WO2007007598A1

WO2007007598A1 - Organosilicone resin having alcoholic hydroxyl groups and process for production of the same

Info

Publication number: WO2007007598A1
Application number: PCT/JP2006/313332
Authority: WO
Inventors: Akinori Kitamura; Hiroshi Suzuki; Daigo Sato
Original assignee: Toagosei Co., Ltd.
Priority date: 2005-07-12
Filing date: 2006-07-04
Publication date: 2007-01-18
Also published as: TW200714637A; JP2008239634A

Abstract

The invention aims at providing a stable organosilicone resin having alcoholic hydroxyl groups which does not change with the lapse of time and a process for the production of the resin which enables easy composition control. The organosilicone resin is one produced from an organosilicon compound represented by the general formula (1) or the like through hydrolysis and condensation: wherein R1, R2, R4, R5 and R6 are each independently alkyl of 1 to 10 carbon atoms, aralkyl of 7 to 10 carbon atoms, or aryl of 7 to 10 carbon atoms; R3 is a divalent organic group having 2 to 20 carbon atoms; and a and b are integers satisfying the relationships: a > 0, b > 1, and a + b = 3, with the proviso that when two -OR2 groups are present, they may be the same or different.

Description

Specification

TECHNICAL FIELD Field of the Invention

[0001] The present invention relates to a novel organic key resin and a method for producing the same. More specifically, the present invention relates to an organic resin having an alcoholic hydroxyl group and a method for producing the same.

Background art

[0002] Organic key resins having various alcoholic hydroxyl groups are known. As a method for producing such an organic key resin, a method of synthesizing an organic key resin precursor in advance and then introducing an alcoholic hydroxyl group into the resin using a polymer reaction. It has been known.

In the methods disclosed in JP-A-8-231924, JP-A-9-176321, JP-A-2001-213963, JP-A-2003-146832 and the like, since a polymer reaction is used, an alcoholic property is used. It is difficult to precisely control the amount of hydroxyl group introduced. Also, if the raw materials remain after the completion of the polymer reaction, it is difficult to remove these and purify the organic resin having an alcoholic hydroxyl group. .

[0003] In JP-A-10-87834, after synthesizing an organic key resin having an alicyclic epoxide, it is converted into an organic key resin having a diol using an oxidation reaction (polymer reaction). A method is disclosed.

Japanese Patent Application Laid-Open No. 11-116681 discloses silica fine particles having an alcoholic hydroxyl group.

[0004] As disclosed in Japanese Unexamined Patent Publication No. 2003-149822, an organic resin having an alcoholic hydroxyl group expresses an alkali-soluble group, so that it can be used for lithography materials, organic-inorganic hybrid materials, etc. Useful as a raw material. In addition, since the resin disclosed in JP-A-2003-149822 easily reacts with a silylating agent, it can be a raw material for various functional materials.

Disclosure of the invention

Problems to be solved by the invention [0005] As described above, in the case of introducing an alcoholic hydroxyl group into an organic key resin, most reports use a polymer reaction, and precise control of the resin composition is very difficult. It was. Power! In other words, the alcoholic hydroxyl group easily reacts with silanol remaining in the resin, and the organic ketone resin having an alcoholic hydroxyl group is easily gelled. An object of the present invention is to provide an organic key resin having an alcoholic hydroxyl group that is stable over time, and a method for producing the same that can be easily controlled.

Means for solving the problem

OOSII

[0006] The present invention is described below.

The organocatheter resin of the present invention comprises an organocatheter compound [A] represented by the following general formula (1), or the organocatheter compound [A], and the organocatheter compound [A]. An organic ketone resin having an alcoholic hydroxyl group, which is obtained by providing a hydrolysis-condensation step of hydrolyzing and condensing a mixture of organic coke compounds [B] capable of hydrolysis and co-condensation.

[Chemical 1]

(OR _a R ⁴

R ¹ -Si ○-R: \ -ORA (1)

R ⁶

[Where

R ² , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 7 to 10 carbon atoms, and R ³ is a divalent organic group having 2 to 20 carbon atoms, and a and b are integers satisfying a≥0, b≥1 and a + b = 3. However, when there are a plurality of —OR ² , each may be the same or different. In the general formula (1), R ³ preferably contains at least one selected from an alkylene group and derivatives thereof, a cycloalkylene group and derivatives thereof, a phenylene group and derivatives thereof, and force.

