JP2006199942A - Process for production of branched polyether resin composition and process for production of acid pendant type branched polyether resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acid pendant type branched polyether resin composition with excellent set to touch property, developing property and flexibility of hardened coated film. <P>SOLUTION: The process for production of the branched polyether resin composition is composed of a first process step of a reaction of hydroxy group and acryloyl group in an aromatic bifunctional epoxy resin diacrylate (A2) in a mixture of an aromatic bifunctional epoxy resin diacrylate (A2), an aromatic bifunctional epoxy resin monoacrylate (A1) and/or an aromatic bifunctional epoxy resin (B) other than aforementioned (A1) and (A2), and a phosphorus catalyst (C) to give a reaction mixture containing a branched polyether resin (X) having a hydroxy, an acryloyl and an epoxy group, and a second process step composed of a reaction of an epoxy group in the aforementioned reaction mixture and a carboxy group in the aforementioned unsaturated monocarboxylic acid by addition of an unsaturated monocarboxylic acid in the aforementioned reaction mixture. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is excellent in touch-drying property during film formation, developability, and flexibility of a cured coating film, and in particular, heat curing and energy ray curing suitable for paints, inks, and adhesives are possible. The present invention relates to a method for producing an acid pendant branched polyether resin composition and a method for producing a branched polyether resin composition used in the production.

  Epoxy (meth) acrylate resins are used as thermosetting resins or active energy ray curable resins in various fields such as paints, adhesives, inks, electronic substrates, and sealing materials. For example, in the case of epoxy (meth) acrylate resins used for the purpose of improving the adhesion between an interlayer insulating layer and a conductor circuit layer in a multilayer printed wiring board which is an example of an electronic substrate, as a resin component, a novolac type epoxy (meth) acrylate is used. A resin composition having an acid pendant epoxy (meth) acrylate resin obtained by reacting an acid anhydride with a resin and an epoxy resin as essential components has been proposed (for example, see Patent Document 1). However, although the cured product using this resin composition has improved heat resistance, it has poor touch-drying properties during film formation, developability, and flexibility of the cured coating film.

JP 2001-094261 A

  An object of the present invention is to provide a method for producing a branched polyether resin composition capable of obtaining a paint, an adhesive, and the like having excellent dryness to touch during film formation and flexibility of a cured coating film, and touch during film formation. An object of the present invention is to provide a method for producing an acid pendant branched polyether resin composition capable of obtaining a resist ink having excellent drying properties, developability and flexibility of a cured coating film.

As a result of intensive studies to solve the above problems, the present inventors have obtained the following findings (1) to (6).
(1) In producing aromatic monofunctional epoxy resin monoacrylate and / or aromatic bifunctional epoxy resin diacrylate (aromatic bifunctional epoxy acrylate resin) in which aromatic bifunctional epoxy resin and acrylic acid are reacted. If necessary, in the presence of an organic solvent, the reaction is carried out under the condition that the epoxy group in the aromatic bifunctional epoxy resin is excessive with respect to the carboxyl group in the acrylic acid, and the acrylic acid in the reaction system is consumed, and the aromatic is consumed. It can be set as the reaction system containing the diacrylate of a bifunctional epoxy resin, the monoacrylate of an aromatic bifunctional epoxy resin, and / or the unreacted aromatic bifunctional epoxy resin. Furthermore, if this reaction system is maintained in the presence of a phosphorus catalyst, a hydroxyl group in the monoacrylate of the aromatic bifunctional epoxy resin and the diacrylate of the aromatic bifunctional epoxy resin (the epoxy in the aromatic bifunctional epoxy resin). Is a new branch having a hydroxyl group, an acryloyl group, and an epoxy group. The hydroxyl group formed by the reaction of a carboxyl group in acrylic acid with a hydroxyl group is repeatedly added to the carbon-carbon double bond of the acryloyl group to increase the molecular weight. Polyether resin (X) is formed. As a result, branched polyether resin (X) and one or more unreacted resins selected from the group consisting of diacrylates of aromatic bifunctional epoxy resins, monoacrylates of aromatic bifunctional epoxy resins, and aromatic bifunctional epoxy resins A resin composition [reaction mixture (I)] containing the components is obtained.

(2) The epoxy group-containing resin component [branched polyether resin (X), monoacrylate of aromatic bifunctional epoxy resin and aromatic bifunctional epoxy resin] in the reaction mixture (I) Branched poly containing a novel branched polyether resin (Y) having a hydroxyl group and an unsaturated group and a di (unsaturated monocarboxylic acid) ester of an aromatic bifunctional epoxy resin by reacting a carboxyl group in the carboxylic acid The ether resin composition (II) can be easily produced. The obtained branched polyether resin composition (II) is excellent in stability, active energy ray curability, touch curability during film formation, and flexibility of the cured coating film.

(3) The branched polyether resin composition (II) and the polycarboxylic acid anhydride are mixed to form a hydroxyl group [branched polyether resin (Y) and aromatic bifunctional in the branched polyether resin composition (II). By reacting the hydroxyl group in the di (unsaturated monocarboxylic acid) ester of the epoxy resin] and the hydroxyl group-free in the polycarboxylic acid anhydride, the acid pendant type branched polyether resin (Z) and the acid pendant type aromatic group 2 are reacted. An acid pendant branched polyether resin composition (III) containing a di (unsaturated monocarboxylic acid) ester of a functional epoxy resin can be easily produced. The resulting acid pendant-type branched polyether resin composition (III) can be developed with a dilute alkaline aqueous solution, has thermosetting and energy ray curable properties, and is dry to touch, developable, and cured during film formation. Excellent flexibility of the coating film.

(4) A carbon-carbon double bond of an acryloyl group of a hydroxyl group in a monoacrylate of an aromatic bifunctional epoxy resin and a diacrylate of an aromatic bifunctional epoxy resin in the presence of the phosphorus catalyst according to (1) When the epoxy group in the aromatic bifunctional epoxy resin is not excessive relative to the carboxyl group in the acrylic acid, the addition reaction to the monoacrylate of the aromatic bifunctional epoxy resin and / or unreacted It is difficult to proceed when there is no epoxy group-containing aromatic compound such as an aromatic bifunctional epoxy resin or when methacrylic acid is used instead of acrylic acid.

(5) The production method of the acid pendant type polyether resin composition (III) using the reaction mixture (I) and the branched polyether resin composition (II) has a high degree of freedom. For example, an aromatic bifunctional epoxy resin By changing the molecular weight, the molar ratio of the epoxy group in the aromatic bifunctional epoxy resin to the carboxyl group in the acrylic acid, the amount of phosphorus catalyst used, the reaction temperature, the reaction time, etc., the resulting branched polyether resin (X ) And branched polyether resin (Y), the introduction amount, introduction density, introduction ratio, etc. of hydroxyl groups, unsaturated groups and epoxy groups can be adjusted over a wide range.

(6) A reaction mixture obtained by a reaction in which a hydroxyl group in the monoacrylate of the aromatic bifunctional epoxy resin and the diacrylate of the aromatic bifunctional epoxy resin described in (1) is added to the carbon-carbon double bond of the acryloyl group. The production of (I) contains a diacrylate of an aromatic bifunctional epoxy resin, a monoacrylate of an aromatic bifunctional epoxy resin and / or an unreacted aromatic bifunctional epoxy resin, and a phosphorus catalyst is present If it is a reaction system For this reason, the reaction mixture (I) does not need to be continuously produced by starting from the reaction of the aromatic bifunctional epoxy resin and acrylic acid as in the above (1). Diacrylate of functional epoxy resin (however, monoacrylate of aromatic bifunctional epoxy resin and / or aromatic bifunctional epoxy resin may be contained) and monoacrylate of aromatic bifunctional epoxy resin produced separately And / or an unreacted aromatic bifunctional epoxy resin and a phosphorus-based catalyst (however, in this reaction, the reaction system further includes a monoacrylate and / or aromatic of an aromatic monoepoxy compound). Group mono-epoxy compound may be contained.)

The present invention is based on such knowledge.
That is, the present invention provides (1-1) a diacrylate (A2) of an aromatic bifunctional epoxy resin,
(1-2) (1-2-1) Aromatic bifunctional epoxy resin monoacrylate (A1)
And / or
(1-2-2) Other than (A1) and (A2)
Aromatic bifunctional epoxy resin (B),
And (1-3) phosphorus catalyst (C)
In the diacrylate (A2) of the aromatic bifunctional epoxy resin in the mixture containing the diacrylate (A2) of the aromatic bifunctional epoxy resin and the monoester of the aromatic bifunctional epoxy resin. Reacting the hydroxyl group and acryloyl group in the acrylate (A1),
(1-A) having a hydroxyl group, an acryloyl group and an epoxy group
Branched polyether resin (X) and (1-B) (1-B-1) aromatic difunctional epoxy resin diacrylate (A2),
(1-B-2) Aromatic bifunctional epoxy resin monoacrylate (A1) and
(1-B-3) Other than (A1) and (A2)
Aromatic bifunctional epoxy resin (B)
A first step of obtaining a reaction mixture containing one or more resin components selected from the group consisting of:
A branched polyether resin comprising a second step of adding an unsaturated monocarboxylic acid to the reaction mixture and reacting an epoxy group in the reaction mixture with a carboxyl group in the unsaturated monocarboxylic acid A method for producing the composition is provided.

