WO2016013467A1

WO2016013467A1 - Resin production method, resin produced thereby, and resin composition containing same

Info

Publication number: WO2016013467A1
Application number: PCT/JP2015/070283
Authority: WO
Inventors: 渋谷　明規; 康智米久田; 研由後藤; 雅史小島
Original assignee: 富士フイルム株式会社
Priority date: 2014-07-25
Filing date: 2015-07-15
Publication date: 2016-01-28
Also published as: TW201609844A

Abstract

The present invention provides: a production method that makes it possible to obtain a high reaction yield of a resin in which the content of metal impurities is reduced and all or a part of phenolic hydroxyl groups are alkylated; a resin that is produced by the production method; and a resin composition that contains the resin. The production method is for producing a resin in which all or a part of phenolic hydroxyl groups are alkylated, and said production method includes a step in which a halogenated alkyl compound and a resin comprising a phenolic hydroxyl group are reacted under the presence of at least one organic base selected from the group consisting of tetraalkyl ammonium hydroxide compounds and nitrogen-containing compounds in which the acid dissociation constant of the conjugate acid is 12 or more.

Description

Resin production method, resin produced by the production method, and resin composition containing the resin

The present invention provides a method for producing a resin in which all or part of the phenolic hydroxyl group is alkylated by reacting a resin having a phenolic hydroxyl group with a halogenated alkyl compound, a resin produced by the production method, And a resin composition containing the resin.

Resins having a phenolic hydroxyl group are widely used in the field of high-functional products such as liquid crystal display materials, polymer electrolytes, ion exchange resins, plastic lenses, semiconductor resist materials, and planarization films. In particular, active research has been conducted on resins imparted with functionality by introducing various substituents into phenolic hydroxyl groups.
As a method for obtaining a resin in which all or part of the phenolic hydroxyl group is alkylated, various production methods have been proposed so far (for example, Non-Patent Documents 1 and 2).

However, as an existing method, there is a method in which an inorganic base containing a metal is used as a reaction reagent. However, in this method, a large amount of metal components may remain as impurities in the finally obtained resin. Another existing method that does not use a metal-containing inorganic base has a problem in productivity and cost because the reaction takes a long time, and when the reaction time is short, the yield becomes remarkably low. There was a case.

An object of the present invention is to provide a production method capable of obtaining a resin obtained by alkylating all or part of the phenolic hydroxyl group with a reduced content of metal impurities with a high reaction yield, and a resin produced by the method. Is to provide. Furthermore, it is providing the resin composition containing the resin.

As a result of intensive studies to solve the above problems, the inventors have not only obtained the target compound in a high reaction yield but also the target product by proceeding the alkylation reaction in the presence of a specific organic base. The present inventors have found that the content of metal impurities contained in can be reduced, and have completed the present invention.
That is, the inventors have found that the above problem can be solved by the following configuration.

(1) A method for producing a resin, wherein a resin in which all or part of a phenolic hydroxyl group is alkylated is produced,
In the presence of at least one organic base selected from the group consisting of a nitrogen-containing compound and a tetraalkylammonium hydroxide compound in which the acid dissociation constant of the conjugate acid is 12 or more, the resin having a phenolic hydroxyl group and the halogenated alkyl compound. The manufacturing method of resin including the process made to react in.
(2) The method for producing a resin according to (1), wherein the organic base is at least one compound selected from the group consisting of a nitrogen-containing compound having an amidine structure and a tetraalkylammonium hydroxide compound.
(3) The method for producing a resin according to (2), wherein the organic base is diazabicycloundecene, diazabicyclononene, or a tetraalkylammonium hydroxide compound.
(4) The method for producing a resin according to any one of (1) to (3), wherein the reaction solvent in the step of reacting the resin having a phenolic hydroxyl group and the alkyl halide compound is an alcohol solvent.
(5) A resin produced by the method for producing a resin according to any one of (1) to (4).
(6) A resin composition comprising the resin according to (5) and a solvent.

As shown below, according to the present invention, a resin in which all or part of the phenolic hydroxyl group in which the content of metal impurities is reduced is alkylated can be produced with a high reaction yield.

