acid ester is a polyhydric alcohol.

The number of carbon atoms in the aliphatic carboxylic acid is preferably 3-32, more preferably 10-22, even more preferably 14-20. Examples of aliphatic carboxylic acids include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanic acid, icosanoic acid, Saturated aliphatic carboxylic acids such as docosanoic acid (behenic acid) and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid and cetoleic acid can be mentioned. The aliphatic carboxylic acid is preferably saturated aliphatic carboxylic acid. Aliphatic carboxylic acids are usually produced from natural oils such as animal oils (beef tallow, lard, etc.) and vegetable oils (palm oil, etc.). Such aliphatic carboxylic acids derived from natural oils and fats are usually mixtures containing two or more carboxylic acids having different numbers of carbon atoms.

The acid value of the fatty acid ester is preferably 20 or less (can be substantially 0). When the fatty acid ester is a full ester (full ester), it preferably contains a small amount of free fatty acid in order to improve releasability, and the acid value of the fatty acid full ester is preferably 3-15. The iodine value of the fatty acid ester is preferably 10 or less (can be substantially 0). The acid value and iodine value of the fatty acid ester can be determined by the method specified in JIS K 0070:1992.

Fatty acid esters may be either partial esters or full esters, but partial esters are preferred in terms of better releasability and durability, and glycerol monoesters are particularly preferred. Glycerin monoester is mainly composed of monoester of glycerin and fatty acid. Suitable fatty acids include saturated fatty acids such as lauric acid, stearic acid, palmitic acid, behenic acid, arachidic acid and montanic acid, oleic acid and linoleic acid. , and unsaturated fatty acids such as sorbic acid, and particularly those containing stearic acid, palmitic acid, or glycerin monoester of behenic acid as the main component are preferred. Fatty acids may be those produced from natural fats and oils, in which case the fatty acid is a mixture containing two or more carboxylic acids having different numbers of carbon atoms, as described above. Even when the fatty acid is derived from natural fats and oils, the proportion of glycerin monoester in the fatty acid ester is preferably 60% by mass or more.

Partial esters are often inferior to full esters in terms of thermal stability. To improve the thermal stability of the partial ester, the sodium metal content of the partial ester is preferably less than 20 ppm, more preferably less than 5 ppm, and even more preferably less than 1 ppm. A fatty acid partial ester having a sodium metal content of less than 1 ppm can be produced by producing a fatty acid partial ester by a conventional method and then purifying it by molecular distillation or the like.

Specifically, after removing gas and low-boiling substances with a spray nozzle type degassing device, glycerin is distilled under the conditions of a distillation temperature of 120 to 150 ° C. and a degree of vacuum of 0.01 to 0.03 kPa using a falling film distillation device. After removing polyhydric alcohols such as alcohol, a centrifugal molecular distillation apparatus is used to distill a high-purity fatty acid partial ester under the conditions of a distillation temperature of 160 to 230 ° C. and a degree of vacuum of 0.01 to 0.2 Torr. and the like, and sodium metal can be removed as a distillation residue. By repeatedly subjecting the obtained distillate to molecular distillation, it is possible to further increase the purity and obtain a fatty acid partial ester with an even lower sodium metal content. It is also important to thoroughly clean the inside of the molecular distillation apparatus in advance by an appropriate method, and to prevent contamination of the sodium metal component from the external environment by, for example, increasing airtightness. Such fatty acid esters are available from specialist vendors (eg, Riken Vitamin Co., Ltd.).

(Phosphorus stabilizer: heat stabilizer)
The organic-inorganic composite material of the present disclosure preferably further contains various phosphorus-based stabilizers mainly for the purpose of improving the thermal stability during molding. Such phosphorus-based stabilizers include, for example, phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and their esters, and tertiary phosphines.

Phosphite compounds include, for example, triphenylphosphite, tris(nonylphenyl)phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, diisopropyl monophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, tris(diethylphenyl)phosphite, tris(di-iso-propylphenyl)phosphite, tris(di-n-butyl phenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, distearylpentaerythritol diphosphite, bis(2,4 -di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4 -ethylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, and dicyclohexylpentaerythritol diphosphite.

