TW201428054A - Thermoplastic resin composition having fluorene skeleton and optical member - Google Patents

Abstract

The purpose of the present invention is to provide: a thermoplastic resin composition which has high transparency, excellent molding fluidity, excellent molding stability and excellent wet heat stability and an optical member which is formed from this thermoplastic resin composition. The present invention is a thermoplastic resin composition having a fluorene skeleton, which contains 100 parts by weight of a thermoplastic resin that has a fluorene skeleton and contains a repeating unit formed of an ester unit or a carbonate unit derived from a monomer represented by general formula (1) and 0.1-10 parts by weight of an aliphatic epoxy compound that has a moiety represented by general formula (2).

Description

Thermoplastic resin composition and optical member having an anthracene skeleton

The present invention relates to a thermoplastic resin composition having an anthracene skeleton which is excellent in transparency, molding fluidity, molding stability, and wet heat stability, and an optical member comprising the same.

Optical glass or optical transparent resin can be used as the material of the optical lens used in the optical system of various cameras such as a camera, a film-integrated camera, and a camera. The optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance, and the like, and various types of materials having a refractive index or an Abbe number are various, but the material cost is high, and the formability is poor. Low productivity.

Further, the optical transparent resin, in which the thermoplastic optical transparent resin has an advantage of being mass-produced by injection molding, can be used as a material for a camera lens. However, in recent years, the optical properties obtained by the lens resin have become higher as the weight of the borrowed product is shortened or the camera is highly pixelated. In particular, in recent years, as the resolution obtained by the increase in the number of pixels has increased, an optical lens having high image forming performance and lower birefringence has been sought.

A resin using a 9,9-biscresol oxime derivative or a 9,9-bis[4-(2-hydroxyethoxy)phenyl]anthracene derivative has a high refractive index, low birefringence, and is excellent. Optical properties can be used for optical lenses.

Thus, optical lenses can be used in a wide variety of applications, but depending on the application, the shape or size is very different. For example, the camera lens for a mobile phone has a diameter of 5 mm and a thickness of about 0.3 mm, and is very small and thin. In recent years, it has been further reduced in size and thickness. When such a small-thin-thickness lens is injection-molded, if the molding fluidity of the resin is insufficient, a lens having a desired shape cannot be obtained, and the molding fluidity is a very important property.

A plasticizer can generally be used for the modification of the molding fluidity of the thermoplastic resin.

As the plasticizer, a phthalate-based plasticizer, a trimellitate-based plasticizer, a phosphate triester-based plasticizer, or the like can be widely used.

In the other modification method of the fluidity, Patent Document 1 proposes a method of adding a polycarbonate oligomer or polycaprolactone to a polycarbonate resin.

Further, in Patent Documents 2 and 3, a method of modifying a molding fluidity of a thermoplastic resin having a fluorene structure has been proposed, and a method of a polyether ester resin or a styrene-based oligomer resin has been proposed.

Further, the characteristics required for the optical lens are not only the optical characteristics and the molding fluidity, but it is difficult to use as a lens if it is used as a lens to affect the focal length or the color difference, and is an indicator of its long-term reliability. Moisture and heat stability is also an important feature. Further, the formation stability such as a small yield at the time of molding is also a very important characteristic.

However, the method using a plasticizer and the compositions of Patent Documents 1 to 3 are problematic in terms of high transparency, shape stability, and heat and humidity stability.

In other words, in the thermoplastic resin using the anthracene derivative, it has high transparency, and the molding fluidity and the molding stability are directly maintained, and the heat and humidity stability resistance cannot be sufficiently satisfied.

(Patent Document 1) Japanese Patent Laid-Open Publication No. 2011-63812

(Patent Document 2) Japanese Patent Laid-Open Publication No. 2006-104322

(Patent Document 3) Japanese Patent Laid-Open Publication No. 2006-143831

Invention disclosure

Therefore, an object of the present invention is to provide a thermoplastic resin composition having an anthracene skeleton which is excellent in transparency, molding fluidity, molding stability, and wet heat stability, and an optical member comprising the same.

The present inventors have accumulated concentrated research for this purpose. As a result, it has been found that the epoxy resin having an anthracene skeleton is mixed with an appropriate amount of an aliphatic epoxy compound, and has high transparency, molding fluidity, mold stability, and heat and humidity stability.

That is, the present invention is

A thermoplastic resin composition having an anthracene skeleton, which comprises 100 parts by weight of a thermoplastic resin (hereinafter sometimes referred to as a thermoplastic resin having an anthracene skeleton) and 0.1 to 10 parts by weight of an aliphatic epoxy compound, which is composed of the thermoplastic resin. The system contains a repeating unit composed of a carbonate unit or an ester unit derived from a monomer represented by the following formula (1);

(wherein R1, R2, R3 and R4 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and a carbon number of 5; a cycloalkyloxy group of -20, an aryl group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms; an alkylene group having 2 to 8 carbon atoms; a cycloalkyl group having 5 to 12 carbon atoms; a carbon number of 6 to 20 exoaryl; n and m are integers of 0 to 10); the aliphatic epoxy compound has a moiety represented by the following formula (2); (wherein R is CH ₃ or H, o is 1 to 20, p is 1 to 10, and I is 1 to 20).

2. The thermoplastic resin composition having an anthracene skeleton according to the above item 1, wherein the aliphatic epoxy compound is an epoxy compound having a glycerin skeleton.

3. The thermoplastic resin composition having an anthracene skeleton according to the above item 2, wherein The epoxy compound having a glycerol skeleton is an epoxidized vegetable oil.

4. The thermoplastic resin composition having an anthracene skeleton according to the above item 3, wherein the epoxidized vegetable oil is epoxidized soybean oil or epoxy linseed oil.

5. The thermoplastic resin composition having an anthracene skeleton according to the above item 4, wherein the number of epoxy groups of the epoxidized soybean oil and the epoxidized linseed oil is 2 to 8.

6. The thermoplastic resin composition having an anthracene skeleton according to any one of the above items 1 to 5, wherein the thermoplastic resin comprises a repeating unit composed of a carbonate unit derived from a monomer represented by the formula (1) and a repeating unit composed of a carbonate unit derived from a monomer represented by the following formula (3); a ratio of the formula (1) to the formula (3) is (1): (3) = 100 in terms of a molar ratio : polycarbonate in the range of 0 to 50:50, and in order to dissolve 0.7 g of methylene chloride in 100 ml, the specific viscosity measured at 20 ° C is 0.12 to 0.55. (In the formula, R5 to R8 are each independently a hydrogen atom, a hydrocarbon group or a halogen atom having an aromatic group having 1 to 9 carbon atoms, and W is a single bond or an aromatic group having 1 to 20 carbon atoms. Hydrocarbyl group, O, S, SO, SO ₂ , CO or COO group).