FIG. 1 is a ¹ H-NMR measurement chart of Resin A obtained in Example 1-1. FIG. 2 is a ¹ H-NMR measurement chart of Resin AA obtained in Example 1-2.

Hereinafter, the best mode for carrying out the present invention will be described.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The present invention is a group consisting of a nitrogen-containing compound and a tetraalkylammonium hydroxide compound in which the acid dissociation constant (pKa) of the conjugate acid is 12 or more when producing a resin in which all or part of the phenolic hydroxyl group is alkylated. A method for producing a resin comprising reacting a resin having a phenolic hydroxyl group with an alkyl halide compound in the presence of at least one organic base selected from the above, a resin obtained by the method, and the resin The present invention relates to a resin composition.
In the production method of the present invention, the organic base is presumed to act as a catalyst for improving the reaction rate.

The resin produced by the production method of the present invention (hereinafter also referred to as the resin of the present invention) is not particularly limited as long as it is a resin having a structure in which all or part of the phenolic hydroxyl group is alkylated, For example, the resin containing the repeating unit represented by the following general formula (1), general formula (2), or general formula (5) can be given. The resin of the present invention includes, for example, a repeating unit in which all or part of the phenolic hydroxyl group represented by the general formula (1), the general formula (2), or the general formula (5) is alkylated, Furthermore, other repeating units may be included.

In formulas (1), (2) and (5), L represents a single bond or a divalent linking group.
R ₁ represents a hydrogen atom or a monovalent organic group.
R ₂ represents an alkyl group.
Ar represents an aromatic ring.
n ₁ represents an integer of 1 to 5.
n ₂ represents an integer of 1 to 5.
n ₃ represents an integer of 0 to 4.
a is a positive number satisfying the relationship of 0 ≦ a <100.
b is a positive number that satisfies the relationship 0 <b ≦ 100 (where a + b = 100).

Examples of the divalent linking group represented by L include an alkylene group, a cycloalkylene group, —O—, —CO ₂ —, —S—, —SO ₃ —, —SO ₂ N (Rd ₁ ) —, Or the bivalent group etc. which combined these can be mentioned. Rd ₁ represents a hydrogen atom or an alkyl group.
Examples of the alkylene group represented by L include a methylene group, an ethylene group, and a propylene group, and a methylene group is preferable.
Examples of the cycloalkylene group represented by L include a cyclohexylene group, a cyclopentylene group, an adamantylene group, and the like, and a cyclohexylene group is preferable.
Examples of the alkyl group represented by Rd ₁ include a methyl group and an ethyl group, and a methyl group is preferable.
The divalent linking group is preferably an alkylene group, —CO ₂ —, more preferably —CO ₂ —.

Examples of the monovalent organic group represented by R ₁ include those having 1 to 30 carbon atoms, such as an alkyl group (eg, methyl group), a cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.). An aryl group (for example, phenyl group), an alkoxycarbonyl group (for example, methoxycarbonyl group), a hydroxycarbonyl group, a hydroxyalkyl group (for example, hydroxymethyl group), and the like. A methyl group, a phenyl group, A methoxycarbonyl group and a hydroxymethyl group are preferable, and a methyl group and a methoxycarbonyl group are more preferable.

As the aromatic ring represented by Ar, a benzene ring and a naphthalene ring are preferable, and a benzene ring is more preferable.
The aromatic ring represented by Ar may have a substituent other than the hydroxyl group and the group represented by OR ₂ , and examples of the substituent include an alkyl group (for example, a methyl group, an ethyl group, etc.). , An alkoxy group (for example, methoxy group, ethoxy group and the like), an alkoxycarbonyl group (for example, methoxycarbonyl group and the like), a hydroxycarbonyl group and the like, and a methyl group and a methoxy group are more preferable.