  Furthermore, the present invention comprises mixing a branched polyether resin composition obtained by the above-described method for producing a branched polyether resin composition and a polycarboxylic acid anhydride, and adding a hydroxyl group in the branched polyether resin composition to a polycarboxylic acid. The present invention provides a method for producing an acid pendant branched polyether resin composition characterized by reacting a hydroxyl group in an acid anhydride.

According to the production method of the present invention, it is possible to provide a method for producing a branched polyether resin composition capable of obtaining a paint, an adhesive, and the like that are excellent in dryness to touch during film formation and flexibility of a cured coating film. Moreover, the manufacturing method of the acid pendant type | mold branched polyether resin composition which can obtain the resist ink etc. which are excellent in the touch drying property at the time of film forming, developability, and the softness | flexibility of a cured coating film can also be provided.

The first step contained in the production method of the branched polyether resin composition of the present invention,
(1-1) Diacrylate (A2) of an aromatic bifunctional epoxy resin,
(1-2) (1-2-1) Aromatic bifunctional epoxy resin monoacrylate (A1)
And / or
(1-2-2) Other than (A1) and (A2)
Aromatic bifunctional epoxy resin (B),
And (1-3) phosphorus catalyst (C)
In the diacrylate (A2) of the aromatic bifunctional epoxy resin in the mixture containing the diacrylate (A2) of the aromatic bifunctional epoxy resin and the monoester of the aromatic bifunctional epoxy resin. Reacting the hydroxyl group and acryloyl group in the acrylate (A1),
(1-A) having a hydroxyl group, an acryloyl group and an epoxy group
Branched polyether resin (X) and (1-B) (1-B-1) aromatic difunctional epoxy resin diacrylate (A2),
(1-B-2) Aromatic bifunctional epoxy resin monoacrylate (A1) and
(1-B-3) Other than (A1) and (A2)
Aromatic bifunctional epoxy resin (B)
A reaction mixture containing at least one resin component selected from the group consisting of [hereinafter referred to as reaction mixture (I). Is a step of obtaining

The branched polyether resin (X) having a hydroxyl group, an acryloyl group and an epoxy group in the reaction mixture (I) is:

The hydroxyl group and acryloyl group in the aromatic bifunctional epoxy resin diacrylate (A2), or the hydroxyl group in the aromatic bifunctional epoxy resin diacrylate (A2) and the monoacrylate (A1) of the aromatic bifunctional epoxy resin A branched polyether resin obtained by reacting with an acryloyl group, comprising an aromatic bifunctional diacrylate (A2), an aromatic bifunctional epoxy resin monoacrylate (A1), and an aromatic epoxy compound (B). One or more kinds of resin components selected from the group are diacrylate (A2) of aromatic bifunctional epoxy resin, monoacrylate (A1) of aromatic bifunctional epoxy resin and / or aromatic bifunctional epoxy resin (B). Reaction of the branched polyether resin (X) in the mixture (in the reaction system) containing the phosphorus catalyst (C) It is unreacted resin component after performing.

In the aromatic bifunctional epoxy resin diacrylate (A2) used in the first step, two epoxy groups in the aromatic bifunctional epoxy resin (b) are acrylated with acrylic acid (a). It is. As an aromatic bifunctional epoxy resin (b) used here, for example,
Biphenol type epoxy resins such as tetramethylbiphenol type epoxy resin; Bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin; Dicyclopentadiene modified aromatic bifunctional epoxy resin; Dihydroxynaphthalene-type epoxy resins obtained by epoxidizing naphthalenes; Glycidyl ester-type resins of aromatic divalent carboxylic acids; Bifunctional epoxy resins derived from xylenol, naphthalene aralkyl epoxy resins; Examples include epoxy resins modified with pentadiene; ester-modified epoxy resins obtained by modifying these aromatic bifunctional epoxy resins with dicarboxylic acids.

  Examples of the ester-modified epoxy resin include those obtained by modification under conditions where the epoxy group in the aromatic bifunctional epoxy resin is excessive with respect to the carboxyl group in the dicarboxylic acid. Examples of the dicarboxylic acids used here include succinic acid, fumaric acid, phthalic acid, maleic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid. Acids, dicarboxylic acids such as cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, maleic anhydride, phthalic anhydride, succinic anhydride, dodecenyl succinic anhydride, tetrahydrophthalic anhydride, 4-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydro Examples thereof include dicarboxylic acid anhydrides such as phthalic anhydride and hexahydrophthalic anhydride.

  The dicarboxylic acids can be used alone or in combination of two or more. Moreover, it is also possible to use aromatic monocarboxylic acids such as benzoic acid, and aliphatic monocarboxylic acids such as propionic acid and stearyllic acid. When modifying an aromatic bifunctional epoxy resin with dicarboxylic acids, it is necessary to react a small molar amount of carboxylic acid with respect to the epoxy group to leave the epoxy group in the molecule.

  The aromatic bifunctional epoxy resin (b) used for the preparation of the diacrylate (A2) of the aromatic bifunctional epoxy resin may be used alone or in combination of two or more.

  Examples of the monoacrylate (A1) and / or aromatic epoxy compound (B) of the aromatic bifunctional epoxy resin include, for example, one of the two epoxy groups in the aromatic bifunctional epoxy resin (b). A monoacrylate (A1) of an aromatic bifunctional epoxy resin having an epoxy group acrylated with acrylic acid, the aromatic bifunctional epoxy resin (b) alone, or a mixture thereof. The aromatic bifunctional epoxy resin (b) used here may be the same as that used for the preparation of the diacrylate (A2) of the aromatic bifunctional epoxy resin, or a different one may be used. Also good. Moreover, the aromatic bifunctional epoxy resin (b) used for the preparation of the monoacrylate (A1) of the aromatic bifunctional epoxy resin may be used alone or in combination of two or more.

  In order to obtain the reaction mixture (I) in the first step, for example, a diacrylate (A2) of an aromatic bifunctional epoxy resin produced separately, a monoacrylate (A1) of an aromatic bifunctional epoxy resin produced separately, and In the mixture containing the aromatic bifunctional epoxy resin (B) and the phosphorus catalyst (C), the diacrylate of the aromatic bifunctional epoxy resin (optionally in the presence of an organic solvent or a reactive diluent). A2) A hydroxyl group and an acryloyl group are reacted, or a hydroxyl group and an acryloyl group in a diacrylate (A2) of an aromatic bifunctional epoxy resin and a monoacrylate (A1) of an aromatic bifunctional epoxy resin are reacted. Just do it. The temperature for the reaction is usually 100 to 170 ° C, preferably 100 to 150 ° C. The reaction time is usually 1 to 20 hours, preferably 2 to 15 hours. In this case, the diacrylate (A2) of the aromatic bifunctional epoxy resin produced separately contains the monoacrylate (A1) of the aromatic bifunctional epoxy resin and / or the aromatic bifunctional epoxy resin (B). As long as it does not cause gelation, an acrylate of a trifunctional or higher functional polyfunctional epoxy resin may be used in combination. In this case, a monoacrylate of an aromatic monoepoxy compound and / or an aromatic monoepoxy compound may be used in combination.

  As described above, to obtain the reaction mixture (I), a diacrylate (A2) of an aromatic bifunctional epoxy resin, a monoacrylate (A1) of an aromatic bifunctional epoxy resin, and / or an aromatic bifunctional epoxy resin A mixture containing (B) and a phosphorus catalyst (C) is used, and as these (A2), (A1) and / or (B), an aromatic bifunctional epoxy resin (b) and acrylic acid (a) Is reacted under the condition that the epoxy group in the aromatic bifunctional epoxy resin (b) is excessive with respect to the carboxyl group in the acrylic acid (a), and the diacrylate of the aromatic bifunctional epoxy resin (A2) And a reaction system containing a monoacrylate (A1) of an aromatic bifunctional epoxy resin and / or an aromatic bifunctional epoxy resin (B) (hereinafter, this step is abbreviated as “Step 1”). With there.) Shall be preferable since it can be performed subsequently the preparation of subsequent reaction mixture (I).

  In this step 1, since it can be easily performed, a reaction system containing a diacrylate (A2) of an aromatic bifunctional epoxy resin and a monoacrylate (A1) of an aromatic bifunctional epoxy resin [however, an unreacted fragrance A group bifunctional epoxy resin (B) may be contained. That is, it is preferable to use a reaction system consisting of (A2) and (A1) or a reaction system consisting of (A2), (A1) and (B).

  In order to produce the reaction mixture (I) using the reaction system obtained in the step 1, a hydroxyl group and an acryloyl group in the diacrylate (A2) of the aromatic bifunctional epoxy resin in the reaction system Alternatively, the hydroxyl group and the acryloyl group in the diacrylate (A2) of the aromatic bifunctional epoxy resin and the monoacrylate (A1) of the aromatic bifunctional epoxy resin are reacted in the presence of the phosphorus catalyst (C). . A hydroxyl group obtained by increasing the molecular weight of a diacrylate (A2) of an aromatic bifunctional epoxy resin or a diacrylate (A2) of an aromatic bifunctional epoxy resin and a monoacrylate (A1) of an aromatic bifunctional epoxy resin. And a branched polyether resin (X) having an acryloyl group and an epoxy group, a diacrylate (A2) of an aromatic bifunctional epoxy resin, a monoacrylate (A1) of an aromatic bifunctional epoxy resin, and an aromatic bifunctional epoxy resin ( A reaction mixture containing one or more unreacted resin components selected from the group consisting of B) is used (hereinafter, this step may be abbreviated as “step 2”).