A phosphite compound having a ring structure formed by reacting with a dihydric phenol compound can also be used. Examples of such phosphite compounds include 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, 2,2′-methylenebis(4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl)phosphite, 2,2′-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2, 2′-methylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite and 2,2′-ethylidenebis(4-methyl-6-tert-butylphenyl) ) (2-tert-butyl-4-methylphenyl)phosphite.

Phosphate compounds include, for example, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tris(butoxyethyl) phosphate, dibutyl phosphate. , dioctyl phosphate, and diisopropyl phosphate, preferably triphenyl phosphate and trimethyl phosphate.

Phosphonite compounds include, for example, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'- biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylenedi Phosphonite, Tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, Tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite , bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6 -di-n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, and bis(2,6-di-tert- butylphenyl)-3-phenyl-phenylphosphonite, preferably tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite, and bis(di-tert-butylphenyl)-phenyl-phenylphosphonite, tetrakis (2,4-Di-tert-butylphenyl)-biphenylenediphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite are more preferred. A phosphonite compound can be preferably used in combination with a phosphite compound having an aryl group substituted with two or more alkyl groups.

Phosphonate compounds include, for example, dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

Tertiary phosphines include, for example, triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p - tolylphosphine, trinaphthylphosphine, and diphenylbenzylphosphine. Tertiary phosphine is preferably triphenylphosphine.

A phosphorus stabilizer can be used individually or in combination of 2 or more types. The phosphorus stabilizer is preferably a phosphite compound or a phosphonite compound. Among these, tris(2,4-di-tert-butylphenyl)phosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite and bis(2,4- Di-tert-butylphenyl)-phenyl-phenylphosphonite is preferred. A combined use of a phosphite compound or a phosphonite compound and a phosphate compound is also preferred.

(Hindered phenol stabilizer: antioxidant)
The organic-inorganic composite material of the present disclosure can be blended with a hindered phenol-based stabilizer for the main purpose of improving the thermal stability during molding and heat aging resistance. Examples of such hindered phenol stabilizers include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β-(4′-hydroxy-3′,5′-di-tert-butyl phenyl)propionate, 2-tert-butyl-6-(3′-tert-butyl-5′-methyl-2′-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis(4-methyl-6-tert-butylphenol), 2,2 '-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis(6-α-methyl-benzyl-p-cresol), 2,2′-ethylidene-bis(4,6-di-tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5- methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl-6-( 3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]- 1,1,-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4′-thiobis(6-tert-butyl-m-cresol), 4,4′- thiobis(3-methyl-6-tert-butylphenol), 2,2′-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, 4,4′-dithiobis(2,6-di-tert-butylphenol), 4,4′-trithiobis(2,6-di-tert-butylphenol) nol), 2,2′-thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4- Hydroxy-3′,5′-di-tert-butylanilino)-1,3,5-triazine, N,N′-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide) , N,N′-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert- Butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl- 4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6- dimethylbenzyl)isocyanurate, 1,3,5-tris[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]isocyanurate, and tetrakis[methylene-3- (3′,5′-Di-tert-butyl-4-hydroxyphenyl)propionate]methane. All of these are readily available. Hindered phenolic antioxidants can be used alone or in combination of two or more.

The amount of the phosphorus stabilizer and the hindered phenol antioxidant is preferably 0.0001 to 1 part by mass, more preferably 0.001 to 0.5 part by mass, and further preferably 0.001 to 0.5 part by mass, based on 100 parts by mass of the polycarbonate resin. It is preferably 0.005 to 0.1 parts by mass. If the amount of the phosphorus-based stabilizer and the hindered phenol-based antioxidant is at least the lower limit of the above range, a good stabilizing effect can be obtained. mold contamination can be suppressed.

In the organic-inorganic composite material of the present disclosure, antioxidants other than the above hindered phenol-based antioxidants can be used as appropriate. Such other antioxidants include, for example, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. The amount of these other antioxidants to be used is preferably 0.001 to 0.05 parts by weight per 100 parts by weight of the polycarbonate resin.