The alkyl group represented by R ₂ is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group represented by R ₂ may have a substituent. Examples of the substituent include a hydroxyl group, a cyano group, an alkoxycarbonyl group (for example, a methoxycarbonyl group), a hydroxycarbonyl group, and the like, and an alkyl group includes a hetero atom, for example, an oxygen atom or a sulfur atom. It may be. Of these, hydroxy groups are preferred.

n ₁ is an integer of 1 to 5, preferably 1 or 2.
n ₂ is an integer of 1 to 5, preferably 1 or 2.
n ₃ is an integer of 0 to 4, preferably 0 to 1.
a is a positive number satisfying the relationship of 0 ≦ a <100, preferably 10 to 90, more preferably 20 to 80.
b is a positive number satisfying a relationship of 0 <b ≦ 100, preferably 10 to 90, and more preferably 10 to 50.

The resin containing the repeating unit represented by the general formula (1) is preferably a resin containing the repeating unit represented by the general formula (1-1).

The definitions of R ₁ , R ₂ , L, n ₁ , n ₂ , n ₃ , a, and b in formula (1-1) are as follows: R ₁ , R ₂ , L, n ₁ , The definitions of n ₂ , n ₃ , a, and b are the same, and the preferred embodiments are also the same.

The resin containing the repeating unit represented by the general formula (2) is preferably a resin containing the repeating unit represented by the general formula (2-1).

Definition of _R 2, a, and b in the formula (2-1) may, _R 2, a, and b of the definition of the general formula (2) and are each the same, preferable embodiments thereof are also the same.

The resin containing the repeating unit represented by the general formula (5) is preferably a resin containing the repeating unit represented by the general formula (5-1).

The definitions of R ₁ , R ₂ , L, n ₁ , n ₂ , n ₃ , a, and b in formula (5-1) are as follows: R ₁ , R ₂ , L, n ₁ , The definitions of n ₂ , n ₃ , a, and b are the same, and the preferred embodiments are also the same.

Specific examples of the resin having a structure in which all or part of the phenolic hydroxyl group produced by the method of the present invention is alkylated are shown below.

The ratio (molar ratio) between the structural unit having a phenolic hydroxyl group and the alkylated structural unit of the resin having a structure in which all or part of the phenolic hydroxyl group produced by the method of the present invention is alkylated is 90 / 10 to 10/90 is preferable, and 80/20 to 20/80 is more preferable.

<Resin having a phenolic hydroxyl group>
In the present invention, a resin having a phenolic hydroxyl group is used as a raw material.
The resin having a phenolic hydroxyl group is preferably a resin containing a repeating unit represented by the following general formula (3), general formula (4), or general formula (6).

In formulas (3), (4) and (6), L represents a single bond or a divalent linking group.
R ₁ represents a hydrogen atom or a monovalent organic group.
Ar represents an aromatic ring.
n ₁ represents an integer of 1 to 5.

As the aromatic ring represented by Ar, a benzene ring and a naphthalene ring are preferable, and a benzene ring is more preferable.
The aromatic ring represented by Ar may have a substituent other than the group represented by the hydroxyl group. Examples of the substituent include an alkyl group (for example, a methyl group, an ethyl group, etc.), an alkoxy group. (For example, a methoxy group, an ethoxy group, etc.), an alkoxycarbonyl group (for example, a methoxycarbonyl group, etc.), a hydroxycarbonyl group, etc. can be mentioned, A methyl group and a methoxy group are more preferable.
n ₁ is an integer of 1 to 5, preferably 1 or 2.

The resin containing a repeating unit represented by the general formula (3) is preferably a resin containing a repeating unit represented by the general formula (3-1).

_R 1, L in the formula (3-1), and the definition of _{n 1} is the general formula (3) is _R 1, L, and defining a respective same _{n 1} of preferred embodiment is also the same.

The resin containing a repeating unit represented by the general formula (4) is preferably a resin containing a repeating unit represented by the general formula (4-1).

The resin containing a repeating unit represented by the general formula (6) is preferably a resin containing a repeating unit represented by the general formula (6-1).

_R 1, L in the formula (6-1), and the definition of _{n 1} is the general formula (6) is _R 1, L, and defining a respective same _{n 1} of preferred embodiment is also the same.

Examples of the resin having a phenolic hydroxyl group suitably used as a raw material include the following resins.

Of these resins, parahydroxystyrene resin is particularly suitable.

The weight average molecular weight in terms of standard polystyrene of the resin having a phenolic hydroxyl group used as a raw material in the present invention is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, still more preferably 2. , 20,000 to 20,000.