  A phosphorus catalyst (C) is present in the reaction system obtained in the step 1, and a diacrylate (A2) of an aromatic bifunctional epoxy resin and a monoacrylate (A1) and / or a fragrance of an aromatic bifunctional epoxy resin. In order to obtain a mixture containing the group 2 bifunctional epoxy resin (B) and the phosphorus catalyst (C), for example, the following method can be given as a preferred example.

Method 1: After the step 1 is completed, a phosphorus catalyst (C) is added. Specifically, the aromatic bifunctional epoxy resin (b) and acrylic acid (a) are used in an excess amount of the epoxy group in the aromatic bifunctional epoxy resin (b) relative to the carboxyl group in the acrylic acid (a). Reaction under the conditions
(1-1) Diacrylate (A2) of an aromatic bifunctional epoxy resin,
(1-2) (1-2-1) Aromatic bifunctional epoxy resin monoacrylate (A1)
And / or
(1-2-2) Other than (A1) and (A2)
Aromatic bifunctional epoxy resin (B)
Then, a phosphorus catalyst (C) is added to the reaction system to obtain a mixture.

  Method 2: Phosphorus catalyst (C) is added in the reaction of Step 1 above. Specifically, the aromatic bifunctional epoxy resin (b) and acrylic acid (a) are mixed with acrylic acid (a) in the presence of the phosphorus catalyst (C). A mixture is obtained by making it react on the conditions which become excess with respect to the carboxyl group in a).

  In the present invention, the method 2 is more preferable for obtaining the mixture used in the first step.

  The aromatic bifunctional epoxy resin (B) used in the present invention is an epoxy resin other than the above (A1) and (A2). In the step 1, the aromatic bifunctional epoxy resin (b) and the acrylic acid (a) are used in an excess amount of the epoxy group in the aromatic bifunctional epoxy resin (b) with respect to the carboxyl group in the acrylic acid (a). Therefore, there is an aromatic bifunctional epoxy resin (b) remaining without reacting with acrylic acid (a). The remaining aromatic bifunctional epoxy resin (b) is an aromatic bifunctional epoxy resin diacrylate (A2) or aromatic which is a reaction product of the aromatic bifunctional epoxy resin (b) and acrylic acid (a). Different from monoacrylate (A1) of bifunctional epoxy resin. Therefore, the remaining aromatic bifunctional epoxy resin (b) becomes an aromatic bifunctional epoxy resin (B) other than (A1) and (A2).

  Examples of the phosphorus catalyst (C) used in the present invention include phosphines and phosphonium salts. Of these, phosphines are most preferable.

  Examples of the phosphines include trialkylphosphine, triphenylphosphine, trialkylphenylphosphine and the like, and triphenylphosphine is particularly preferable because of easy reaction control.

  As the amount of the phosphorus catalyst (C) used, the larger the catalyst amount, the hydroxyl group and acryloyl in the diacrylate (A2) of the aromatic bifunctional epoxy resin and the monoacrylate (A1) of the aromatic bifunctional epoxy resin in the mixture In consideration of the fact that the reaction with the group tends to proceed, but the gelation is likely to occur and the stability of the composition is deteriorated, the total weight of the aromatic bifunctional epoxy resin (b) and acrylic acid (a) A range of 10 to 30,000 ppm is preferred.

  As said aromatic bifunctional epoxy resin (b) and aromatic bifunctional epoxy resin (B), since the resin composition excellent in sclerosis | hardenability is obtained especially, an epoxy equivalent is 135-2,000 g / equivalent. The thing whose epoxy equivalent is 135-500 g / equivalent is more preferable. Moreover, since a resin composition having excellent mechanical properties of a cured product can be obtained, biphenol type epoxy resins such as tetramethylbiphenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, etc. A bisphenol type epoxy resin and a dihydroxynaphthalene type epoxy resin obtained by epoxidizing dihydroxynaphthalene are preferable, a bisphenol A type epoxy resin or a 1,6-dihydroxynaphthalene type epoxy resin is more preferable, and a bisphenol A type epoxy resin is most preferable.

  In addition, when manufacturing reaction mixture (I) by the said process 1 and the process 2, the ester modified aromatic bifunctional epoxy resin which modified the aromatic bifunctional epoxy resin with dicarboxylic acid as aromatic bifunctional epoxy resin (b) is used. Instead of using the aromatic difunctional epoxy resin (b) and acrylic acid (a) in combination with dicarboxylic acids for modification in the step 1, the aromatic bifunctional epoxy resin (b) is modified with dicarboxylic acids. May be.

  In the step 1, the range in which the epoxy group in the aromatic bifunctional epoxy resin (b) is excessive with respect to the carboxyl group in the acrylic acid (a) is not particularly limited. Reaction of hydroxyl group and acryloyl group in diacrylate (A2) of aromatic bifunctional epoxy resin, or hydroxyl group in diacrylate (A2) of aromatic bifunctional epoxy resin and monoacrylate (A1) of aromatic bifunctional epoxy resin Since the reaction between the acryloyl group and the acryloyl group proceeds smoothly, the equivalent ratio of the epoxy group in the aromatic bifunctional epoxy resin (b) and the carboxyl group in the acrylic acid (a) [(epoxy group equivalent) / (carboxyl group equivalent) )] Is preferably in the range of 1.1 to 5.5. In addition, since the molecular weight of the obtained branched polyether resin can be easily adjusted, the equivalent ratio [(epoxy group equivalent) / (carboxyl group equivalent)] is 1.25 to 3.0. More preferably.

  The reaction starting from the reaction of the aromatic bifunctional epoxy resin (b) and acrylic acid (a) is considered to proceed in a reaction scheme as shown in the following diagram, for example.

〔式中、Ａr_０は芳香族二官能エポキシ樹脂（ｂ）から１つのグリシジルエーテル基を除いた残基、Ａrはそれぞれ独立に芳香族二官能エポキシ樹脂（ｂ）から１つのグリシジルエーテル基を除いた残基または芳香族二官能エポキシ樹脂のモノアクリレート（Ａ１）から１つのグリシジルエーテル基を除いた残基であり、またＲはそれぞれ独立に下記構造式（１）または（２）で表される２種の連結基のいずれかである。〕

[In the formula, Ar ₀ is a residue obtained by removing one glycidyl ether group from the aromatic bifunctional epoxy resin (b), and Ar is independently obtained by removing one glycidyl ether group from the aromatic bifunctional epoxy resin (b). Or a residue obtained by removing one glycidyl ether group from a monoacrylate (A1) of an aromatic bifunctional epoxy resin, and each R is independently represented by the following structural formula (1) or (2) Either of two types of linking groups. ]

  In Method 1 of Step 1, a catalyst may be used as necessary for the reaction of the aromatic bifunctional epoxy resin (b) and acrylic acid (a). The catalyst used is preferably a basic catalyst, and among these, a non-halogen catalyst or a halogen catalyst can be used.

  Examples of the catalyst include tertiary amines such as triethylamine, tributylamine, trisdimethylaminomethylphenol, benzyldimethylamine, and diethanolamine; quaternary ammonium hydroxides such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide; Imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; Nitrogen compounds such as diethylamine hydrochloride and diazabiscycloundecene; Trialkylphosphines such as triphenylphosphine; Tetra-n-butylphosphonium Tetraalkylphosphonium hydroxides such as hydroxide; metal salts such as chromium naphthenate; trimethylbenzylammonium chloride, tetramethyl Quaternary ammonium salts such as Le chloride; tetra -n- butyl phosphonium bromide, silver-based catalysts such as phosphonium salts such as ethyltriphenylphosphonium bromide; sodium hydroxide, and inorganic catalysts such as lithium hydroxide.

  As these catalysts, non-halogen catalysts are preferable, and nitrogen compounds such as tertiary amines and quaternary ammonium salts; phosphorus catalysts such as phosphines and phosphonium salts are preferable. Among these, phosphorus catalysts such as phosphines and phosphonium salts are more preferable, and phosphines are most preferable because they can be used as an essential catalyst in the first step.

  Examples of the phosphines include trialkylphosphine, triphenylphosphine, trialkylphenylphosphine and the like, and triphenylphosphine is particularly preferable because of easy reaction control.

  As the amount of the catalyst used, the larger the amount of the catalyst, the more easily the reaction in Steps 1 and 2 proceeds. However, in view of the fact that gelation and the stability of the composition deteriorate, The range of 10-30,000 ppm is preferable with respect to the total weight of an epoxy resin (b) and acrylic acid (a). Further, if it is a phosphorus catalyst, the catalyst used in step 1 may be used as it is in step 2, and an additional or different phosphorus catalyst may be added in step 2, or may be added during the reaction. good.