(Ultraviolet absorber)
The organic-inorganic composite material of the present disclosure can contain an ultraviolet absorber. Benzophenone-based UV absorbers include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2 -hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfoxylate hydrate, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4 '-Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sodium sulfonate, bis(5-benzoyl-4- hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Benzotriazole-based UV absorbers include, for example, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2- hydroxy-3,5-dicumylphenyl)benzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2′-methylenebis[4-(1, 1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-( 2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy- 5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2′-methylenebis( 4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis(1,3-benzoxazin-4-one), and 2-[2-hydroxy-3-(3,4,5, 6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole and 2-(2′-hydroxy-5′-methacryloxyethylphenyl)-2H-benzotriazole, and a vinyl system copolymerizable with the benzotriazole monomer 2, such as a copolymer with a monomer, a copolymer of 2-(2'-hydroxy-5'-acryloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the benzotriazole monomer; A polymer having a -hydroxyphenyl-2H-benzotriazole skeleton can be mentioned.

Examples of UV absorbers in the hydroxyphenyltriazine series include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl -1,3,5-triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5 -butyloxyphenol, and 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol. , 4-dimethylphenyl group-substituted compounds.

Cyclic iminoester-based UV absorbers include, for example, 2,2′-p-phenylenebis(3,1-benzoxazin-4-one), 2,2′-(4,4′-diphenylene)bis (3,1-benzoxazin-4-one), and 2,2′-(2,6-naphthalene)bis(3,1-benzoxazin-4-one).

Examples of cyanoacrylate-based UV absorbers include 1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3 ,3-diphenylacryloyl)oxy]methyl)propane, and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

The UV absorber may be a polymer-type UV absorber obtained by copolymerizing a UV-absorbing monomer having a radically polymerizable group and a monomer such as an alkyl (meth)acrylate. Examples of suitable UV-absorbing monomers include compounds containing a benzophenone skeleton, a benzotriazole skeleton, a hydroxyphenyltriazine skeleton, a cyclic iminoester skeleton, or a cyanoacrylate skeleton in the ester substituent of the (meth)acrylic acid ester. are mentioned.

Benzotriazole-based and hydroxyphenyltriazine-based UV absorbers are preferable from the viewpoint of UV-absorbing ability, and cyclic iminoester-based and cyanoacrylate-based UV absorbers are preferable from the viewpoint of heat resistance and hue. A ultraviolet absorber can be used individually or in combination of 2 or more types.

The amount of the ultraviolet absorber is generally 0.01 to 2 parts by mass, preferably 0.03 to 2 parts by mass, more preferably 0.04 to 1 part by mass, still more preferably 0.04 to 1 part by mass, with respect to 100 parts by mass of the polycarbonate resin. 05 to 0.5 parts by mass.

(flow modifier)
The organic-inorganic composite material of the present disclosure can contain a flow modifier within a range that does not impair the effects of the present disclosure. Such flow modifiers include, for example, styrene-based oligomers, polycarbonate oligomers (including highly branched, hyperbranched and cyclic oligomer types), polyalkylene terephthalate oligomers (including highly branched, hyperbranched and cyclic oligomer types). ), highly branched and hyperbranched aliphatic polyester oligomers, terpene resins, and polycaprolactones. The amount of the flow modifier is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, still more preferably 2 to 15 parts by mass, based on 100 parts by mass of the polycarbonate resin. Polycaprolactone is preferred as the fluidity modifier, and the amount of polycaprolactone is preferably 2 to 7 parts by mass with respect to 100 parts by mass of the polycarbonate resin. The number average molecular weight of polycaprolactone is generally 1,000 to 70,000, preferably 1,500 to 40,000, more preferably 2,000 to 30,000, even more preferably 2,500 to 15,000. Number average molecular weight is a value determined by gel permeation chromatography (GPC) using standard polystyrene.