The thermoplastic resin composition having an anthracene skeleton according to any one of the above items 1 to 5, wherein the thermoplastic resin contains an ester unit derived from a monomer represented by the following formula (4) and/or The monomer-derived ester-based unit represented by the formula (5); the ratio of the formula (1) to the total of the formula (4) and the formula (5) is (1) in terms of a molar ratio: ((4)+ (5)) a polyester carbonate in the range of 50:50 to 95:5, and in order to dissolve 0.7 g of methylene chloride in 100 ml, the specific viscosity measured at 20 ° C is 0.12 to 0.55. (wherein R13 and R14 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aromatic oxygen having 6 to 20 carbon atoms. base) (wherein R15 and R16 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aromatic oxygen having 6 to 20 carbon atoms. base).

8. The thermoplastic resin composition having an anthracene skeleton according to any one of items 1 to 7, wherein the monomer represented by the formula (1) is 9,9-bis(4-hydroxy-3-methylbenzene). (茀) or 9,9-bis(4-(2-hydroxyethoxy)phenyl)anthracene.

An optical member comprising a thermoplastic resin composition having an anthracene skeleton according to any one of items 1 to 8 above.

10. The optical member according to the above item 9, wherein the optical member is a camera Optical lens for mirror, optical pickup lens, microarray lens, projector lens or Fresnel lens.

11. The optical member according to item 10 above, wherein the thickness of the optical lens is 0.5 mm or less.

The best form for implementing the invention <Aliphatic epoxy compound>

The aliphatic epoxy compound of the present invention has a moiety represented by the following formula (2)

(wherein R is CH ₃ or H, o is 1 to 20, p is 1 to 10, and I is 1 to 20).

When o is from 1 to 20, the effect of the alkyl group can be directly maintained, and the forming fluidity can be improved. When o is less than 1, the molding fluidity is insufficient, and when it is more than 20, the compatibility with the resin is deteriorated, and transparency cannot be maintained.

When p is from 1 to 10, the epoxy group can capture moisture, inhibit hydrolysis of the thermoplastic resin composition, and improve wet heat stability. When p is less than 1, the heat and humidity stability is lowered. When it is more than 10, the aliphatic epoxy compounds react with each other to form a multi-volume, and the moisture-heat stability is lowered. Further preferably, it is 2-8, more preferably 3-8.

In the formula, when I is from 1 to 20, the molding fluidity which maintains high transparency and moisture and heat stability is improved. When I is less than 1, the molding fluidity is insufficient, and the moist heat resistance is deteriorated. Further, there is a possibility that bleeding due to the resin occurs. Further, when I is more than 20, the compatibility with the resin is deteriorated, and transparency cannot be maintained.

The aliphatic epoxy compound used in the present invention is a compound having one or more epoxy groups in a molecular skeleton. When one or more epoxy groups are contained, an epoxy group reacts with water to inhibit hydrolysis of the resin, and the heat and humidity stability is improved.

The above aliphatic epoxy compound used in the present invention is a compound having a glycerin skeleton and an aliphatic chain of an epoxy group bonded via an ester, and particularly, a methylene group of a fatty chain excluding the carbonyl group of the above formula (2) The number is from 2 to 20, and is preferable from the viewpoints of high transparency, molding fluidity, moisture and heat stability, and formation stability such as suppression of gas generation during molding.

Among such aliphatic epoxide compounds having a glycerin skeleton, epoxidized vegetable oil is preferred, and epoxidized soybean oil and epoxidized linseed oil are more preferred. In particular, it is preferred that the epoxidized soybean oil and the epoxidized linseed oil having a number of epoxy groups of 2 to 6 are excellent from the viewpoint of heat and humidity stability.

The aliphatic epoxy compound is required to be contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the thermoplastic resin having an anthracene skeleton described later. When the content is less than 0.1 part by weight, the molding fluidity is poor. In addition, when it is more than 10 parts by weight, it is not compatible with the resin, and transparency cannot be maintained. Further, when it is used under high temperature and high humidity, the molecular weight of the thermoplastic resin having a ruthenium skeleton is lowered, and the heat resistance of the resin such as hue and strength is lowered. Reduced sex.

The content of the above aliphatic epoxy compound used in the present invention is It is preferably 0.1 to 8 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the thermoplastic resin having an anthracene skeleton.

<茀 compound>

The following formula (1) is used in the present invention.

(wherein R1, R2, R3 and R4 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and a carbon number of 5; a cycloalkyloxy group of ~20, an aryl group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms; an alkylene group having 2 to 8 carbon atoms and a cycloalkyl group having 5 to 12 carbon atoms or The monomer represented by the aryl group having 6 to 20 carbon atoms; n and m being an integer of 0 to 10 is an anthracene compound.

R1, R2, R3 and R4 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, and a carbon number of 5 to 10. Cycloalkoxy.

Specifically, the ruthenium compound is preferably 9,9-bis(4-hydroxy-3-methylphenyl)anthracene, 9,9-bis(4-hydroxyphenyl)anthracene, 9,9-bis(4-hydroxy- 3-phenylphenyl)anthracene, 9,9-bis(4-hydroxyethoxyphenyl)anthracene, 9,9-bis(4-hydroxypropoxyphenyl)anthracene, 9,9-bis-( 4-hydroxybutoxyphenyl)anthracene and the like. Among them, 茀 合 The system is more preferably 9,9-bis(4-hydroxy-3-methylphenyl)anthracene or 9,9-bis(4-(2-hydroxyethoxy)phenyl)anthracene.

<thermoplastic resin>

The thermoplastic resin used in the present invention contains a repeating unit composed of a carbonate unit or an ester unit derived from the oxime compound of the above formula (1), and examples thereof include polycarbonate and polyester carbonate.

[polycarbonate]

The polycarbonate used in the present invention may be copolymerized with the hydrazine compound represented by the above formula (1) or may have a carbonate unit derived from a dihydroxy compound represented by the following formula (3). Repeat unit.