  In the step 1, the reaction is usually performed at a temperature of 70 to 170 ° C., preferably 100 to 150 ° C. while stirring. At this time, a polymerization inhibitor and an antioxidant may be used. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, trimethylhydroquinone, tertiary butylhydroquinone, 2-6-ditertiarybutyl-4-methoxyphenol, Examples thereof include copper salts and phenothiazine. Examples of the antioxidant include phosphorous acid, phosphorous acid esters, phosphorous acid diesters, and the like.

  In the step 1, the reaction between the hydroxyl group and the carbon-carbon double bond of the acryloyl group hardly proceeds during the reaction between the aromatic bifunctional epoxy resin (b) and acrylic acid (a), and acrylic acid (a). At the end of step 1, when the carboxyl group in the aromatic bifunctional epoxy resin (b) is consumed by the reaction with the epoxy group, the ether bond is formed by the reaction between the hydroxyl group and the carbon-carbon double bond of the acryloyl group. As a result, formation of high molecular weight proceeds, and Step 2 is started.

  In the step 2, the aromatic bifunctional epoxy resin diacrylate (A2), the aromatic bifunctional epoxy resin monoacrylate (A1) and / or the aromatic bifunctional epoxy resin (B), and the phosphorus catalyst (C ) In the diacrylate (A2) of the aromatic bifunctional epoxy resin, or the carbon-carbon double bond of the acryloyl group reacts, or the diacrylate of the aromatic bifunctional epoxy resin. (A2) and the carbon-carbon double bond of the acryloyl group react with the hydroxyl group in the monoacrylate (A1) of the aromatic bifunctional epoxy resin and the diacrylate (A2) of the aromatic bifunctional epoxy resin has a high molecular weight. Or aromatic bifunctional epoxy resin diacrylate (A2) and aromatic bifunctional epoxy resin monoacrylate ( 1) is the branch polyether resin (X) having a novel hydroxyl group and an acryloyl group and an epoxy group is a high molecular weight. This reaction system includes this branched polyether resin (X), an aromatic bifunctional epoxy resin diacrylate (A2), an aromatic bifunctional epoxy resin monoacrylate (A1), and an aromatic bifunctional epoxy resin (B). The reaction mixture (I) contains one or more unreacted resin components selected from the group consisting of:

  By the way, as described above, the mixture used in step 1 is a mixture containing diacrylate (A2) of aromatic bifunctional epoxy resin and monoacrylate (A1) of aromatic bifunctional epoxy resin [however, unreacted aromatic A group bifunctional epoxy resin (B) may be contained. ] Is preferable. That is, a mixture containing (A2) and (A1) or a mixture containing (A2), (A1) and (B) is preferable. The following reaction mixture is obtained by performing step 2 using each of these mixtures.

When a mixture containing (A2) and (A1) is used as the mixture,
(1-A) having a hydroxyl group, an acryloyl group and an epoxy group
Of branched polyether resin (X) and (1-B) (1-B-1) aromatic bifunctional epoxy resin
Diacrylate (A2) and
(1-B-2) of aromatic bifunctional epoxy resin
Monoacrylate (A1)
A reaction mixture containing one or more resin components selected from the group consisting of:

When a mixture containing (A2), (A1) and (B) is used as the mixture,
(1-A) having a hydroxyl group, an acryloyl group and an epoxy group
Branched polyether resin (X) and (1-B) (1-B-1) aromatic difunctional epoxy resin diacrylate (A2),
(1-B-2) Aromatic bifunctional epoxy resin monoacrylate (A1) and
(1-B-3) Other than (A1) and (A2)
Aromatic bifunctional epoxy resin (B)
A reaction mixture containing one or more resin components selected from the group consisting of:

  In Step 2, the reaction between the hydroxyl group and the carbon-carbon double bond of the acryloyl group is an aromatic bifunctional epoxy resin monoacrylate (A1) or an aromatic bifunctional epoxy resin (B) or other epoxy group-containing aromatic. It does not happen if the compound is not present. The present inventors believe that this is because the epoxy group-containing aromatic compound serves as a kind of catalyst for the reaction of the carbon-carbon double bond of the hydroxyl group and the acryloyl group in Step 2.

  Next, the process proceeds to the second step. In the second step, the reaction mixture (I) obtained in the first step and the unsaturated monocarboxylic acid are mixed, and the epoxy group in the reaction mixture reacts with the carboxyl group in the unsaturated monocarboxylic acid. It is a process to make. By reacting the epoxy group in the reaction mixture (I) with the carboxyl group in the unsaturated monocarboxylic acid, most or all of the epoxy group is consumed, and the hydroxyl group and acryloyl group-containing unsaturated monocarboxylic acid ester structure A branched polyether resin composition (II) containing the branched polyether resin (Y) and a di (unsaturated monocarboxylic acid) ester of an aromatic bifunctional epoxy resin (II). (Hereinafter, this step may be abbreviated as “step 3”.)

  The reaction mixture (I) comprises a branched polyether resin (X) having a hydroxyl group, an acryloyl group, and an epoxy group, an aromatic bifunctional diacrylate (A2), an aromatic bifunctional epoxy resin monoacrylate (A1), and an aromatic Since it contains one or more resin components selected from the group consisting of epoxy compounds (B), the carboxyl group in the unsaturated monocarboxylic acid actually reacts in the branched polyether resin (X). An epoxy group and an epoxy group in the monoacrylate (A1) of the aromatic bifunctional epoxy resin and an epoxy group in the aromatic epoxy compound (B).

  The branched polyether resin composition (II) obtained in the step 3 has a hydroxyl group and acryloyl group-containing unsaturated monocarboxylic acid ester structure which is a reaction product of the branched polyether resin (X) and the unsaturated monocarboxylic acid. Branched polyether resin (Y) and di (unsaturated monocarboxylic acid) ester of aromatic bifunctional epoxy resin which is a reaction product of monoacrylate (A1) of aromatic bifunctional epoxy resin and unsaturated monocarboxylic acid, aromatic A di (unsaturated monocarboxylic acid) ester of an aromatic bifunctional epoxy resin, which is a reaction product of an aromatic bifunctional epoxy resin (B) and an unsaturated monocarboxylic acid, and a diacrylate (A2) of an aromatic bifunctional epoxy resin It contains one or more aromatic difunctional epoxy resin di (unsaturated monocarboxylic acid) esters selected from the group. Here, when the unsaturated monocarboxylic acid is (meth) acrylic acid, it contains a branched polyether resin (Y1) having a hydroxyl group and a (meth) acryloyl group and a di (meth) acrylate of an aromatic bifunctional epoxy resin. It will be a thing.

  Examples of the unsaturated monocarboxylic acid used in the second step (the step 3) include compounds having one polymerizable unsaturated group and one carboxyl group, and specifically include acrylic acid, methacrylic acid, Crotonic acid, cinnamic acid, monomethylmalate, monoethylmalate, monopropylmalate, monobutylmalate, mono (2-ethylhexyl) malate, sorbic acid, etc. are usually used, but hydroxyethyl (meth) acrylate, hydroxy (Meth) acrylate compounds having a hydroxyl group such as propyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxycyclohexyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. And dicarboxylic anhydride It may be an unsaturated half-esterified product obtained by the reaction, a lactone-modified unsaturated monocarboxylic acid obtained by reacting a compound having a polymerizable unsaturated group and one carboxyl group with ε-caprolactone, a dimer of acrylic acid, or the like. . Among these, acrylic acid and / or methacrylic acid are preferable.

  In the second step (step 3), the reaction mixture (I) and the unsaturated monocarboxylic acid are mixed with an equivalent ratio of the epoxy group in the reaction mixture (I) and the carboxyl group in the unsaturated monocarboxylic acid. It is preferable that the reaction is performed within a range of (epoxy group / carboxyl group) of 0.9 / 1 to 1 / 0.9 because a branched polyether resin composition (II) having excellent temporal stability and curability is obtained. . Furthermore, in the said process 3, since branched polyether resin composition (II) excellent in active energy ray curability is obtained, as unsaturated monocarboxylic acid, acrylic acid and / or methacrylic acid are preferable.

  In the second step (step 3), the reaction temperature is usually 80 to 160 ° C., among which 100 to 140 ° C. is preferable because the stability during synthesis is good. Moreover, the reaction time of the process 3 is 1 to 20 hours normally, Preferably it is 2 to 15 hours. At this time, the above-described catalyst may be added as a reaction catalyst.

  Furthermore, it is preferable to use a mixture containing a methacryloyl group as the mixture in the first step because a branched polyether resin composition having excellent heat resistance can be produced.

  To obtain a reaction mixture (I ′) using a mixture containing a methacryloyl group, for example, an aromatic bifunctional epoxy resin di (meth) acrylate (A2 ′) and an aromatic bifunctional epoxy resin mono (meta) ) A mixture of acrylate (A1 ′) and / or aromatic bifunctional epoxy resin (B ′) and phosphorus catalyst (C) is used, but these (A2 ′) and (A1 ′) and / or (B ), The aromatic bifunctional epoxy resin (b), acrylic acid (a) and methacrylic acid (a ′), and the epoxy group in the aromatic bifunctional epoxy resin (b) is acrylic acid (a) and methacrylic acid. The reaction is carried out under an excess condition with respect to the total carboxyl groups in the acid (a ′), and the di (meth) acrylate (A2 ′) of the aromatic bifunctional epoxy resin and the aromatic bifunctional epoxy resin are mixed. When a reaction system containing (meth) acrylate (A1) and / or aromatic bifunctional epoxy resin (B) is used (hereinafter, this step may be abbreviated as “step 1 ′”), The subsequent reaction mixture (I ′) is preferably produced because it can be subsequently carried out. Here, the aromatic bifunctional epoxy resin (B ′) is an aromatic bifunctional epoxy resin other than the above (A2 ′) and (A1 ′). In addition, (meth) acrylate means a general term for acrylate and methacrylate.