The resin having a phenolic hydroxyl group used as a raw material in the present invention preferably has 0 to 10% by mass of residual monomer and oligomer components, and more preferably has few impurities such as metals. Is 0 to 5% by mass, more preferably 0 to 1% by mass. The molecular weight distribution (Mw / Mn, also referred to as the degree of dispersion), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is preferably 1 to 3, more preferably 1 to 2, and still more preferably 1 to 1.8.
In addition, in this-application specification, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are the polystyrene conversion values calculated | required from gel permeation chromatography (GPC).

As the resin having a phenolic hydroxyl group used as a raw material in the present invention, various commercially available products can be used, or they can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Examples include propylene glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol), cyclohexanone, and the like.

The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. The concentration of the reaction is usually 5 to 50% by mass, preferably 30 to 50% by mass. The reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 to 100 ° C.

After the reaction is complete, cool to room temperature and purify. Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. , Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent A normal method such as a method can be applied. For example, the resin is precipitated as a solid by contacting a solvent in which the resin is hardly soluble or insoluble (poor solvent) in a volume amount of 10 times or less, preferably 10 to 5 times the volume of the reaction solution.

The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the resin solution may be a poor solvent for the above resin, and may be a hydrocarbon, halogenated hydrocarbon, nitro, depending on the type of resin. A compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.

The amount of the precipitation or reprecipitation solvent to be used can be appropriately selected in consideration of efficiency, yield, etc. Generally, it is generally 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the resin solution, More preferably, it is 300 to 1000 parts by mass.

The temperature at the time of precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.

Precipitated or re-precipitated resin is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).

It should be noted that once the resin is precipitated and separated, it may be dissolved again in a solvent and contacted with a solvent in which the resin is hardly soluble or insoluble. That is, after completion of the radical polymerization reaction, a solvent in which the resin is hardly soluble or insoluble is brought into contact, the resin is precipitated (step a), the resin is separated from the solution (step b), and the resin solution A is dissolved again in the solvent. (Step c), and then contact the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less volume). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).

<Halogenated alkyl compounds>
In the present invention, the alkyl halide compound used as a raw material includes halogenated alkyl compounds such as ethyl bromide, n-propyl bromide, allyl bromide, n-butyl bromide, isopropyl bromide, cyclohexyl bromide, chloroethane, chloropropane, bromopropanol, Examples include halogenated alkyl compounds having a hydroxyl group such as bromoethanol, bromobutanol, bromohexanol, and chloropropanol, and halogenated alkyl compounds substituted with an ester group such as ethyl α-bromobutyrate and ethyl 4-bromobutyrate.
Of these, halogenated alkyl compounds having a hydroxyl group such as bromopropanol, bromoethanol, bromobutanol, and bromohexanol are particularly suitable.

<Organic base>
In the production method of the present invention, a halogenated resin and a resin having a phenolic hydroxyl group in the presence of an organic base selected from a nitrogen-containing compound and a tetraalkylammonium hydroxide compound whose acid dissociation constant (pKa) of the conjugate acid is 12 or more. Reacts with alkyl compounds.
The pKa value is defined as a value obtained by adding a negative sign to the common logarithm of the dissociation constant Ka in an aqueous solution of a weak electrolyte, that is, pKa = −log ₁₀ Ka, for example, in ethanol / water (7/3) The pKa value in the present invention is a value calculated by commercially available software ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08).

Examples of pKa of the conjugate acid calculated by the above method for nitrogen-containing compounds are given below.

Examples of the nitrogen-containing compound used in the present invention include the nitrogen-containing compounds disclosed in JP-A-2008-127462, paragraphs 0128 to 0132, that is, compounds having partial structures represented by the following general formulas (A) to (E) Among these, compounds having a pKa of a conjugate acid of 12 or more can be mentioned.
In the present invention, the upper limit value of PKa is not particularly limited, but is preferably 15 or less, more preferably 14 or less.