(Antistatic agent)
An antistatic agent can be blended into the organic-inorganic composite material of the present disclosure for the main purpose of improving antistatic properties. Antistatic agents include, for example, phosphonium sulfonates, phosphites, and caprolactone-based polymers, with phosphonium sulfonates being preferred. Examples of sulfonic acid phosphonium salts include tetrabutylphosphonium dodecylsulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tributyloctylphosphonium dodecylbenzenesulfonate, tetraoctylphosphonium dodecylbenzenesulfonate, tetraethylphosphonium octadecylbenzenesulfonate, and dibutylbenzenesulfonate. tributylmethylphosphonium acid, triphenylmethylphosphonium dibutylnaphthalenesulfonate, and trioctylmethylphosphonium diisopropylnaphthalenesulfonate. Tetrabutylphosphonium dodecylbenzenesulfonate is preferred in terms of compatibility with polycarbonate and easy availability. The amount of the antistatic agent is preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 3.0 parts by mass, and still more preferably 0.3 to 2.0 parts by mass with respect to 100 parts by mass of the polycarbonate resin. 0 parts by weight, particularly preferably 0.5 to 1.8 parts by weight. If the amount of the antistatic agent is 0.1 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin, an antistatic effect can be obtained, and if it is 5.0 parts by mass or less, transparency or mechanical strength It is possible to obtain a molded product excellent in the surface of the molded product, and it is possible to suppress the occurrence of appearance defects such as silver or peeling on the surface of the molded product.

The organic-inorganic composite material of the present disclosure may further contain various additives such as bluing agents, fluorescent dyes, flame retardants, and dyes and pigments. These can be appropriately selected and used as long as the effects of the present disclosure are not impaired.

The bluing agent is preferably contained in the organic-inorganic composite material in an amount of 0.05 to 3.0 ppm (mass ratio) based on the polycarbonate resin. Bluing agents include, for example, Macrolex Violet B and Macrolex Blue RR from Bayer, and Polysynthrene Blue RLS from Clariant.

Examples of fluorescent dyes (including fluorescent brighteners) include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, thioindigo-based fluorescent dyes, xanthene-based fluorescent dyes, and xanthone-based fluorescent dyes. , thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiazine-based fluorescent dyes, and diaminostilbene-based fluorescent dyes. The amount of the fluorescent dye (including the fluorescent brightening agent) is preferably 0.0001 to 0.1 parts by weight per 100 parts by weight of the polycarbonate resin.

Examples of flame retardants include metal sulfonate flame retardants, halogen-containing compound flame retardants, phosphorus-containing compound flame retardants, and silicon-containing compound flame retardants. Among these, metal sulfonate flame retardants are preferred. The amount of the flame retardant is preferably 0.01 to 1 part by mass, more preferably 0.05 to 1 part by mass, with respect to 100 parts by mass of the polycarbonate resin.

The organic-inorganic composite material of the present disclosure may appropriately contain other components in addition to those mentioned above as long as the effects of the present disclosure are not significantly impaired. Other components include, for example, resins other than polycarbonate resins. Other components can be used alone or in any combination and ratio of two or more. Examples of resins other than polycarbonate resins include thermoplastic polyester resins such as polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), polybutylene terephthalate resin (PBT resin); Impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylene propylene system Styrene resin such as rubber-styrene copolymer (AES resin); polyethylene resin (PE resin), polypropylene resin (PP resin), cyclic cycloolefin resin (COP resin), cyclic cycloolefin copolymer (COP) resin, etc. polyolefin resin; polyamide resin (PA resin); polyimide resin (PI resin); polyetherimide resin (PEI resin); polyurethane resin (PU resin); polysulfone resins (PSU resins); and polymethacrylate resins (PMMA resins).

The method for adding the additive to the organic-inorganic composite material of the present disclosure is not particularly limited, and known methods can be used. As the most common method, after pre-mixing polycarbonate resin and additives, it is put into an extruder and melt-kneaded, and the extruded threads are cooled and cut by a pelletizer to produce a pellet-shaped molding material. method.

Both a single-screw extruder and a twin-screw extruder can be used as the extruder in the above method, but the twin-screw extruder is preferable from the viewpoint of productivity and kneadability. A representative example of the twin-screw extruder is ZSK (manufactured by Werner & Pfleiderer, trade name). Specific examples of similar types include TEX (manufactured by Japan Steel Works, Ltd., trade name), TEM (manufactured by Toshiba Machine Co., Ltd., trade name), and KTX (manufactured by Kobe Steel, Ltd., trade name). can. As the extruder, it is preferable to use an extruder having a vent capable of degassing moisture in the raw material or volatile gas generated from the melt-kneaded resin. A vacuum pump is preferably installed to efficiently discharge the generated moisture or volatile gas from the vent to the outside of the extruder. A screen for removing foreign matters and the like mixed in the extruded raw material may be installed in a zone in front of the die part of the extruder to remove foreign matters from the resin composition. Screens can include, for example, wire mesh, screen changers, and sintered metal plates (such as disc filters).