The organic key compound [B] is preferably a polyfunctional alkoxysilane compound other than the organic key compound [A] represented by the general formula (1).

The organic cage resin of the present invention comprises the above hydrolysis condensation step and a sealing step of sealing the terminal silanol group of the condensate obtained by this hydrolysis condensation step with a silylating agent. It can also be an organic resin having an alcoholic hydroxyl group obtained by providing.

[0007] The method for producing an organic key resin according to the present invention includes an organic key compound [A] represented by the general formula (1), or the organic key compound [A], and It comprises a hydrolytic condensation step of hydrolyzing and condensing a mixture of the organic key compound [A] and the hydrolytic co-condensable organic key compound [B].

Furthermore, a sealing step of sealing the terminal silanol group of the condensate obtained by the hydrolysis condensation step with a silylating agent can be provided.

[0008] According to the production method of the present invention, in the hydrolysis-condensation step, the organic key compound having an alcoholic hydroxyl group is obtained by hydrolysis of the organic key compound [A] represented by the general formula (1) or the mixture. A fat precursor is obtained. Furthermore, the terminal silanol is present in the organic ketone resin precursor immediately after hydrolysis, and is easily coupled by a desolubilization or heating process to cause a change in molecular weight. Therefore, it is dehydrated after hydrolysis, and in the sealing step, silanol present in the organic key resin is sealed using a silylating agent. Subsequently, by washing with water and de-dissolving, a stable organic key resin having no change in molecular weight can be constructed.

The invention's effect

[0009] The organic key resin of the present invention is an organic key resin having an alcoholic hydroxyl group, using an organic key compound having a specific structure, and having an easily controlled composition. Excellent stability.

According to the method for producing an organic key resin of the present invention, an organic key resin that is easy to control the composition and that is stable with time can be obtained.

BEST MODE FOR CARRYING OUT THE INVENTION

[0010] The present invention provides the ability to use an organic key compound [A] represented by the following general formula (1) alone, or the organic key compound [A], and the organic key compound [A] A) and a hydrolytic co-condensable organosilicon compound [B] are used in combination to hydrolyze and condense, so that the composition is easily controlled and changes over time. The present invention relates to a stable organic cage resin having an alcoholic hydroxyl group and a method for producing the same. 2

R (〇-R (1)

£ R

[Where

R, R 2, R ⁵ and R are each independently an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 7 to 10 carbon atoms, and R ³ is A divalent organic group having 2 to 20 carbon atoms, and a and b are integers satisfying a≥0, b≥1 and a + b = 3

OOSII

is there. However, there are multiple —OR ² .LRR

| 46 may be the same or different. ] o

R

In addition, the composition of the present invention can be easily controlled by providing a sealing step of sealing a terminal silanol group of the condensate obtained by the hydrolysis condensation step with a silylating agent. The present invention also relates to a stable organic key resin having an alcoholic hydroxyl group that does not change with time and a method for producing the same.

Hereinafter, the present invention will be described in detail.

The above organic silicon compound [A] is composed of a carbon-containing group [≡ SIR ¹ ] in which one hydrocarbon group is bonded to a silicon atom, one hydrocarbon group and one alkoxy group (phenoxy group). Etc.) bonded to a silicon-containing group ^ SiR ¹ (OR ² )], or a silicon-containing group to which one hydrocarbon group and two alkoxy groups (including a phenoxy group, etc.) are bonded. Silane compounds having [—SiR ^ OR ² )] and when these groups are protecting groups

2

After elimination, it becomes HO—R ³ —, that is, a compound that forms a compound having a hydroxyl group. In the above general formula (1), when R ² , R ⁴ , R ⁵ and R ^{6 are} alkyl groups, specific examples which may be linear, branched or cyclic include methyl group, ethyl group, propyl Group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nor group, decyl group, cyclopropyl group, cyclohexyl group, etc. It is done. Specific examples of the aralkyl group include benzyl group and phenethyl group. Specific examples of aryl groups include a phenol group and a tolyl group. Of these, R ¹ is preferably a methyl group or a phenyl group. R ² , R ⁴ , R ⁵ and R ⁶ are preferably a methyl group and an ethyl group.