(In the formula, R5 to R8 are each independently a hydrogen atom, a hydrocarbon group or a halogen atom having an aromatic group having 1 to 9 carbon atoms, and W is a single bond or an aromatic group having 1 to 20 carbon atoms. Hydrocarbyl, O, S, SO, SO ₂ , CO or COO groups)

In the polycarbonate used in the present invention, W of the formula (3) is preferably a group represented by the following formula (6).

(wherein R9 and R10 are the same or different, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R11 and R12 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n is an integer of 4 to 7. ).

Preferred dihydroxy compounds used are, for example, 4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)ethane (bisphenol E), 2,2-bis(4-hydroxyl). Phenyl)propane (bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C), 2,2-bis(4-hydroxyphenyl)butane, 1 ,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z), 1,1-bis(4-hydroxybenzene) -3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)pentane, 4,4'-(p-phenylphenyldiisopropylidene)diphenol , α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene (bisphenol M), 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, etc. The aromatic diol is preferably bisphenol A, bisphenol Z, bisphenol C, bisphenol E or bisphenol M. Especially suitable for bisphenol A. These may be used alone or in combination of two or more.

Further, an aromatic dihydroxy compound such as hydroquinone or m-xylenol which does not correspond to the general formula (3), an aliphatic diol such as ethylene glycol, or a tricyclic ring may be contained in a range which does not inhibit optical characteristics [ 5.2.1.02,6]decane dimethanol, cyclohexyl Alkane-1,4-dimethanol, decahydronaphthalene-2,6-dimethanol, norbornane dimethanol, pentacyclopentadecyldiethanol, cyclopentane-1,3-dimethanol, spiroglycol, 1 , 4:3,6-dianhydride-D-sorbitol, 1,4:3,6-dianhydride-D-mannitol, 1,4:3,6-dianhydride-L-iditol The carbonate unit derived from an alicyclic diol. These may be used singly or in combination of two or more types.

The ratio of the formula (1) to the formula (3) is in the range of (1): (3) = 100: 0 to 50: 50 in terms of molar ratio, preferably in the range of 98:2 to 50:50. More preferably, it is in the range of 95:5~50:50.

[Manufacturing method of polycarbonate]

Such a polycarbonate resin can be produced by a conventionally known reaction means for producing a general polycarbonate resin, for example, a method in which a dihydroxy compound reacts a carbonate precursor such as phosgene or a carbonic acid diester.

In the case of a carbonate precursor, for example, a reaction using phosgene is generally carried out in the presence of an acid binder and a solvent. As the acid binder, an amine compound such as pyridine or the like can be used. As the solvent, a halogenated hydrocarbon such as dichloromethane or chlorobenzene can be used. At this time, the reaction temperature is generally from 0 to 40 ° C, and the reaction time is from several minutes to 5 hours.

In the polycarbonate resin of the present invention, a monofunctional phenol which is generally used as a terminal blocking agent can be used in the polymerization reaction. In particular, when phosgene is used as a reaction of a carbonate precursor, monofunctional phenols are generally used as a blocking agent to adjust the molecular weight, and the obtained aromatic polycarbonate resin is based on a terminal group of a monofunctional phenol. It is sealed, so it is excellent in thermal stability compared with not.

A well-known melt polycondensation method in which a carbonic acid diester is used as a carbonate precursor, or a basic compound catalyst, a transesterification catalyst, or a mixed catalyst composed of the two is reacted ( Transesterification reaction).

Examples of the carbonic acid diester include diphenyl carbonate, xylyl carbonate, bis(chlorophenyl) carbonate, m-cresol carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. , dicyclohexyl carbonate, and the like. Among these, diphenyl carbonate is particularly preferable. The carbonic acid diester is preferably used in a ratio of from 0.97 to 1.20 moles, more preferably from 0.98 to 1.10 moles, relative to the diol component of 1 mole.

Examples of the basic compound catalyst include an alkali metal compound, an alkaline earth metal compound, and a nitrogen-containing compound.

Such a compound is preferably an organic acid salt, an inorganic salt, an oxide, a hydroxide, a hydride or an alkoxide of an alkali metal or an alkaline earth metal, a quaternary ammonium hydroxide, a salt thereof, an amine, or the like. The nitrogen-containing compound, these compounds may be used singly or in combination.

Specific examples of such an alkali metal compound include sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, potassium carbonate, sodium acetate, sodium benzoate, sodium salt of bisphenol A, sodium salt of phenol, and the like.

As the alkaline earth metal compound, magnesium hydroxide, calcium hydroxide or the like can be specifically used.

The nitrogen-containing compound may specifically be a tetraammonium hydroxide having an alkyl group, an aryl group or the like, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide. Class, triethylamine, dimethylbenzyl a tertiary amine such as an amine or triphenylamine; a secondary amine such as diethylamine or dibutylamine; a primary amine such as propylamine or butylamine; 2-methylimidazole or 2-phenylimidazole; An imidazole such as benzimidazole.

The transesterification catalyst is preferably a salt of zinc, tin, zirconium or lead, which may be used singly or in combination.

Specifically, the transesterification catalyst may be zinc acetate, zinc benzoate, zinc 2-ethylcarboxylate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, Dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, lead (IV) acetate, and the like.

These catalysts are used in a ratio of 10 ^-9 to 10 ^-3 moles, preferably 10 ^-7 to 10 ^-4 moles, based on 1 mole of the total amount of the dihydroxy compound.

The melt polycondensation method is a method in which a by-product and a catalyst are used, and a by-product is removed by a transesterification reaction under normal pressure or reduced pressure while heating, and melt-condensation is carried out. The reaction is generally carried out in a plurality of stages of two or more stages.

Specifically, the reaction of the first stage is carried out at a temperature of 120 to 260 ° C, preferably 180 to 240 ° C for 0.1 to 5 hours, preferably 0.5 to 3 hours. Then, while increasing the degree of pressure reduction of the reaction system, the reaction temperature is raised to carry out a reaction between the dihydroxy compound and the carbonic acid diester, and finally, the polycondensation reaction is carried out at a temperature of 200 to 350 ° C under a reduced pressure of 1 mmHg or less. hour. Such a reaction can be carried out continuously or batchwise. The reaction device used in the above reaction may be equipped with an anchor type stirring blade, a Maxblend mixing blade, and a spiral belt type stirring blade. The vertical type can also be a horizontal type equipped with paddle blades, lattice blades, eyeglass blades, etc., or can be equipped with a screw extrusion type. In particular, it is suitable to appropriately combine the reaction devices in consideration of the viscosity of the polymer.