Although the additives can be supplied to the extruder independently of the polycarbonate resin, they are preferably premixed with the polycarbonate resin as described above. Means for premixing include, for example, Nauta mixers, V-blenders, Henschel mixers, mechanochemical devices, and extrusion mixers. A more suitable method is, for example, to prepare a master agent by mixing a portion of the polycarbonate resin and additives with a high-speed agitator such as a Henschel mixer, and then mix the master agent with the remaining polycarbonate resin and a high-speed agitator such as a Nauta mixer. It is a method of mixing with a stirrer that is not

The resin extruded from the extruder is directly cut and pelletized, or is pelletized by forming strands and then cutting the strands with a pelletizer. It is preferable to clean the atmosphere around the extruder when it is necessary to reduce the influence of external dust and the like. In the production of pellets, various methods that have already been proposed for polycarbonate resins for optical discs are used to narrow the shape distribution of pellets, further reduce miscuts, and further reduce fine powder generated during transportation. It is preferable to reduce the amount of air bubbles (vacuum bubbles) generated inside the strands or pellets. In order to reduce miscuts, measures such as temperature control of threads during cutting with a pelletizer, blowing of ionized air during cutting, optimization of the rake angle of the pelletizer, and appropriate formulation of release agent, as well as measures such as cutting and filtering the mixture of pellets and water to separate pellets, water and miscuts. An example of the method is the method disclosed in Patent Document 6, for example. In this way, the molding can be made into a high cycle, and the occurrence of defects such as silver can be reduced.

The amount of miscuts in the molding material (pellet) is preferably 10 ppm or less, more preferably 5 ppm or less. Here, the miscut material means a powder or granular material finer than a pellet of a desired size that passes through a JIS standard sieve with an opening of 1.0 mm. The shape of the pellet may be a general shape such as a cylinder, a prism, and a sphere, preferably a cylinder (including an elliptical cylinder), and the diameter of such a cylinder is preferably 1.5 to 4 mm, more preferably 2 to 3.5 mm. The ratio of the minor axis to the major axis of the elliptic cylinder is preferably 60% or more, more preferably 65% or more. The length of the cylinder is preferably 2-4 mm, more preferably 2.5-3.5 mm.

<Method for producing organic-inorganic composite material>
A method for producing an organic-inorganic composite material of the present disclosure includes obtaining a polycarbonate resin having a group represented by Formula 1, and dispersing inorganic fine particles in the polycarbonate resin. The steps for obtaining the polycarbonate resin having the group represented by Formula 1 are as described above for the method for producing the polycarbonate resin.

The step of dispersing the inorganic fine particles in the polycarbonate resin is not particularly limited. Specific examples include a method of mixing a polycarbonate resin solution and an inorganic fine particle dispersion, and a method of melting and mixing a polycarbonate resin powder and an inorganic fine particle powder.

For example, in the method of mixing the polycarbonate resin solution and the inorganic fine particle dispersion, the polycarbonate resin solution and the inorganic fine particle dispersion may be mixed at once, or the polycarbonate resin solution is gradually added dropwise to the inorganic fine particle dispersion. may be mixed. A plasticizer may be used in the dispersing step. The plasticizer may be added in advance to the polycarbonate resin solution or the inorganic fine particle dispersion, or may be added at the time of mixing the polycarbonate resin solution and the inorganic fine particle dispersion.

<Method of forming organic-inorganic composite material>
As a method for molding the organic-inorganic composite material of the present disclosure, general polycarbonate resin molding methods such as injection molding, extrusion molding, compression molding, and cast molding can be employed. Compression molding and cast molding are preferred from the viewpoint of fluidity of the organic-inorganic composite material.

The organic-inorganic composite material of the present disclosure can be used as various molded articles, and can be suitably used as molded articles that particularly require transparency or a high refractive index. The organic-inorganic composite material of the present disclosure is, for example, optical lenses, optical discs, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, evaporated plastic reflectors, structural materials for optical parts such as displays, personal computers or mobile phones. It can be advantageously used as molded articles for electric and electronic parts such as exteriors or front panels, automobile applications such as automobile headlamps or windows, and functional material applications, and is particularly suitable for optical lenses and optical films.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto. In addition, "parts" in the examples means "mass parts". The polycarbonate resins, inorganic fine particles and respective evaluation methods used in the examples are as follows.