In the general formula (A), R ²⁵⁰ , R ²⁵¹ and R ²⁵² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or an aryl having 6 to 20 carbon atoms. R ²⁵⁰ and R ²⁵¹ may be bonded to each other to form a ring. These may have a substituent. Examples of the alkyl group and cycloalkyl group having a substituent include an aminoalkyl group having 1 to 20 carbon atoms, an aminocycloalkyl group having 3 to 20 carbon atoms, and 1 to A 20 hydroxyalkyl group or a hydroxycycloalkyl group having 3 to 20 carbon atoms is preferred. These may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain.

In the general formula (E), R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ each independently represent an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms.

As the nitrogen-containing compound having a pKa of a conjugate acid of 12 or more, nitrogen-containing compounds having an amidine structure such as diazabicycloundecene, diazabicyclononene and imidazole are preferable, and among them diazabicycloundecene and diazabicyclononene. Is preferred.

Examples of the tetraalkylammonium hydroxide compound used in the present invention include tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide.

In the present invention, it is preferable to use at least one compound selected from the group consisting of a nitrogen-containing compound having an amidine structure and a tetraalkylammonium hydroxide compound as the organic base, and diazabicycloundecene and diazabicyclononene. Alternatively, it is more preferable to use a tetraalkylammonium hydroxide compound. By using the organic base, the yield can be further improved.

The addition amount of the organic base used in the production method of the present invention is preferably 1 to 2 equivalents, more preferably 1 to 1.5 equivalents, relative to the alkyl halide compound to be reacted.

In the production method of the present invention, two or more kinds of organic bases may be used in combination. For example, a combination of two nitrogen-containing compounds, a combination of two tetraalkylammonium hydroxide compounds, or a combination of a nitrogen-containing compound and a tetraalkylammonium hydroxide compound may be used.

In the production method of the present invention, the reaction proceeds in a state in which a resin having a phenolic hydroxyl group, a halogenated alkyl compound, and an organic base are dissolved in a solvent.

The reaction solvent used in the reaction of the present invention is not particularly limited. For example, alcohol solvents such as methanol, ethanol, propanol, isopropanol and 1-methoxy-2-propanol, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, Ether solvents such as tetrahydrofuran, pyridine, methylpyridine, α-picoline, β-picoline, γ-picoline, N, N-dimethylaniline, N, N-diethylaniline, N-methylpiperidine, N-ethylpiperidine, N-methyl Tertiary such as piperazine, N-ethylpiperazine, N-methylmorpholine, N-ethylmorpholine, N, N, N ′, N′-tetramethyldiaminoethane, N, N, N ′, N′-tetramethyldiaminopropane Amine solvent, N, N-dimethylformami , N, N- diethylformamide, N, N- dimethylacetamide, N, N- diethylacetamide, N- methylpyrrolidone, amide solvent such as N- ethyl pyrrolidone. Among them, alcohol solvents such as methanol, ethanol, propanol, isopropanol, and 1-methoxy-2-propanol are preferable in order to dissolve well a salt of a resin having a phenolic hydroxyl group that is generated as an intermediate during this reaction. Is more preferable.

The reaction concentration of the reaction according to the present invention is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, based on the weight of the reaction solvent.

The reaction temperature of the reaction according to the present invention is not particularly limited, but is preferably 30 to 150 ° C, more preferably 60 to 90 ° C.

The reaction time of the reaction according to the present invention may be appropriately set so that the reaction is completed, and is not particularly limited, but is generally about 1 to 8 hours. The reaction pressure is not particularly limited, and may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure.

After completion of the reaction, the reaction solution is directly added to a poor solvent such as water, hexane, or heptane, and the precipitated powder is separated by filtration, or after separation with an organic solvent such as ethyl acetate and water, the organic layer is concentrated. Alternatively, the target resin can be recovered by separating it after addition to a poor solvent.

The production method of the present invention may further include a purification step for removing metal impurities after the alkylation reaction step.

Examples of a method for removing impurities such as metals from the resin obtained by the production method of the present invention include filtration using a filter. The pore size of the filter is preferably 50 nm or less, more preferably 10 nm or less, and still more preferably 5 nm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination. Moreover, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.