  In this step 1 ′, since it can be easily carried out, the di (meth) acrylate (A2 ′) of the aromatic bifunctional epoxy resin and the mono (meth) acrylate (A1 ′) of the aromatic bifunctional epoxy resin are contained. Reaction system [however, it may contain an unreacted aromatic bifunctional epoxy resin (B ′). That is, a reaction system consisting of (A2 ′) and (A1 ′) or a reaction system consisting of (A2 ′), (A1 ′) and (B ′) is preferable.

In order to produce the reaction mixture (I ′) using the reaction system obtained in the step 1 ′, an aromatic bifunctional epoxy resin di (meth) acrylate (A2 ′) in the reaction system is further used.
Hydroxyl group and acryloyl group in aromatic difunctional epoxy resin di (meth) acrylate (A2 ′) and aromatic bifunctional epoxy resin mono (meth) acrylate (A1 ′) In the presence of a phosphorus catalyst (C) to increase the molecular weight of the diacrylate (A2) of the aromatic bifunctional epoxy resin, or the diacrylate (A2) of the aromatic bifunctional epoxy resin. And a branched polyether resin (X) having a hydroxyl group, an acryloyl group, and an epoxy group, and a di (meth) acrylate of an aromatic bifunctional epoxy resin, obtained by increasing the molecular weight of the monoacrylate (A1) of the aromatic bifunctional epoxy resin (A2 '), mono (meth) acrylate (A1') of aromatic bifunctional epoxy resin and aromatic bifunctional epoxy resin B ') and one or more unreacted resin components selected from the group may be a reaction mixture containing consisting (hereinafter, this step "process 2' may be abbreviated as".).

  A phosphorus catalyst (C) is present in the reaction system obtained in the step 1 ′, and the di (meth) acrylate (A2 ′) of the aromatic bifunctional epoxy resin and the mono (meth) of the aromatic bifunctional epoxy resin. In order to obtain a mixture containing the acrylate (A1 ′) and / or the aromatic bifunctional epoxy resin (B ′) and the phosphorus catalyst (C), for example, the following method can be given as a preferred example.

Method 3: Phosphorus catalyst (C) is added after completion of step 1 ′. Specifically, the aromatic bifunctional epoxy resin (b), acrylic acid (a), and methacrylic acid (a ′), and the epoxy group in the aromatic bifunctional epoxy resin (b) is acrylic acid (a) The reaction is carried out under an excess condition with respect to the total carboxyl groups in methacrylic acid (a ′),
(1-1) Di (meth) acrylate (A2 ′) of an aromatic bifunctional epoxy resin,
(1-2) (1-2-1) of aromatic bifunctional epoxy resin
Mono (meth) acrylate (A1 ')
And / or
(1-2-2) Other than (A1 ′) and (A2 ′)
Aromatic bifunctional epoxy resin (B ')
Is obtained by adding a phosphorus catalyst (C) to the reaction system.

  Method 4: Phosphorus catalyst (C) is added in the reaction of the step 1 ′. Specifically, the aromatic bifunctional epoxy resin (b), acrylic acid (a), and methacrylic acid (a ′), and the epoxy group in the aromatic bifunctional epoxy resin (b) is acrylic acid (a) It is obtained by reacting under an excess condition with respect to the total carboxyl groups in methacrylic acid (a ′).

  In the present invention, the method 4 is more preferable for obtaining the mixture used in the first step.

  The aromatic bifunctional epoxy resin (B ′) is an epoxy resin other than (A1 ′) and (A2 ′). In the step 1, the aromatic bifunctional epoxy resin (b), acrylic acid (a) and methacrylic acid (a ′) are mixed, and the epoxy group in the aromatic bifunctional epoxy resin (b) is acrylic acid (a) and Since the reaction is carried out under an excess condition with respect to the total carboxyl groups in methacrylic acid (a ′), the aromatic bifunctional epoxy resin remaining without reacting with acrylic acid (a) and methacrylic acid (a ′) ( b) exists. The remaining aromatic bifunctional epoxy resin (b) is a difunctional aromatic bifunctional epoxy resin that is a reaction product of the aromatic bifunctional epoxy resin (b) with acrylic acid (a) and methacrylic acid (a ′). Different from acrylate (A2 ′) and monoacrylate (A1 ′) of aromatic bifunctional epoxy resin. Therefore, the remaining aromatic bifunctional epoxy resin (b) becomes an aromatic bifunctional epoxy resin (B ′) other than (A1 ′) and (A2 ′).

  In the step 1 ′, the range in which the epoxy groups in the aromatic bifunctional epoxy resin (b) are excessive with respect to the total carboxyl groups in the acrylic acid (a) and methacrylic acid (a ′) is particularly limited. In particular, in step 2 ′, the hydroxyl and acryloyl groups in the di (meth) acrylate (A2 ′) of the aromatic bifunctional epoxy resin and the mono (meth) acrylate (A1 ′) of the aromatic bifunctional epoxy resin are not. Since the reaction proceeds smoothly, the equivalent ratio of the epoxy group in the aromatic bifunctional epoxy resin (b) and the total carboxyl group in acrylic acid (a) and methacrylic acid (a ′) [(epoxy group equivalent ) / (Carboxyl group equivalent)] is preferably in the range of 1.1 to 5.5. In addition, since the molecular weight of the obtained branched polyether resin can be easily adjusted, the equivalent ratio [(epoxy group equivalent) / (carboxyl group equivalent)] is 1.25 to 3.0. More preferably.

  By the way, as mentioned above, the mixture used in step 1 ′ contains di (meth) acrylate (A2 ′) of aromatic bifunctional epoxy resin and mono (meth) acrylate (A1 ′) of aromatic bifunctional epoxy resin. [However, it may contain an unreacted aromatic bifunctional epoxy resin (B ′). ] Is preferable. That is, a mixture composed of (A2 ′) and (A1 ′) or a mixture composed of (A2 ′), (A1 ′) and (B ′) is preferable. The following reaction mixture is obtained by performing step 2 using each of these mixtures.

When a mixture containing (A2 ′) and (A1 ′) is used as the mixture,
(1-A) having a hydroxyl group, an acryloyl group and an epoxy group
Of branched polyether resin (X) and (1-B) (1-B-1) aromatic bifunctional epoxy resin
Di (meth) acrylate (A2 ') and
(1-B-2) of aromatic bifunctional epoxy resin
Mono (meth) acrylate (A1 ')
A reaction mixture containing one or more resin components selected from the group consisting of:

When a mixture containing (A2 ′), (A1 ′) and (B ′) is used as the mixture,
(1-A) having a hydroxyl group, an acryloyl group and an epoxy group
Of branched polyether resin (X) and (1-B) (1-B-1) aromatic bifunctional epoxy resin
Di (meth) acrylate (A2 ′),
(1-B-2) of aromatic bifunctional epoxy resin
Mono (meth) acrylate (A1 ′) and
(1-B-3) Other than (A1 ′) and (A2 ′)
Aromatic bifunctional epoxy resin (B ')
A reaction mixture containing one or more resin components selected from the group consisting of:

  When reacting the hydroxyl group and acryloyl group in the aromatic bifunctional epoxy resin di (meth) acrylate (A2 ′) and the mono (meth) acrylate (A1 ′) of the aromatic bifunctional epoxy resin in the mixture. The methacryloyl group does not react with the hydroxyl group. Therefore, the obtained branched polyether resin (X) is obtained by the same reaction mechanism as the system not containing a methacryloyl group.

  Next, for the purpose of imparting the performance of photopatterning, the branched polyether resin composition (II) obtained by the production method of the present invention and the polycarboxylic acid anhydride are mixed, and the branched polyether resin composition (II) is mixed. The hydroxyl groups contained [the hydroxyl groups in the branched polyether resin (Y) and the hydroxyl groups in the di (unsaturated monocarboxylic acid) ester of the aromatic bifunctional epoxy resin] and the hydroxyl groups in the monocarboxylic anhydride. By reacting, an acid pendant type branched polyether resin composition (III) containing an acid pendant type branched polyether resin (Z) and an acid pendant type aromatic bifunctional epoxy resin di (unsaturated monocarboxylic acid) ester is obtained. (Hereinafter, this step may be abbreviated as “Step 4”.)

  Examples of the polycarboxylic acid anhydride include maleic anhydride, phthalic anhydride, succinic anhydride, dodecenyl succinic anhydride, tetrahydrophthalic anhydride, 4-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride. , Hexahydrophthalic anhydride, trimellitic anhydride, methyl nadic anhydride, itaconic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, etc. Among them, acid pendant branched polyether resins with excellent developability Since a composition (III) is obtained, a dicarboxylic acid anhydride is preferable, and an aliphatic polycarboxylic acid anhydride (including a cyclic aliphatic polycarboxylic acid anhydride) is more preferable.

