KR20120038363A - Polyarylenesulfide, and composition, optical member and optical element containing the same - Google Patents

Abstract

PURPOSE: Polyarylenesulfide is provided to have excellent reflectivity, and transparency, and to have high solubility as solvent, thereby having high suitability to solution process like a spin coating process. CONSTITUTION: An optical unit contains polyarylenesulfide having fluorene structure. The polyarylenesulfide has structure in chemical formula 1. In chemical formula 1, Rm is arylene group, Rn is respectively and independently aryl group or C1-4 alkyl group, a is a number from 0-4, * is bonded material. The polyarylenesulfide has fluorine structure. A composition contains the polyarylenesulfide, and contains one or more kinds selected from organic solvent, surface surfactant, and crosslinking agent.

Description

POLYARYLENESULFIDE, AND COMPOSITION, OPTICAL MEMBER AND OPTICAL ELEMENT CONTAINING THE SAME

The present invention relates to polyarylene sulfides, compositions and optical elements.

High refractive materials are required for optical components such as CCD or CMOS image sensors. As a material used for such a use, the material containing the polyimide and titania containing a sulfur atom is proposed.

On the other hand, the polymer which has a sulfur atom in a high content rate is expected to be easy to process at high refractive index, For example, Non-patent document 1 shows the amorphous polyphenylene sulfide which has a sulfur atom in high content.

 J. Polym. Sci. Part A: Polym. Chem. 2009, 47, 2453.

However, in the polyimide containing a sulfur atom and the material containing titania, transparency can be ensured, but in the polyimide containing a sulfur atom, refractive index becomes easy to be less than 1.7 (633 nm), and it is insufficient as a material of an optical component. did. In addition, since the material containing titania is difficult to process, such as ashing and etching, use as a material of an optical component has a limitation.

On the other hand, the polyphenylene sulfide disclosed in Non-Patent Document 1 can have a refractive index, but since it has crystallinity, scattering due to the crystal occurs and transparency may be insufficient when the optical member is used. . Moreover, since polyphenylene sulfide is melt | dissolved only in a special solvent, there also existed a problem that it was difficult to use for manufacture of the optical member which requires solution processes, such as a spin coating process.

One object of some aspects of the present invention is to provide a polyarylene sulfide having good refractive index and transparency and good process suitability.

One object of some aspects of the present invention is to provide an optical element having high refractive index and high transparency.

This invention is made | formed in order to solve at least one part of the above-mentioned subject, and can be implement | achieved as the following aspects or application examples.

[Application Example 1]

One aspect of the polyarylene sulfide according to the present invention,

It is characterized by having a fluorene skeleton.

[Application example 2]

In Application Example 1, it may have a structure represented by the following formula (1).

[In formula (1), Rm represents an arylene group, Rn represents an aryl group or a C1-C4 alkyl group each independently, and a represents the number of 0-4 each independently; * Indicates combined.

[Application Example 3]

In Application Example 1 or Application Example 2,

The number of repeating units which have a structure represented by said formula (1) may be 10% or more of the number of all repeating units.

[Application example 4]

In any one of the application examples 1 to 3,

It may contain 10 mass% or more of sulfur atoms.

[Application Example 5]

In any one of Application Examples 1 to 4,

The refractive index at the wavelength 633 nm may be 1.70 or more.

[Application Example 6]

In any one of the application examples 1-5,

As amorphous, the glass transition temperature may be at least 120 ° C.

[Application Example 7]

In any one of the application examples 1 to 6,

It may have a thianthrene ring.

[Application Example 8]

One aspect of the composition according to the present invention,

It contains the polyarylene sulfide of any one of the application examples 1-7.

[Application Example 9]

One aspect of the optical element according to the present invention,

The optical member obtained using the resin composition of application example 8 is provided.

The polyarylene sulfide which concerns on this invention has favorable refractive index and transparency. In addition, the polyarylene sulfide according to the present invention has high solubility in a solvent, for example, high suitability in a solution process such as a spin coating process. Moreover, since the polyarylene sulfide which concerns on this invention consists of organic substance, it is hard to generate | occur | produce residue in processes, such as an ashing process and an etching process, for example, and process suitability is high.