<Evaluation method>
(Carboxyl group amount)
A sample of the organic-inorganic composite material was dissolved in benzyl alcohol under a nitrogen atmosphere, and titration was performed with a benzyl alcohol solution of sodium hydroxide using phenol red as an indicator.

(Glass transition temperature (Tg))
Using a thermal analysis system DSC-2910 manufactured by TA Instruments Co., Ltd. using 8 mg of an organic-inorganic composite sample, under a nitrogen atmosphere (nitrogen flow rate: 40 mL / min) in accordance with JIS K7121, Temperature rising rate: Measured under the condition of 20°C/min.

(Transmittance)
The light transmittance at a wavelength of 589 nm at 25° C. of the film formed using the organic-inorganic composite material was measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

(refractive index)
The refractive index (wavelength: 589 nm) at 25° C. of the film formed using the organic-inorganic composite material was measured using an ATAGO DR-M2 Abbe refractometer.

(transparency)
By visual observation, the case where there was no white turbidity was evaluated as good, and the case where there was white turbidity was evaluated as poor.

(Average particle size)
Using a methylene chloride dispersion of inorganic fine particles, the average particle size of the inorganic fine particles was measured by dynamic light scattering (DLS).

<Polycarbonate resin>
(Manufacturing method of PC1)
A reactor equipped with a thermometer and a stirrer was charged with 89.7 parts of a 48% aqueous sodium hydroxide solution and 448 parts of ion-exchanged water, and 0.1 part of hydrosulfite and 2,2-bis(4- After dissolving 63.9 parts of hydroxyphenyl)propane (hereinafter referred to as BPA), 9.6 parts of 2,2-bis(3-allyl-4-hydroxyphenyl)propane (hereinafter referred to as BPDAL) was dissolved in 264 parts of methylene chloride. After adding the solution, 40.0 parts of phosgene was blown into the mixture at 15 to 25° C. over about 70 minutes while stirring. After phosgene was blown in, 12.8 parts of a 48% aqueous sodium hydroxide solution and 1.9 parts of p-tert-butylphenol were added, stirring was resumed, and after emulsification, 0.1 part of triethylamine was added, and the mixture was further stirred at 25 to 35°C. The reaction was terminated after stirring for 1 hour.

After completion of the reaction, the product was diluted with methylene chloride and washed with water, then hydrochloric acid was added to make it acidic, and the water was washed with water. Evaporation gave polycarbonate resin flakes (PC1). Various evaluations were performed on the obtained flakes. The results are listed in Table 1.

(Manufacturing method of PC2)
A flask equipped with a stirrer tip was charged with 30.0 parts of PC1 flakes, 7.0 parts of azobisisobutyronitrile (hereinafter referred to as AIBN), and 9.0 parts of 3-mercaptopropanoic acid, and 105 parts of toluene and 178 parts of chloroform. After adding and dissolving parts, the mixture was heated to 70° C. under a nitrogen atmosphere and reacted for 4 hours.

After completion of the reaction, the reaction solution was added to methanol to precipitate the polycarbonate resin, and the precipitate was collected by filtration under reduced pressure. Then, after dissolving the obtained precipitate in methylene chloride, it was added to hexane to precipitate the polycarbonate resin. The resulting precipitate was collected by filtration under reduced pressure and dried to obtain a polycarbonate resin powder (PC2). The obtained powder was evaluated in the same manner. The results are listed in Table 1.

(Manufacturing method of PC3)
The same operation as the production method of PC1 was performed except that 67.4 parts of BPA and 4.8 parts of BPDAL were used as raw materials. The same evaluation was performed on the obtained flakes. The results are listed in Table 1.

(Manufacturing method of PC4)
30.0 parts of flakes of PC3 were used instead of PC1, and the same operation as in the production method of PC2 was performed except that 3.5 parts of AIBN and 4.5 parts of 3-mercaptopropanoic acid were used. The obtained powder was evaluated in the same manner. The results are listed in Table 1.