All of —OR ⁴ , —OR ⁵ and —OR ⁶ in the general formula (1) are the same. But it may be different. Also, two of the three may be the same.

[0012] R ³ in the general formula (1) is a divalent organic group having 2 to 20 carbon atoms, and is at least one of an alkylene group, a cycloalkylene group, a phenylene group, and derivatives thereof. It is preferable to contain. The organic group may have any of linear, branched and cyclic structures.

[0013] Examples of the alkylene group include dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, otatamethylene group, nonamethylene group, decamethylene group, 2-methyltrimethylene group, 3-methyl. A trimethylene group etc. are mentioned. Examples of the cycloalkylene group include 1,4-cyclohexylene group and 1,3-cyclohexylene group.

[0014] R ³ is exemplified below, which may be a combination of two or three selected alkylene groups, cycloalkylene groups, and phenylene groups.

[Chemical 3]

R ³ in the general formula (1) is particularly preferably a trimethylene group.

In addition, as derivatives of the above-mentioned alkylene group, cycloalkylene group and phenylene group, Examples include a hydrogen atom, a cycloalkyl group, a phenyl group, an aralkyl group, an aryl group, an alkoxyl group atom and the like that each of the above groups has. Examples of the group substituted with an alkoxy group are shown below.

[0016] In the above general formula (1), when a = 0 and b = 3, there are three

OR ⁴

-O -R ³ — Si -OR ⁵

I

All of the OR ⁶ groups may be the same or different. Also, two of the three groups may be the same. Also, when & = 1 and ¾ = 2, the two groups described above may be the same or different.

Furthermore, in the general formula (1), when a = 2 and b = 1, the two —OR ² may be the same or different.

[0017] Specific examples of the organosilicon compound [A] are listed below.

[Chemical 4]

OC ₂ H ₅ OC ₂ H ₅

H ₃ C— Si— CL ^ ^^, βί— OC ₂ H ₅

OC ₂ h OC ₂ H ₅

Next, the organocatheter compound [B] that can be hydrolyzed and co-condensed with the organocatheter compound [A] will be described.

The organic key compound [B] is a compound other than the organic key compound [A], and examples thereof include polyfunctional alkoxysilanes and halogenosilane compounds. Of these, polyfunctional alkoxysilanes are preferred. Examples of the polyfunctional alkoxysilane include triethoxysilane, tetraethoxysilane, trimethoxymethylsilane, triethoxymethylsilane, triethoxyphenylsilane, triethoxynorbornalsilane, and the like. Examples of the halogenosilane compound include 2- (3-tert-butoxyphenyl) ethylchlorodimethylsilane, 1- (3-tert-butoxyphenyl) ethylchlorodimethylsilane, and the like.

When the hydrolysis condensation is carried out using a mixture of the above organic key compounds [A] and [B], the amount of the above organic key compound [A] used is 100 parts by mass. In such a case, the amount of the organic cage compound [B] used is usually 1 to 10,000 parts by mass. In addition, the organic cage compound [B] can be used alone or in combination of two or more.

[0019] Through the hydrolysis and condensation step, the above-mentioned organocatheter compound [A] or a mixture of organocatheter compounds [A] and [B] is known in the case of hydrolysis and condensation. This method can be applied. By performing the hydrolysis and condensation under acidic or basic conditions, it is possible to introduce a hydroxyl group into the rosin skeleton at the same time as forming the skeleton of the organic cage resin. In the present invention, it is preferable to perform hydrolysis and condensation under acidic conditions. Examples of preferable acids include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, formic acid and the like.

Preferred examples of the base include sodium hydroxide, potassium hydroxide, lithium hydroxide, tetramethylammonium hydroxide, triethylamine, pyridine and the like.

The amount of water is preferably more than the theoretical amount, and preferably 1.5 to 2 times the theoretical amount! / ,.

Examples of preferable organic solvents used in the hydrolysis include acetone, methanol, ethanol, isopropyl alcohol (2-propanol), methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, toluene, hexane and the like. These may be used alone or in combination of two or more.