1 is an infrared absorption spectrum of a compound according to Example 1. FIG.
2 is an infrared absorption spectrum of the compound according to Example 2.
3 is an infrared absorption spectrum of the compound according to the comparative example.

EMBODIMENT OF THE INVENTION Embodiment of this invention is described below. Embodiment described below demonstrates an example of this invention. In addition, this invention is not limited to the following embodiment, Also includes various modified examples implemented in the range which does not change the summary of this invention. In addition, not all of the structures demonstrated by the following embodiment are essential components of this invention.

1.Polyarylene sulfide

The polyarylene sulfide which concerns on this embodiment has a fluorene skeleton. In addition, in this invention, polyarylene sulfide means the polymer obtained by condensation of an aromatic dithiol compound and an aromatic dihalogen compound.

1.1. Skeleton of polyarylene sulfide

The polyarylene sulfide of this embodiment has a structure in which an arylene group is linked by a sulfide bond (-S-) (thioether bond). That is, the polyarylene sulfide of this embodiment has a structure represented by following formula (1).

　

[In formula (1), Rm represents an arylene group, Rn represents an aryl group or a C1-C4 alkyl group each independently, and a represents the number of 0-4 each independently; * Indicates combined.

Arylene corresponds to arylene in English notation. In addition, an arylene group refers to the group generated by leaving two hydrogen atoms couple | bonded with an aromatic ring. As this aromatic ring, condensed polycyclic hydrocarbons, such as monocyclic hydrocarbon, such as a benzene ring, a naphthalene ring, anthracene ring, an indene ring, a biphenylene ring, a fluorene ring, a phenanthrene ring, a pyrene ring, and these rings, for example Examples of the ring include a heterocyclic ring in which single or plural substitutions are made by sulfur, nitrogen, or the like. In addition, in this embodiment, the said aromatic ring may not comprise the conjugated system as a whole of the said aromatic ring, and may comprise the polycyclic ring set. Further, in the present embodiment, the aromatic ring may have a structure in which a plurality of the aromatic rings are bonded to each other by a single or a plurality of methylene bonds, ether bonds, sulfide bonds, sulfonyl bonds, or the like.

As a more specific example of the arylene group of the polyarylene sulfide of this embodiment, group which generate | occur | produced by leaving two hydrogen atoms from aromatic rings, such as thianthrene, diphenyl sulfone, thiobisbenzene, 9, 9-bisphenyl fluorene, is mentioned. Can be.

As for the molecular weight of polyarylene sulfide, about 3,000 or more and about 10,000 or less are preferable. When the molecular weight of polyarylene sulfide exists in this range, the solubility to a solvent is hard to be impaired, for example, in the coating property to a board | substrate, or a board | substrate, Harvesting of the formed irregularities can be ensured, so handling can be facilitated.

1.2. Content of sulfur atom

It is preferable that the polyarylene sulfide which concerns on this embodiment contains 10 mass% or more of sulfur atoms. That polyarylene sulfide contains 10 mass% or more of sulfur atoms means that the mass of a sulfur atom with respect to the mass of the whole polyarylene sulfide is 10% or more. Content of the sulfur atom in polyarylene sulfide can be computed from the chemical structure of a repeating unit, for example. In addition, content of the sulfur atom in polyarylene sulfide can also be measured by general elemental analysis.

As one of the effects by containing 10 mass% or more of sulfur atoms, what raises the refractive index of polyarylene sulfide is mentioned. In addition, from the viewpoint of increasing the refractive index of the polyarylene sulfide, the mass of the sulfur atom with respect to the total mass of the polyarylene sulfide is more preferably 15% or more, and even more preferably 20% or more.