Moreover, as a method of reducing impurities such as metals contained in the resin obtained by the production method of the present invention, a method of selecting a raw material with a low metal content as a raw material, or performing filter filtration on the raw material Can be mentioned. Preferred conditions for filter filtration performed on the raw material are the same as those described above.

In addition to filter filtration, impurities may be removed by an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

According to the production method of the present invention, a resin with a reduced content of metal impurities can be obtained. As an application application of the resin of the present invention, it is conceivable to use it for a material having a severe demand for metal impurities. An example of a material having a strict requirement for metal impurities is a resin composition used in a manufacturing process of a semiconductor integrated circuit. Examples of such a resin composition include a composition for forming an upper layer film as disclosed in US2014 / 093826A and US2013 / 0889820A, a composition for forming a lower layer film as disclosed in WO2012 / 105648A and US2013 / 256264A, and WO2012. / 111459A and a composition for forming a planarizing layer as disclosed in JP 2010-217306 A, and a resist composition as disclosed in WO 2014 / 030724A and WO 2014 / 109337A.

When the resin of the present invention is used as a resin composition, it is usually used in the form of a resin solution in which the resin is dissolved in a solvent.
The solvent is not particularly limited. For example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone, monoketone compound which may contain a ring, alkylene carbonate, Examples thereof include organic solvents such as alkyl alkoxyacetates and alkyl pyruvates.

Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate And propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.

Examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene Preferred is glycol monoethyl ether.

Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.

Preferred examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-methoxypropionate.

Examples of the cyclic lactone include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-octano. Preferred are iclactone and α-hydroxy-γ-butyrolactone.

Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2 -Methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3- Methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methyl Preferred is cycloheptanone.

Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.

Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.

Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

As a solvent that can be preferably used, a solvent having a boiling point of 130 ° C. or higher under normal temperature and normal pressure can be mentioned. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, acetic acid Examples include -2- (2-ethoxyethoxy) ethyl and propylene carbonate.

As a solvent of a resin composition, the said solvent may be used independently and 2 or more types may be used together.
It is preferable that the said solvent and the solvent used for the synthesis | combination of resin of this invention do not contain impurities, such as a metal. The content of impurities contained in the solvent is preferably 1 ppm or less, more preferably 100 ppt or less, still more preferably 10 ppt or less, and particularly preferably (not more than the detection limit of the measuring device).
Examples of the method for removing impurities such as metals from the solvent include filtration using a filter. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination. Moreover, the filtration process may be a process of filtering a plurality of times, and the process of filtering a plurality of times may be a circulation filtration process. As another method of removing impurities such as metals from the solvent, there is a method of performing distillation under a condition in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark). it can.

A surfactant may be added to the resin composition for the purpose of improving coating properties.
The surfactant is not particularly limited. For example, fluorine and / or silicon surfactant (fluorine surfactant, silicon surfactant, surfactant having both fluorine atom and silicon atom) is used. it can.

Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US2008 / 0248425A. For example, F-top EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 4430 (manufactured by Sumitomo 3M Co., Ltd.), Megafac F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104 105, 106, KH-20 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (manufactured by Toagosei Co., Ltd.), Surflon S-393 (Manufactured by Seimi Chemical Co., Ltd.), F-top EF121, EF122A, EF12 B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 208G, 218G, 230G, 204G 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.) and the like. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to the known surfactants described above, surfactants are derived from fluoroaliphatic compounds produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.
As surfactants corresponding to the above, Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by DIC Corporation), acrylates having C ₆ F ₁₃ groups (or methacrylate) and (poly (oxyalkylene)) acrylate (copolymer of or methacrylate), and acrylate having a C ₃ F ₇ group (or methacrylate) (poly (oxyethylene) and) acrylate (or methacrylate) (poly ( And a copolymer with oxypropylene)) acrylate (or methacrylate).

Further, other surfactants other than the fluorine-based and / or silicon-based surfactants described in [0280] of US2008 / 0248425A can also be used.

These surfactants may be used alone or in some combination.

In addition to the solvent and the surfactant, an appropriate component can be added to the resin composition depending on its use. For example, when the resin composition is used as a resist composition, suitable components such as a photoacid generator, a crosslinking agent, a basic compound and a hydrophobic resin as disclosed in WO2014 / 030724A and WO2014 / 109337A are used. May be appropriately selected and added to the resin composition.

