JP6656531B2 - Triazine compounds and polymers - Google Patents

Description

  The present invention relates to a triazine compound and a polymer.

  Optical materials field, specifically, high-performance substrates for display devices, (interlayer) insulating films, protective films, flattening films, optical adhesives, antireflection films, sealing materials, microlens components for CMOS and CCD image sensors Optoelectronic devices require a high refractive index polymer having high light transmittance.

  As such polymers, sulfur-containing polyimides have attracted attention because they generally exhibit high refractive index, low birefringence, high thermal stability, and high mechanical strength. For example, they are applied to the internal lens material of CMOS image sensors. (Non-Patent Document 1). Non-Patent Document 2 discloses that a polymer having a triazine structure in the main chain shows high visible light transmittance and has a high refractive index.

  The internal lens is required to be small and highly integrated. In order to satisfy these demands, photo-functionalization of polymer materials and microfabrication processes by photolithography are generally used, and imparting photosensitivity to high refractive index materials is a very important technological development item. I have.

Y. Suzuki et al., Macromolecules, Volume 40, Number 22, 7902-7909. Y. Nakagawa et al., Macromolecules, 2011, 44 (23), 9180-9186

Although the polymers described in the above documents show excellent properties, there is room for improvement when used as a positive photosensitive material.
Specifically, the polymer described in Non-Patent Document 1 has a problem that the solubility of an intermediate polyamic acid in an alkali developing solution (eg, a 2.38 wt% aqueous solution of tetramethylammonium hydroxide) is too high. there were. It is considered that the main cause of this problem is that polyamic acid, which is a monomer, has two carboxy groups at relatively close positions, and the amide bond in the main chain increases water solubility.
Further, the polymer described in Non-Patent Document 2 has room for improvement in that the solubility in an alkali developer is too low.

  The present invention has been made in view of the above, and it is possible to obtain a cured film having a high refractive index, a low birefringence, and a high visible light transmission property, and is more alkaline than a conventional high bending polymer. An object of the present invention is to provide a triazine compound capable of obtaining a polymer having improved solubility in a developer and the polymer.

  The present inventors have made intensive studies to solve the above problems. As a result, they have found that a triazine compound having a specific structure and a polymer having a structure derived from the compound can solve the above problems, and have completed the present invention. Embodiments of the present invention are as follows.

（式（１）および（２）中のＸはハロゲン原子であり、式（２）中のＲは、水素原子、ｔ−ブチル基、テトラヒドロピラニル基または１-エトキシエチル基である。） [1] A triazine compound represented by the following formula (1) or (2).

(X in the formulas (1) and (2) is a halogen atom, and R in the formula (2) is a hydrogen atom, a t-butyl group, a tetrahydropyranyl group, or a 1-ethoxyethyl group.)

（式（４）中のＲは、式（２）と同義であり、Ａｒ₁およびＡｒ₂はそれぞれ独立して、芳香環を有する２価の基である。＊は、結合部位を示す。） [2] A polymer having a structure represented by the following formula (3) or (4), obtained using the triazine compound according to [1].

(R in the formula (4) has the same meaning as in the formula (2), and Ar ₁ and Ar ₂ are each independently a divalent group having an aromatic ring. * Indicates a binding site.)

（式（５）および（６）中のＲ¹〜Ｒ¹²はそれぞれ独立して、水素原子、ハロゲン原子、水酸基、カルボキシ基、スルホ基、炭素数１〜１０のアルキル基または炭素数１〜１０のアルコキシ基である。） [3] The polymer according to [2], wherein Ar ₁ and Ar ₂ are each independently a group represented by the following formula (5) or (6).

(R ^{1 to} R ¹² in the formulas (5) and (6) are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Is an alkoxy group.)

  According to the present invention, it is possible to easily form a cured film having a high refractive index, a low birefringence, and a high visible light transmittance, and to improve the solubility in an alkali developing solution as compared with a conventional high refractive polymer. Coalescence can be easily obtained.

FIG. 1 is an ultraviolet-visible (UV-vis) absorption spectrum of the polymers (PPT1 to PPT4) obtained in Examples 1 to 4.

≪Triazine compound≫
The triazine compound according to the present invention is represented by the following formula (1) or (2).
By using this compound as a raw material, a polymer and a cured film having the above effects can be easily obtained.