1.3. Repeat units

The repeating unit of the polyarylene sulfide of the present embodiment is a unit which is repeated by a sulfide bond (thioether bond) of the main chain and can be expressed in the form of "-R _h -SR _i -S-". Here, R _h and R _i correspond to the arylene group described above, respectively. Furthermore, R _h corresponds to the structure excluding the thiol group of the aromatic dithiol compound, and R _i corresponds to the structure excluding the halogen of the aromatic dihalogen compound. That is, R _h and R _i each represent a group generated by the separation of two hydrogen atoms bonded to an aromatic ring, and examples of the aromatic ring include monocyclic hydrocarbons such as benzene rings, naphthalene rings, anthracene rings, and indene rings. Condensed polycyclic hydrocarbons, such as a biphenylene ring, a fluorene ring, a phenanthrene ring, a pyrene ring, and the heterocyclic ring of which the reduction of these rings is single or plural substitution by sulfur, nitrogen, etc. are mentioned. In addition, in this embodiment, the said aromatic ring may not comprise the conjugated system as a whole of the said aromatic ring, and may comprise the polycyclic ring set. Further, in the present embodiment, the aromatic ring may have a structure in which a plurality of the aromatic rings are bonded to each other by a single or a plurality of methylene bonds, ether bonds, sulfide bonds, sulfonyl bonds, or the like.

The polyarylene sulfide of this embodiment can have a repeating unit, for example, 5-1000.

Therefore, polyarylene sulfide has the repeating unit which has a fluorene structure among the some repeating unit, and the repeating unit which does not have a fluorene structure as needed.

In the polyarylene sulfide of this embodiment, it is more preferable that the number of repeating units which have a structure represented by the said General formula (1) is 10% or more of the number of all the repeating units. By doing in this way, the solubility to the solvent of polyarylene sulfide can be improved further.

1.4. Method for producing polyarylene sulfide

Below, the example of the manufacturing method of the polyarylene sulfide of this embodiment is described.

The polyarylene sulfide of this embodiment can be obtained by the polycondensation reaction of an aromatic dihalogen compound and an aromatic dithiol compound.

As an aromatic dihalogen compound, for example,

2,7-difluorothianthrene,

2,7-dichlorothianthrene,

　

2,7-dibromothiantrene,

And, 4,4'-difluorodiphenylsulfone,

Compounds, such as these, can be used.

As an aromatic dithiol compound, For example, thiobisbenzene thiol,

9,9-bis (4-mercaptophenyl) fluorene,

And, 2,7-dimercaptothianthrene,

Compounds, such as these, can be used.

The polycondensation reaction can usually be carried out in the presence of a base. Examples of the base that can be used at this time include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium-t-butoxide, potassium carbonate, sodium carbonate, pyridine, triethylamine and the like.

As a reaction solvent of a polycondensation reaction, if a polymer after reaction melt | dissolves, it will not specifically limit, For example, N, N'- dimethyl propylene urea (DMPU), N-methyl- 2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), cyclohexanone (CHN), N, N-dimethylacetamide (DMAc), N, N-diethylacetamide, N, N-dimethoxyacetamide, 1,3-dimethyl 2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxy Ethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyrroline, picoline, dimethylsulfoxide Said, dimethyl sulfone, tetramethylurea, hexamethylphosphoramide, propylene glycol monomethyl ether (PGME), γ-butyrolactone (GBL), phenol, ο-cresol, m-cresol, p-cresol, m-cresol Acid, p-chlorophenol, anisole, benzene, toluene, Xylene and the like. These organic solvents may be used alone or as a mixture of two or more kinds.

If necessary, an azeotropic solvent for removing water or alcohol generated by the reaction of thiol and base can be added. As such an azeotropic solvent, for example, benzene, toluene or the like is preferable. .

As a density | concentration of the monomer in a polycondensation reaction, 5%-40% are preferable, More preferably, they are 10%-30%. Moreover, as reaction temperature in a polycondensation reaction, 50 degreeC-250 degreeC is preferable, More preferably, it is 80 degreeC-200 degreeC. Moreover, as reaction time of a polycondensation reaction, 1 hour-20 hours are preferable, More preferably, it is 2-10 hours.

The polyarylene sulfide of this embodiment can be synthesized by the method exemplified above, for example.

1.5. Effect

The polyarylene sulfide of this embodiment contains a sulfur atom and has a fluorene skeleton, and thus has high refractive index and good transparency. Moreover, the polyarylene sulfide of this embodiment has high solubility in a solvent, for example, high suitability to the solution process like a spin coating process. Moreover, since the polyarylene sulfide of this embodiment is comprised from organic substance, it is hard to generate | occur | produce residue in processes, such as an ashing process and an etching process, for example, and process suitability is high. The reason why the solubility of the polyarylene sulfide of this embodiment is high is not certain at this time, but it is estimated that having a fluorene skeleton is one factor.