[0020] The reaction temperature during the hydrolysis and condensation is usually 0 to 100 ° C, preferably 0 to 60 ° C. Moreover, although reaction time is based on the usage-amount of a raw material component, it is 0.1-100 hours normally, Preferably it is 1-24 hours. [0021] After the above hydrolysis and condensation, when water that is not consumed by hydrolysis remains, the water and the organic solvent used in the reaction are removed. Examples of the method include use of a dehydrating agent (drying agent) that has a dehydrating effect and does not contaminate rosin, such as anhydrous sodium sulfate and anhydrous magnesium sulfate, and distillation under normal pressure or reduced pressure. When the above dehydrating agent (desiccant) is used, it is filtered by a known method and then proceeds to the sealing step.

[0022] The hydrolysis product obtained by the hydrolysis-condensation step varies depending on the structures of the organic key compounds [A] and [B] used as raw materials, but is an organic key element having an alcoholic hydroxyl group. And a resin precursor having a structure in which a hydrolyzable group such as an alkoxy group, an aryloxy group, or a halogen atom is eliminated from the organic silicon compound. In the subsequent condensation reaction, the silicon atom, which is the residue after the hydrolyzable group is eliminated, forms Si—O—Si. Moreover, it is an example of a hydrolysis product,

OR ⁴

HO -R ³ — Si -OR ⁵

The HO—R ³ — site in OR ⁶ remains substantially even after the condensation reaction, and this site becomes an “alcoholic hydroxyl group” possessed by the organic cage resin of the present invention.

[0023] The sealing step performed after the hydrolysis-condensation step is usually performed at a temperature of 0 to: L00 ° C, preferably 0 to 60 ° C, and the hydroxyl group of the terminal silanol group possessed by the precursor The amount of silylating agent that gives 1 to 100 mol, more preferably 1 to 20 mol, of silyl group per mol is used.

[0024] Examples of the silylating agent include 1, 1, 1, 3, 3, 3-hexamethyldisilazane, 1, 1, 3, 3-tetramethyldisilazane, heptamethyldisilazane, 1, 3— Divinyl-1,1,3,3-tetramethyldisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, tris (trimethylsilyl) amine, bis (jetylamino) dimethylsilane, bis (dimethylamino) ) Aminosilanes such as dimethylsilane, bis (dimethylamino) diphenylsilane, bis (dimethylamino) methylphenol silane, tert-butylaminotrimethylsilane; Silanols such as trimethylsilanol; Chlorotrimethylsilane, chlorodimethylsilane, chloromethylphenol Enilshi Examples include chlorosilanes such as orchid. In addition, this base may be used in combination with a base such as triethylamine or pyridine, and this base is removed when a halogenosilane compound is used as the organic key compound [B] in the hydrolysis condensation step. The hydrogen halide reaction can be promoted, which is preferable.

[0025] By the sealing step, the active hydrogen atom of the terminal silanol group of the precursor is replaced with an inactive organosilyl group. For example, when the silylating agent is hexamethyldisilazane, the terminal silanol group is converted to a trimethylsiloxy group. Therefore, the terminal silanol group is almost completely converted to an organosiloxy group and becomes inactive by this sealing step.

[0026] After the sealing step, the organic ketone resin having an organosiloxy group and an alcoholic hydroxyl group is isolated by a known method. For example, the solvent in the reaction product is distilled off under reduced pressure. Thereafter, an organic solvent and water or an aqueous solution are added to wash the organic key resin. Examples of the organic solvent used for washing with water include acetone, methanol, ethanol, isopropyl alcohol (2-propanol), methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, toluene, hexane and the like. These may be used alone or in combination of two or more. As the water, ultrapure water is generally used, but an acidic aqueous solution such as an aqueous hydrochloric acid solution, a basic aqueous solution such as an aqueous sodium hydroxide solution, or a saturated aqueous sodium chloride solution may be used. The washing with water is preferably performed until the aqueous layer becomes neutral.