  X is a halogen atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom. A plurality of Xs in one formula may be different halogen atoms, but are usually the same halogen atom.

  R is a hydrogen atom, a t-butyl group, a tetrahydropyranyl group or a 1-ethoxyethyl group, and the solubility of the triazine compound in the solvent, and the solubility of the obtained polymer in the solvent and the deprotection step. A t-butyl group is preferable from the viewpoint of excellent solubility in a subsequent alkali developing solution (eg, an aqueous solution of 2.38 wt% tetramethylammonium hydroxide).

As the triazine compound, a compound represented by the formula (2) is preferable from the viewpoint that a polymer having excellent solubility in a solvent is obtained.
Further, the polymer obtained by using the compound represented by the formula (1) becomes a base resin of various modified products, which can be easily obtained according to a desired purpose. From this point, it is also preferable to use the compound represented by the formula (1).

<Synthesis method of triazine compound>
The triazine compound represented by the formula (1) is obtained by reacting a halogenated triazine such as cyanuric chloride, which is a raw material compound, with 4-hydroxybenzenethiol in a solvent in the presence of a catalyst such as an amine. Can be synthesized.

The triazine compound represented by the above formula (2) is obtained by first converting 4-hydroxybenzenethiol and XCH ₂ COOR (X and R are the same as X and R in the formula (2)) to an alkali metal salt or the like. The reaction is carried out in a solvent in the presence of a catalyst, and the obtained intermediate is synthesized by reacting the obtained intermediate with a halogenated triazine such as cyanuric chloride in a solvent in the presence of a catalyst such as an amine. be able to.
According to these synthesis methods, the target compound can be synthesized in a high yield of 70% or more.

  The catalyst such as the amine is not particularly limited, and examples thereof include diisopropylethylamine, triethylamine, and 2,4,6-trimethylpyridine.

Examples of the solvent include, but are not particularly limited to, ethers such as tetrahydrofuran, propylene glycol monomethyl ether, and diethylene glycol ethyl methyl ether; alkyl halides such as CHCl ₃ , tetrachloroethane, and dichloromethane; N, N-dimethylacetamide; Examples thereof include amides such as -2-pyrrolidone, sulfoxides such as dimethyl sulfoxide, acetates such as propylene glycol monomethyl ether acetate, and aromatic hydrocarbons such as toluene and xylene.

  Examples of the catalyst such as the alkali metal salt include alkali metals such as lithium, potassium and sodium; alkali metal hydrides such as lithium hydride, potassium hydride and sodium hydride; lithium hydroxide, potassium hydroxide and sodium hydroxide. Alkali metal hydroxides; alkali metal carbonates such as lithium carbonate, potassium carbonate and sodium carbonate; and alkali metal-containing compounds such as alkali metal bicarbonates such as lithium bicarbonate, potassium bicarbonate and sodium bicarbonate.

4-hydroxybenzenethiol has a strong nucleophilic property of the thiol group due to the electron donating effect of the hydroxy group present at the para position, and the intermediate has an electron donating effect of the sulfide bond present at the para position. , The nucleophilic nature of the phenol group is strong.
Therefore, in order to reduce the reactivity of the thiol group or the phenol group, the reaction is performed while the starting compound is added dropwise, the concentration of the reaction solution is reduced, a low-polar solvent is used, or the reaction is performed at a low temperature. To optimize the reaction conditions.

  The amount of the starting compound used in synthesizing the compounds represented by the formulas (1) and (2) is not particularly limited, but is usually about equimolar.

  The reaction temperature when synthesizing the compounds represented by the formulas (1) and (2) is preferably -100 to 0C, more preferably -80 to -10C, and the reaction time is preferably Is from 3 to 48 hours, more preferably from 6 to 24 hours.

≪Polymer≫
The polymer according to the present invention is a polymer having a structure represented by the following formula (3) or (4), and is obtained by using the triazine compound.
The polymer has a high refractive index, a low birefringence, a high visible light transmittance and a high heat resistance, but is excellent in solubility in an alkali developing solution or a solvent. Further, since the polymer has excellent solubility in a solvent, a solution containing the compound can be prepared, and a cured film is easily formed on a substrate by a simple method such as a coating method or a dipping method. be able to.

（式（４）中のＲは、前記式（２）中のＲと同義である。）

(R in the formula (4) has the same meaning as R in the formula (2).)