  Examples of the aliphatic polycarboxylic acid anhydride include maleic anhydride, succinic anhydride, dodecenyl succinic anhydride, tetrahydrophthalic anhydride, 4-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, anhydrous Examples include hexahydrophthalic acid and itaconic anhydride.

  The reaction ratio between the branched polyether resin composition (II) obtained by the production method of the present invention and the polycarboxylic acid anhydride is 0.1 to 1 mol with respect to 1 mol of the epoxy group in the branched polyether resin composition. It is preferable to make it react so that.

  The reaction of the hydroxyl group in the branched polyether resin composition (II) in the step 4 and the hydroxyl group-free in the polycarboxylic acid anhydride is carried out by an esterification reaction by ring opening of the hydroxyl group to produce one hydroxyl group and one hydroxyl group. Hydroxyl groups are reacted, and the reaction temperature is usually 50 to 160 ° C., among which 80 to 120 ° C. is preferable because the stability during synthesis is good. Moreover, the reaction time of the process 4 is 1 to 20 hours normally, Preferably it is 2 to 10 hours.

  The acid pendant branched polyether resin composition (III) thus obtained can be dissolved in a dilute alkaline aqueous solution because a carboxyl group is introduced into the resin component. Therefore, when an active energy ray such as ultraviolet rays is irradiated using a mask having a desired pattern, a portion irradiated with ultraviolet rays undergoes a curing reaction and becomes insoluble in a dilute alkaline aqueous solution (cannot be developed). On the contrary, the part which is not irradiated with ultraviolet rays by the mask dissolves in a dilute alkaline aqueous solution (can be developed). That is, by using the acid pendant branched polyether resin composition (III) obtained by the production method of the present invention, a negative pattern in which a desired pattern is inverted can be obtained.

  In obtaining the acid pendant branched polyether resin composition (III) in the step 4, since it has excellent developability, the branched polyether resin composition until the resin solid acid value becomes 30 to 140 (mgKOH / g). It is preferable to react the hydroxyl group in (II) with the polycarboxylic acid anhydride, and it is more preferable to react until it becomes 50-120 (mgKOH / g).

  In addition, the reactions in Steps 1 to 4 can be performed in the absence of a solvent, in the presence of an organic solvent and / or in the presence of a reactive diluent. The resin component comprising (X) and one or more unreacted resin components selected from the group consisting of (A2), (A1) and (B), (X) and (A2 ′ ), (A1 ′) and (B ′) are selected from the group consisting of one or more unreacted resin components, the amount of the organic solvent and the reactive diluent with respect to the resin component is increased. Since the reaction rate becomes slow, the ratio of the resin component during synthesis is preferably 50% by weight or more, and more preferably 70% by weight or more.

  Various solvents and reactive diluents can be used. Specific examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; cellosolve Cellosolves such as butyl cellosolve; carbitols such as carbitol and butyl carbitol; ether solvents such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, and butyl carbitol acetate; Examples include acetates. As reactive diluents, various acrylate and methacrylate monomers, oligomers, vinyl monomers, and the like can be used.

  The molecular weight of the branched polyether resin (X) obtained by the step 1 and the step 2 is such that the epoxy group in the aromatic bifunctional epoxy resin (b) and the carboxyl group in the acrylic acid (a) and methacrylic acid (a ′). The equivalent ratio [(epoxy group equivalent) / (carboxyl group equivalent)], catalyst type, catalyst amount, reaction temperature, reaction time, etc. The reaction temperature in Step 2 is usually 100 ° C. or higher because a sufficient reaction rate can be obtained, but 170 ° C. or lower is preferable because rapid polymerization hardly occurs and the control of the reaction is good, and particularly 100 to 150 ° C. It is preferable that it exists in the range.

  In addition, the reaction times of the step 1, step 1 ′, step 2 and step 2 ′ are affected by temperature. Within the above temperature range, Step 1 and Step 1 ′ are each 0.5 to 10 hours, preferably 1 to 5 hours. Step 2 and step 2 ′ are each 1 to 20 hours, preferably 2 to 15 hours.

  In order to adjust the molecular weight of the reaction mixture (I) used in the production method of the present invention and the branched polyether resin (X) contained therein, for example, the diacrylate (A2) of an aromatic bifunctional epoxy resin is used. Molar ratio of monoacrylate (A1) of aromatic bifunctional epoxy resin [excess ratio of epoxy group in aromatic bifunctional epoxy resin (b) to carboxyl group in acrylic acid (a) in step 1], phosphorus catalyst What is necessary is just to adjust the usage-amount of (C), reaction temperature, reaction time, etc. suitably. For example, the molar ratio (A1 / A2) of the monoacrylate (A1) of the aromatic bifunctional epoxy resin to the diacrylate (A2) of the aromatic bifunctional epoxy resin is reduced (for example, the molar ratio is set to 0 to 1). [In the step 1, the molar ratio (B / a) excess ratio of the epoxy group in the aromatic bifunctional epoxy resin (b) to the carboxyl group in the acrylic acid (a) is reduced (for example, b / a = 1. 25-3), increasing the amount of the phosphorus catalyst (C) used, increasing the reaction temperature, increasing the reaction time, increasing the concentration of the resin component in the reaction system, etc. Thus, a branched polyether resin having a higher molecular weight can be obtained.

  Moreover, in order to adjust the introduction amount of the acryloyl group and the epoxy group which the branched polyether resin (X) in the reaction mixture (I) has, for example, the excess of the epoxy group with respect to the carboxyl group which the acrylic acid in the reaction system has The ratio of the epoxy equivalent of the diacrylate (A2) of the aromatic bifunctional epoxy resin and the monoacrylate (A1) of the aromatic bifunctional epoxy resin may be appropriately adjusted. For example, by using diacrylate or monoacrylate of aromatic bifunctional epoxy resin having a small epoxy equivalent as diacrylate (A2) of aromatic bifunctional epoxy resin and monoacrylate (A1) of aromatic bifunctional epoxy resin A branched polyether resin having a high introduction amount (content ratio) of acryloyl group and epoxy group can be obtained, and acryloyl in the polyether resin can be adjusted by adjusting the excess ratio of the epoxy group to the carboxyl group in the reaction system. The amount of introduction of groups and epoxy groups can be adjusted.

  In the production method of the present invention, the reaction mixture (I) and the branched polyether resin (X) contained therein are synthesized so as to have a molecular weight sufficient to satisfy the performance required in terms of various applications. However, in order to satisfy various application suitability, the resin component in the reaction mixture (I) [branched polyether resin (X), aromatic difunctional diacrylate (A2), aromatic difunctional epoxy] A composition comprising one or more unreacted resin components selected from the group consisting of a resin monoacrylate (A1) and an aromatic epoxy compound (B). The same applies below. ] The aromatic bifunctional diacrylate (A2) and the monoacrylate (A1) of the aromatic bifunctional epoxy resin so that the average molecular weight in terms of polystyrene is within the range of 800 to 10,000 in terms of polystyrene-reduced number average molecular weight (Mn) It is preferable to react the hydroxyl group in the acryloyl group, and it is more preferable to react so that it may become in the range of 800-5,000. Moreover, the monofunctional aromatic difunctional diacrylate (A2) and the aromatic bifunctional epoxy resin so that the average molecular weight of the resin component is in the range of 1,000 to 50,000 in terms of polystyrene equivalent weight average molecular weight (Mw). It is preferable to react the hydroxyl group and acryloyl group in the acrylate (A1), and it is more preferable that the weight average molecular weight (Mw) is in the range of 2,000 to 30,000.

  In addition, the aromatic bifunctional diacrylate (A2) and the aromatic difunctional diacrylate (A2) so that the molecular weight of the branched polyether resin (X) is in the range of 1,500 to 10,000 in terms of polystyrene-equivalent number average molecular weight (Mn). It is preferable to react the hydroxyl group and the acryloyl group in the monoacrylate (A1) of the functional epoxy resin, and it is more preferable to cause the reaction to be within the range of 1,500 to 8,000. Aromatic bifunctional diacrylate (A2) and aromatic bifunctional epoxy so that the molecular weight of the branched polyether resin (X) is within the range of 3,000 to 100,000 in terms of polystyrene-equivalent weight average molecular weight (Mw). It is preferable to react the hydroxyl group and acryloyl group in the monoacrylate (A1) of the resin, and it is more preferable to cause the reaction to be within the range of 3,000 to 50,000.

  In the production method of the present invention, the epoxy equivalent of the resin component in the reaction mixture (I) is 250 to 10,000 g / equivalent because it becomes a branched polyether resin composition (II) having excellent curability and mechanical properties of the cured product. It is preferable to variously adjust the raw material charging ratio, the amount of catalyst, the reaction conditions, and the like so that the epoxy equivalent is 400 to 5,000 g / equivalent. Moreover, since it becomes branched polyether resin composition (II) excellent in sclerosis | hardenability and the mechanical property of hardened | cured material, it is raw material so that the epoxy equivalent of branched polyether resin (X) may be 500-10,000 g / equivalent. It is preferable to variously adjust the charging ratio, the amount of catalyst, the reaction conditions, and the like, and it is more preferable to adjust variously so that the epoxy equivalent is 800 to 8,000 g / equivalent.