After the obtained polycarbonate resin was terminated by polymerization, the catalyst was removed or the activity was lost in order to maintain thermal stability and hydrolysis stability. A method of adding a known deactivator to the loss of activity of a catalyst is generally suitably carried out. As the substance, an ester such as butyl benzoate or an aromatic sulfonic acid such as p-toluenesulfonic acid, butyl p-toluenesulfonate or hexyl p-toluenesulfonate can be suitably used. Phosphoric acid such as phosphorous acid, phosphoric acid, or phosphonic acid, benzamidine chloride, p-toluenesulfonic acid chloride, and the like. These inactivating agents are used in an amount of 0.01 to 50 moles relative to the amount of the catalyst, preferably 0.3 to 20 moles. If the amount of the catalyst is less than 0.01 times the molar amount, the deactivation effect is insufficient. Moreover, if it is more than 50 times the molar amount with respect to the amount of the catalyst, the heat resistance is lowered, and the molded body is easily colored.

After the catalyst is deactivated, a step of volatilizing and removing the low boiling point compound in the polymer at a pressure of from 13.3 to 1133.3 Pa and a temperature of from 200 to 350 ° C may be provided. Therefore, the paddle blade, the lattice blade, and the paddle blade may be suitably used. A horizontal device or a thin film evaporator that is excellent in the surface renewal of the lens blade or the like.

The polycarbonate resin of the present invention is obtained by dissolving 0.7 g of the polymer in 100 ml of dichloromethane, and the specific viscosity measured at 20 ° C is in the range of 0.12 to 0.55, more preferably in the range of 0.15 to 0.45. When the specific viscosity is less than 0.12, the molded article becomes brittle. If it is higher than 0.55, the melt viscosity and the solution viscosity become high.

<Polyester carbonate>

The acid component of the polyester carbonate-forming ester unit used in the present invention is a dicarboxylic acid component represented by the above formula (4) and/or formula (5), and is represented by the formula (1). The ratio of the body component to the total of the dicarboxylic acid components represented by the general formula (4) and/or the general formula (5) is (1): ((4) + (5)) = 50 in terms of the molar ratio. : 50~95:5, preferably 70:30~95:5, better 75:25~90:10. If the latter ratio exceeds 50:50, the performance as an optical material sometimes decreases.

Such a polyester carbonate may be copolymerized with the dihydroxy compound represented by the above formula (3) by copolymerization with the hydrazine compound represented by the above formula (1).

The ratio of the dihydroxy compound represented by the formula (3) to the molar ratio of the hydrazine compound represented by the formula (1) is preferably the formula (1): the formula (3) = 80 to 100: 20 ~0, better 90~100:10~0.

The dihydroxy compound represented by the formula (3) which is preferably used is the same as those described for the above polycarbonate. Further, similarly, other dihydroxy compounds may be used in combination insofar as the optical properties are not inhibited.

[dicarboxylic acid]

The acid component forming the ester unit is a dicarboxylic acid represented by the following formula (4) and/or a dicarboxylic acid represented by the formula (5).

(wherein R13 and R14 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aromatic oxygen having 6 to 20 carbon atoms. base)

(wherein R15 and R16 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aromatic oxygen having 6 to 20 carbon atoms. base).

The dicarboxylic acid represented by the formula (4) is preferably, for example, p-citric acid or isodecanoic acid, and particularly preferably p-citric acid. Further, as the dicarboxylic acid represented by the formula (5), which may be preferably used, for example, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, etc. It is preferably 2,6-naphthalenedicarboxylic acid. Among them, the dicarboxylic acid is preferably p-citric acid or isophthalic acid, and particularly preferably p-citric acid.

Moreover, the dicarboxylic acid component other than the dicarboxylic acid represented by the general formula (4) or the general formula (5) may be contained in the range which does not inhibit optical characteristics.

[Method for producing polyester carbonate]

Examples of the carbonate precursor used in the production of such a polyester carbonate resin include phosgene, diphenyl carbonate, bischloroformate of the above divalent phenol, di-p-tolyl carbonate, and phenyl. - p-tolyl carbonate, di-p-chlorophenyl carbonate, dinaphthyl carbonate or the like, among which diphenyl carbonate is preferred.

The method for producing the polyester carbonate resin is arbitrarily employable for the production of a general polyester carbonate resin. It is preferred to use, for example, a transesterification reaction of a diol with a dicarboxylic acid or a dicarboxylic acid chloride with phosgene or a transesterification of a diol with a dicarboxylic acid or a dialkyl dicarboxylate with a bisaryl carbonate.

The reaction of a diol, a dicarboxylic acid or its acid chloride with phosgene is carried out in the presence of an acid binder and a solvent in a nonaqueous manner. As the acid binder, for example, pyridine, dimethylaminopyridine, a tertiary amine or the like can be used. As the solvent, a halogenated hydrocarbon such as dichloromethane or chlorobenzene can be used. As the molecular weight modifier, for example, a blocking agent such as phenol or p-tert-butylphenol or the like is used. The reaction temperature is generally from 0 to 40 ° C, and the reaction time is preferably from several minutes to 5 hours.

In the transesterification reaction, the diol and the dicarboxylic acid or a diester thereof and the bisaryl carbonate are mixed in the presence of an inert gas, and the reaction is generally carried out at 120 to 350 ° C, preferably 150 to 300 ° C under reduced pressure. The degree of decompression is a stepwise change, and finally, the alcohol produced under 1 mmHg is distilled off to the outside of the system. The reaction time is usually about 1 to 4 hours. However, it is not preferable to form a phenyl vinyl ether or acetaldehyde by a polymerization temperature of 350 ° C or more.

Further, in the transesterification reaction, a reaction is promoted, and a polymerization catalyst can be used. Such a polymerization catalyst uses an alkali metal compound or an alkaline earth metal compound or a heavy metal compound as a main component, and a nitrogen base may be used as needed. The compound is a dependent component.

The alkali metal compound may, for example, be sodium hydroxide, potassium hydroxide or a sodium salt of bisphenol A. The alkaline earth metal compound may, for example, be calcium hydroxide, magnesium hydroxide or calcium carbonate.

The nitrogen-containing basic compound may, for example, be tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylamine or triethylamine. Dimethylbenzylamine, triphenylamine, dimethylaminopyridine, and the like.