Ar ₁ and Ar ₂ are each independently a divalent group having an aromatic ring, and a cured film having a higher refractive index, a lower birefringence, a higher visible light transmittance and a higher heat resistance can be obtained. From the viewpoint of being able to do so, a group represented by the following formula (5) or (6) is preferable.
Further, from the viewpoint that a polymer having more excellent solubility in a solvent and solubility in an alkali solution can be obtained, and a cured film having a lower birefringence can be obtained, the following formula (5) is preferable. ), And is preferably a group represented by the following formula (6) from the viewpoint that a cured film having a higher refractive index can be obtained.

R ^{1 to} R ¹² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a sulfo group, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, preferably a hydrogen atom It is.

<Polymer synthesis method>
The polymer can be synthesized by subjecting the compound represented by the formula (1) or (2) and various dithiol compounds to an aromatic nucleophilic substitution polycondensation reaction.
In this synthesis method, two or more starting compounds may be used.

As the synthesis method, specifically, a polymer having a structure represented by the formula (3) is represented by a compound represented by the formula (1) and a compound represented by the following formula (5A) or (6A). With a compound in a solvent in the presence of a catalyst such as an amine. From the viewpoint of obtaining a polymer having excellent solubility in a solvent and solubility in an alkaline solution, the polymer obtained in this manner and XCH ₂ COOR (X and R are represented by the formula (2) The same as X and R of the above) may be reacted in a solvent in the presence of a catalyst such as an alkali metal salt.
Further, the polymer having the structure represented by the formula (4) is obtained by combining a compound represented by the formula (2) with a compound represented by the following formula (5A) or (6A) such as an amine. It can be synthesized by reacting in a solvent in the presence of a catalyst.
According to these synthesis methods, the target polymer can be synthesized with a high yield of 70% or more.

  Examples of the catalyst such as the amine, the solvent, and the catalyst such as the alkali metal salt include those similar to those used in the method for synthesizing the triazine compound.

  The amount of the starting compound used in synthesizing the polymer having the structure represented by the formula (3) or (4) is not particularly limited, but the compound represented by the formula (1) or (2) is used. : The dithiol compound is preferably about 1: 1 to 1.4, more preferably about 1: 1 to 1.2, by mole ratio.

  The reaction temperature at the time of synthesizing the polymer having the structure represented by the above formulas (3) and (4) is preferably -10 to 50C, more preferably -5 to 30C, and the reaction time. Is preferably 3 to 48 hours, more preferably 6 to 24 hours.

<Physical properties of polymer>
The weight average molecular weight (Mw) is preferably 2,000 to 100,000, more preferably 5,000 to 50,000, from the viewpoint that the polymer becomes a polymer having excellent heat resistance and solubility in a solvent. The distribution (Mw / Mn) is preferably from 1.5 to 8, and more preferably from 1.8 to 6.
In addition, the said molecular weight can be measured by the method described in the following example.

From the viewpoint that the polymer becomes a polymer having excellent heat resistance, the pyrolysis temperature (5% weight loss temperature) measured by thermogravimetric analysis (TGA) is preferably 300 to 500 ° C, more preferably 310-500 ° C.
The thermal decomposition temperature can be measured by the method described in the following examples.

The polymer is preferably soluble in an alkali developing solution, specifically, an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide at 25 ° C.
The term "soluble" means that when the polymer is immersed in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 60 seconds, 1 g or more of the polymer is dissolved.
In the case of a polymer having the structure represented by the formula (4), it is only necessary that the polymer from which the protecting group R is deprotected is soluble in an alkali developing solution. The method for deprotection is not particularly limited, and may be performed by a conventionally known method.

<Use of polymer>
Since the polymer has the above-mentioned effects, for example, a high-performance substrate for a display device, an (interlayer) insulating film, a protective film, a flattening film, an optical adhesive, an antireflection film, a sealing material, a CMOS or a CCD image sensor For use in an optoelectronic device such as a microlens component.
The polymer can be suitably used as a resist, specifically, a positive resist material by using the polymer together with a photosensitizer, preferably a positive photosensitizer such as a diazonaphthoquinone compound.