(Manufacturing method of PC5)
30.0 parts of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (hereinafter BPEF), 1.1 parts of BPDAL, 15.4 parts of diphenyl carbonate (hereinafter DPC) and 2 parts of sodium hydroxide as a catalyst. 9×10 ⁻⁶ parts and 6.7×10 ⁻⁴ parts of tetramethylammonium hydroxide were melted by heating at 180° C. in a nitrogen atmosphere. After that, the temperature was raised to 220° C. over 20 minutes, and the degree of pressure reduction was adjusted to 13.7 kPa. After that, the temperature was further raised to 260° C. over 40 minutes, and the degree of pressure reduction was adjusted to 1 kPa. After holding at that temperature for 10 minutes, the degree of pressure reduction was reduced to 133 Pa or less. After completion of the reaction, nitrogen was discharged from the bottom of the reaction tank under pressure, and while cooling in a water tank, pellets were obtained by cutting with a pelletizer (PC5). Various evaluations were performed on the obtained pellets. The results are listed in Table 1.

(Manufacturing method of PC6)
The same operation as the production method of PC2 was performed except that 30.0 parts of PC5 pellets were used as raw materials instead of PC1, and 2.0 parts of AIBN and 2.6 parts of 3-mercaptopropanoic acid were used. The obtained powder was evaluated in the same manner. The results are listed in Table 1.

(Manufacturing method of PC7)
30.5 parts of BPEF, 0.1 part of 2,4-dihydroxybenzoic acid (hereinafter referred to as DHBA), 14.8 parts of DPC, and 4.5×10 ⁻³ parts of zinc oxide as a catalyst are heated at 180° C. in a nitrogen atmosphere to melt. rice field. After that, the temperature was raised to 200° C., and the degree of pressure reduction was adjusted to 20 kPa. After that, the temperature was further raised to 240° C., the degree of pressure reduction was adjusted to 1 kPa, and the reaction was carried out for 1 hour. After that, the temperature was raised to 270° C., and the degree of pressure reduction was set to 200 Pa or less. After completion of the reaction, nitrogen was discharged from the bottom of the reactor under pressure, and while cooling in a water tank, pellets were obtained by cutting with a pelletizer (PC7). Similar evaluation was performed on the obtained pellets. The results are listed in Table 1.

(Manufacturing method of PC8)
The same operation as the production method of PC7 was performed except that 28.1 parts of BPEF, 1.4 parts of DHBA and 15.6 parts of DPC were used as raw materials. The obtained polycarbonate did not dissolve in methylene chloride, and uniform pellets could not be produced.

<Surface modification of zirconia fine particles>
A surface modifier equivalent to 10 to 30% by mass of ZrO ₂ is placed in a 100 mL eggplant flask equipped with a stirrer tip, and dissolved in 10 g _of methanol and 15 g of toluene. Kogyo Co., Ltd.: SZR-W) was added dropwise and mixed. After the mixture was stirred at room temperature for 1 hour, the solvent was distilled off with a rotary evaporator until the volume became about 3 to 5 mL. Distillation was carried out by reducing the pressure to such an extent that bumping does not occur in the liquid phase.

Further, 10 g of methanol and 15 g of toluene were added to the mixed solution to obtain a transparent dispersion without an interface, and the solvent was again distilled off until the volume became about 3 to 5 mL. By repeating this operation several times, the mixed solvent of water/methanol/toluene was replaced with methylene chloride alone to obtain a methylene chloride dispersion of _ZrO2 fine particles. Further, the methylene chloride dispersion was vacuum-dried at room temperature for 24 hours to remove methylene chloride and obtain surface-modified ZrO ₂ powder. Table 2 shows the results.

<Organic-inorganic composite materials>
(Manufacturing method of cast film)
The methylene chloride solution of the polycarbonate resin was added dropwise to the methylene chloride dispersion of the surface-modified _ZrO2 fine particles over 5 minutes, followed by stirring for 30 minutes. This dispersion was cast on a glass petri dish, dried sufficiently at room temperature, and then dried at a temperature of 100° C. or less for 12 hours to prepare a film having a thickness of about 100 μm. Various evaluations of the produced film were performed. The results are listed in Table 3. Table 3 shows the types of surface modifiers used and the amounts added as inorganic components.