Other ester exchange catalysts include, for example, zinc, tin, zirconium, lead, titanium, strontium, barium, strontium, and aluminum. For example, zinc acetate, zinc benzoate, zinc 2-ethylcarboxylate, and chlorine can be used. Tin (II), tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylate, oxygen Zirconium acetate, zirconium tetrabutoxide, lead (II) acetate, lead (IV) acetate, titanium tetraoxide (IV), and the like.

These catalysts may be used singly or in combination of two or more. The amount of the polymerization catalyst used is 1 mol relative to the total of the diol and the dicarboxylic acid, and may be 10 ^-9 to 10 ^-3 mol. The ratio of the ear is used. These may be used singly or in combination of two or more. Further, in the transesterification reaction, in order to reduce the hydroxyl end group, a diaryl carbonate having an electrophilic substituent may be added after the end of the polycondensation reaction or after the termination. Further, in order to improve the hue, an antioxidant or a heat stabilizer may be added.

Further, after the termination of the polymerization reaction, in order to maintain thermal stability and hydrolysis stability, the catalyst may be removed or the catalyst may be deactivated. Regarding an alkali metal compound or an alkaline earth metal compound, it is generally suitable to carry out the addition of a known deactivating agent. A method of deactivating a catalyst. Specific examples of such materials include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonates such as butyl p-toluenesulfonate, phosphorous acid, phosphoric acid, and phosphine. Phosphoric acid such as acid, triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, triphenyl phosphate, etc. Phosphates, phosphonates of diphenylphosphonic acid, phosphonates such as diethyl phenylphosphonate, phosphorus such as triphenylphosphine, etc., tetrabutylphosphonium dodecylbenzenesulfonate, etc. Aromatic sulfonates.

These inactivating agents can be used in an amount of 0.01 to 50 moles, preferably 0.3 to 20 moles, per mole of the amount of the catalyst. If the amount is less than 0.01 times the molar amount with respect to the amount of the catalyst, the deactivation effect becomes insufficient. Moreover, when it is more than 50 times of mol with respect to the amount of catalyst, heat resistance is lowered, and the molded body becomes easy to be colored.

After the catalyst is deactivated, a step of volatilizing the low boiling point compound in the resin at a pressure of 133 to 13.3 Pa and a temperature of 200 to 320 ° C may be provided.

The polyester carbonate resin of the present invention is preferably one in which 0.7 g of the polymer is dissolved in 100 ml of methylene chloride, and the specific viscosity measured at 20 ° C is in the range of 0.12 to 0.55, more preferably in the range of 0.15 to 0.45. When the specific viscosity is less than 0.12, the molded article becomes brittle. If it is higher than 0.55, the melt viscosity and the solution viscosity become high, and the handleability becomes difficult.

<additive>

In the thermoplastic resin composition of the present invention, the object of the present invention is not impaired The range is to impart various characteristics and may also contain various additives. In terms of additives, it can be blended with a release agent, a thermal stabilizer, a UV absorber, a bluing agent, an antistatic agent, a flame retardant, a heat shield, a fluorescent dye (containing a fluorescent whitening agent), and a light diffusing agent. Other resins or elastomers.

Preferably, 90% by weight or more of the release agent is composed of an ester of an alcohol and a fatty acid. The ester of an alcohol and a fatty acid may specifically be, for example, an ester of a monohydric alcohol and a fatty acid and/or a partial ester or a full ester of a polyhydric alcohol and a fatty acid. Among these esters, a mixture of stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, stearic acid triglyceride and stearyl stearyl ester is preferably used.

The amount of the above-mentioned ester in the release agent is preferably 90% by weight or more, and more preferably 95% by weight or more, based on 100% by weight of the release agent.

The heat stabilizer may, for example, be a phosphorus-based heat stabilizer, a sulfur-based heat stabilizer, or a phenol-resistant heat stabilizer. Examples of the phosphorus-based thermal stabilizer include phosphorous acid, phosphoric acid, phosphinic acid, phosphonic acid, and the like. Preferably, ruthenium (2,4-di-t-butylphenyl)-4,4' can be used. - a phenyldiphosphonate.

The content of the phosphorus-based heat stabilizer in the thermoplastic resin composition is preferably 0.001 to 0.2 parts by weight based on 100 parts by weight of the thermoplastic resin composition.

The ultraviolet absorber is preferably a benzotriazole-based ultraviolet absorber, a dibenzocresol-based ultraviolet absorber, a triazine-based ultraviolet absorber, a cyclic imido ester-based ultraviolet absorber, and a cyanoacrylate. At least one type of ultraviolet absorber selected from the group consisting of.

The blending amount of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0, based on 100 parts by weight of the thermoplastic resin composition. The parts by weight are preferably 0.05 to 0.8 parts by weight. In the range of such a blending amount, sufficient weather resistance can be imparted to the thermoplastic resin composition depending on the application.

The bluing agent may, for example, be Macrolex Violet B and Macrolex Blue RR from Bayer, and Polysynthren Blue RLS from Clariant.

The blending amount of the bluing agent is preferably 0.05 to 1.5 ppm, more preferably 0.1 to 1.2 ppm, based on the thermoplastic resin composition.

<Method for Producing Thermoplastic Resin Composition>

The thermoplastic resin composition having an anthracene skeleton of the present invention can be obtained by blending a thermoplastic resin having an anthracene skeleton, an aliphatic epoxy compound, and various additives by any blending method. Each component is uniformly dispersed in a mixture of a mixer, a kneader, a Banbery mixer, a roller, an extruder, or the like, simultaneously or separately.

Further, a method in which the composition which has been previously dry-blended is melt-kneaded by a heated extruder and homogenized, and then extruded into a metal needle shape, and then cut into a desired length to be granulated.

<Physical property value of thermoplastic resin composition>

The thermoplastic resin to be used in the present invention is preferably a glass transition temperature (Tg) measured at a temperature increase rate of 20 ° C /min of 130 ° C or more and less than 200 ° C. When the Tg is less than 130 ° C, the use of the optical member formed by using the thermoplastic resin composition is insufficient in heat resistance, and on the other hand, Tg When it is 200 ° C or more, the melt viscosity becomes high, and it becomes difficult to form a molded body.

The thermoplastic resin composition of the present invention is preferably a molded sheet having a thickness of 0.1 mm obtained from the thermoplastic resin composition, and has a haze of 2% or less, more preferably 1% or less.