Next, although an Example is given and this invention is demonstrated, this invention is not limited to this. The structure, weight average molecular weight (polystyrene basis), and degree of dispersion of the synthesized resin were identified by ¹ H-NMR (nuclear magnetic resonance) and GPC (developing solvent: THF (tetrahydrofuran)).

<Example 1-1 (Synthesis of Resin A)>
20 g of parahydroxystyrene (Nippon Soda VP-2500) and 113 g of methanol were added to a four-necked flask equipped with a thermometer, a gas blowing tube, a cooling tube, a stirrer and a water bath, and completely dissolved at room temperature. Later, 12.1 g of bromopropanol was added. The obtained solution was heated to 65 ° C. with stirring, and 7.6 g of diazabicycloundecene dissolved in 20 g of methanol was added dropwise over 30 minutes, followed by further stirring for 6 hours while refluxing. Then, after cooling to room temperature, 3.0 g of acetic acid was added and added dropwise to 610 g of pure water. The precipitated powder was filtered off, washed with 200 g of pure water, and then blown and dried at 40 ° C. It was confirmed by ¹ H-NMR and GPC that the desired resin A was obtained (see FIG. 1). The yield of resin A and the content of metal components are shown in Table 1. The content of the metal component was measured by an inductively coupled plasma mass spectrometer (ICP-MS apparatus) Agilent 7500cs manufactured by Agilent Technologies.

<Example 1-2 (Synthesis of Resin AA)>
20 g of parahydroxystyrene (Nippon Soda VP-2500) and 113 g of methanol were added to a four-necked flask equipped with a thermometer, a gas blowing tube, a cooling tube, a stirrer and a water bath, and completely dissolved at room temperature. Later, 9.3 g of bromopropanol was added. The obtained solution was heated to 65 ° C. with stirring, and 7.6 g of diazabicycloundecene dissolved in 20 g of methanol was added dropwise over 30 minutes, followed by further stirring for 6 hours while refluxing. Thereafter, after cooling to room temperature, 3.0 g of acetic acid was added, and 100 g of the solvent was distilled off under reduced pressure. To the remaining reaction solution, 70 g of ethyl acetate and 40 g of water were added and stirred for 30 minutes, and then 40 g of the solvent of the mixed solution was distilled off under reduced pressure. Further, 40 g of ethyl acetate was added to the remaining reaction solution and stirred for 30 minutes, and then 40 g of the solvent of the mixed solution was distilled off under reduced pressure. Finally, 40 g of ethyl acetate was added and stirred for 30 minutes. The aqueous layer was removed, the organic layer was washed twice with 80 g of distilled water, the solvent was distilled off under reduced pressure, and PGMEA was added so that the solid content was 20%. A PGMAE solution of AA was obtained. It was confirmed by ¹ H-NMR (see FIG. 2) and GPC that the desired resin AA was obtained. The yield of the resin AA and the content of the metal component are shown in Table 1. The content of the metal component was measured by an inductively coupled plasma mass spectrometer (ICP-MS apparatus) Agilent 7500cs manufactured by Agilent Technologies.

<Examples 2 to 9>
Resins C, F, I, J, K, L, M, and O were synthesized under the same conditions as in Example 1 except that the resin having a phenolic hydroxyl group, the alkyl halide compound, and the organic base were changed. In addition to the reaction conditions, the yield of the target compound and the content of the metal component are shown in Table 1.

<Example 10>
Resin O was synthesized under the same conditions as in Example 9 except that the organic base was changed. In addition to the reaction conditions, the yield of the target compound and the content of the metal component are shown in Table 1.

<Comparative Example 1>
The compound was synthesized under the same conditions as in Example 1 except that the organic base was changed to potassium carbonate, which was an inorganic base. The results are also shown in Table 1.

<Comparative example 2>
It implemented on the conditions similar to Example 1 except having changed the organic base into the pyrrolidine. The results are also shown in Table 1.