<Curing film>
The polymer is preferably used as a cured film containing the polymer.
Since the polymer has excellent solubility in a solvent, a composition in which the polymer is dissolved in a solvent is prepared, and a cured film is easily formed using the composition by a coating method, a dipping method, or the like. can do.
Conventionally known additives such as a surfactant can be added to the composition. When a polymer having a structure represented by the formula (4) is used, a thermal acid generator or the like is added to the composition for deprotecting the protecting group, R, and the like. Is preferred.

  The cured film can be produced, for example, by heating the composition. The heating conditions are not particularly limited, and may be appropriately set according to the polymer or the like used, and may be one-stage heating or two or more stages of heating.

  The thickness of the cured film may be appropriately selected depending on the desired use, and is not particularly limited.

The cured film is preferably a high-refractive-index cured film. Specifically, the average refractive index (n _AV ) of a 3.0-μm-thick cured film when using light of a wavelength of 633 nm is preferably It is from 1.60 to 1.80, more preferably from 1.63 to 1.80. Further, the cured film is preferably a cured film having a low birefringence, and specifically, the birefringence of the cured film having a thickness of 3.0 μm is preferably 0.001 to 0.01. , More preferably 0.001 to 0.009.
The refractive index and the birefringence can be measured by the methods described in the following examples.

The cured film preferably has a high visible light transmittance. Specifically, the transmittance of the cured film having a thickness of 3.0 μm at a wavelength of 400 nm is preferably 90% or more, more preferably It is at least 92%, more preferably at least 94%.
The visible light transmittance can be measured by the method described in the following examples.

  Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples.

  The analysis conditions of the compound obtained in the following synthesis example and the polymer obtained in the following example are as shown below.

<Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)>
Mw and Mn were measured by gel permeation chromatography (GPC) under the following conditions. The molecular weight distribution (Mw / Mn) was calculated from the obtained Mw and Mn.
Equipment: "GPC-101" of Showa Denko KK
GPC column: “GPC-KF-801”, “GPC-KF-802”, “GPC-KF-803” and “GPC-KF-804” manufactured by Shimadzu GC Co., Ltd. Mobile phase: tetrahydrofuran (THF )
Column temperature: 40 ° C
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard substance: Monodisperse polystyrene

<NMR spectrum>
The NMR (Nuclear Magnetic Resonance) spectra of the compounds obtained in the following synthesis examples and the polymers obtained in the examples, specifically ¹ H NMR spectrum and ¹³ C NMR, are measured by JEM- It was measured under the following conditions using EX400 FT NMR.
The solvent used was any of deuterated chloroform, deuterated dichloromethane, deuterated dimethyl sulfoxide, and deuterated tetrahydrofuran, and tetramethylsilane (0 ppm) was used as a reference substance. For the analysis, an analysis program Delta version. 4.3.4 manufactured by JEOL Ltd. was used. As the chemical shift, the value analyzed by the program was used as it was.

<FT-IR spectrum>
The FT-IR spectrum of the polymer obtained in the following examples was measured by a reflection method using FTS6000 manufactured by BIO-RAD.

[Synthesis Example 1] Synthesis of compound (a-1)

  Under nitrogen, 5.53 parts by mass of cyanuric chloride was added to a 300 mL two-necked flask, dissolved in 100 parts by mass of THF, and cooled to −40 ° C. Next, a solution prepared by dissolving 2.52 parts by mass of 4-hydroxybenzenethiol and 2.04 parts by mass of triethylamine (TEA) in 25 parts by mass of THF was added dropwise to the cooled solution, and the reaction was started. After stirring overnight, the mixture was separated and washed with a saturated aqueous ammonium chloride solution, and then separated and washed with a saturated aqueous sodium chloride solution. The organic layer was collected, dried over magnesium sulfate, concentrated using an evaporator, and purified by flash chromatography to obtain 4.44 parts by mass of compound (a-1).

The result of NMR measurement of the obtained compound (a-1) is as follows.
¹ H-NMR (400 MHz, CDCl ₃ -d ₁ , ppm): 7.41 (d, J = 8.40 Hz, 2H; ArH), 6.91 (d, J = 8.40 Hz, 2H; ArH), 5.43 (s, 1H; Ar-OH).
¹³ C-NMR (400 MHz, CDCl ₃ -d ₁ , ppm): 187.33, 170.52, 157.94, 137.20, 116.98, 116.11.