  The average molecular weight of the branched polyether resin composition (II) and the acid pendant type branched polyether resin composition (III) obtained by the production method of the present invention is 1,000 in terms of polystyrene-equivalent number average molecular weight (Mn). It is preferably within the range of ˜12,000, and more preferably within the range of 1,000 to 7,000. The average molecular weight of the branched polyether resin composition (II) or the acid pendant type branched polyether resin composition (III) obtained by the production method of the present invention is 2,000-60 in terms of polystyrene-equivalent weight average molecular weight (Mw). , Preferably in the range of 3,000, more preferably in the range of 3,000 to 40,000.

The molecular weight of the branched polyether resin (Y) or the acid pendant branched polyether resin (Z) is preferably in the range of 2,000 to 15,000 in terms of polystyrene-equivalent number average molecular weight (Mn). More preferably, it is in the range of 2,500 to 10,000. The molecular weight of the branched polyether resin (Y) and the acid pendant branched polyether resin (Z) is preferably in the range of 4,000 to 100,000 in terms of polystyrene-equivalent weight average molecular weight (Mw). More preferably, it is in the range of 000 to 70,000.

  The epoxy group in the branched polyether resin composition (II) and the epoxy group in the branched polyether resin (Y) are unsaturated monocarboxylic acids because the stability of the branched polyether resin composition (II) is improved. It is preferable that all is consumed by the reaction with, but a partially unreacted epoxy group may remain. The epoxy equivalent of the branched polyether resin composition (II) when the epoxy group remains is preferably 10,000 g / equivalent or more because the stability of the branched polyether resin composition is good. More preferably, it is 15,000 g / equivalent or more. In addition, the branched polyether resin (Y) in the branched polyether resin composition (II) is also preferably epoxy equivalent to 10,000 g / equivalent or more because the stability of the branched polyether resin composition is good, Further, it is more preferably 15,000 g / equivalent or more.

  Furthermore, the reaction mixture (I) used in the present invention preferably has an acryloyl group content of 0.2 to 4.0 mmol per gram of resin component, and more preferably 0.3 to 3.5 mmol. In the reaction mixture (I) used in the present invention, the hydroxyl group content per 1 g of the resin component is preferably 0.2 to 4.0 mmol, and more preferably 0.3 to 3.5 mmol. Further, the branched polyether resin (X) preferably has an acryloyl group content per 1 g of resin of 0.2 to 3.5 mmol, and more preferably 0.3 to 3.3 mmol. The branched polyether resin (X) preferably has a hydroxyl group content of 0.2 to 3.5 mmol, more preferably 0.3 to 3.3 mmol, per gram of resin.

  The branched polyether resin composition (II) obtained in the present invention has an excellent curability and a cured product having a good balance between heat resistance and flexibility. Therefore, the unsaturated group content per gram of resin component is 1. It is preferably 0.0 to 4.2 mmol, and more preferably 1.5 to 4.0 mmol. Since the branched polyether resin composition (II) obtained in the present invention is excellent in curability and has a good balance between heat resistance and flexibility, the hydroxyl group content per 1 g of resin component is 1. It is preferably 0 to 4.2 mmol, and more preferably 1.5 to 4.0 mmol.

  In addition, the branched polyether resin (Y) is excellent in curability, and a cured product having a good balance between heat resistance and flexibility is obtained, so that the unsaturated group content per 1 g of the resin is 0.5 to 3.5. It is preferably a millimolar, more preferably 1.0 to 3.3 millimolar. The branched polyether resin (Y) is excellent in curability and has a good balance between heat resistance and flexibility, so that the hydroxyl group content per 1 g of the resin is 0.5 to 3.5 mmol. Is more preferable, and 1.0 to 3.3 mmol is more preferable.

  The acid pendant-type branched polyether resin composition (III) obtained in the present invention contains an unsaturated group per gram of resin component because a cured product having excellent curability and a good balance between heat resistance and flexibility can be obtained. The amount is preferably 0.8 to 3.8 mmol, and more preferably 1.0 to 3.5 mmol. The acid pendant branched polyether resin composition (III) obtained in the present invention is excellent in curability and has a good balance between heat resistance and flexibility, so that the hydroxyl group content per gram of resin component is 3 0.5 mmol or less (may be 0) is preferable, and 3.0 mmol or less (may be 0) is more preferable.

  In addition, the acid pendant branched polyether resin (Z) is excellent in curability and provides a cured product having a good balance between heat resistance and flexibility, so that the unsaturated group content per 1 g of the resin is 0.4 to It is preferably 3.2 mmol, and more preferably 0.8 to 2.8 mmol. The acid pendant branched polyether resin (Z) has a curability and a cured product having a good balance between heat resistance and flexibility, so that the hydroxyl group content per 1 g of resin is 2.8 mmol or less (at 0). May be present), and 2.3 mmol or less (may be 0) is particularly desirable.

  Further, the acid pendant branched polyether resin composition (III) preferably has a resin solid content acid value of 30 to 140 (mgKOH / g) because of its excellent developability, and in particular, 50 to 120 (mgKOH / g). More preferably, g). The acid pendant branched polyether resin (Z) preferably has a resin solid content acid value of 50 to 120 (mgKOH / g), particularly 60 to 110 (mgKOH / g) because of its excellent developability. It is more preferable that

  The reaction mixture (I) used in the present invention contains the branched polyether resin (X) as an essential component, and 20% of the branched polyether resin (X) is contained in 100% by weight of the total resin components contained. Those containing ˜90% by weight are preferred. In addition to the branched polyether resin (X), the resin composition (I) includes an aromatic bifunctional epoxy resin diacrylate (A2), an aromatic bifunctional epoxy resin monoacrylate (A1), and an aromatic epoxy. 1 or more types of unreacted resin components chosen from the group which consists of a compound (B) are contained. These one or more unreacted resin components are preferably contained in a total of 10 to 80% by weight in a total of 100% by weight of the resin components in the resin composition (I). 5 to 50% by weight of acrylate (A2) and 5 to 30% by weight of monomethacrylate (A1) of aromatic bifunctional epoxy resin [however, diacrylate (A2) of aromatic bifunctional epoxy resin and aromatic bifunctional A total of 10 to 80% by weight of the epoxy resin monomethacrylate (A1)] and 0 to 30% by weight of the aromatic bifunctional epoxy resin (B) are preferable. In addition, when making this resin composition (I) contain an aromatic bifunctional epoxy resin (B) as an unreacted resin component, the content rate of an aromatic bifunctional epoxy resin (B) is 5 to 30 weight% Is more preferable.

  The branched polyether resin composition (II) obtained in the present invention contains the branched polyether resin (Y) as an essential component, and is excellent in the touch drying property during film formation and the flexibility of the cured coating film. Therefore, it is preferable to contain 30 to 95% by weight of the branched polyether resin (Y) in the total 100% by weight of the resin components contained, and among them, the one containing 50 to 90% by weight. More preferred. This branched polyether resin composition (II) includes, as main resin components other than the branched polyether resin (Y), diacrylate (A2) of an aromatic bifunctional epoxy resin, monoacrylate (A1) of an aromatic bifunctional epoxy resin. And an aromatic bifunctional epoxy resin (B) obtained by reacting an epoxy group in one or more resin components selected from the group consisting of an aromatic bifunctional epoxy resin (B) and a carboxyl group in an unsaturated monocarboxylic acid. Contains di (unsaturated monocarboxylic acid) esters. The di (unsaturated monocarboxylic acid) ester of the aromatic bifunctional epoxy resin preferably contains 5 to 70% by weight in 100% by weight of the total resin components in the branched polyether resin composition (II), Among these, those containing 10 to 50% by weight are more preferable.

  The acid pendant type branched polyether resin composition (III) obtained in the present invention has a carboxylic acid pendant by reacting a hydroxyl group in the branched polyether resin (Y) with a hydroxyl group in a polycarboxylic acid anhydride. The acid pendant type branched polyether resin (Z) is contained as an essential component, and is contained because it is excellent in touch drying at the time of film formation, curability, and flexibility of the cured coating film. What contains 30-95 weight% of branched polyether resin (Z) in the total 100 weight% of a resin component is preferable, and what contains 50-90 weight% is especially preferable. The acid pendant branched polyether resin composition (II) is used as a main resin component other than the acid pendant branched polyether resin (Z) in the di (unsaturated monocarboxylic acid) ester of the aromatic bifunctional epoxy resin. It contains an acid pendant type aromatic bifunctional epoxy resin di (unsaturated monocarboxylic acid) ester in which a carboxylic acid is pendant by reacting a hydroxyl group of this group with a hydroxyl group in a polycarboxylic acid anhydride. The acid pendant type aromatic bifunctional epoxy resin di (unsaturated polycarboxylic acid anhydride) ester is 5 to 70% by weight in a total of 100% by weight of the resin components in the acid pendant type branched polyether resin composition (III). % Containing is preferable, and what contains 10 to 50% by weight is more preferable.