<Basic compound>
DBU: Diazabicycloundecene
DBN: Diazabicyclononene
TMAH: Tetramethylammonium hydroxide
BIZ: benzimidazole

<Solvent>
THF: Tetrahydrofuran NMP: N-methyl-2-pyrrolidone

From Table 1, it is clear that according to the production method of the present invention, a resin in which all or part of the phenolic hydroxyl group in which the content of metal impurities is reduced is alkylated can be produced with a high reaction yield. .
That is, in Comparative Example 1 (using potassium carbonate), the yield was relatively high, but the content of the metal component in the resin was very high. In Comparative Example 2 (pKa is less than 12), the content of the metal component in the resin was reduced, but the yield was significantly lower under the same conditions as in Examples 1 to 10.
On the other hand, when Example 10 and Examples 1 to 9 are compared, when diazabicycloundecene, diazabicyclononene or a tetraalkylammonium hydroxide compound is used as the organic base, the yield tends to be higher. It was.

The resin obtained by alkylating all or part of the phenolic hydroxyl groups obtained by the production method of the present invention has a reduced metal component content, and is therefore suitable for a semiconductor production process that requires less metal impurities. Can be used.
In a semiconductor manufacturing process, there are many steps in which a resin composition in which a resin is dissolved in a solvent is applied on a substrate and used. Therefore, the applicability of the resin composition on the substrate is an important performance in evaluating the applicability of the resin obtained by the production method of the present invention to the semiconductor production process.

In the application examples shown below, the coating performance of a resin composition containing a resin obtained by the production method of the present invention on a substrate was evaluated.

<Application Example 1>
A resin composition was prepared by dissolving 5 g of the resin A synthesized in Example 1 and 1 g of the surfactant Troysol S366 (manufactured by Troy Chemical Co., Ltd.) in 94 g of PGMEA (propylene glycol monomethyl ether acetate). After applying the resin composition onto a 12-inch (300 mm diameter) silicon wafer by spin coating, the wafer substrate was heated at 210 ° C. for 60 seconds to form a coating film having a thickness of 250 nm on the wafer substrate. The film thickness was measured at 625 points on the wafer surface by SCD-100 manufactured by KLA-Tencor, and the film thickness uniformity in the wafer surface was evaluated. The average film thickness and variation 3σ were calculated and shown in Table 2.

<Application Reference Example 1>
The resin composition was prepared by dissolving 5 g of the following resin X and 1 g of surfactant Troisol S366 (manufactured by Troy Chemical Co.) in 94 g of PGMEA (propylene glycol monomethyl ether acetate), and after forming a coating film as in Application Example 1 The film thickness uniformity in the wafer plane was evaluated. The average film thickness and variation 3σ were calculated and shown in Table 2.

Table 2 shows that the resin composition (application example 1) containing resin obtained by the manufacturing method of this invention can be apply | coated on a board | substrate with a uniform film thickness.
The resin obtained by the production method of the present invention can be applied to semiconductor production process applications such as a photoresist composition, a composition for forming an underlayer film, a composition for forming a protective film, and a composition for forming a planarization layer. .

Claims

A method for producing a resin, comprising producing a resin in which all or part of a phenolic hydroxyl group is alkylated,
In the presence of at least one organic base selected from the group consisting of a nitrogen-containing compound and a tetraalkylammonium hydroxide compound in which the acid dissociation constant of the conjugate acid is 12 or more, the resin having a phenolic hydroxyl group and the halogenated alkyl compound. The manufacturing method of resin including the process made to react in.
The method for producing a resin according to claim 1, wherein the organic base is at least one compound selected from the group consisting of a nitrogen-containing compound having an amidine structure and a tetraalkylammonium hydroxide compound.
The method for producing a resin according to claim 2, wherein the organic base is diazabicycloundecene, diazabicyclononene, or a tetraalkylammonium hydroxide compound.
The method for producing a resin according to any one of claims 1 to 3, wherein a reaction solvent in the step of reacting the resin having a phenolic hydroxyl group and the alkyl halide compound is an alcohol solvent.
A resin produced by the resin production method according to any one of claims 1 to 4.
A resin composition comprising the resin according to claim 5 and a solvent.