JP2022061763A - Novel polythiol compound - Google Patents

Abstract

To provide a polythiol compound with a biaryl skeleton improved in solubility to solvents.SOLUTION: The polythiol compound is represented by the general formula (1) in the figure.SELECTED DRAWING: None

Description

The present invention relates to a novel polythiol compound having a 1,1'-binaphthyl skeleton.

Polythiol compounds are used as cross-linking agents for various resins such as urethane resin, maleimide resin, acrylic resin, epoxy resin, allyl resin, vinyl resin, unsaturated polyester and polybutadiene, but their chemical structure is an aliphatic polyol. Polythiol compounds used as the basic skeleton are the mainstream.
There are still few reports of polythiol compounds having an aromatic polyol as a basic skeleton. For example, Patent Document 1 describes a polythiol compound having a bisphenol A as a basic skeleton, and a black matrix resist composition using this is described. In terms of sensitivity, it has been reported that the line width retention of the fine line pattern during alkaline development, that is, the development margin is excellent.
Further, a polythiol compound having a biphenol as a basic skeleton is also described in Non-Patent Document 1, but its basic physical characteristics have not been clarified.
Compounds based on the biaryl skeleton, which has a rigid chemical structure, such as biphenol, are expected to have high heat resistance, and are also expected to have a high refractive index due to the increase in polarizability due to π electrons in the aromatic ring. Due to its rigid chemical structure, its poor solvent solubility was a problem.

Japanese Unexamined Patent Publication No. 2006-154774

Inorganica Chemica Acta, 359 (11), 3605-3616, 2006

The present invention has been made in the background of the above-mentioned circumstances, and an object of the present invention is to improve the solvent solubility of a polythiol compound having a biaryl skeleton.

As a result of diligent studies to solve the above-mentioned problems, the present inventor has found that the polythiol compound having a 1,1'-binaphthyl skeleton has the same heat resistance as the conventionally known biaryl compound. Further, they have found that they are soluble in a solvent and have an excellent refractive index, and have completed the present invention.

（式中、Ｒ^１は各々独立して炭素原子数２～６の直鎖状または分岐状のアルキレン基を示し、Ｒ^２は各々独立して炭素原子数１～６の直鎖状または分岐状のアルキレン基を示し、Ｒ^３は各々独立して炭素原子数６～１２のアリール基を示し、ｍは１～４の整数を示し、ｎは０～４の整数を示す。ただし、ｍ、ｎが２以上の整数の場合のＲ^１、Ｒ^３は、それぞれ同一でも異なっていてもよい。） The present invention is as follows.
1. 1. A polythiol compound represented by the following general formula (1).

(In the formula, R ¹ independently represents a linear or branched alkylene group having 2 to 6 carbon atoms, and R ² independently represents a linear or branched alkylene group having 1 to 6 carbon atoms. Independently, R ³ indicates an aryl group having 6 to 12 carbon atoms, m indicates an integer of 1 to 4, and n indicates an integer of 0 to 4. However, m and n. When is an integer of 2 or more, R ¹ and R ³ may be the same or different, respectively.)

Although the novel polythiol compound of the present invention is a compound having a rigid biaryl skeleton, it is very useful because it has the same heat resistance as the conventionally known biaryl compound and has high solvent solubility. Is.
Moreover, since it has a high refractive index, it is also useful as a functional monomer.

（式中、Ｒ^１は各々独立して炭素原子数２～６の直鎖状または分岐状のアルキレン基を示し、Ｒ^２は各々独立して炭素原子数１～６の直鎖状または分岐状のアルキレン基を示し、Ｒ^３は各々独立して炭素原子数６～１２のアリール基を示し、ｍは１～４の整数を示し、ｎは０～４の整数を示す。ただし、ｍ、ｎが２以上の整数の場合のＲ^１、Ｒ^３は、それぞれ同一でも異なっていてもよい。） Hereinafter, the present invention will be described in detail.
<Compound of the present invention>
The compound of the present invention is a polythiol compound represented by the following general formula (1).