The thermoplastic resin composition of the present invention is preferably used in an amount of 30 g or more, more preferably 40 g or more, at 300 ° C and a weight of 1.2 kgf for 10 minutes.

The thermoplastic resin composition of the present invention has a molecular weight retention ratio of 95% or more after standing at 85 ° C and 85% RH for 400 hours, and is preferably incomplete in hue change. More preferably, the molecular weight retention is 97% or more.

<Method of Manufacturing Optical Member>

In the optical member of the present invention, the thermoplastic resin composition having an anthracene skeleton of the present invention can be subjected to, for example, injection molding, compression molding, injection compression molding, or cast molding.

(optical lens)

When an optical lens comprising the thermoplastic resin composition of the present invention is produced by injection molding, it is preferably formed under the conditions of a cylinder temperature of 260 to 350 ° C and a mold temperature of 90 to 170 ° C. More preferably, the cylinder is formed at a cylinder temperature of 270 to 320 ° C and a mold temperature of 100 to 160 ° C. When the cylinder temperature is higher than 350 ° C, the resin is decomposed and colored, and when it is less than 230 ° C, the melt viscosity is high and it cannot be formed. Also, when the mold temperature is higher than 170 ° C, the resin does not harden and is not taken out from the mold. Formed piece. Further, when it is less than 90 ° C, the resin is quickly solidified in the mold during molding, and the formed sheet cannot be obtained, or the mold can not be transferred.

The optical lens of the present invention can be suitably used in the shape of an aspherical lens as needed. Since the aspherical lens system can make the spherical surface difference substantially zero by one lens, it is not necessary to remove the spherical aberration by a combination of a plurality of spherical lenses, and the weight can be reduced and the production cost can be reduced. Therefore, the aspherical lens system can be particularly used as a camera lens even in an optical lens.

Further, the thermoplastic resin composition of the present invention is particularly useful as a material for an optical lens having a small and complicated shape of a sheet because of high molding fluidity.

The upper limit of the thickness of the center portion is preferably 0.5 mm or less, and more preferably 0.4 mm or less, in terms of the specific lens size. Further, the lower limit of the thickness of the central portion of the lens is preferably 0.05 mm or more, and more preferably 0.1 mm or more.

Further, the diameter is 1.0 mm to 20.0 mm, more preferably 1.0 to 10.0 mm, and most preferably 3.0 to 10.0 mm.

Further, in terms of its shape, it is preferable that the one side is convex and the one side is a concave meniscus lens.

Example

The invention will be further illustrated by the following examples.

Examples 1 to 7 and Comparative Examples 1 to 9

The evaluation is based on the following methods.

(evaluation method)

(1) Specific viscosity of resin: The resin obtained after termination of polymerization was dried at 120 ° C for 4 hours, and 0.35 g of the resin was dissolved in a solution of 50 cc of dichloromethane as a measurement sample. The measurement was carried out in a thermostat at 20 ± 0.01 ° C to measure the passage time between the lines of the Oswald system viscosity tube, and the specific viscosity (η _sp ) of the solution at 20 ° C was obtained from the following formula.

η _sp =(t ₁ -t ₀ )/t ₀

Here, t ₁ : the passing time between the lines of the resin solution, t ₀ : the passage time between the lines of the dichloromethane.

(2) Copolymerization ratio: The polymer after polymerization was measured using proton NMR of JNM-AL 400 manufactured by JEOL Ltd.

(3) Glass transition temperature (Tg): Measured by a Model 910 DSC manufactured by Dupont.

(4) Molding fluidity (melt viscosity (MVR)): The melt viscosity was measured by CAPIROGRAH1D manufactured by Toyo Seiki Co., Ltd. using a nozzle having a diameter of 1 mm and a length of 10 mm, and the amount of resin extruded at 300 ° C, 1.2 kgf, and 10 minutes.

(5) Haze: The haze was measured using a Haze Meter NDH 2000 manufactured by Nippon Denshoku Industries Co., Ltd. on a forming plate having a thickness of 1 mm.

(6) Moisture and heat stability Molecular weight retention rate: After the molded piece having a thickness of 1 mm was allowed to stand at 85 ° C and 85% RH for 2,000 hours, the specific viscosity retention ratio was evaluated as the molecular weight retention from the change in the specific viscosity described below. rate.

From the solution in which 0.7 g of the molded piece was dissolved in 100 ml of dichloromethane, the specific viscosity (η _sp ) of the solution at 20 ° C was measured, and the specific viscosity retention ratio (molecular weight retention ratio) after the damp heat test was determined. The specific viscosity retention ratio (molecular weight retention ratio) was used as an index of moist heat resistance.

Δη _sp =(η _sp 1/η _sp 0)×100※Δη _sp : specific viscosity retention ratio, η _sp 0: specific viscosity before the test, η _sp 1: specific viscosity after the test

(7) Forming Stability of Optical Lens: The filling failure of the aspherical lens after molding, the molding failure, and the insufficient strength of the lens were visually confirmed. In the evaluation, 100 shots were formed, and the probability of becoming a defective product was classified as less than 1% (◎), 1 to 5% (○), 5 to 20% (Δ), and 20% or less (×).

In the case of poor filling, the resin is insufficient to form a lens shape, and it is defined as a poor filling, and the defective silver or air bubbles are present in one or more lenses, or the additive is exuded. Further, the strength of the lens is insufficient, and the lens portion and the injection port/stovel portion are broken from the mold at the time of molding, and the like.

(synthesis) PC (1): Polycarbonate

In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 21540 parts by weight of ion-exchanged water and 4930 parts by weight of a 48% aqueous sodium hydroxide solution were added to make a 9,9-bis (4-hydroxy group) having a b value of 3.0 in an ethanol solution. -3-methyl Phenyl) hydrazine (hereinafter sometimes abbreviated as "BCF") 3231 parts by weight, 2,2-bis(4-hydroxyphenyl)propane (hereinafter sometimes referred to as "BPA") 1949 parts by weight and hydrotalcite 15 After dissolving the parts by weight, after adding 14530 parts by weight of dichloromethane, it was necessary to blow 2200 parts by weight of phosgene at 15 to 25 ° C for 60 minutes while stirring. After the phosgene was terminated, 163.1 parts by weight of cumene phenol and 705 parts by weight of a 48% aqueous sodium hydroxide solution were added, and after emulsification, 5.9 parts by weight of triethylamine was added thereto, and the mixture was stirred at 28 to 33 ° C for 1 hour to terminate the reaction. . After the reaction was terminated, the product was diluted with dichloromethane and washed with water to form hydrochloric acid acidic and washed with water. The conductivity of the aqueous phase was approximately the same as that of the ion-exchanged water, and then the dichloromethane was evaporated by a kneader to obtain a ratio of BCF to BPA. A white polymer having a specific viscosity of 50:50 in a molar ratio of 0.297 and a Tg of 197 °C.