1.6. Use of polyarylene sulfide

The polyarylene sulfide of this embodiment can be applied to an optical element etc., for example. That is, since the polyarylene sulfide of this embodiment has a high refractive index, it is suitable for members, such as an optical waveguide part. In addition, the polyarylene sulfide of this embodiment has the property which is easy to melt | dissolve in a solvent as mentioned above. Therefore, the composition in the state in which the polyarylene sulfide of this embodiment was melt | dissolved in the solvent is suitable for wet processes, such as a spin coating method and an etching method, when forming members, such as an optical waveguide part.

In addition, the polyarylene sulfide of this embodiment can be used as a composition which mixed with another substance etc. besides using independently. For example, the polyarylene sulfide of the present embodiment may be blended with other polymers to impart high refractive index properties to the other polymers or to add the properties of the other polymers to the polyarylene sulfides. Can be. In addition, in such mixing, since the solubility in a solvent is favorable for the polyarylene sulfide of this embodiment, methods, such as a solution blend, can be employ | adopted and a more uniform composition can be formed.

1.7. Composition

The composition can be manufactured using the polyarylene sulfide of this invention. Specifically, the composition is obtained by dissolving the polyarylene sulfide of the present invention in at least one solvent selected from organic solvents exemplified as the reaction solvent of the polycondensation reaction. In addition, since the composition of this embodiment is apply | coated to various base materials, surfactant may be mix | blended in order to improve applicability | paintability, and you may mix | blend a crosslinking agent in order to raise the intensity | strength of a coating film.

2. Examples and Comparative Examples

Although an Example and a comparative example are shown to the following and this invention is demonstrated further more concretely, the scope of the present invention is not limited by these. In addition, in an Example, unless otherwise indicated, "%" and "part" mean a "mass%" and a "mass part", respectively.

2.1. Synthesis of Monomers

Various monomers for synthesizing the polyarylene sulfide of Examples and Comparative Examples were synthesized as follows.

Synthesis | combination of 2,7- difluoro thianthrene: 290 ml of fuming sulfuric acid (25%) was added to 50 g of p-fluorothiophenols, and reaction was performed at room temperature for 20 hours. The reaction mixture was poured into 500 ml of ice water, and then extracted with methylene chloride. The methylene chloride layer was dried over anhydrous magnesium sulfate and concentrated to obtain 40 g of crude product containing the desired product. 500 mL of acetic acid and 10 g of powdered zinc were added to the crude product, and the reaction was carried out under reflux for 18 hours. Powdered zinc was filtered off and the filtrate was poured into 500 ml of water to precipitate the desired product. The target product was recovered by filtration and recrystallized from ethanol to obtain 30 g of 2,7-difluorothianthrene represented by the following formula.

Synthesis of 9,9-bis (4-mercaptophenyl) fluorene: 21.65 g (0.39 mol) of potassium hydroxide was dissolved in 320 g of cooled methanol. 59.47 g (0.17 mol) of 9,9-bis (4-phenoxy) fluorene was added to this solution, and then 48 g (0.39 mol) of N, N-dimethylthiocarbamoyl chloride was added thereto, and the temperature was raised to 60 ° C. Time reaction was performed. After cooling the reaction solution, the precipitated solid was collected by filtration and washed with 400 ml of a methanol / water mixed solution (50/50 (volume ratio)). The obtained solid was dissolved in 400 ml of chloroform and washed three times with 400 ml of water. The chloroform layer was concentrated and poured into 400 ml of methanol, and the precipitate was separated by filtration to dry the obtained solid. 77 g of 9-bis [4- (N, N-dimethylthiocarbamoyloxy) phenyl] fluorene was obtained.

Then, 30 g of diphenyl ether was added to 52 g of bis (N, N-dimethyl-O-thiocarbamate), and the mixture was reacted at 250 ° C. for 5 hours under a nitrogen atmosphere. After cooling the reaction mixture, it was added to 500 ml of methanol, and the precipitate was recovered by filtration and dried to obtain 48 g of 9,9-bis [4- (N, N-dimethylcarbamoylthio) phenyl] fluorene represented by the following formula. Got it.

Furthermore, after dissolving 50 g (0.9 mol) of potassium hydroxide in 160 g of cooled methanol, 47 g of bis (N, N-dimethyl-S-carbamate) and 160 g of tetrahydrofuran were added and reacted under reflux for 10 hours. After cooling the reaction mixture, 2 liters of water was added and concentrated hydrochloric acid was added until pH = 5. The aqueous layer was separated by decantation to obtain a viscous precipitate. This was dissolved in 600 ml of chloroform and washed three times with 600 ml of water. The chloroform layer was dried over anhydrous magnesium sulfate and concentrated. This was poured into 1.5 liters of methanol, the precipitate was collected by filtration and dried. The obtained solid was 9,9-bis (4-mercaptophenyl) fluorene shown by following formula. The yield was 28 g.

As mentioned above, the raw material compound (monomer) for synthesizing the polyarylene sulfide of an Example and a comparative example was obtained. P-fluorothiophenol, fuming sulfuric acid (25%), methylene chloride, anhydrous magnesium sulfate, acetic acid, powder zinc, ethanol, methanol, potassium hydroxide, N, N-dimethylthiocarbamoyl chloride, chloroform, Both diphenyl ether and tetrahydrofuran obtained and used the commercial item as a reagent. In addition, the above-mentioned water used ion-exchange water.

2.2. Synthesis of Polyarylene Sulfide

<Example 1>

0.706 g (2.8 mmol) of 2,7-difluoro thianthrene synthesize | combined above, 0.526 g (2.1 mmol) of thiobisbenzene thiols, 9,9-bis (4-mercaptophenyl) flu synthesize | combined above 0.268 g (0.7 mmol) of orene, 0.58 g (4.2 mmol) of potassium carbonate, 4.3 g of N, N'-dimethylpropylene urea (hereinafter abbreviated as DMPU) and 10 g of toluene were measured and attached to a Dean-Stark trap. The reaction was carried out at 160 ° C. in one reaction vessel. After about 2 hours, about 11 ml of water and toluene generated in the Dean-Stark trap were collected. Then, reaction temperature was heated up at 180 degreeC and reaction was continued for 6 hours. The reaction mixture was diluted with DMPU, precipitated in acetic acid methanol, and the polymer was recovered by filtration. The obtained polymer was poured into water, washed for 1 hour under reflux conditions, recovered by filtration and dried to obtain polyarylene sulfide (hereinafter abbreviated as PAS-1) of Example 1. The inherent viscosity measured at 30 ° C. in DMPU (concentration 0.5 g / dL) using a Uberode viscometer was 0.3 dL / g.

PAS-1 of Example 1 contains 25 mol% of 9,9-bis (4-mercaptophenyl) fluorene as a (equivalent) unit corresponding to dithiol, and is represented by the formula (1). The number of repeating units having a structure is 25% of the number of all repeating units. In addition, the infrared absorption spectrum of PAS-1 is shown in FIG.

<Example 2>

0.59 g (2.4 mmol) of 2,7-difluoro thianthrene and 0.904 g (2.4 mmol) of 9,9-bis (4-mercapto phenyl) fluorene were used as a monomer, and 0.49 g of potassium carbonate ( 3.5 mmol), 4.3 g of N, N-dimethylimidazolidinone and 10 g of toluene were weighed out, and the reaction was carried out at 160 ° C in a reaction vessel with a Dean-Stark trap. After about 2 hours, about 11 ml of water and toluene generated in the Dean-Stark trap were collected. Then, reaction temperature was heated up to 190 degreeC and reaction was continued for 4 hours. Purification was carried out in the same manner as in Example 1 to obtain polyarylene sulfide (hereinafter abbreviated as PAS-2) in Example 2. The weight average molecular weight of the standard polystyrene conversion measured by gel permeation chromatography using tetrahydrofuran as the eluent was Mw = 6500, and the number average molecular weight was Mn = 3300. The logarithmic viscosity measured at 30 degreeC in DMPU (concentration 0.5 g / dL) using the Uberode viscometer was 0.5 dL / g.