(In the formula, R ¹ independently represents a linear or branched alkylene group having 2 to 6 carbon atoms, and R ² independently represents a linear or branched alkylene group having 1 to 6 carbon atoms. Independently, R ³ indicates an aryl group having 6 to 12 carbon atoms, m indicates an integer of 1 to 4, and n indicates an integer of 0 to 4. However, m and n. When is an integer of 2 or more, R ¹ and R ³ may be the same or different, respectively.)

（式中、＊は、それぞれ酸素原子との結合部を示す。）
上記一般式（１）中のｍは１～４の整数を示す。ｍが２～４である場合のＲ^１は、全て同一であってもよく、異なっていてもよい。中でも、ｍが２～４である場合のＲ^１は全て同一であることが好ましい。特に、ｍが１であることが好ましい。 R ¹ in the above general formula (1) independently represents a linear or branched alkylene group having 2 to 6 carbon atoms. ^R1 is preferably a linear or branched alkylene group having 2 or 3 carbon atoms independently, and among these, the alkylene group of the group (A) shown below is preferable.

(In the formula, * indicates the bond with the oxygen atom.)
In the above general formula (1), m represents an integer of 1 to 4. When m is 2 to 4, R ¹ may be the same or different. Above all, it is preferable that R ¹ is the same when m is 2 to 4. In particular, it is preferable that m is 1.

（式中、＊はそれぞれ硫黄原子、＃はそれぞれ炭素原子との結合部を示す。）
これらの中でも、炭素原子数１または２のアルキレン基が特に好ましい。 R ² in the general formula (1) independently represents a linear or branched alkylene group having 1 to 6 carbon atoms. Among these, a linear or branched alkylene group having 1 to 4 carbon atoms is preferable, and a linear or branched alkylene group having 1 to 3 carbon atoms is more preferable. The alkylene group of group (B) shown below is a preferred embodiment.

(In the formula, * indicates a sulfur atom and # indicates a bond with a carbon atom.)
Among these, an alkylene group having 1 or 2 carbon atoms is particularly preferable.

Each of R ³ in the general formula (1) independently represents an aryl group having 6 to 12 carbon atoms. Specific examples of the aryl group having 6 to 12 carbon atoms include a phenyl group (6 carbon atoms), a naphthyl group (8 carbon atoms), an anthryl group (10 carbon atoms), and a phenanthryl group (carbon). The number of atoms is 10), the biphenyl group (the number of carbon atoms is 12), and the like.
Among them, an aryl group having 6 to 10 carbon atoms is preferable, an aryl group having 6 to 8 carbon atoms is more preferable, and an aryl group having 6 carbon atoms, that is, a phenyl group is particularly preferable.
In the above general formula (1), n represents an integer of 0 to 4. When n is 2 to 4, R ³ may be all the same or different. When n represents an integer of 1 to 4, it is preferable that the position where R ³ is bonded to the naphthalene ring includes the 3-position or the 6-position.
Among them, n is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.

Among the compounds of the present invention represented by the general formula (1), the following compounds (1-1) to (1-20) are particularly preferable.

（式中、Ｒ^１、Ｒ^３、ｍ、ｎは一般式（１）と同義である。）

（式中、Ｒ^２は一般式（１）と同義である。）
一般式（２）、（３）中のＲ^１、Ｒ^２、Ｒ^３、ｍ、ｎの具体例や好ましい態様は、一般式（１）と同じである。
本発明の化合物の製造方法において、一般式（３）で表されるチオール類に代えて、一般式（３）で表されるチオール類のヒドロキシカルボニル基がハロゲン化カルボニル基または低級（炭素数１～３）アルコキシカルボニル基である、酸ハロゲン化物やエステル化物を使用しても良い。 <Raw material for the compound of the present invention>
The production method of the compound of the present invention is not particularly limited, but the compound may be produced, for example, by reacting a dihydroxy compound represented by the general formula (2) with thiols represented by the general formula (3). Can be done.

(In the formula, R ¹ , R ³ , m, n are synonymous with the general formula (1).)