  Examples of the acid pendant branched polyether resin (Z) in the acid pendant branched polyether resin composition (III) obtained through the steps 1 to 4 include an unsaturated group such as an acryloyl group, a carboxyl group, and the following: Examples thereof include an acid pendant branched polyether resin (Z1) having a structure represented by the general formula (3) and a structure represented by the following general formula (4) and having a weight average molecular weight of 4,000 to 100,000.

〔一般式（１）中、Ｒは下記構造式（１）または（２）で表される連結基を示す。〕

[In general formula (1), R represents a linking group represented by the following structural formula (1) or (2). ]

〔一般式（４）中、Ｒ_１は２価の芳香族二官能エポキシ樹脂（Ｂ）から２個のグリシジルエーテル基を除いた構造の芳香族連結基を示す。〕

[In General Formula (4), R ₁ represents an aromatic linking group having a structure in which two glycidyl ether groups are removed from the divalent aromatic bifunctional epoxy resin (B). ]

  The acid pendant branched polyether resin (Z1) has a number average molecular weight of 2,000 to 15 because it has excellent dryness to touch during film formation, curability and flexibility of the cured coating film. The weight average molecular weight is preferably 4,000 to 100,000, the acid value is preferably 50 to 120 (KOH-mg / g), the number average molecular weight is 2,500 to 10,000, and the weight average molecular weight. Is more preferably 5,000 to 70,000, and the acid value is more preferably 60 to 110 (KOH-mg / g).

  The acid pendant branched polyether resin (Z1) has an unsaturated group content of 0.4 to 3.2 millimoles per gram of resin and a hydroxyl group content per gram of resin because of its excellent curability. Are preferably 2.8 mmol or less (may be 0), the unsaturated group content is 0.8 to 2.8 mmol, and the hydroxyl group content is 2.3 mmol or less (0). It is also preferable that each of them is.

  Further, the acid pendant branched polyether resin (Z1) is preferably an acid pendant branched polyether resin (Z2) represented by the following general formula (5).

〔一般式（５）中、ｎは２〜１００の繰り返し単位数を表し、このｎ個の繰り返し単位中のＲはそれぞれ独立に前記構造式（１）または（２）で表される連結基を示す。また、前記ｎ個の繰り返し単位中および繰り返し単位外におけるＡrはそれぞれ独立に下記一般式（６）または（７）で表される構造を示す。〕

[In General Formula (5), n represents the number of repeating units of 2 to 100, and R in the n repeating units independently represents a linking group represented by Structural Formula (1) or (2). Show. Further, Ar in the n repeating units and outside the repeating units each independently represents a structure represented by the following general formula (6) or (7). ]

〔一般式（６）、（７）中、Ｒ_１は芳香族二官能エポキシ樹脂（Ｂ）から２個のグリシジルエーテル基を除いた構造の芳香族連結基を示し、ｐ、ｑはそれぞれ独立に０〜２０の繰り返し単位を示す。Ｒ_２は、不飽和モノカルボン酸からカルボキシル基を除いた残基構造を示し、不飽和モノカルボン酸がアクリル酸の場合は一般式（６）は一般式（７）と同一の構造となる。また、Ｒ_３はそれぞれ独立に水素原子、下記一般式（８）で表される構造またはジカルボン酸無水物と水酸基のハーフエステル化により得られる構造、例えば下記一般式（９）で示される構造を示す。〕

[In the general formulas (6) and (7), R ₁ represents an aromatic linking group having a structure obtained by removing two glycidyl ether groups from the aromatic bifunctional epoxy resin (B), and p and q are each independently 0 to 20 repeating units are shown. R ₂ represents a residue structure obtained by removing a carboxyl group from an unsaturated monocarboxylic acid. When the unsaturated monocarboxylic acid is acrylic acid, the general formula (6) has the same structure as the general formula (7). R ₃ each independently represents a hydrogen atom, a structure represented by the following general formula (8), or a structure obtained by half esterification of a dicarboxylic acid anhydride and a hydroxyl group, for example, a structure represented by the following general formula (9). Show. ]

〔一般式（８）中、ｒは１〜５０の繰り返し単位を示し、このｒ個の繰り返し単位中のＲはそれぞれ独立に前記構造式（１）または（２）で表される連結基を示す。また、前記ｒ個の繰り返し単位中のＡrはそれぞれ独立に前記一般式（６）または（７）で表される構造を示すが、この一般式（６）または（７）中のＲ_３として前記一般式（８）で表される構造がさらに連結して分岐を繰り返している構造であってもよい。〕

[In the general formula (8), r represents 1 to 50 repeating units, and R in the r repeating units each independently represents a linking group represented by the structural formula (1) or (2). . Further, Ar in the r repeating units each independently represents a structure represented by the general formula (6) or (7), and R ₃ in the general formula (6) or (7) A structure in which the structure represented by the general formula (8) is further connected to repeat branching may be used. ]

〔一般式（９）中、Ｒ_４は炭素数２〜１２のカルボキシル基を有しても良い飽和または不飽和の炭化水素を示す。〕

[In General Formula (9), R ₄ represents a saturated or unsaturated hydrocarbon which may have a C 2-12 carboxyl group. ]

In addition, as R ₁ in the general formulas (4), (6) and (7) [aromatic linking group having a structure obtained by removing two glycidyl ether groups from the aromatic bifunctional epoxy resin (B)], A naphthylene group or an aromatic linking group having a structure represented by the following general formula (10) is preferable.

〔一般式（１０）中、Ｒ_５は単結合又は２価の連結基を表し、Ｒ_６は水素原子または炭素数１〜５のアルキル基を表す。〕

[In General Formula (10), R ₅ represents a single bond or a divalent linking group, and R ₆ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ]

  The branched polyether resin (Y) in the branched polyether resin composition (II) used in the production of the acid pendant branched polyether resin composition (III) is, for example, an unsaturated group such as an acryloyl group. Examples thereof include a branched polyether resin (Y1) having a weight average molecular weight of 4,000 to 100,000 having a group, a hydroxyl group, a structure represented by the general formula (3), and a structure represented by the general formula (4).

  As the branched polyether resin (Y1), the number average molecular weight is 2,000 to 15,000, and the weight average molecular weight is 4 because it is excellent in touch drying at the time of film formation and flexibility of the cured coating film. It is preferable that the epoxy equivalent is 10,000 g / equivalent or more, the number average molecular weight is 2,500 to 10,000, the weight average molecular weight is 5,000 to 70,000, and the epoxy equivalent is More preferably, it is 15,000 g / equivalent or more.

  Moreover, as said branched polyether resin (Y1), since the hardened | cured material excellent in sclerosis | hardenability and favorable balance of heat resistance and a softness | flexibility is obtained especially, unsaturated group content per 1g of resin is 0.5. It is preferable that the hydroxyl group content per 1 g of resin is 0.5 to 3.5 mmol, the unsaturated group content is 1.0 to 3.3 mmol, and the hydroxyl group content is It is more preferable that it is 1.0-3.3 mmol, respectively.

  Further, the branched polyether resin (Y1) is preferably a branched polyether resin (Y2) represented by the following general formula (11).

〔一般式（１１）中、ｎは２〜１００の繰り返し単位数を表し、このｎ個の繰り返し単位中のＲはそれぞれ独立に前記構造式（１）または（２）で表される連結基を示す。また、前記ｎ個の繰り返し単位中および繰り返し単位外におけるＡrはそれぞれ独立に下記一般式（１２）または（１３）で表される構造を示す。〕

[In General Formula (11), n represents the number of repeating units of 2 to 100, and R in the n repeating units independently represents a linking group represented by Structural Formula (1) or (2). Show. In addition, Ar in the n repeating units and outside the repeating unit each independently represents a structure represented by the following general formula (12) or (13). ]

〔一般式（１２）、（１３）中、Ｒ_１は芳香族二官能エポキシ樹脂（Ｂ）から２個のグリシジルエーテル基を除いた構造の芳香族連結基を示し、ｐ、ｑはそれぞれ独立に０〜２０の繰り返し単位を示す。Ｒ_２は、不飽和モノカルボン酸からカルボキシル基を除いた残基構造を示し、不飽和モノカルボン酸がアクリル酸の場合は一般式（１２）は一般式（１３）と同一の構造となる。また、Ｒ_３は水素原子または下記一般式（１４）で表される構造を示す。〕

[In the general formulas (12) and (13), R ₁ represents an aromatic linking group having a structure obtained by removing two glycidyl ether groups from the aromatic bifunctional epoxy resin (B), and p and q are each independently 0 to 20 repeating units are shown. R ₂ represents a residue structure obtained by removing a carboxyl group from an unsaturated monocarboxylic acid. When the unsaturated monocarboxylic acid is acrylic acid, the general formula (12) has the same structure as the general formula (13). R ₃ represents a hydrogen atom or a structure represented by the following general formula (14). ]

〔一般式（１４）中、ｒは１〜５０の繰り返し単位を示し、このｒ個の繰り返し単位中のＲはそれぞれ独立に前記構造式（１）または（２）で表される連結基を示す。また、前記ｒ個の繰り返し単位中のＡrはそれぞれ独立に前記一般式（１２）または（１３）で表される構造を示すが、この一般式（１２）または（１３）中のