Method for producing modified resin

Abstract

To provide a method for producing a modified resin that allows efficient production of a desired modified resin by enabling smooth progress of a modification reaction of a resin having an epoxy group by using a tertiary phosphine as a catalyst.SOLUTION: A method for producing a modified resin comprises a step (A-1) of reacting a nucleophile having no polymerizable unsaturated bond with a resin containing an epoxy group, under the presence of a catalyst containing a tertiary phosphine and under an atmosphere in which the oxygen concentration of a gas phase part within a reaction vessel is less than 2 vol.%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a modified resin, and more particularly to a method for producing a modified resin in which a modification reaction proceeds well and a modified resin can be produced efficiently. [Background technology]

[0002] Various applications of resins or resin compositions have been studied for various uses in various optical components and electric / electronic devices, such as color filters, inks, printing plates, printed wiring boards, semiconductor devices, photoresists, organic insulating films, and organic protective films used in liquid crystal displays and solid-state imaging devices, and resins and resin compositions excellent in the properties required for each use have been developed.

[0003] In recent years, optical components and electrical and electronic devices have become smaller, thinner, and more energy-efficient, and this has led to demands for higher performance from the various components used in these devices. To meet these demands, research is being conducted on resins and resin compositions that are used as materials for these components.

[0004] As one of such resins, a resin modified with an epoxy group is known (Patent Documents 1 to 4). For example, Patent Document 1 describes a modified epoxy resin with excellent heat resistance, moisture resistance, and flexibility, which is obtained by reacting an epoxy resin (a) having two or more epoxy groups in one molecule, a phenol (b) having a substituent containing an aryl group, and an unsaturated monobasic acid (c). Furthermore, Patent Document 4 describes a method for producing an ethylenically unsaturated resin by reacting an epoxy group-containing compound with a carboxy group-containing compound, and describes that the carboxy group-containing compound is a modified epoxy resin having a carboxy group obtained by reacting an epoxy resin with a polyfunctional carboxylic acid. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 11-49840 [Patent Document 2] Japanese Patent Application Laid-Open No. 2008-250307 [Patent Document 3] Japanese Patent Application Laid-Open No. 2013-181911 [Patent Document 4] Japanese Patent Application Publication No. 2020-84089 Summary of the Invention [Problem to be solved by the invention]

[0006] Because epoxy groups have low reactivity, an appropriate catalyst is required to promote the desired reaction, and tertiary phosphines are used as such catalysts. However, when a modification reaction of a resin having epoxy groups is carried out using a tertiary phosphine as a catalyst, conventional methods have had problems such as the catalyst being easily deactivated and the modification reaction not proceeding sufficiently.

[0007] The present invention has been made in view of the above-mentioned problems, and aims to provide a method for producing a modified resin, in which, when a modification reaction of a resin having an epoxy group is carried out using a tertiary phosphine as a catalyst, the modification reaction proceeds well and a desired modified resin can be produced efficiently. [Means for solving the problem]

[0008] The present inventors have conducted extensive research into the modification of various resins in the presence of a catalyst containing a tertiary phosphine and have found that the modification of epoxy-containing resins proceeds satisfactorily by reacting an epoxy-containing resin with a nucleophile having no polymerizable unsaturated bond in the presence of a catalyst containing a tertiary phosphine and in an atmosphere in which the oxygen concentration in the gas phase of a reaction vessel is below a certain level. Similarly, the present inventors have found that the modification of hydroxyl-containing resins and acid-containing resins proceeds satisfactorily by reacting an electrophile with the resin in the presence of a catalyst containing a tertiary phosphine and in an atmosphere in which the oxygen concentration in the gas phase of a reaction vessel is below a certain level, thereby completing the present invention.

[0009] That is, the present invention includes the following aspects. <1> A method for producing a modified resin, comprising the step (A-1) of reacting an epoxy group-containing resin with a nucleophilic agent having no polymerizable unsaturated bond in the presence of a catalyst containing a tertiary phosphine and in an atmosphere in which the oxygen concentration in the gas phase of a reaction vessel is less than 2% by volume. <2> The method of the present invention further comprises a step (A-2) of reacting the resin obtained in the reaction step (A-1) with an electrophilic agent in an atmosphere in which the oxygen concentration in the gas phase of the reaction vessel is less than 2% by volume. <1> A method for producing the modified resin described in <3> The resin obtained in the reaction step (A-1) is a hydroxyl group-containing resin. <1> or <2> A method for producing the modified resin described in <4> The nucleophilic agent is at least one active proton-containing acidic compound selected from the group consisting of thiol compounds, carboxylic acid compounds, alcohol compounds, phenolic compounds, and phosphoric acid compounds. <1> ~ <3> 1. A method for producing the modified resin according to any one of the preceding claims. <5> A method for producing a modified resin, comprising step (B) of reacting a hydroxyl group-containing resin with an electrophile in the presence of a catalyst containing a tertiary phosphine in an atmosphere in which the oxygen concentration in the gas phase of a reaction vessel is less than 2% by volume. <6> A method for producing a modified resin, comprising step (C) of reacting an acid group-containing resin with an electrophilic agent in the presence of a catalyst containing a tertiary phosphine in an atmosphere in which the oxygen concentration in the gas phase of a reaction vessel is less than 2% by volume. <7> The electrophilic agent is an electrophilic agent having no polymerizable unsaturated bond. <2> ~ <6> 1. A method for producing the modified resin according to any one of the preceding claims. <8> The electrophilic agent is at least one compound selected from the group consisting of epoxy compounds, acid anhydrides, and isocyanate compounds. <2> ~ <6> 1. A method for producing the modified resin according to any one of the preceding claims. [Effects of the Invention]

[0010] In the method for producing a modified resin of the present invention, the modification reaction of the epoxy group-containing resin proceeds smoothly, and the desired modified resin can be produced efficiently. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. Note that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

[0012] <First Invention> The first method for producing a modified resin of the present invention is characterized by including a step (A-1) of reacting an epoxy group-containing resin with a nucleophile having no polymerizable unsaturated bonds in the presence of a catalyst containing a tertiary phosphine in an atmosphere in which the oxygen concentration in the gas phase of a reaction vessel is less than 2% by volume. It is believed that the reason why the first method for producing a modified resin of the present invention can smoothly proceed with the modification reaction is that by keeping the oxygen concentration in the gas phase of the reaction vessel below a certain level, deactivation of the tertiary phosphine catalyst can be suppressed, allowing the modification reaction to smoothly proceed. Hereinafter, the first method for producing a modified resin of the present invention will also be referred to as "production method (A)."

[0013] In the production method (A) of the present invention, the gas phase in the reaction vessel refers to the portion of the space in the reaction vessel occupied by gas. That is, in the reaction step (A-1) of the production method (A), a nucleophilic agent having no polymerizable unsaturated bond is reacted with an epoxy group-containing resin in an atmosphere in which the oxygen concentration in the gas phase is less than 2% by volume, to carry out a modification reaction of the resin. The oxygen concentration in the gas phase is preferably 1.5% by volume or less, and more preferably 1.0% by volume or less, in order to allow the modification reaction to proceed more smoothly. The oxygen concentration in the gas phase in the reaction vessel can be measured using an oxygen concentration meter (for example, XP-3380II manufactured by New Cosmos Electric Co., Ltd.).

[0014] Examples of methods for adjusting the oxygen concentration in the gas phase in the reaction vessel to the above-mentioned range include a method of blowing an inert gas into the gas phase in the reaction vessel and a method of bubbling an inert gas into a resin solution (liquid phase) containing an epoxy group-containing resin. Among these, bubbling with an inert gas is preferred because it can better prevent deactivation of the tertiary phosphine catalyst. The introduction of the inert gas may be carried out either before or during the reaction, but is preferably carried out continuously from before the reaction until the end of the reaction.

[0015] Examples of the inert gas include nitrogen, argon, and a mixture thereof. Among these, nitrogen is preferred because it is easily available.

[0016] When the inert gas is introduced into the reaction vessel before the reaction, the amount of the inert gas introduced is preferably 1.0 to 10 times, more preferably 1.5 to 5 times, and even more preferably 2 to 4 times the volume of the reaction vessel, in order to easily adjust the oxygen concentration in the gas phase within the above-mentioned range. When the inert gas is introduced before the reaction, the inert gas may be introduced after the pressure inside the reaction vessel is reduced to a vacuum.

[0017] Furthermore, the flow rate of the inert gas during the reaction is preferably 1 to 1000 ml / min per 100 ml of reaction vessel volume, more preferably 3 to 100 ml / min, and even more preferably 15 to 80 ml / min, in order to easily adjust the oxygen concentration in the gas phase within the above-mentioned range. The flow rate of the inert gas during the reaction may be constant or may be changed in multiple stages.

[0018] The reaction vessel is not particularly limited as long as it is made of a material that does not adversely affect the reaction process. The size of the reaction vessel is also not particularly limited and can be appropriately selected by a known method.

[0019] The reaction step (A-1) is carried out in the presence of a catalyst containing a tertiary phosphine, such as trimethylphosphine, tributylphosphine, tricyclohexylphosphine, or triphenylphosphine.

[0020] The amount of the tertiary phosphine used in the reaction step (A-1) is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the epoxy group-containing resin, in order to achieve both a good reaction rate during synthesis and good storage stability after synthesis.

[0021] The epoxy group-containing resin is not particularly limited as long as it is a resin having at least one epoxy group in one molecule, and any known resin having an epoxy group can be used.

[0022] Examples of the epoxy group-containing resin include bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol S type epoxy resins; biphenyl type epoxy resins; alicyclic epoxy resins; polyfunctional glycidylamine resins such as tetraglycidylaminodiphenylmethane; polyfunctional glycidyl ether resins such as tetraphenylglycidyl ether ethane; novolac type epoxy resins such as phenol novolac type epoxy resins, cresol novolac type epoxy resins, and naphthalene-containing novolac type epoxy resins; phenol, Examples of epoxy resins include reaction products of epichlorohydrin with polyphenol compounds obtained by the condensation reaction of phenolic compounds such as o-cresol, m-cresol, and naphthol with aromatic aldehydes having a phenolic hydroxyl group; reaction products of epichlorohydrin with polyphenol compounds obtained by the addition reaction of phenolic compounds with diolefin compounds such as divinylbenzene and dicyclopentadiene; products obtained by epoxidizing ring-opening polymerization products of 4-vinylcyclohexene-1-oxide with peracid; and epoxy resins having heterocycles such as triglycidyl isocyanurate. Other examples include resins obtained by reacting two or more molecules of these epoxy resins with a chain extender such as a polybasic acid, a polyphenol compound, a polyfunctional amino compound, or a polyvalent thiol to bond and extend the chain. Alternatively, it may be a homopolymer of a monomer having an epoxy group, such as glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, vinylbenzyl glycidyl ether, allyl glycidyl ether, or (3,4-epoxycyclohexyl)methyl (meth)acrylate, or a copolymer of the above-mentioned monomer having an epoxy group with another monomer, such as (meth)acrylic acid.Furthermore, as the epoxy group-containing resin, bifunctional epoxy resins such as 4,4'-biphenyldiylbis(glycidyl ether) and 3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl may be used; fluorene-based bifunctional epoxy resins such as 9,9-bis(4-glycidyloxyphenyl)fluorene 4,4'-(9-fluorenylidene)bis(1,2-epoxy-3-phenoxypropane); binol-based bifunctional epoxy resins such as 2,2'-diglycidyloxy-1,1'-binaphthalene; polyethylene glycol diglycidyl ether; neopentyl glycol diglycidyl ether; 1,4-butanediol diglycidyl ether; and resorcinol diglycidyl ether. The epoxy group-containing resin may contain one or more types.

[0023] The epoxy equivalent of the epoxy group-containing resin is preferably 100 to 100,000 g / equivalent, more preferably 140 to 1,000 g / equivalent, and even more preferably 180 to 500 g / equivalent, in terms of good reactivity.

[0024] The epoxy equivalent of the epoxy group-containing resin can be determined by dividing the resin solid content by the number of moles of epoxy groups contained in the resin. Alternatively, the epoxy equivalent can be determined by a method in accordance with JIS K7236:2001.

[0025] The weight average molecular weight of the epoxy group-containing resin is preferably 100 to 100,000, more preferably 200 to 20,000, and even more preferably 300 to 5,000, in view of good reactivity. The weight average molecular weight is a value obtained by measurement using gel permeation chromatography (GPC) (standard polystyrene equivalent). When the epoxy group-containing resin is a low molecular weight compound, the weight average molecular weight corresponds to the molecular weight.

[0026] The nucleophilic agent having no polymerizable unsaturated bond may be an active proton-containing acidic compound generally known as a nucleophile, but having no polymerizable unsaturated bond. Examples of the polymerizable unsaturated bond include a (meth)acryloyl group, a vinyl group, an allyl group, and a methallyl group. The addition of a compound having a polymerizable unsaturated bond is not suitable (or suitable) for the present invention because gelation occurs due to the progress of radical polymerization when the addition reaction is carried out under conditions of low oxygen concentration.

[0027] As the nucleophile, at least one active proton-containing acidic compound selected from the group consisting of thiol compounds, carboxylic acid compounds, alcohol compounds, phenol compounds, and phosphoric acid compounds is preferred, as they have good reactivity; thiol compounds, carboxylic acid compounds, and phenol compounds are more preferred, and thiol compounds are even more preferred.

[0028] The thiol compound is preferably a compound having a thiophenol skeleton, and examples thereof include benzenethiol, toluenethiol, and naphthalenethiol.

[0029] Specific examples of the carboxylic acid compound include aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, heptyl acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid, monocarboxylic acid compounds such as formic acid and benzoic acid, and dicarboxylic acid compounds such as oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, gluconic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and 5-norbornene dicarboxylic acid. Among these, monocarboxylic acid compounds are preferred in terms of their ability to suppress gelation, and aliphatic carboxylic acids and formic acid are more preferred, with acetic acid, propionic acid, butyric acid, and formic acid being even more preferred.

[0030] Preferred examples of the alcohol compound include monoalcohols having 1 to 10 carbon atoms, such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, isobutyl alcohol, isoamyl alcohol, propylene glycol monomethyl ether, and propylene glycol monobutyl ether; and polyhydric alcohols having 1 to 10 carbon atoms, such as (poly)ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, tetraethylene glycol, and (poly)propylene glycol. Of these, monoalcohols are preferred, and butanol is more preferred, in that they can suppress gelation.

[0031] Examples of the phenol compound include phenol and its derivatives, and bisphenol compounds such as bisphenol S, bisphenol A, bisphenol F, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z.

[0032] The phosphoric acid compound may, for example, be octyl phosphate.

[0033] The above nucleophilic agents may be used alone or in combination of two or more.

[0034] The amount of the nucleophilic agent used is not particularly limited, but is preferably 0.01 to 2 equivalents, more preferably 0.3 to 1.5 equivalents, and even more preferably 0.5 to 1.1 equivalents relative to 1 equivalent of the epoxy group of the epoxy group-containing resin, in order to increase the refractive index of the product.

[0035] In the reaction step (A-1), a solvent may be used in addition to the above-mentioned components. The solvent may be appropriately selected depending on the type of epoxy group-containing resin and nucleophilic agent used. Examples of the solvent include hydrocarbons such as toluene and xylene; cellosolves such as cellosolve and butyl cellosolve; carbitols such as carbitol and butyl carbitol; esters such as cellosolve acetate, carbitol acetate, (di)propylene glycol monomethyl ether acetate, (di)methyl glutarate, (di)methyl succinate, and (di)methyl adipate; ketones such as methyl isobutyl ketone and methyl ethyl ketone; and ethers such as (di)ethylene glycol dimethyl ether. The solvent may be used alone or in combination of two or more. Among these, the solvent preferably contains an ester, and more preferably contains propylene glycol monomethyl ether acetate, because of its good solubility.

[0036] In the reaction step (A-1), in addition to the above-mentioned components and solvent, commonly used additives such as a polymerization inhibitor may also be used.

[0037] The reaction temperature in the reaction step (A-1) is not particularly limited and may be appropriately selected depending on the resin and nucleophilic agent used, but is usually 30 to 140°C, preferably 50 to 130°C, and more preferably 60 to 120°C.

[0038] The reaction time in the reaction step (A-1) is not particularly limited and may be appropriately selected depending on the resin and nucleophilic agent used, but is usually 0.1 to 30 hours, preferably 1 to 15 hours, and more preferably 4 to 12 hours.

[0039] In the reaction step (A-1), the epoxy group of the epoxy group-containing resin is preferably opened to generate a hydroxyl group. Thus, the resin obtained in the reaction step (A-1) is preferably a hydroxyl group-containing resin.

[0040] Another preferred embodiment of the reaction step (A-1) involves modifying and linking an epoxy group-containing resin with a nucleophilic agent having multiple nucleophilic sites to obtain an epoxy resin with an increased molecular weight. Such a molecular weight-increasing reaction of an epoxy group-containing resin is not limited except that both starting materials are polyfunctional. However, from the viewpoint of inhibiting gelation, it is preferable that both the epoxy group-containing resin and the nucleophilic agent as starting materials are bifunctional. In this case, preferred nucleophiles include bifunctional carboxylic acid compounds, thiol compounds, or phenolic compounds among the above-mentioned nucleophiles. Bifunctional phenolic compounds (bisphenol compounds) are more preferred, and bisphenol S is particularly preferred.

[0041] The modified resin production method (A) of the present invention preferably further comprises a step (A-2) of reacting the resin obtained in the above-mentioned reaction step (A-1) with an electrophile in an atmosphere in which the oxygen concentration in the gas phase of the reaction vessel is less than 2% by volume. By reacting the resin obtained in the above reaction step (A-1) with the electrophile, the electrophile reacts with the hydroxyl groups of the resin obtained in the above reaction step (A-1), and the structure possessed by the electrophile can be added to the resin.

[0042] As the electrophilic agent, at least one compound selected from the group consisting of epoxy compounds, acid anhydrides, and isocyanate compounds is preferred in terms of good reactivity, with acid anhydride compounds being more preferred. The electrophilic agent is preferably a compound that does not have a polymerizable unsaturated bond. This is because when a compound having a polymerizable unsaturated bond is added, gelation of the adduct proceeds when the oxygen concentration is low. Examples of polymerizable unsaturated bonds include those mentioned above.

[0043] The epoxy compound may be, for example, a compound having at least one epoxy group in the molecule, and examples thereof include the above-mentioned epoxy group-containing resins that do not have a polymerizable unsaturated bond, aliphatic epoxy compounds such as butyl glycidyl ether, etc. Among these, aliphatic epoxy compounds are preferred because of their easy availability.

[0044] Examples of the acid anhydride include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, tetrabromophthalic anhydride, and trimellitic acid; aromatic polycarboxylic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride; and polycarboxylic acid anhydride derivatives associated therewith, such as 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride. Among these, succinic anhydride and tetrahydrophthalic anhydride are preferred due to their good reactivity, and succinic anhydride is more preferred.

[0045] Examples of the isocyanate compound include methyl isocyanate, phenyl isocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, etc. Among these, monofunctional isocyanates are preferred in terms of being able to suppress gelation, and phenyl isocyanate is more preferred.

[0046] The electrophilic agents may be used alone or in combination of two or more.

[0047] The amount of the electrophilic agent used is not particularly limited, but in terms of good reactivity, it is preferably 0.01 to 0.9 equivalents, more preferably 0.1 to 0.8 equivalents, and even more preferably 0.2 to 0.7 equivalents relative to 1 equivalent of the nucleophilic site of the epoxy group-containing resin. Examples of the nucleophilic site include a hydroxyl group.

[0048] In the reaction step (A-2), in addition to the above-mentioned components and solvent, commonly used additives such as a polymerization inhibitor may also be used.

[0049] The reaction temperature in the reaction step (A-2) is not particularly limited, but is usually 30 to 140°C, preferably 50 to 130°C, and more preferably 60 to 120°C.

[0050] The reaction time in the reaction step (A-2) is not particularly limited, but is usually 0.1 to 30 hours, preferably 1 to 15 hours, and more preferably 4 to 12 hours.

[0051] The modified resin production method (A) may include other steps in addition to the above-mentioned reaction steps (A-1) and (A-2). Examples of the other steps include an aging step, a neutralization step, a dilution step, a drying step, a concentration step, a solvent substitution step, a dissolution step, etc. These steps can be carried out by known methods.

[0052] <Second Invention> The second invention of the present invention is a method for producing a modified resin, characterized in that it comprises a step (B) of reacting a hydroxyl-containing resin with an electrophile in the presence of a catalyst containing a tertiary phosphine in an atmosphere in which the oxygen concentration in the gas phase of a reaction vessel is less than 2% by volume. Hereinafter, this method for producing a modified resin of the second invention will also be referred to as "production method (B)."

[0053] The method (B) for producing a modified resin of the present invention includes a step (B) of reacting a hydroxyl-containing resin with an electrophile in the presence of a catalyst containing a tertiary phosphine in an atmosphere in which the oxygen concentration in the gas phase of a reaction vessel is less than 2% by volume. The inclusion of such a reaction step (B) allows the modification reaction of the hydroxyl-containing resin to be carried out efficiently. It is presumed that, as with the above-described production method (A), reducing the oxygen concentration in the gas phase of the reaction vessel to a certain level or lower prevents the deactivation of the tertiary phosphine catalyst, allowing the modification reaction of the hydroxyl-containing resin to proceed smoothly.

[0054] In the reaction step (B), the oxygen concentration in the gas phase of the reaction vessel is preferably 1.5% by volume or less, and more preferably 1.0% by volume or less, in order to allow the modification reaction to proceed more smoothly. The oxygen concentration in the gas phase can be measured by the same method as in the production method (A) described above. The oxygen concentration in the gas phase can be adjusted by the same method as in the production method (A) described above.

[0055] Tertiary phosphines used in the reaction step (B) include the same as those used in the production method (A) described above, and preferred examples include trimethylphosphine, tributylphosphine, tricyclohexylphosphine, and triphenylphosphine.

[0056] The amount of the tertiary phosphine used in the reaction step (B) is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the epoxy group-containing resin, in order to achieve both a good reaction rate during synthesis and good storage stability after synthesis.

[0057] The hydroxyl group-containing resin is not particularly limited as long as it is a resin having a hydroxyl group, and examples thereof include resins obtained by polymerizing a monomer component containing a hydroxyl group-containing monomer. Further examples include resins obtained by adding an acid group-containing compound to a polymer (base polymer) or epoxy resin obtained by polymerizing a monomer component containing an epoxy group-containing monomer, and resins obtained by adding an epoxy group-containing compound to a polymer (base polymer) obtained by polymerizing a monomer component containing an acid group-containing monomer.

[0058] Examples of the hydroxyl group-containing monomer include compounds having a hydroxyl group and a polymerizable double bond in the molecule, and preferred examples include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2,3-hydroxypropyl (meth)acrylate.

[0059] The epoxy group-containing monomer may be a compound having an epoxy group and a polymerizable double bond in the molecule, preferably an epoxy group-containing (meth)acrylate. Specific examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, vinylbenzyl glycidyl ether, allyl glycidyl ether, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and vinylcyclohexene oxide.

[0060] Examples of the epoxy resin include the same epoxy resins as those described in the above-mentioned production method (A).

[0061] The acid group-containing compound may be an acid group-containing monomer having a polymerizable double bond, or an acid group-containing compound having no polymerizable double bond. Examples of the acid group-containing monomer include compounds having the above-mentioned acid group and polymerizable double bond in the molecule. Specific examples of the acid group-containing monomer include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, and vinylbenzoic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid; long-chain unsaturated monocarboxylic acids in which the unsaturated group and the carboxyl group are chain-extended, such as β-carboxyethyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, and mono(2-methacryloyloxyethyl) succinate; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; and phosphoric acid group-containing unsaturated compounds such as Light Ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.). Among these, carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, long-chain unsaturated monocarboxylic acids, and unsaturated acid anhydrides) are preferred from the viewpoints of versatility and availability. In terms of reactivity, alkali solubility, etc., the acid group-containing monomer is more preferably an unsaturated monocarboxylic acid, and even more preferably (meth)acrylic acid.

[0062] Examples of the acid group-containing compound having no polymerizable double bond include thiol compounds, carboxylic acid compounds, phosphoric acid compounds, etc. These include the same compounds as those described in the above-mentioned Production Method (A).

[0063] Examples of the epoxy group-containing compound include the above-mentioned epoxy group-containing monomers as well as epoxy group-containing compounds that do not have a polymerizable double bond, such as butyl glycidyl ether.

[0064] The polymerization method or addition reaction for obtaining the hydroxyl group-containing resin is not particularly limited, and may be appropriately selected from known polymerization methods. In the polymerization, commonly used additives such as a polymerization initiator, a chain transfer agent, a solvent, a catalyst, etc. The types and amounts of these additives may be appropriately selected from known additives.

[0065] The hydroxyl value of the hydroxyl-containing resin is preferably 10 to 200 mgKOH / g, more preferably 30 to 150 mgKOH / g, and even more preferably 50 to 100 mgKOH / g. The hydroxyl value can be determined in accordance with the method of JIS K0070-1992.

[0066] The weight-average molecular weight of the hydroxyl group-containing resin is preferably 1,000 to 1,000,000, from the viewpoint of good reactivity, more preferably 2,000 to 50,000, and even more preferably 4,000 to 20,000. The weight-average molecular weight is a value obtained by measurement using gel permeation chromatography (GPC) (standard polystyrene equivalent).

[0067] The electrophilic agent in the reaction step (B) may be the same as the electrophilic agent used in the production method (A). Among them, at least one compound selected from the group consisting of epoxy compounds, acid anhydrides, and isocyanate compounds is preferred in terms of good reactivity, and acid anhydride compounds are more preferred. The electrophilic agents may be used alone or in combination of two or more.

[0068] The amount of electrophilic agent used in the reaction step (B) is preferably 0.01 to 0.9 equivalents relative to 1 equivalent of hydroxyl groups in the hydroxyl group-containing resin, more preferably 0.1 to 0.8 equivalents, and even more preferably 0.2 to 0.7 equivalents, in terms of good reactivity.

[0069] A solvent may be used in the reaction step (B) above. Examples of the solvent include the same solvents as those used in the reaction step (A-1) above.

[0070] In the reaction step (B), in addition to the above-mentioned components and solvent, commonly used additives such as a polymerization inhibitor may also be used.

[0071] The reaction temperature in the reaction step (B) is not particularly limited, but is usually 30 to 140°C, preferably 50 to 130°C, and more preferably 60 to 120°C.

[0072] The reaction time in the reaction step (B) is not particularly limited, but is usually 0.1 to 30 hours, preferably 1 to 15 hours, and more preferably 4 to 12 hours.

[0073] The modified resin production method (B) may include other steps in addition to the reaction step (B). Examples of the other steps include an aging step, a neutralization step, a dilution step, a drying step, a concentration step, a solvent substitution step, a dissolution step, etc. These steps can be carried out by known methods.

[0074] <Third Invention> The third invention of the present invention is a method for producing a modified resin, characterized in that it comprises a step (C) of reacting an acid group-containing resin with an electrophile in the presence of a catalyst containing a tertiary phosphine in an atmosphere in which the oxygen concentration in the gas phase of a reaction vessel is less than 2% by volume. Hereinafter, this method for producing a modified resin of the third invention will also be referred to as "production method (C)."

[0075] The method (C) for producing a modified resin of the present invention includes a step (C) of reacting an electrophile with an acid group-containing resin in the presence of a catalyst containing a tertiary phosphine in an atmosphere in which the oxygen concentration in the gas phase of a reaction vessel is less than 2% by volume. The inclusion of this reaction step (C) allows the modification reaction of the acid group-containing resin to be carried out efficiently. It is presumed that, as with the above-described production method (A), reducing the oxygen concentration in the gas phase of the reaction vessel to a certain level or lower can prevent the deactivation of the tertiary phosphine catalyst, allowing the modification reaction of the acid group-containing resin to proceed smoothly.

[0076] In the reaction step (C), the oxygen concentration in the gas phase of the reaction vessel is preferably 1.5% by volume or less, more preferably 1.0% by volume or less. The oxygen concentration in the gas phase can be measured by the same method as in the above-mentioned production method (A). The oxygen concentration in the gas phase can be adjusted by the same method as in the above-mentioned production method (A).

[0077] The tertiary phosphine used in the reaction step (C) may be the same as that used in the production method (A) described above, and trimethylphosphine, tributylphosphine, tricyclohexylphosphine, and triphenylphosphine are preferred, with triphenylphosphine being more preferred.

[0078] The amount of the tertiary phosphine used in the reaction step (C) is preferably 0.01 to 0.9 equivalents relative to 1 equivalent of the acid group of the acid group-containing resin, more preferably 0.1 to 0.8 equivalents, and even more preferably 0.2 to 0.7 equivalents, in terms of good reactivity.

[0079] The acid group-containing resin is not particularly limited as long as it is a resin having an acid group, and examples thereof include resins obtained by polymerizing a monomer component containing an acid group-containing monomer. Examples of the acid group include functional groups that undergo a neutralization reaction with alkaline water, such as a carboxy group, a phenolic hydroxyl group, a carboxylic anhydride group, a phosphoric acid group, and a sulfonic acid group. Among these, a carboxy group is preferred because of its good reactivity. Examples of the acid group-containing monomer include the same acid group-containing monomers as those described in the above-mentioned production method (B).

[0080] Examples of the acid group-containing resin include a resin obtained by adding an acid group-containing monomer to a polymer (base polymer) obtained by polymerizing a monomer component containing an epoxy group-containing monomer, and then further reacting with a polybasic acid or a polybasic acid anhydride; and a resin obtained by adding an epoxy group-containing monomer to a polymer (base polymer) obtained by polymerizing a monomer component containing an acid group-containing monomer, and then further reacting with a polybasic acid or a polybasic acid anhydride.

[0081] Examples of the epoxy group-containing monomer include the same epoxy group-containing monomers as those described in the above-mentioned production method (B).

[0082] Examples of the polybasic acid or polybasic acid anhydride include polybasic acids such as succinic acid, maleic acid, phthalic acid, and tetrahydrophthalic acid; dibasic acid anhydrides such as succinic anhydride (also known as succinic anhydride), maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, and itaconic anhydride; trimellitic anhydride; etc. Among these, succinic anhydride and tetrahydrophthalic anhydride are preferred, and succinic anhydride is more preferred, in terms of good reactivity.

[0083] The polymerization reaction or addition reaction method for obtaining the acid group-containing resin is not particularly limited, and may be appropriately selected from known polymerization reaction or addition reaction methods. In the polymerization reaction or addition reaction, commonly used additives such as a polymerization initiator, a chain transfer agent, a solvent, a catalyst, etc. The types and amounts of these additives may be appropriately selected from known additives.

[0084] The acid value of the acid group-containing resin is preferably 10 to 200 mgKOH / g, more preferably 30 to 150 mgKOH / g, and even more preferably 50 to 100 mgKOH / g. The acid value is a value obtained by measurement by neutralization titration using a potassium hydroxide (KOH) solution, and is the acid value per 1 g of resin solid content.

[0085] In terms of good reactivity, the weight average molecular weight is preferably 1,000 to 1,000,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 20,000. The weight average molecular weight is a value obtained by measurement using gel permeation chromatography (GPC) (standard polystyrene equivalent).

[0086] The electrophilic agent in the reaction step (C) may be the same as the electrophilic agent used in the production method (A). Among them, at least one compound selected from the group consisting of epoxy compounds, acid anhydrides, and isocyanate compounds is preferred, and epoxy compounds are more preferred, because of their good reactivity. The electrophilic agent may be used alone or in combination of two or more.

[0087] The amount of electrophilic agent used in the reaction step (C) is preferably 0.01 to 0.9 equivalents relative to 1 equivalent of the acid group of the acid group-containing resin, more preferably 0.1 to 0.8 equivalents, and even more preferably 0.2 to 0.7 equivalents, in terms of good reactivity.

[0088] In the reaction step (C), a solvent may be used, and examples of the solvent include the same solvents as those used in the reaction step (A-1).

[0089] In the reaction step (C), in addition to the above-mentioned components and solvent, commonly used additives such as a polymerization inhibitor may also be used.

[0090] The reaction temperature in the reaction step (C) is not particularly limited, but is usually 30 to 140°C, preferably 50 to 130°C, and more preferably 60 to 120°C.

[0091] The reaction time in the reaction step (C) is not particularly limited, but is usually 0.1 to 30 hours, preferably 1 to 15 hours, and more preferably 4 to 12 hours.

[0092] The modified resin production method (C) may include other steps in addition to the reaction step (C). Examples of the other steps include an aging step, a neutralization step, a dilution step, a drying step, a concentration step, a solvent substitution step, a dissolution step, etc. These steps can be carried out by known methods.

[0093] As described above, according to the method for producing a modified resin of the present invention, when a nucleophile is reacted with an epoxy group-containing resin in the presence of a catalyst containing a tertiary phosphine, or when an electrophile is reacted with a hydroxyl group-containing resin or an acid group-containing resin, the desired modification reaction can be smoothly carried out, and the modified resin can be efficiently produced. [Example]

[0094] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass." The various evaluation methods used in the present examples are as follows.

[0095] <Quantitative determination of acid compounds or modifying compounds in reaction solution> Measurement was carried out by gas chromatography (GC) under the conditions below, and the amount (g) of the acid compound or modifying compound in the reaction solution was determined from the area value of the chromatography. Equipment: Shimadzu Corporation "GC-2014" Syringe injection volume: 1.0 μL Inlet temperature: 210℃ Gas type and pressure: He, 33.5 psi Detection method: FID Detector temperature: 250℃ The reaction rate of the acid compound or modifying compound was calculated as follows: Reaction rate (%) = 100 × (charge amount (g) - remaining amount in reaction solution (g)) / charge amount (g)

[0096] <Quantitative determination of acid anhydride in reaction solution> 3 g of the reaction solution was precisely weighed and dissolved in a mixed solvent of 90 g of acetone and 10 g of water. Using a 0.1 N KOH aqueous solution as a titrant, the acid value of the polymer solution was measured using an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd., product name: COM-555) to quantify the amount of acid (mol) in the reaction solution. The reaction rate of the acid anhydride was calculated as follows. Reaction rate (%) = 100 × (2 × charge amount (mol) - amount of acid in reaction solution (mol)) / (charge amount (mol))

[0097] <Oxygen concentration in the gas phase> The air in the reaction vessel during the reaction was sucked out, and the oxygen concentration (vol %) in the gas phase was measured using an oxygen concentration meter manufactured by New Cosmos Electric.

[0098] (Example 1) Preparation of Resin Solution (A-1) A 500 ml separable flask equipped with a thermometer, stirrer, gas inlet, and condenser was charged with 197.5 g of propylene glycol monomethyl ether acetate and 207.7 g (1 mol of epoxy group) of cresol novolac epoxy resin (YDCN-704A, epoxy equivalent weight 207.7 g / equivalent, manufactured by Nippon Steel Chemical & Material Co., Ltd.). Nitrogen gas was bubbled through the gas inlet at a flow rate of 100 ml / min for 10 minutes (1 L total), after which the flow rate was changed to 150 ml / min and bubbling continued until the end of the reaction. After changing the nitrogen gas flow rate, the resin solution was heated to 100 °C and held for 30 minutes to dissolve the epoxy resin. After lowering the temperature of the reaction vessel to 70°C, 88.1 g (0.8 mol) of benzenethiol (BT) as an acid compound and 0.44 g of triphenylphosphine (TPP) as a tertiary phosphine catalyst were added and the addition reaction was carried out for 12 hours to obtain resin solution (A-1). Samples of the reaction solution were taken at 0 h, 1 h, 3 h, and 6 h of reaction time, and the reaction rate of the acid compound was calculated by gas chromatography. The results are shown in Table 1. The oxygen concentration in the gas phase during the reaction was 1.0 vol%.

[0099] (Example 2) Preparation of resin solution (A-2) A 500 ml separable flask equipped with a thermometer, stirrer, gas inlet, and condenser was charged with 197.5 g of propylene glycol monomethyl ether acetate and 207.7 g (1 mol of epoxy group) of cresol novolac epoxy resin (YDCN-704A, epoxy equivalent 207.7 g / equivalent, manufactured by Nippon Steel Chemical & Material Co., Ltd.). Nitrogen gas was bubbled through the gas inlet at a flow rate of 100 ml / min for 10 minutes (1 L total), after which the flow rate was changed to 100 ml / min and bubbling continued until the end of the reaction. After changing the nitrogen gas flow rate, the resin solution was heated to 100 °C and held for 30 minutes to dissolve the epoxy resin. After lowering the temperature of the reaction vessel to 70°C, 88.1 g (0.8 mol) of benzenethiol (BT) as an acid compound and 0.44 g of triphenylphosphine (TPP) as a tertiary phosphine catalyst were added and the addition reaction was carried out for 12 hours to obtain resin solution (A-2). Samples of the reaction solution were taken at 0 h, 1 h, 3 h, 6 h, and 12 h of reaction time, and the reaction rate of the acid compound was tracked by gas chromatography. The results are shown in Table 1. The oxygen concentration in the gas phase during the reaction was 1.5% by volume.

[0100] (Example 3) Preparation of resin solution (A-3) A 500 ml separable flask equipped with a thermometer, stirrer, gas inlet, and condenser was sealed and evacuated. After reducing the pressure, nitrogen gas was introduced through the gas inlet until atmospheric pressure was reached, completely replacing the system with nitrogen. The sealed condition was released, and 493.8 g of resin solution (A-1) (0.2 mol of epoxy groups) was added while nitrogen gas was introduced through the gas inlet at 200 ml / min. Nitrogen gas bubbling continued until the reaction was complete. After the temperature of the reaction vessel was raised to 120 °C, 12.4 g (0.225 mol) of propionic acid (PA) as an acid compound and 1.88 g of triphenylphosphine (TPP) as a tertiary phosphine catalyst were introduced to carry out an addition reaction. The reaction was continued for 12 hours to obtain resin solution (A-3). Samples of the reaction solution were taken at 0, 1, 3, 6, and 12 hours, and the conversion of the acid compound was monitored by gas chromatography. The results are shown in Table 1. The oxygen concentration in the gas phase during the reaction was 0.4% by volume.

[0101] (Example 4) Preparation of resin solution (A-4) A 2 L separable flask equipped with a thermometer, stirrer, gas inlet, and condenser was charged with 219.2 g of propylene glycol monomethyl ether acetate and 187.0 g (1 mol of epoxy group) of a bifunctional epoxy resin (3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl, epoxy equivalent: 187.0 g / eq). Argon gas was blown into the gas phase through the gas inlet at a flow rate of 100 mL / min for 40 minutes (4 L total). The flow rate was then changed to 190 mL / min and continued until the end of the reaction. After switching the nitrogen gas flow rate, the resin solution was heated to 100 °C and held for 30 minutes to dissolve the epoxy resin. After lowering the temperature of the reactor to 70°C, 31.3 g (0.25 mol) of bisphenol S (BPS) as an acid compound and 0.5 g of tricyclohexylphosphine (TCP) as a tertiary phosphine catalyst were added and the addition reaction was carried out for 12 hours to obtain resin solution (A-4). Samples of the reaction solution were taken at 0 h, 1 h, 3 h, and 6 h of reaction time, and the reaction rate of the acid compound was tracked by gas chromatography. The results are shown in Table 1. The oxygen concentration in the gas phase during the reaction was 0.7% by volume.

[0102] (Example 5) Preparation of resin solution (A-5) A 500 ml separable flask equipped with a thermometer, stirrer, gas inlet, and condenser was charged with 493.8 g (0.8 mol hydroxyl groups) of the fat solution (A-1). Nitrogen gas was bubbled through the gas inlet at a flow rate of 100 ml / min for 10 minutes (1 L total), then the flow rate was changed to 150 ml / min and bubbling continued until the reaction was complete. After changing the nitrogen gas flow rate, the temperature of the reaction vessel was lowered to 110 °C, and 40.0 g (0.4 mol) of succinic anhydride (SAH) and 1.0 g of triphenylphosphine (TPP) were added as the acid anhydride and the tertiary phosphine catalyst, triphenylphosphine, were added. The reaction was continued for 12 hours to obtain resin solution (A-5). Samples of the reaction solution were taken at 0 h, 1 h, 3 h, 6 h, and 12 h, and the acid value was measured to track the reaction rate of the acid anhydride. The results are shown in Table 2. The oxygen concentration in the gas phase during the reaction was 1.0% by volume.

[0103] (Example 6) Preparation of resin solution (A-6) A 500 ml separable flask equipped with a thermometer, stirrer, gas inlet, condenser, and a dropping tank inlet was charged with 97.1 g of propylene glycol monomethyl ether acetate and 47.5 g of propylene glycol monomethyl ether. Nitrogen gas was bubbled through the gas inlet at a flow rate of 100 ml / min for 10 minutes (total of 1 L), after which the flow rate was changed to 200 ml / min and bubbling continued until the end of the reaction. After changing the nitrogen gas flow rate, the mixture was heated to 90°C. Separately, a beaker containing 66.0 g of methyl methacrylate (MMA), 34.0 g (0.46 mol) of acrylic acid (AA), and 2.0 g of t-butylperoxy-2-ethylhexanoate was stirred and mixed to prepare the dropping tank (A). A dropping tank containing 2.0 g of n-dodecyl mercaptan and 8.0 g of propylene glycol monomethyl ether acetate was also prepared to prepare the dropping tank (B). After the temperature of the reaction tank reached 90°C, the dropping tank was started over 3 hours while maintaining the same temperature, and polymerization was carried out. After the dropping was completed, the temperature was maintained at 90°C for 30 minutes, after which the temperature was raised to 115°C and aged for 90 minutes. After cooling to room temperature, 27.1 g (0.21 mol) of butyl glycidyl ether (BGE) was added as a modifying compound, and 0.38 g of triphenylphosphine (TPP) was added as a tertiary phosphine catalyst. The addition reaction was carried out at 115°C for 12 hours to obtain resin solution (A-6). Samples of the reaction solution were taken at 0, 1, 3, 6, and 12 hours after the reaction, and the conversion of the modifying compound was monitored by gas chromatography. The results are shown in Table 3. The oxygen concentration in the gas phase during the reaction was 0.5% by volume.

[0104] (Comparative Example 1) Preparation of Resin Solution (B-1) A 500 ml separable flask equipped with a thermometer, stirrer, gas inlet, and condenser was charged with 197.5 g of propylene glycol monomethyl ether acetate and 207.7 g (1 mol of epoxy group) of cresol novolac epoxy resin (YDCN-704A, epoxy equivalent 207.7 g / equivalent, manufactured by Nippon Steel Chemical & Material Co., Ltd.). Nitrogen gas was blown into the gas phase through the gas inlet at a flow rate of 100 ml / min for 6 minutes (600 ml total). The flow rate was then changed to 20 ml / min and continued until the reaction was complete. After changing the nitrogen gas flow rate, the resin solution was heated to 100 °C and held for 30 minutes to dissolve the epoxy resin. After lowering the temperature of the reaction vessel to 70°C, 88.1 g (0.8 mol) of benzenethiol (BT) as an acid compound and 0.44 g of triphenylphosphine (TPP) as a tertiary phosphine catalyst were added and the addition reaction was carried out for 12 hours to obtain resin solution (B-1). Samples of the reaction solution were taken at 0 h, 1 h, 3 h, 6 h, and 12 h of reaction time, and the reaction rate of the acid compound was calculated by gas chromatography. The results are shown in Table 1. The oxygen concentration in the gas phase during the reaction was 5.0 vol%.

[0105] (Comparative Example 2) Preparation of Resin Solution (B-2) A 500 mL separable flask equipped with a thermometer, stirrer, gas inlet, and condenser was charged with 493.8 g of resin solution (A-1) (0.2 mol of epoxy groups). Nitrogen gas was introduced into the gas phase through the gas inlet at a flow rate of 100 mL / min for 6 minutes (600 mL total). The flow rate was then changed to 50 mL / min and continued until the reaction was complete. After changing the nitrogen gas flow rate, the reactor temperature was raised to 120 °C. 12.4 g (0.225 mol) of propionic acid (PA) as an acid compound and 1.88 g of triphenylphosphine (TPP) as a tertiary phosphine catalyst were added to carry out the addition reaction. The reaction was continued for 12 hours to obtain resin solution (B-2). Samples of the reaction solution were taken at 0, 1, 3, 6, and 12 hours, and the conversion of the acid compound was monitored by gas chromatography. The results are shown in Table 1. The oxygen concentration in the gas phase during the reaction was 2.5% by volume.

[0106] (Comparative Example 3) Preparation of Resin Solution (B-3) A 500 mL separable flask equipped with a thermometer, stirrer, gas inlet, condenser, and a dropping tank inlet was charged with 493.8 g (0.2 mol of epoxy groups) of resin solution (A-1). A nitrogen-air mixture (mix gas) adjusted to a 7% oxygen concentration (volume) was blown into the gas phase through the gas inlet at a flow rate of 100 mL / min for 6 minutes (600 mL total). The flow rate was then changed to 150 mL / min and continued until the reaction was complete. After the nitrogen gas flow rate was changed, the reactor temperature was raised to 120 °C. Then, 16.2 g (0.225 mol) of acrylic acid (AA) as an acid compound, 1.88 g of triphenylphosphine (TPP) as a tertiary phosphine catalyst, and 1.9 g of topanol as a polymerization inhibitor were added and the reaction was continued for 12 hours to obtain resin solution (B-3). The reaction solution was sampled at 0, 1, 3, 6, and 12 hours after the reaction, and the reaction rate of the acid compound was monitored by gas chromatography. The results are shown in Table 1. The oxygen concentration in the gas phase during the reaction was 8.0% by volume.

[0107] (Comparative Example 4) Preparation of Resin Solution (B-4) A 2 L separable flask equipped with a thermometer, stirrer, gas inlet, and condenser was charged with 219.2 g of propylene glycol monomethyl ether acetate and 187.0 g (1 mol of epoxy group) of a bifunctional epoxy resin (3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl, epoxy equivalent: 187.0 g / eq). Argon gas was blown into the gas phase through the gas inlet at a flow rate of 100 mL / min for 20 minutes (total of 2 L). The flow rate was then changed to 40 mL / min and continued until the end of the reaction. After switching to the nitrogen gas flow rate, the resin solution was heated to 100 °C and held for 30 minutes to dissolve the epoxy resin. After lowering the temperature of the reactor to 70°C, 31.3 g (0.25 mol) of bisphenol S (BPS) as an acid compound and 0.5 g of tricyclohexylphosphine (TCP) as a tertiary phosphine catalyst were added and the addition reaction was carried out for 12 hours to obtain resin solution (B-4). Samples of the reaction solution were taken at 0 h, 1 h, 3 h, 6 h, and 12 h of reaction time, and the reaction rate of the acid compound was tracked by gas chromatography. The results are shown in Table 1. The oxygen concentration in the gas phase during the reaction was 5.0 vol%.

[0108] (Comparative Example 5) Preparation of Resin Solution (B-5) A 500 mL separable flask equipped with a thermometer, stirrer, gas inlet, and condenser was charged with 493.8 g (0.8 mol hydroxyl groups) of resin solution (A-1). Nitrogen gas was introduced into the gas phase through the gas inlet at a flow rate of 100 mL / min for 6 minutes (600 mL total). The flow rate was then changed to 20 mL / min and continued until the reaction was complete. After the nitrogen gas flow rate was changed, the reactor temperature was lowered to 110 °C. 40.0 g (0.4 mol) of succinic anhydride (SAH) and 1.0 g of triphenylphosphine (TPP) were added as the acid anhydride and the tertiary phosphine catalyst, triphenylphosphine, were added. The reaction was continued for 12 hours to obtain resin solution (B-5). Samples of the reaction solution were taken at 0, 1, 3, 6, and 12 hours, and the acid value was measured to monitor the reaction rate of the acid anhydride. The results are shown in Table 2. The oxygen concentration in the gas phase during the reaction was 7.0% by volume.

[0109] (Comparative Example 6) Preparation of Resin Solution (B-6) A 500 ml separable flask equipped with a thermometer, stirrer, gas inlet, condenser, and a dropping tank inlet was charged with 97.1 g of propylene glycol monomethyl ether acetate and 47.5 g of propylene glycol monomethyl ether. Nitrogen gas was blown into the gas phase through the gas inlet at a flow rate of 100 ml / min for 10 minutes (600 ml in total), after which the flow rate was changed to 20 ml / min and continued until the end of the reaction. After changing the nitrogen gas flow rate, the flask was heated to 90°C. Separately, a beaker containing 66.0 g of methyl methacrylate (MMA), 34.0 g (0.46 mol) of acrylic acid (AA), and 2.0 g of t-butylperoxy-2-ethylhexanoate was stirred and mixed to prepare the dropping tank (A). A dropping tank containing 2.0 g of n-dodecyl mercaptan and 8.0 g of propylene glycol monomethyl ether acetate was also prepared to prepare the dropping tank (B). After the temperature of the reaction tank reached 90°C, the dropping tank was started over 3 hours while maintaining the same temperature, and polymerization was carried out. After the dropping was completed, the temperature was maintained at 90°C for 30 minutes, after which the temperature was raised to 115°C and aged for 90 minutes. After cooling to room temperature, 27.1 g (0.21 mol) of butyl glycidyl ether (BGE) was added as a modifying compound, and 0.38 g of triphenylphosphine (TPP) was added as a tertiary phosphine catalyst. The addition reaction was carried out at 115°C for 12 hours to obtain resin solution (B-6). Samples of the reaction solution were taken at 0, 1, 3, 6, and 12 hours after the reaction, and the conversion rate of the modifying compound was monitored by gas chromatography. The results are shown in Table 3. The oxygen concentration in the gas phase during the reaction was 6.0% by volume.

[0110] [Table 1]

[0111] [Table 2]

[0112] [Table 3]

[0113] Tables 1–3 demonstrate that maintaining an oxygen concentration in the gas phase below 2% by volume suppresses oxidative degradation of the tertiary phosphine catalyst in the reactions of nucleophiles with epoxy-containing resins, electrophiles with hydroxyl-containing resins, and electrophiles with acid-containing resins, thereby ensuring smooth reaction progress. To control the oxygen concentration in the gas phase to the above values, it is effective to reduce the oxygen concentration at the initial stage of the reaction by flowing an inert gas volume equal to or greater than twice the volume of the reaction vessel or by creating a vacuum by reducing the pressure and then injecting an inert gas. Furthermore, continuous introduction of an inert gas during the reaction can prevent the intrusion of air from external sources, such as the cooling tube, and stabilize the oxygen concentration at a low level during the reaction. Bubbling nitrogen gas directly into the solution, rather than injecting it into the gas phase, can extend the catalytic life of the tertiary phosphine. In particular, in the reaction of an epoxy group-containing compound with a thiol, the difference in reaction rate due to the oxygen concentration in the gas phase is large, making this a potentially effective production method.

Claims

1. A method for producing a modified resin, comprising: The production method includes a step (A-1) of reacting an epoxy group-containing resin with a nucleophilic agent having no polymerizable unsaturated bond in the presence of a catalyst containing a tertiary phosphine and in an atmosphere in which the oxygen concentration in the gas phase of a reaction vessel is less than 2% by volume. A method for producing a modified resin, comprising:

2. The method for producing a modified resin according to claim 1, further comprising a step (A-2) of reacting the resin obtained in the reaction step (A-1) with an electrophilic agent in an atmosphere in which the oxygen concentration in the gas phase of a reaction vessel is less than 2% by volume.

3. 2. The method for producing a modified resin according to claim 1, wherein the resin obtained in the reaction step (A-1) is a hydroxyl group-containing resin.

4. 2. The method for producing a modified resin according to claim 1, wherein the nucleophilic agent is at least one active proton-containing acidic compound selected from the group consisting of thiol compounds, carboxylic acid compounds, alcohol compounds, phenolic compounds, and phosphoric acid compounds.

5. A method for producing a modified resin, comprising: The production method is a method for producing a modified resin, characterized by including a step (B) of reacting a hydroxyl group-containing resin with an electrophile in the presence of a catalyst containing a tertiary phosphine and in an atmosphere in which the oxygen concentration in the gas phase part of a reaction vessel is less than 2% by volume.

6. A method for producing a modified resin, comprising: The production method is a method for producing a modified resin, characterized by including a step (C) of reacting an acid group-containing resin with an electrophilic agent in the presence of a catalyst containing a tertiary phosphine and in an atmosphere in which the oxygen concentration in the gas phase part of a reaction vessel is less than 2% by volume.

7. 7. The method for producing a modified resin according to claim 2, 5 or 6, wherein the electrophilic agent does not have a polymerizable unsaturated bond.

8. 7. The method for producing a modified resin according to claim 2, 5 or 6, wherein the electrophilic agent is at least one compound selected from the group consisting of epoxy compounds, acid anhydrides and isocyanate compounds.

Images