(In the formula, R ² is synonymous with the general formula (1).)
Specific examples and preferred embodiments of R ¹ , R ² , R ³ , m, and n in the general formulas (2) and (3) are the same as those in the general formula (1).
In the method for producing a compound of the present invention, instead of the thiols represented by the general formula (3), the hydroxycarbonyl group of the thiols represented by the general formula (3) is a halide carbonyl group or a lower (carbon number 1). ~ 3) An acid halide or an esterified product, which is an alkoxycarbonyl group, may be used.

The dihydroxy compound represented by the above general formula (2) includes, for example, 1,1'-bi-2-naphthol which may have a substituent and alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide. Alternatively, it can be obtained by a known production method in which an alkylene carbonate such as ethylene carbonate (ethylene carbonate), propylene carbonate (propylene carbonate), butylene carbonate (butylene carbonate) is reacted in the presence of an alkali catalyst.

Examples of the thiols represented by the general formula (3) include thioglycolic acid, thiolactic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid and the like. The thiol compound represented by the general formula (3) is a thiol compound obtained by a known production method such as a production method in which α, β-unsaturated carboxylic acids and hydrogen sulfide are reacted in the presence of an acid catalyst. It may be used, or a commercially available thiol compound may be used.

An example of a method for producing the above compound (1-1), which is one of the preferred embodiments of the compound of the present invention, is shown by the following reaction formula.

<Reaction conditions>
The reaction conditions for producing the compound of the present invention by reacting the dihydroxy compound represented by the general formula (2) with the thiols represented by the general formula (3) will be described below.
(catalyst)
It is preferable to use a catalyst in the reaction between the dihydroxy compound represented by the general formula (2) and the thiols represented by the general formula (3). Suitable catalysts include 60-98% sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid (or monohydrate thereof), among others, methanesulfonic acid, p-toluenesulfonic acid (or one thereof). Hydrate) is more preferred.
The amount of catalyst is preferably 0.01 to 1 equivalent, more preferably 0.01 to 0.1 equivalent, with respect to one hydroxy group of the dihydroxy compound represented by the general formula (2). An equal amount of 01 to 0.05 is more preferable.

(Reaction temperature, pressure)
The reaction temperature is usually in the range of 25 to 120 ° C, preferably in the range of 50 to 110 ° C, more preferably in the range of 80 to 100 ° C. If the reaction temperature is higher than the above range, side reactions will proceed, which is not preferable.
The reaction pressure may be normal pressure or reduced pressure, but it is preferable to carry out the reaction under reduced pressure because the generated water can be efficiently removed by reduced pressure and the reaction time is shortened.

(Reaction solvent)
When the compound of the present invention is produced by reacting the dihydroxy compound represented by the general formula (2) with the thiols represented by the general formula (3), an auxiliary solvent is used from the viewpoint of solubility and stirring property. You may. Specific examples of the auxiliary solvent include aromatic hydrocarbons such as toluene, xylene and benzene, and saturated hydrocarbons such as n-hexane, cyclohexane and n-pentane. Among these, toluene and the like can be mentioned. Aromatic hydrocarbons are preferred.
Such a solvent is usually used in a range of 0.1 to 10 times by weight, preferably 0.5 to 2 times by weight, based on 1 part by weight of the dihydroxy compound represented by the general formula (2). It is not limited to this.
Since the above reaction is an equilibrium reaction, it is important to take out water generated from the reaction system in order to complete the reaction, and among the above solvent groups, a solvent that azeotropes with water is more preferable.
Further, in order to efficiently remove the generated water from the reaction system, the reaction may be carried out while flowing a nitrogen stream into the reaction solution.