PAS-2 of Example 2 is comprised only by the structure represented by said formula (1), and the number of repeating units which have a structure represented by said formula (1) is 100% of the number of all repeating units. In addition, the infrared absorption spectrum of PAS-2 is shown in FIG.

<Comparative Example 1>

Example 1 except that 0.753 g (3.0 mmol) of 2,7-difluorothianthrene and 0.747 g (3.0 mmol) of thiobisbenzenethiol were used as the monomer, and 0.62 g (4.5 mmol) of potassium carbonate was used. In the same manner as in the above, polyarylene sulfide (hereinafter abbreviated as PAS-3) of Comparative Example 1 was obtained. The logarithmic viscosity measured at 30 degreeC in DMPU (concentration 0.5 g / dL) using the Uberode viscometer was 0.13 dL / g.

PAS-3 of Comparative Example 1 does not contain 9,9-bis (4-mercaptophenyl) fluorene as the monomer (repeated) unit, and the number of repeating units having the structure represented by Formula (1) is And 0% of the number of all repeating units. In addition, the infrared absorption spectrum of PAS-3 is shown in FIG.

In addition, thiobisbenzene thiol, potassium carbonate, N, N'-dimethylpropylene urea (DMPU) and toluene used for the synthesis | combination of the polyarylene sulfide of Example 1, 2 and the comparative example 1 all acquired the commercial item as a reagent, Used. In addition, water used ion-exchange water.

2.3. Assessment Methods

<Evaluation of polyarylene sulfide>

In Table 1, the number (%) of the repeating unit which has a structure represented by said Formula (1) with respect to the sulfur content rate (mass%) of the polyarylene sulfide of each case, and the number of all the repeating units was described, respectively.

Solubility test: The polyarylene sulfide was put in the solvent shown in Table 1 at 20 degreeC so that it may be set to 15%, and what was melt | dissolved was evaluated as (circle) and the thing which was not partially dissolved (triangle | delta) and what was not dissolved as x. In addition, DMPU represents N, N'-dimethylpropylene urea, CHN represents cyclohexanone, and NMP represents N-methyl-2-pyrrolidone.

In addition, glass transition temperature (Tg) was measured at 10 degree-C / min of the temperature increase rate under nitrogen using DSC, and it showed in Table 1.

<Evaluation of composition>

Preparation of composition: It melt | dissolves in DMPU or CHN so that the density | concentration of solid content which added the polyarylene sulfide and various additives of each case may be 15%, respectively, and DC-190 (Torre Dow) with respect to 100 mass parts of polyarylene sulfides. The composition which added 0.2 mass part of Corning Co., Ltd. products) was prepared like Table 2.

The coating property, the refractive index evaluation, and the transparency evaluation were performed using the composition (solution of polyarylene sulfide) of Table 2.

Applicability evaluation: Each composition shown in Table 2 was apply | coated to a silicon wafer by the spin coating method, and when visual observation observed, there was no surface asperity, (circle), if there was a little unevenness, △, and if there was an uneven | corrugated unevenness | corrugation, the result was table | surface. It described in 2.

Evaluation of refractive index and film thickness: The composition of Table 2 was apply | coated to a silicon wafer by the spin coating method, respectively, and this was made to heat-dry sequentially at 120 degreeC for 1 minute and 250 degreeC for 5 minutes, and it was set as the evaluation sample. And the average value of the refractive index and film thickness of wavelength 633nm in 25 degreeC was calculated | required by the prism coupler, and the result was shown in Table 3.

Transparency evaluation: Each composition of Table 2 was apply | coated to a glass wafer by the spin coating method, respectively, and this was sequentially heated and dried at 120 degreeC for 5 minutes at 250 degreeC, and it was set as the evaluation sample. Using an ultraviolet visible spectrophotometer, the transmittance of the light having a wavelength of 400 nm was measured using P polarized light extracted by the glen taylor prism as the incident light, and the incident angle as the Brewster angle obtained from the refractive index of the sample. Listed. Moreover, about the composition of the comparative example 1, since the smoothness was inferior, the transmittance | permeability could not be measured.