[0027] After washing with water, by performing dehydration, distillation and the like in the same manner as in the hydrolysis-condensation step, it is possible to recover the organic hydrocarbon having an alcoholic hydroxyl group. A preferred weight average molecular weight (by GPC) of the organic cage resin of the present invention thus obtained is usually 1,000,000 to 100,000, preferably 1,000,000 to 100,000. The hydroxyl group concentration of the alcoholic hydroxyl group is usually 0.1 to 6 mmol Zg, preferably 0.5 to 3 mmol, g.

In the present invention, by providing the hydrolysis condensation step and the sealing step, the organic resin having the hydroxyl group (alcoholic hydroxyl group) concentration and the weight average molecular weight within the above range can be efficiently obtained. Can be manufactured. In the above general formula (1), when R ¹ is a methyl group, R ² is an ethyl group, a = 2, and b = l, an organosilicon compound [A] is used In addition, an organic key resin having a structure containing an alcoholic hydroxyl group R ³ —OH as described below can be obtained.

■ C-Si -O-

〇 Examples

Hereinafter, the present invention will be specifically described with reference to examples. It should be noted that the present invention is not limited to these examples.

[0029] Example 1

To a 100-ml volume flask, 8.16 g (23 mmol) of 3-triethoxysilylpropyloxydiethoxymethylsilane (TESPODEMS) and 2.99 g of 2-propanol were charged and stirred at 30 ° C. Thereafter, 2.52 g of a 1.5 mass% hydrochloric acid aqueous solution (hydrogen chloride 1. Ommol, water 138mmol) was added dropwise, and the mixture was stirred at room temperature.

Then, anhydrous magnesium sulfate was added to the reaction mixture and stirred a little, and the mixture was left to stand and dried. Thereafter, the dried mixture was filtered through a filter paper, and the anhydrous magnesium sulfate that had absorbed water was separated. The filtrate obtained was separated into hexamethyldisilazane (HMDS) 2.58 g (16. Ommol) at 30 ° C. ) Was added dropwise, stirred as it was, and allowed to stand at room temperature. The residue obtained by distilling off the solvent under reduced pressure was dissolved in 30 g of ethylmethylketone, and after adding an aqueous hydrochloric acid solution of ImolZ liter, it was separated and washed with a saturated saline solution until the aqueous layer became neutral. (Until the water layer is neutral). After adding anhydrous sodium sulfate to the organic layer and stirring and drying at room temperature for 2.5 hours, the solvent from the filtrate was distilled off under reduced pressure to obtain 3.65 g of a white foam solid containing organic key resin. Obtained. The yield was 89%.

The obtained organic cage resin had a weight average molecular weight (Mw) of 6,300. In addition, the ¹ H-NMR ^ vector (270 MHz, heavy acetone) of this organic cage resin was measured, Broad signal strength derived from limethylene was observed at 3.53, 1.66 and 0.69 ppm, respectively. The proton power derived from methyl group was observed at 0.14 ppm. The integration ratio of these signals was 2: 2: 2: 4.6.

Furthermore, a result of measuring the IR ^ vector of the organic Kei element榭脂, is observed a characteristic absorption derived from OH groups 3330cm ^{_ 1,} the organic Kei containing榭脂was confirmed to have a hydroxyl group

[0030] Example 2

Additional TESPODEMS, triethoxy Hue - Rushiran, 2-propanol, the amount of 1.5 mass ^_0/0 hydrochloric acid aqueous solution and HMDS, respectively, 8. 16g, 1. 23g, 3. 68g, 2. 80g and 2. 26 g In the same manner as in Example 1 except that the hydrolysis and condensation reaction and silylation reaction were carried out to obtain 4.47 g of a white foamy solid containing an organic ketone resin. Yield was 94% o

Mw of the obtained organic key resin was 5500. Moreover, as a result of measuring ¹ H NMR spectrum (270 MHz, heavy acetone) of this organic resin, a broad signal derived from the phenol group was 7.70 to 7.41 ppm, and a broad signal derived from trimethylene was observed. Signanore force 3.52, 1.66 and 0.68 ppm, and broad Signole force S derived from methinore group, 0.14 ppm, respectively. The integration ratio of these signals was 5: 9: 9: 9: 24. As a result of measuring an IR spectrum of this organic Kei element榭脂, it is observed a characteristic absorption derived from OH groups 3340Cm ^_1, organic Kei containing榭脂it was confirmed that the hydroxyl group.

[0031] Example 3

In the following manner, o (diethoxymethylsilyl) eugenol (EUDEMS) and triethoxy [3- (4 diethoxymethylsilyloxy 3-methoxyphenyl) propyl] silan (TESEUDEMS) were synthesized in sequence, and TESEUDEMS • Organic organic resin using 7 la.

[0032] In a two-necked flask with a volume of 100 milliliters, 22.0 g (134 mmol) of eugenol and 59.8 g (335 mol) of triethoxymethylsilane were charged and stirred. Thereafter, 1.281 g (6.74 mmol) of p-toluenesulfonic acid monohydrate was added and reacted with stirring. Furthermore, The temperature of the reaction system was gradually raised from 100 ° C to 160 ° C, and the reaction was allowed to proceed for 8 hours while distilling off by-produced ethanol.

Next, the reaction mixture was distilled under reduced pressure to obtain a colorless and transparent liquid. Yield was 18.3g, 46%.

The chemical shift of ¹ H-NMR ^ vector of this colorless and transparent liquid is as follows, and the generation of EUDEMS was confirmed.

'H-NMR (270MHz, CDC1)

Three

δ 6.92-6.89 (m, 1Η),

δ 6.70-6.63 (m, 2H),

δ 6.03-5.88 (m, 1H),

δ 5.11-5.03 (m, 2H),

δ 3.88 (q, J = 7.0Hz, 4H),

δ 3.81 (s, 3H),

δ 3.32 (d, J = 6.6Hz, 2H),

δ 1.22 (t, J = 7.0Hz, 6H),

δθ.23 (s, 3H).

The boiling point at a pressure of 130 Pa was 90 to 100 ° C.

[0033] The synthesis flow of the above reaction is as follows.

[Chemical 5]

EUDEMS

[0034] Next, TESEUDEMS was synthesized using EUDEMS in the following manner.

In a 50 ml two-necked flask, 18.3 g (59.8 mmol) of EUDEMS obtained above was charged and stirred. Thereafter, about 3 ml was added into the reaction system from a dropping funnel charged with 10.8 g (65.7 mmol = about 12 ml) of triethoxysilane.

The reaction system is then heated to 70 ° C and stirred with 0. ImolZ liters of Pt-dvds key. The reaction was started by adding 0.25 ml of silylene solution (Pt concentration 2.1-2.4%). After stirring for 2 hours, the remaining triethoxysilane was added dropwise and reacted for a total of 8 hours after addition of the catalyst. After completion of the reaction, 14.2 g of a colorless and transparent liquid was obtained by distillation under reduced pressure. The yield was 52%. The chemical shift of the ¹ H-NMR ^ vector of this colorless and transparent liquid was as follows, and the generation of TESEUDEMS was confirmed.

'H-NMR (270MHz, CDC1)

Three

δ 6.89-6.86 (m, 1Η),

δ 6.70-6.69 (m, 1H),

δ 6.65-6.62 (m, 1H),

δ 3.89 (q, J = 7.0Hz, 4H),

δ 3.81 (s, 3H),

δ 3.80 (q, J = 7.0Hz, 6H),

δ 2.58 (t, J = 7.6Hz, 2H),

δ 1.78-1.66 (m, 2H),

δ 1.222 (t, J = 7.0Hz, 6H),

δ 1.217 (t, J = 7. OHz, 9H),

δθ.23 (s, 3H).

The boiling point at a pressure of 130 Pa was 133 to 160 ° C.

The synthesis flow of the above reaction is as follows.

[Chemical 6]

The TESEUDEMS 3.69 g (8 mmol) obtained above and 3.01 g of 2-propanol were charged into a 100 ml-shaped flask and stirred at 30 ° C. Thereafter, 0.91 g of 1.5 mass% hydrochloric acid aqueous solution (hydrogen chloride 0.4 mmol, water 48 mmol) was added dropwise, and the mixture was stirred at room temperature. Next, after anhydrous magnesium sulfate was added to the reaction mixture and dried, 1.12 g (6.9 mmol) of hexamethyldisilazane (HMDS) was added dropwise to the filtrate with stirring at 30 ° C overnight at room temperature. I left it alone. The residue obtained by distilling off the solvent under reduced pressure was dissolved in 30 g of methyl ethyl ketone, and 0.4 g of an aqueous ImolZ liter hydrochloric acid solution was added, followed by separation with saturated brine until the aqueous layer became neutral. Washed. After adding anhydrous sodium sulfate to the organic layer and drying, the solvent was distilled off from the filtrate under reduced pressure to obtain 2.32 g of an orange oily material containing an organic ketone resin. The yield was 10 2%.