PC(2)

In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 21540 parts by weight of ion-exchanged water and 4930 parts by weight of a 48% aqueous sodium hydroxide solution were added to make a 9,9-bis (4-hydroxy group) having a b value of 3.0 in an ethanol solution. -3-methylphenyl) hydrazine (hereinafter sometimes abbreviated as "BCF") 3231 parts by weight, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene (hereinafter, sometimes referred to as "BPM") 2958 parts by weight and 15 parts by weight of hydrotalcite were dissolved, and after adding 14530 parts by weight of dichloromethane, it was necessary to blow 2200 parts by weight of phosgene at 15 to 25 ° C for 60 minutes while stirring. After the phosgene was terminated, 163.1 parts by weight of cumene phenol and 705 parts by weight of a 48% aqueous sodium hydroxide solution were added, and after emulsification, 5.9 parts by weight of triethylamine was added thereto, and the mixture was stirred at 28 to 33 ° C for 1 hour to terminate the reaction. . After the reaction is terminated, the product is diluted with dichloromethane and washed with water to form hydrochloric acid. After washing, the conductivity of the aqueous phase is about the same as that of the ion-exchanged water, and the methylene chloride is evaporated by a kneader to obtain a ratio of BCF to BPM. The specific viscosity of the 50:50 molar ratio is 0.297, and the Tg is 156 ° C. White polymer.

PC(3)

There are 1403.2 parts by weight of 9,9-bis(4-(2-hydroxyethoxy)phenyl)anthracene (hereinafter sometimes omitted as "BPEF"), B2.7 182.7 parts by weight, and diphenyl carbonate (hereinafter sometimes 878.0 parts by weight, and 5.0×10 ^-3 parts by weight of sodium hydrogencarbonate, which was omitted as "DPC", were placed in a reaction vessel equipped with a stirrer and a distillation apparatus, and after nitrogen substitution for 3 times, the nitrogen atmosphere was 101.3×10 ³ Pa. Heat to 215 ° C and stir for 20 minutes. After completely dissolving, the mixture was adjusted to 20 × 10 ³ Pa for 15 minutes, and kept at 215 ° C and 20 × 10 ³ Pa for 20 minutes to carry out a transesterification reaction. Further, the temperature was raised to 240 ° C at a rate of 37.5 ° C / hr, and held at 240 ° C, 20.0 × 10 ³ Pa for 10 minutes. Thereafter, it was adjusted to 16.0 × 10 ³ Pa for 10 minutes, and kept at 240 ° C and 16.0 × 10 ³ Pa for 70 minutes. Subsequently, over 10 minutes and adjusted to 13.3 × 10 ³ Pa, at 240 ℃, 13.3 × 10 ³ Pa for 10 minutes. Further, the mixture was adjusted to 133.3 Pa or less in 40 minutes, and stirred at 240 ° C and 133.3 Pa for 10 minutes to carry out a polymerization reaction. After the reaction was terminated, nitrogen gas was blown into the reactor, pressurized, and the produced resin was pulverized while being extracted. A colorless transparent particle having a ratio of BPEF to BPA of 80:20 in terms of molar ratio of 0.192 and a Tg of 145 ° C was obtained.

PEC (1): Polyester carbonate

1403.2 parts by weight of BPEF, 155.4 parts by weight of dimethyl perruthenate (hereinafter sometimes omitted as "DMT"), 548.4 parts by weight of DPC, and 13.6×10 ^-4 parts by weight of titanium tetrabutoxide were placed in a mixer and distillation. In the reaction vessel of the apparatus, the mixture was heated to 180 ° C under a nitrogen atmosphere of 101.3 × 10 ³ Pa, and stirred for 20 minutes. Thereafter, the pressure was adjusted to 20 × 10 ³ Pa for 20 minutes, and the temperature was raised to 250 ° C at a rate of 60 ° C / hr to carry out a transesterification reaction. Thereafter, the mixture was directly held at 250 ° C, and the pressure was reduced to 133.3 Pa or less for 120 minutes, and the polymerization was carried out under stirring at 250 ° C and 133.3 Pa for 1 hour. Thereafter, the produced resin was extracted while being pelletized. A colorless transparent particle having a ratio of BPEF to citric acid of 80:20 in a molar ratio of 0.201 and a Tg of 150 ° C was obtained.

(formed piece)

The granulated resin composition was dried by heating at 120 ° C for 8 hours. Thereafter, a molded piece having a width of 2.5 cm, a length of 5 cm, and a thickness of 1 mm was injection-molded using a SE 30 DU injection molding machine manufactured by Sumitomo Heavy Industries Co., Ltd. at a molding temperature of Tg + 110 ° C and a mold temperature of Tg - 10 ° C. The evaluation results of the haze and the heat and humidity resistance are shown in Table 1.

(optical lens)

The SE 30 DU injection molding machine manufactured by Sumitomo Heavy Industries Co., Ltd. was used to set the molding temperature to Tg + 170 ° C of the resin used, the mold temperature Tg - 5 ° C, the injection molding thickness of 0.3 mm, the convex curvature radius of 5 mm, and the concave curvature radius of 4 mm. Aspherical lens with a diameter of 5 mm. Forming stability of optical lenses The evaluation is shown in Table 1.

(additive)

Additive 1: epoxidized soybean oil (number of epoxy groups 4) Kapox S-6

Additive 2: epoxidized linseed oil (number of epoxy groups 6) Adeca Sizer-O-180A made by ADEKA

Additive 3: Alkyl monoester, alkyl triglyceride mixture Rikemal SL-900

Additive 4: 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate

Additive 5: bisphenoxyethanol hydrazine diepoxypropyl ether

Additive 6: Trioctyl trimellitate

Additive 7: Polyetherester resin ECDEL 9966 manufactured by Eastman Chemical Company

Additive 8: Styrene-based oligomer FTR 2140 manufactured by Mitsui Chemicals Co., Ltd.