Evaluation of embedding properties and resistance to chemicals were performed as practical physical property evaluations when using it as a light guide material of an image sensor. The composition shown in Table 2 was apply | coated by the spin coating method using the board | substrate with which the hole of 1 micrometer diameter and 3 micrometers depth was formed in 2 micrometer pitch on the silicon wafer, and this was spin-coated at 120 degreeC for 1 minute, and 250 degreeC for 5 minutes. It was sequentially dried by heating to obtain an evaluation sample. This board | substrate was cut out, and the cross section was observed with the field emission scanning electron microscope, and when there was no defect, such as a void, (circle) and it was set as x if there was a defect. Further, the substrate was immersed in 2.38% tetramethylammonium hydroxide (TMAH) or propylene glycol monomethyl ether acetate (PGMEA) for 5 minutes, respectively, and the presence or absence of delamination was observed. If there was, it was X.

2.4. Evaluation results

Looking at Table 1, it turned out that polyarylene sulfide is easy to melt | dissolve in a solvent by having a fluorene structure. In addition, it has been found that as the number of repeating units represented by the formula (1) relative to the total number of repeating units increases, the kind of solvent that can be dissolved increases. Moreover, when the number of repeating units represented by said formula (1) with respect to the number of all repeating units becomes large, it turned out that Tg becomes high and it turned out that heat resistance improves.

From Table 2, it was found that when the polyarylene sulfide has a fluorene structure, the coating property is improved to 1.7 or more while maintaining a high refractive index. Moreover, in the composition of the comparative example 1, since the coating property was bad, the smooth film | membrane was not obtained and the transparency was bad result (visual evaluation), but the relatively smooth film | membrane is obtained from the polyarylene sulfide containing the structure represented by said formula (1). It turned out that it was high transmittance.

From the above results, it was found that the polyarylene sulfide of the example had a combination of high transparency, high refractive index, high heat resistance, and high solubility.

In addition, the composition of the present invention was found to be excellent in the harvesting and chemical resistance to the fine shape required for the light guide material of the image sensor by the selection of additives.

The polyarylene sulfide of this invention can be used, for example as a light guide material of a CCD or CMOS image sensor, a micro lens material, and a planarization film. Moreover, since it is an organic polymer, it can be used suitably for ashing, an etching process, etc.

Claims (17)

An optical member comprising polyarylene sulfide having a fluorene skeleton. The method of claim 1,
The polyarylene sulfide is an optical member having a structure represented by the following formula (1):

[In formula (1), Rm represents an arylene group, Rn represents an aryl group or a C1-C4 alkyl group each independently, and a represents the number of 0-4 each independently; * Indicates combined. The method of claim 2,
The polyarylene sulfide is an optical member having a thianthrene ring. 4. The method according to any one of claims 1 to 3,
Optical member that is a lens. 4. The method according to any one of claims 1 to 3,
An optical member which is a planarization film. 4. The method according to any one of claims 1 to 3,
An optical member that is a light guide path. The optical element provided with the optical member of any one of Claims 1-3. Polyarylene sulfide which has a fluorene skeleton. The method of claim 8,
Polyarylene sulfide which has a structure represented by following formula (1):

[In formula (1), Rm represents an arylene group, Rn represents an aryl group or a C1-C4 alkyl group each independently, and a represents the number of 0-4 each independently; * Indicates combined. 10. The method of claim 9,
Polyarylene sulfide which has a thianthrene ring. 10. The method of claim 9,
The number of repeating units which have a structure represented by said formula (1) is 10% or more of the number of all repeating units, The polyarylene sulfide characterized by the above-mentioned. The method according to any one of claims 8 to 11,
A polyarylene sulfide containing 10 mass% or more of sulfur atoms. The method according to any one of claims 8 to 11,
The refractive index in wavelength 633nm is 1.70 or more, The polyarylene sulfide characterized by the above-mentioned. The method according to any one of claims 8 to 11,
The polyarylene sulfide as amorphous, whose glass transition temperature is 120 degreeC or more. The composition containing the polyarylene sulfide as described in any one of Claims 8-11. 16. The method of claim 15,
A composition containing at least one selected from the group consisting of organic solvents, surfactants and crosslinking agents. The resin composition containing the composition containing the polyarylene sulfide of Claim 15, and polymers other than the said polyarylene sulfide.

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