The weight average molecular weight (Mw) of the obtained organic keywax was 2200. In addition, as a result of measuring ¹ H-NMR spectrum (270 MHz, heavy acetone) of this organic resin, broad signals derived from phenyl groups are derived from methoxy groups at 6.77 and 6.62 ppm. Signals were measured at 3.82 ppm and trimethylene-derived signals at 2.51, 1.66 and 0.62 ppm, respectively. In addition, a signal derived from a methyl group was observed around 0.1 lOppm. The integration ratio of these signals was 1: 2: 3.5: 2: 2: 2: 4.1. Furthermore, a result of measuring the IR ^ vector of the organic Kei element榭脂, characteristic absorption derived from OH group was observed at 3430cm ^{_ 1,} the organic Kei containing榭脂was confirmed to have.

Industrial applicability

The organic resin resin of the present invention is suitable for the field of lithography.

Claims

Claims [1] An organic key compound [A] represented by the following general formula (1), or the organic key compound [A], and hydrolytic cocondensation with the organic key compound [A] An organic cage resin having an alcoholic hydroxyl group, which is obtained by providing a hydrolysis-condensation step for hydrolyzing and condensing a mixture of possible organic cage compounds [B].

[Chemical 1]

(O ² ) _a OR ⁴

R ¹ -Si—— h O —R ³ — Si —OR ⁵ J (1)

OR ⁶ Roh ^b

[Where

R ² , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 7 to 10 carbon atoms, and R ³ is a divalent organic group having 2 to 20 carbon atoms, and a and b are integers satisfying a≥0, b≥1 and a + b = 3. However, when there are a plurality of —OR ² , each may be the same or different. ]

[2] In Claim 1, R ³ in the general formula (1) includes at least one selected from an alkylene group and derivatives thereof, a cycloalkylene group and derivatives thereof, a phenylene group and derivatives thereof, and force. The organic key resin as described.

[3] The organic key according to claim 1, wherein the organic key compound [B] is a polyfunctional alkoxysilane compound other than the organic key compound [A] represented by the general formula (1). Natural fat.

[4] The organic ketone resin according to claim 1, further comprising a sealing step of sealing a terminal silanol group of the condensate obtained by the hydrolysis condensation step with a silylating agent.

[5] The organic key compound [A] represented by the following general formula (1), or the organic key compound [A], and the organic compound capable of hydrolytic co-condensation with the organic key compound [A] A method for producing an organic resin having an alcoholic hydroxyl group, comprising a hydrolysis-condensation step of hydrolyzing and condensing a mixture of a key compound [B].

[Chemical 2]

[Wherein, RR ² , R ⁴ , R ⁵ and R ⁶ are independently of each other a C 1-: LO alkyl group, a C 7-10 aralkyl group, or a C 7-10 aryl. R ³ is a divalent organic group having 2 to 20 carbon atoms, and a and b are integers satisfying a≥0, b≥1 and a + b = 3. However, when there are a plurality of —OR ² , each may be the same or different. ]

[6] In claim 5, wherein R ³ in the general formula (1) includes at least one selected from an alkylene group and derivatives thereof, a cycloalkylene group and derivatives thereof, a phenylene group and derivatives thereof, and force. The manufacturing method of the organic key resin as described.

[7] The organic key according to claim 5, wherein the organic key compound [B] is a polyfunctional alkoxysilane compound other than the organic key compound [A] represented by the general formula (1). Manufacturing method of raw resin.

[8] The method for producing an organic resin resin according to claim 5, further comprising a sealing step of sealing a terminal silanol group of the condensate obtained by the hydrolysis-condensation step with a silylating agent. Law.