Stabilizer: bismuth (2,4-di-t-butylphenyl)-4,4'-linked phenyl diphosphonate

Release agent: glyceryl monostearate

Regarding the blending amount, the unit of Table 1 is parts by weight.

[Examples 1 to 7 and Comparative Examples 1 to 9]

The components were uniformly dry-mixed in the amounts indicated in Table 1, and then a KZ-W15-30MG twin-axis extruder made of TECHNOVEL Co., Ltd. was used. The TECHNOVEL system was melted and pelletized under the conditions described in Table 1 below, and a molded article was appropriately produced and evaluated.

In Examples 1 to 7 shown in Table 1, the haze and the heat and humidity stability were directly maintained, and the molding fluidity was improved, and the moldability of the optical lens was also good, and it was useful for use in an optical member. Further, in Comparative Example 1, the aliphatic epoxy compound was not added, and the fluidity was poor, so that a lens having a small thickness could not be formed. In Comparative Example 2, the amount of addition was small, fluidity was lacking, and a lens having a small thickness could not be formed. Further, in Comparative Example 4, since the additive did not have an epoxy group, the wet heat stability was poor. Comparative Example 5 is an aliphatic epoxy compound which is inferior in molding fluidity and has many molding defects during molding. Comparative Example 6 is an aromatic epoxy compound and has poor molding fluidity. In Comparative Example 7, the molding fluidity was improved, but the additive was volatilized during molding, and the molding defects were large. Further, the wet heat stability was poor, and the environment for use as an optical member was limited, and the generality was lacking. Comparison Examples 8 and 9 were inferior in formability and moist heat resistance by decomposition of an additive. In Comparative Example 3, the amount of addition was large, and transparency could not be maintained, so that it could not be used for an optical member.

Effect of invention

Since the thermoplastic resin composition having an anthracene skeleton of the present invention has high transparency, molding fluidity, molding stability, and moisture-and-heat stability, it is possible to form a thin optical member which is difficult to be formed by injection molding. Provides thinner optical components. The thermoplastic resin composition having an anthracene skeleton is particularly suitable for a lens such as a camera lens for an action camera, an optical pickup lens, a microarray lens, a projector lens, and a Fresnel lens.

Industrial use possibility

The optical member using the thermoplastic resin composition having an anthracene skeleton of the present invention can be used for various cameras, telescopes, double glasses, television projectors, cymbals, and the like for digital cameras and the like. In particular, it can be effectively used as a small lens of a thin lens such as a camera lens for a mobile phone, a digital camera lens, a vehicle camera lens, or a web camera lens.

Claims (11)

A thermoplastic resin composition having an anthracene skeleton, which comprises 100 parts by weight of a thermoplastic resin composition and 0.1 to 10 parts by weight of an aliphatic epoxy compound, and the thermoplastic resin composition is contained by the following formula (1) a repeating unit composed of a monomer-derived carbonate unit or an ester unit; (wherein R1, R2, R3 and R4 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and a carbon number of 5; a cycloalkyloxy group of ~20, an aryl group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms; an alkylene group having 2 to 8 carbon atoms and a cycloalkyl group having 5 to 12 carbon atoms or a aryl group having 6 to 20 carbon atoms; n and m are integers of 0 to 10); the aliphatic epoxy compound having a moiety represented by the following formula (2); (wherein R is CH ₃ or H, o is 1 to 20, p is 1 to 10, and I is 1 to 20). A thermoplastic resin composition having an anthracene skeleton according to the first aspect of the invention, wherein the aliphatic epoxy compound is an epoxy compound having a glycerin skeleton. A thermoplastic resin composition having an anthracene skeleton according to claim 2, wherein the epoxy compound having a glycerin skeleton is an epoxidized vegetable oil. A thermoplastic resin composition having an anthracene skeleton according to claim 3, wherein the epoxidized vegetable oil is epoxidized soybean oil or epoxy linseed oil. The thermoplastic resin composition having an anthracene skeleton according to claim 4, wherein the number of epoxy groups of the epoxidized soybean oil and the epoxidized linseed oil is 2 to 8. The thermoplastic resin composition having an anthracene skeleton according to any one of claims 1 to 5, wherein the thermoplastic resin comprises a repeating unit composed of a carbonate unit derived from a monomer represented by the formula (1) And a repeating unit composed of a carbonate unit derived from a monomer represented by the following formula (3); the ratio of the formula (1) to the formula (3) is (1) in terms of a molar ratio: (3)= a polycarbonate in the range of 100:0 to 50:50, and in order to dissolve 0.7 g of methylene chloride in 100 ml, the specific viscosity measured at 20 ° C is 0.12 to 0.55. (In the formula, R5 to R8 are each independently a hydrogen atom, a hydrocarbon group or a halogen atom having an aromatic group having 1 to 9 carbon atoms, and W is a single bond or an aromatic group having 1 to 20 carbon atoms. Hydrocarbyl group, O, S, SO, SO ₂ , CO or COO group). The thermoplastic resin composition having an anthracene skeleton according to any one of claims 1 to 5, wherein the thermoplastic resin contains an ester unit derived from a monomer represented by the following formula (4) and/or An ester-based unit derived from a monomer represented by the formula (5); a ratio of the formula (1) to the total of the formula (4) and the formula (5) is (1) in terms of a molar ratio: ((4)+ (5)) a polyester carbonate in the range of 50:50 to 95:5, and in order to dissolve 0.7 g of methylene chloride in 100 ml, the specific viscosity measured at 20 ° C is 0.12 to 0.55. (wherein R13 and R14 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aromatic oxygen having 6 to 20 carbon atoms. base) (wherein R15 and R16 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aromatic oxygen having 6 to 20 carbon atoms. base). The thermoplastic resin composition having an anthracene skeleton according to any one of claims 1 to 7, wherein the monomer represented by the formula (1) is 9,9-bis(4-hydroxy-3-methyl group). Phenyl) hydrazine or 9,9-bis(4-(2-hydroxyethoxy)phenyl)indole. An optical member comprising a thermoplastic resin composition having an anthracene skeleton according to any one of claims 1 to 8. The optical member of claim 9, wherein the optical member is an optical lens of a camera lens, an optical pickup lens, a microarray lens, a projector lens, or a Fresnel lens. The optical member according to claim 10, wherein the thickness of the optical lens is 0.5 mm or less.