[Synthesis Example 2] Synthesis of compound (a-2)

  In a 20 ml flask, 0.505 parts by mass of 4-hydroxybenzenethiol, 0.835 parts by mass of t-butyl bromoacetate (tBu), 0.354 parts by mass of potassium carbonate, and 5 parts by mass of N, N-dimethylformamide (DMF) Parts were added. Thereafter, the reaction was carried out at room temperature (25 ° C.) for 24 hours, and the extracted ethyl acetate solution was washed with pure water. After drying over magnesium sulfate, the mixture was concentrated using an evaporator and purified by flash chromatography to obtain 0.86 parts by mass of an intermediate of the compound (a-2).

The results of NMR measurement of the intermediate of the obtained compound (a-2) are as follows.
¹ H-NMR (400 MHz, CDCl ₃ -d ₁ , ppm): 7.34 (d, J = 11.4 Hz, 2H; ArH), 6.71 (d, J = 11.4 Hz, 2H; ArH), 5.597 (s, 1H; Ar- OH), 3.41 (s, 2H; S-CH 2 -COOtBu), 1.40 (s, 9H; -CH 3).

  Under nitrogen, 0.65 parts by mass of cyanuric chloride was added to a 50 mL two-necked flask, dissolved in 10 parts by mass of THF, and cooled to -40 ° C. Next, a solution obtained by dissolving 0.81 part by mass of the intermediate compound (a-2) obtained above and 0.66 part by mass of diisopropylethylamine (DIPEA) in 10 parts by mass of THF was added dropwise to the cooled solution. The reaction was started. After stirring overnight, the mixture was separated and washed with a saturated aqueous ammonium chloride solution, and then separated and washed with a saturated aqueous sodium chloride solution. The organic layer was collected, dried over magnesium sulfate, concentrated using an evaporator, and purified by flash chromatography to obtain 0.92 parts by mass of compound (a-2).

The result of NMR measurement of the obtained compound (a-2) is as follows.
¹ H-NMR (400 MHz, CDCl ₃ -d ₁ , ppm): 7.49 (d, J = 8.72 Hz, 2H; ArH), 7.10 (d, J = 8.90 Hz, 2H; ArH), 3.57 (s, 2H; S- CH 2 -COOtBu), 1.39 (s, 9H; -CH 3).
¹³ C-NMR (400 MHz, CDCl ₃ -d ₁ , ppm): 173.22, 171.11, 168.62, 149.87, 134.26, 131.54, 121.68, 82.32, 37. 89, 27.99.

[Synthesis Example 3] Synthesis of compound (a-3)

  At room temperature and under nitrogen, 10.00 parts by mass of cyanuric chloride and 7.01 parts by mass of DIPEA were added to a 300 mL two-necked flask, dissolved in 100 parts by mass of THF, and stirred in an ice bath (0 ° C.) for 20 minutes. Thereafter, a solution in which 6.73 parts by mass of p-toluenethiol was dissolved in 80 parts by mass of THF was added, and the reaction was started. The solution reacted for 3 hours was filtered, concentrated using an evaporator, and recrystallized to obtain a compound (a-3).

The result of NMR measurement of the obtained compound (a-3) is as follows.
¹ H-NMR (400 MHz, DMSO-d ₆ , ppm): 7.42 (d, J = 8.40 Hz, 2H; ArH), 7.29 (d, J = 8.00 Hz, 2H; ArH), 2 _{.42 (s, 3H; -CH 3} ).
¹³ C-NMR (400 MHz, DMSO-d ₆ , ppm): 186.84, 170.38, 141.09, 134.97, 130.46, 121.85, 77.00.

[Example 1] Synthesis of polymer (PPT1)

  Under nitrogen, 0.143 parts by mass of bis (4-mercaptophenyl) sulfide was added to a 10 mL two-necked flask, dissolved in 1.78 parts by mass of THF, cooled to 0 ° C., and 0.115 parts by mass of TEA was added dropwise. And stirred for 30 minutes. Thereafter, 0.156 parts by mass of the compound (a-1) was added, and the mixture was vigorously stirred. After reacting overnight at room temperature, the precipitate was reprecipitated with methanol, and the obtained solid was vacuum-dried at 70 ° C. to obtain 0.468 parts by mass of a polymer (PPT1). Mw of the obtained polymer was 12,400 and Mw / Mn was 4.52.

The results of NMR measurement and FT-IR measurement of the obtained polymer (PPT1) are as follows.
^{1 H-NMR (400MHz, THF} -d 8, ppm): 8.81 (s, 1H; Ar-OH), 7.33 (d, J = 8.4Hz, 2H; ArH), 7.24 (d , J = 8.4 Hz, 2H; ArH), 7.16 (d, J = 8.4 Hz, 2H; ArH), 6.69 (d, J = 8.4 Hz, 2H; ArH).
FT-IR (cm ^-1 ): IR (ATR), ν (cm ^-1 ): 3200 br (Ar-OH), 1581 and 1461 (triazine ring), 1227 (Ar-S-Ar).

[Example 2] Synthesis of polymer (PPT2)

  A polymer (PPT2) was obtained in the same manner as in Example 1 except that 0.0812 parts by mass of 1,3-benzenedithiol was used instead of bis (4-mercaptophenyl) sulfide. Mw of the obtained polymer was 28,800, and molecular weight distribution Mw / Mn was 2.43.

The results of NMR measurement and FT-IR measurement of the obtained polymer (PPT2) are as follows.
^{1 H-NMR (400MHz, DMSO} -d 6, ppm): 10.04 (s, 1H; Ar-OH), 7.43 (d, J = 8.0Hz, 2H; ArH), 7.39 (d , J = 8.0 Hz, 2H; ArH), 7.15 (s, 1H; ArH), 6.83 (d, J = 8.4 Hz, 2H; ArH), 6.68 (d, J = 8. 4 Hz, 1H; ArH).
FT-IR (cm ^-1 ): IR (ATR), ν (cm ^-1 ): 3200 br (Ar-OH), 1585 and 1464 (triazinering), 1231 (Ar-S-triazinering), 845 (benzenring).

[Example 3] Synthesis of polymer (PPT3)

  Under nitrogen, to a 10 mL two-necked flask, 0.424 parts by mass of bis (4-mercaptophenyl) sulfide was added, dissolved in 3.56 parts by mass of THF, cooled to 0 ° C., and 0.600 parts by mass of DIPEA was added dropwise. And stirred for 30 minutes. Thereafter, 0.731 parts by mass of the compound (a-2) was added, followed by vigorous stirring. After reacting at room temperature overnight, the precipitate was reprecipitated with methanol, and the obtained solid was vacuum-dried at 70 ° C. to obtain 0.745 parts by mass of a polymer (PPT3). Mw of the obtained polymer was 9530, and Mw / Mn was 2.86.

The results of NMR measurement and FT-IR measurement of the obtained polymer (PPT3) are as follows.
¹ H-NMR (400 MHz, CD ₂ Cl ₂ , ppm): 7.36 (d, J = 8.8 Hz, 2H; ArH), 7.31 (d, J = 8.4 Hz, 2H; ArH), 7 .26 (d, J = 8.8Hz, 2H; ArH), 6.92 (d, J = 8.4Hz, 2H; ArH), 3.53 (s, 2H; S-CH 2 -COOtBu), 1 _{.35 (s, 9H; -CH 3} ).
^{FT-IR (cm -1):} 2978 (-CH 3), 1726 (C = O), 1581and1461 (triazine ring), 1227 (Ar-S-Ar).

[Example 4] Synthesis of polymer (PPT4)

  A polymer (PPT4) was obtained in the same manner as in Example 4, except that 0.241 parts by mass of 1,3-benzenedithiol was used instead of bis (4-mercaptophenyl) sulfide. Mw of the obtained polymer was 14,300, and Mw / Mn was 1.88.

The results of NMR measurement and FT-IR measurement of the obtained polymer (PPT4) are as follows.
¹ H-NMR (400 MHz, DMSO-d ₆ , ppm): 7.46 (d, J = 8.8 Hz, 2H; ArH), 7.40 (d, J = 8.8 Hz, 2H; ArH), 7 .15 (s, 1H; ArH), 6.83 (d, J = 8.4 Hz, 2H; ArH), 6.68 (m, J = 8.4 Hz, 1H; ArH), 3.54 (s, _{2H; S-CH 2 -COOtBu)} , 1.38 (s, 9H; -CH 3).
FT-IR (ATR) (cm ^-1 ): 2978 (-CH ₃ ), 1726 (C = O), 1585 and 1464 (triazine ring), 1231 (Ar-S-triazine ring), 845 (benzen ring).

Example 5 Synthesis of Polymer (PPT5)

Under nitrogen, to a 10 mL two-necked flask, 0.569 parts by mass of the polymer (PPT2) was added, dissolved in 2.82 parts by mass of THF, cooled to 0 ° C., and 0.256 parts by mass of DIPEA was added dropwise. Stirred. Thereafter, 0.344 parts by mass of t-butyl bromoacetate was added. After reacting at 60 ° C. overnight, the precipitate was reprecipitated with methanol, and the obtained solid was vacuum-dried at 70 ° C. to obtain 0.472 parts by mass of a polymer (PPT5). ^From the result of ¹ H-NMR, the conversion was 25 mol%.

The results of NMR measurement and FT-IR measurement of the obtained polymer (PPT5) are as follows.
^{1 H-NMR (400MHz, DMSO} -d 6, ppm): 10.04 (s, 1H; Ar-OH), 7.43 (d, J = 8.0Hz, 2H; ArH), 7.39 (d , J = 8.0 Hz, 2H; ArH), 7.15 (s, 1H; ArH), 6.83 (d, J = 8.4 Hz, 2H; ArH), 6.68 (d, J = 8. 4Hz, 1H; ArH), 4.71 (s, 0.5H; O-CH 2 -COOtBu), 1.38 (s, 2.25H; -CH 3).
FT-IR (ATR) (cm ^-1 ): 3200 br (Ar-OH), 2978 (-CH ₃ ), 1726 (C = O), 1585 and 1464 (triazine ring), 1231 (Ar-S-Ar), 845 ( benzene ring).

Comparative Example 1 Synthesis of Polymer (c-1)

  At room temperature and under nitrogen, 5.59 parts by mass of bisphenol A, 4.02 parts by mass of cetyltrimethylammonium bromide (CTAB) and 75.3 parts by mass of a 1 M aqueous sodium hydroxide solution were added to a 300 mL two-necked flask, and added for 1 hour. Reacted. Thereafter, a solution of 10.00 parts by mass of the compound (a-3) in dichloromethane was added to initiate polymerization. After 4 hours, the pH of the reaction solution was acidified and reprecipitated with methanol. The dried precipitate was dissolved in THF, an ion exchange resin was added, and the mixture was stirred for 1 hour. The filtered solution was reprecipitated with n-hexane. The precipitate was filtered and dried under vacuum at 50 ° C. for 8 hours to obtain the desired polymer (c-1). Mw of the obtained polymer was 8,200, and Mw / Mn was 3.2.

<Evaluation>
The polymers obtained in Examples and Comparative Examples were evaluated by the method described below.

[Solubility in solvent]
THF, CHCl ₃ , tetrachloroethane (TCE), N, N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate of the obtained polymers PPT1 to PPT4 (PGMEA), N-methyl-2-pyrrolidone (NMP) and diethylene glycol ethyl methyl ether (EDM) solubility were evaluated.

  At room temperature, 10 mg of the polymer was placed in 1 mL of each solvent, and after stirring for 10 minutes, the case where the polymer was dissolved was defined as (++). The polymer was not dissolved at room temperature for 10 minutes, but was dissolved when heated to 60 ° C. (+), The case where only a part was dissolved by heating at 60 ° C. was evaluated as (−), and the case where it was not dissolved by heating at 60 ° C. was evaluated as (−−). Table 1 shows the results.

[Evaluation of heat resistance]
Thermogravimetric analysis (TGA) was performed to evaluate the heat resistance of the obtained polymer.
The TGA used was TGA / 6200 manufactured by Seiko Instruments Inc., and the temperature was raised at a rate of 10 ° C./min in a nitrogen atmosphere using an aluminum pan, and the 5% weight loss temperature was measured. The case where the 5% weight loss temperature was 300 ° C. or higher was evaluated as “A”, and the case where the temperature was 300 ° C. or lower was evaluated as “B”.

[Evaluation of applicability]
0.5 part by mass of a surfactant (“FTX-218” manufactured by Neos Corporation) was mixed with 100 parts by mass of the polymer. Further, a mixed solution of EDM and cyclohexanone was added as a solvent so that the solid content concentration became 20% by mass, and the solution was filtered through a membrane filter having a pore size of 0.2 μm to prepare an evaluation solution.

  After a solution for evaluation was applied on a silicon substrate using a spinner, it was prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film. The surface state of the obtained coating film was visually observed and observed with an optical microscope, and was evaluated as “A” when no repelling or unevenness was found, and “B” when there was repelling or unevenness. Table 2 shows the results.

[Evaluation of transmittance]
An evaluation solution prepared in the same manner as described above was applied on a glass substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film. Next, this glass substrate was heated on a hot plate at 230 ° C. for 30 minutes. The transmittance of the obtained cured film (thickness: 60 μm) was measured with a “V-630” ultraviolet-visible spectrophotometer manufactured by JASCO Corporation. The results are shown in FIG.
When the transmittance of a cured film having a wavelength of 400 nm of 94% or more when the thickness of the cured film was converted to 3 μm, the transparency was judged to be excellent “A”. Table 2 shows the results.

[Evaluation of refractive index]
After applying an evaluation solution prepared in the same manner as above using a spinner on a silicon substrate, pre-baking was performed at 90 ° C. for 2 minutes on a hot plate, and then at 230 ° C. for 30 minutes in a clean oven. Post baking was performed to form a cured film having a thickness of 3.0 μm. The refractive index of the obtained cured film was measured by "Prism Coupler Model 2010" manufactured by Metricon. Specifically, the in-plane refractive index (n _TE ) and the out-of-plane refractive index (n _TM ) were measured at a wavelength of 633 nm. The birefringence (Δn) was calculated as Δn = n _TE −n _TM , and the average refractive index (n _AV ) was calculated as n _AV = [(2n _TE ² + n _TM ² ) / 3] ^1/2 . Dielectric constant (ε) was calculated as ε = 1.0 n _AV ² . Table 3 shows the values of the refractive index and the birefringence.
The case where the refractive index (n _AV ) was 1.630 or more was evaluated as “A”, and the case where it was 1.600 or more and less than 1.630 was evaluated as “B”. Table 2 shows the results.

[Evaluation of alkali solubility]
0.5 part by mass of a surfactant (FTX-218) was mixed with 100 parts by mass of the polymer. When the polymers PPT3 to PPT5 were used, 10 parts by mass of the thermal acid generator was further mixed during this mixing. After adding a mixed solution of EDM and cyclohexanone as a solvent to the obtained mixture so as to have a solid content concentration of 20% by mass, the mixture was filtered through a membrane filter having a pore size of 0.2 μm to evaluate the alkali solubility. A solution was prepared.

  After a solution for evaluating alkali solubility is applied on a silicon substrate treated with hexamethyldisilazane (HMDS) at 60 ° C. for 60 seconds using a spinner, if a polymer PPT1 to PPT2 is used, the solution is 2 ° C. at 90 ° C. For 3 minutes to form a coating film having a thickness of 3.0 μm, and when using polymers PPT3 to PPT5, bake on a hot plate for 2 minutes at 150 ° C. The deprotecting group was deprotected by the acid of the above to form a coating film having a thickness of 3.0 μm. Next, using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide as a developer, development was performed at 25 ° C. for 60 seconds. At this time, the case where the coating was completely dissolved on the substrate is referred to as “A”, and the case where the coating was removed from the substrate was referred to as “B”, and the case where the coating was dissolved in the developer was referred to as “B”. The case where the film was not dissolved in the developing solution was evaluated as “C”, and the case where the film was not dissolved on the substrate and the film was not peeled off from the substrate was evaluated as “D”. Table 2 shows the results.

  “S” in Table 3 indicates the amount (wt%) of sulfur atoms in the polymer. This amount is a value calculated from the unit structural formula of the polymer.

Claims (3)

A triazine compound represented by the following formula (1) or (2).

(X in the formulas (1) and (2) is a halogen atom, and R in the formula (2) is a hydrogen atom, a t-butyl group, a tetrahydropyranyl group, or a 1-ethoxyethyl group.) A polymer obtained by using the triazine compound according to claim 1 and having a structure represented by the following formula (3) or (4).

(R in the formula (4) has the same meaning as in the formula (2), and Ar ₁ and Ar ₂ are each independently a divalent group having an aromatic ring. * Indicates a binding site.) The polymer according to claim 2, wherein Ar ₁ and Ar ₂ are each independently a group represented by the following formula (5) or (6).

(R ^{1 to} R ¹² in the formulas (5) and (6) are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Is an alkoxy group.)

Images