(Method for manufacturing molded article)
A methylene chloride dispersion containing surface-modified _ZrO2 fine particles and a polycarbonate resin, which was made into a molded article in the same manner as the cast film production method, was dried at 80 ° C. for 4 hours to distill off the methylene chloride, resulting in an organic-inorganic composite. Got flakes. The flakes were press-molded with a vacuum heat press machine (compression molding machine: SFV-10, vacuum pump unit: GXD-360 manufactured by Shindo Kinzoku Kogyo Co., Ltd.) to obtain a molded plate having a thickness of about 1 mm. Press molding conditions were a mold temperature of 240° C., a primary pressure of 1 MPa (30 seconds), and a secondary pressure of 1.5 MPa (5 minutes). Transparency evaluation of the manufactured molded plate was performed. The results are listed in Table 3. Table 3 shows the types of surface modifiers used and the amounts added as inorganic components.

<result>
As is clear from Table 3, in Examples 1 to 9, the refractive index was improved and an organic-inorganic composite material having transparency could be provided. When a polycarbonate resin having no carboxyl group is used as in Comparative Examples 1 and 2, the inorganic fine particles cannot be uniformly dispersed, and the aggregation of the fine particles results in a low transmittance. Refractive index measurement could not be performed.

Further, as is clear from Tables 1 and 3, when a polycarbonate resin obtained by copolymerizing a diol having a carboxyl group was used as in Comparative Examples 3 and 4, a large amount of carboxyl groups were introduced into the polycarbonate resin. It was not possible to maintain a uniform dispersion state in the molded product.

The organic-inorganic composite material of the present disclosure has a high refractive index and excellent transparency, and desired properties such as a refractive index can be obtained by adjusting the content of the inorganic fine particles. Molded articles (for example, films and sheets) obtained using the organic-inorganic composite material of the present disclosure can be used in various fields.

Claims (8)

Including a polycarbonate resin having a group represented by the following formula 1, and inorganic fine particles,
the surface of the inorganic fine particles is modified with a surface modifier,
the surface modifier has at least one acidic functional group selected from the group consisting of a sulfonic acid group, a phosphonic acid group, a phosphinic acid group, and a carboxylic acid group;
Organic-inorganic composites:

In formula 1,
R ¹ and R ² each independently represent a group selected from the group consisting of an alkylene group, an aralkylene group, an arylene group and a cycloalkylene group, and the hydrogen atom of R ² may be substituted with a carboxyl group. The organic-inorganic composite material according to claim 1, wherein the polycarbonate resin comprises a structural unit represented by the following formula 2:

In formula 2,
R ³ and R ⁴ represent a group represented by the formula 1,
a and b are each independently an integer of 0 to 4 that satisfies a+b≧1;
^R5 and ^R6 each independently represent a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an alkenyl group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a nitro group, an aldehyde group; , and represents a group selected from the group consisting of a cyano group,
c and d are each independently an integer of 0 to 4 that satisfies c ≤ 4-a and d ≤ 4-b;
X represents a single bond, an alkylene group, an aralkylene group, an arylene group, a cycloalkylene group, a sulfur atom, or an oxygen atom. 3. The organic-inorganic composite material according to claim 1 , wherein the surfaces of said inorganic fine particles are modified with 1 to 30% by mass of said surface modifier relative to said inorganic fine particles. The organic-inorganic composite material according to any one of claims 1 to 3 , wherein the inorganic fine particles have an average particle size of 1 to 20 nm. The organic-inorganic composite material according to any one of claims 1 to 4 , wherein the content of the inorganic fine particles is 1 to 95% by mass with respect to the polycarbonate resin. The organic-inorganic composite material according to any one of claims 1 to 5 , wherein the inorganic fine particles are at least one selected from the group consisting of zirconium oxide, titanium oxide, tin oxide, silicon oxide, and aluminum oxide. A molded article obtained using the organic-inorganic composite material according to any one of claims 1 to 6 . reacting a polycarbonate resin having a carbon-carbon double bond and a thiol compound having a carboxyl group to prepare a polycarbonate resin having a group represented by the formula 1;
7. The method for producing an organic-inorganic composite material according to any one of claims 1 to 6 , comprising mixing a polycarbonate resin having a group represented by formula 1 and the inorganic fine particles.