(Purification method)
After completion of the reaction, a known method can be appropriately used to purify the desired polythiol compound represented by the general formula (1) from the obtained reaction-terminated mixture. For example, alkaline water such as an aqueous solution of sodium hydroxide or an aqueous solution of sodium hydrogen carbonate is added to the reaction-terminated mixture to neutralize the mixture. After neutralization, a solvent separable from water such as toluene, xylene, methyl isobutyl ketone, butyl acetate or ether was added to separate and remove the aqueous layer, and then the aqueous layer was separated and obtained. Rinse the oil layer with water. Then, if necessary, the solvent is distilled off, an appropriate crystallization solvent is added thereto, and the mixture is crystallized or deposited, and filtered to obtain a crystalline or non-crystalline (amorphous) substance. A polythiol compound represented by the general formula (1) can be obtained.
Further, depending on the compound, it can also be obtained as an adduct crystal with the solvent used for crystallization.
The crystallization solvent is appropriately selected in consideration of crystallization conditions, purification effect, economy and the like. For example, aromatic hydrocarbons such as toluene, xylene and ethylbenzene, aliphatic alcohols such as methanol, butanol and ethanol, aliphatic ketones such as methyl ethyl ketone and methyl isobutyl ketone, chains such as methyl acetate, ethyl acetate and γ-butyrolactone. Examples thereof include cyclic and cyclic aliphatic esters, aliphatic hydrocarbons such as n-heptane, n-hexane and cyclohexane, and aliphatic carboxylic acids such as acetic acid and butanoic acid.

If necessary, such as when the purity of the obtained target product is low, further purification may be performed according to the properties of the obtained target product.
As the purification method, when the target product is a crystal, recrystallization or reprecipitation may be performed once or multiple times for purification, or the solvent used for crystallization or recrystallization may be used. , The obtained crystalline or non-crystalline may be poured and washed again for purification.
When the obtained target product is an adduct crystal (adduct crystal) with a low boiling point compound (solvent), the adduct crystal is thermally decomposed at about 100 to 200 ° C. under reduced pressure, and the adduct is added. You may purify by removing (solvent).
Further, when the obtained target product cannot be obtained as a crystal or a solid (amorphous), the raw material is removed from the obtained reaction mixture by distillation or the like, and then the target product is crudely prepared as a distillation residue thereof. A product can be obtained, and this can be made into a high-purity product by a column separation method or the like.

<Use>
The polythiol compound of the present invention has a high refractive index and is excellent in solvent solubility. Therefore, the resin composition containing the polythiol compound of the present invention and a resin such as urethane resin, maleimide resin, acrylic resin, epoxy resin, allyl resin, vinyl resin, unsaturated polyester, and polybutadiene can be used for coating technology, lithography technology, and various other moldings. It is useful when it is used to form a cured molded product (thin film, lens, etc.) with improved optical properties such as refractive index by utilizing the technique.
The obtained cured film may be peeled off from the base material or used together with the base material as an optical film or the like, if necessary.
Further, since the compound of the present invention has a binaphthyl skeleton, it can be expected to exhibit excellent etching resistance when used as a resist material used in a manufacturing process of an electronic material.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
The analysis method is as follows.
<Analysis method>
1. 1. Method for determining the composition ratio of component A and component B in the present invention The composition of component A and component B in the resin composition obtained in Examples and Comparative Examples by performing high performance liquid chromatography analysis under the following conditions in the present invention. The ratio was determined.
(1) Analytical device and analytical conditions Measuring device: High performance liquid chromatography analyzer (Prominence UFLC) (manufactured by Shimadzu Corporation)
Pump: LC-20AD
Column oven: CTO-20A
Detector: SPD-20A (UFLC), cell length 5 mm
Column: HALO C18 (column 3.0 x 75 mm, particle size 2.7 μm, manufactured by advanced materials technology)
Oven temperature: 50 ° C
Flow rate: 0.7 mL / min
Mobile phase: (A) 0.1 vol% phosphate water, (B) acetonitrile gradient conditions: (B) volume% (time from the start of analysis)
30% (0 min) → 30% (3 min) → 100% (16 min) → 100% (20 min)
Detection wavelength: 280 nm
Sample concentration: 2 mg / ml (Compound 1-1)
0.5 mg / ml (Compound a)
Sample injection volume: 5 μl
The purity of the polythiol compound of the present invention was calculated from the chart obtained by the above analysis method by the area percentage of the component of the target compound with respect to all the detected components.

ディーン・スターク装置を取り付けた３００ｍＬ４つ口フラスコに、２，２’－ビス（２－ヒドロキシエトキシ）－１，１’－ビナフタレン（３０．６ｇ）、トルエン（９０．５ｇ）、ｐ－トルエンスルホン酸一水和物（０．９ｇ）を加え、１１０℃まで昇温して均一溶液とした。チオ乳酸（１９．５ｇ）を５０分かけて滴下した後、脱水させながら１１０℃で６時間加熱撹拌した。４０℃まで降温させた後、１０％炭酸水素ナトリウム水溶液（４５．０ｇ）を加えて中和を行い、水層を除去した。水（４５．０ｇ）を加えて反応液を水洗し、水層を除去した。同様の水洗操作をさらに２回繰り返した後、減圧条件下で溶剤を留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸ブチル＝２：１（ｗｔ／ｗｔ））により精製し、目的である化合物（１－１）を透明粘性液体として２９．０ｇ得た（純度９１％，収率６４％）。 <Example 1: Synthesis of compound (1-1)>

2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene (30.6 g), toluene (90.5 g), p-toluenesulfonic acid in a 300 mL four-necked flask equipped with a Dean-Stark apparatus. Monohydrate (0.9 g) was added and the temperature was raised to 110 ° C. to obtain a uniform solution. After adding thiolactic acid (19.5 g) over 50 minutes, the mixture was heated and stirred at 110 ° C. for 6 hours while dehydrating. After lowering the temperature to 40 ° C., a 10% aqueous sodium hydrogen carbonate solution (45.0 g) was added for neutralization, and the aqueous layer was removed. Water (45.0 g) was added and the reaction solution was washed with water to remove the aqueous layer. After repeating the same washing operation twice more, the solvent was distilled off under reduced pressure conditions. The obtained residue was purified by silica gel column chromatography (hexane: butyl acetate = 2: 1 (wt / wt)) to obtain 29.0 g of the target compound (1-1) as a transparent viscous liquid (purity 91). %, Yield 64%).

It was confirmed to be the target product by ¹ H NMR and LC-MS analysis shown below.
^{1 1} H NMR: (400 MHz, DMSO-d6)
δ (ppm): 1.15 (t-like, 6H), 2.87 (m, 2H), 4.06 (m, 4H), 4.21 (m, 4H), 6.91 (dd, 2H) ), 7.19-7.24 (m, 2H), 7.34 (brt, 2H), 7.62 (dd, 2H), 7.94 (d, 2H), 8.05 (d, 2H) ..
LC-MS
ESI-nega: 549.14 ([MH] ^- )

ディーン・スターク装置を取り付けた３００ｍＬ４つ口フラスコに、４，４’－ビス（２－ヒドロキシエトキシ）－１，１’－ビフェニル（３０．０ｇ）、トルエン（９０．０ｇ）、ｐ－トルエンスルホン酸一水和物（１．０ｇ）を加え、１１０℃まで昇温して溶解させた。チオ乳酸（２６．７ｇ）を３０分かけて滴下した後、脱水させながら１１０℃で５時間加熱撹拌した。７０℃まで降温させた後、１０％炭酸水素ナトリウム水溶液（３４．２ｇ）を加え中和を行い、水層を除去した。水（３０．０ｇ）を加えて反応液を水洗し、水層を除去した。同様の水洗操作をさらに１回繰り返して実施した後、５０℃まで冷却した。イソオクタン（７３．９ｇ）を３０分かけて添加し、室温まで冷却した。析出した固体を濾別し、イソオクタン（４９．３ｇ）で洗浄後、５０℃で乾燥を行うことで、目的である化合物（ａ）を白色固体として４１．７ｇ得た（純度９４％、収率８４．６％）。 <Comparative Example 1: Synthesis of compound (a)>

4,4'-bis (2-hydroxyethoxy) -1,1'-biphenyl (30.0 g), toluene (90.0 g), p-toluenesulfonic acid in a 300 mL four-necked flask equipped with a Dean-Stark apparatus. Monohydrate (1.0 g) was added, and the temperature was raised to 110 ° C. to dissolve it. After dropping thiolactic acid (26.7 g) over 30 minutes, the mixture was heated and stirred at 110 ° C. for 5 hours while dehydrating. After lowering the temperature to 70 ° C., a 10% aqueous sodium hydrogen carbonate solution (34.2 g) was added for neutralization, and the aqueous layer was removed. Water (30.0 g) was added and the reaction solution was washed with water to remove the aqueous layer. The same washing operation was repeated once more, and then the mixture was cooled to 50 ° C. Isooctane (73.9 g) was added over 30 minutes and cooled to room temperature. The precipitated solid was separated by filtration, washed with isooctane (49.3 g), and dried at 50 ° C. to obtain 41.7 g of the target compound (a) as a white solid (purity 94%, yield). 84.6%).

It was confirmed to be the target product by ¹ H NMR and LC-MS analysis shown below.
^{1 1} H NMR: (400 MHz, CDCl ₃ )
δ (ppm): 1.53 (d, 6H), 2.19 (d, 2H), 3.55 (m, 2H), 4.22 (m, 4H), 4.50 (m, 4H), 6.96 (dt, 4H), 7.47 (dt, 4H).
LC-MS
ESI-nega: 449.13 ([MH] ^- )
Melting point (DSC)
71.3 ° C, 73.6 ° C

(Heat resistance evaluation)
Using the compound (1-1) obtained in Example 1 and the compound (a) obtained in Comparative Example 1, the heat resistance was evaluated according to the following evaluation method.
10 to 20 mg of each compound was weighed into an aluminum cell and heated to 400 ° C. to measure the decomposition start temperature (5% weight loss temperature). The measurement was carried out using STA-200 manufactured by Hitachi High-Tech Science Corporation under the following conditions.
Measurement environment: Nitrogen atmosphere, open temperature rise rate: 10 ° C / min
(result)
The decomposition start temperature obtained by the measurement is as follows.
Compound (1-1): 317 ° C.
Compound (a): 318 ° C.
It was suggested that the heat resistance of the compound (1-1) obtained in Example 1 and the compound (a) obtained in Comparative Example 1 were equivalent.

(Measurement of refractive index)
Using the compound (1-1) obtained in Example 1 and the compound (a) obtained in Comparative Example 1, the respective refractive indexes were confirmed according to the following measurement methods.
Each compound was mixed with N-methylpyrrolidone at an arbitrary weight ratio, and the refractive index of each solution at 20 ° C. was measured. A refractometer RA-500 manufactured by Kyoto Electronics Manufacturing Co., Ltd. was used for measuring the refractive index. The obtained refractive index and the weight of the compound in the solution were plotted to create a linear function. For the obtained function, the value at the point where the weight of the compound was 100% was obtained, and it was estimated as the refractive index of each compound by the extrapolation method.
The estimated refractive index is as follows.
Compound (1-1): 1.617
Compound (a): 1.579
It was confirmed that the compound (1-1) obtained in Example 1 was a compound having a higher refractive index than the compound (a) obtained in Comparative Example 1.

(Measurement of solubility)
Using the compound (1-1) obtained in Example 1 and the compound (a) obtained in Comparative Example 1 with respect to propylene glycol monomethyl ether acetate (PGMEA) and ethyl lactate (EL) of the respective compounds. Solubility at 25 ° C was confirmed. Since compound (1-1) is an oily compound, the point of miscibility with the solvent was judged to be solubility.
The measured solubilities are as follows.
(I) Solubility in Propylene Glycol Monomethyl Ether Acetate Compound (1-1): 67 g / 100 g or more Compound (a): 31 g / 100 g
(Ii) Solubility in ethyl lactate Compound (1-1): 67 g / 100 g or more Compound (a): 18 g / 100 g
It was confirmed that the compound (1-1) obtained in Example 1 was superior in solvent solubility to the compound (a) obtained in Comparative Example 1.

Claims (1)

A polythiol compound represented by the following general formula (1).

(In the formula, R ¹ independently represents a linear or branched alkylene group having 2 to 6 carbon atoms, and R ² independently represents a linear or branched alkylene group having 1 to 6 carbon atoms. Independently, R ³ indicates an aryl group having 6 to 12 carbon atoms, m indicates an integer of 1 to 4, and n indicates an integer of 0 to 4. However, m and n. When is an integer of 2 or more, R ¹ and R ³ may be the same or different, respectively.)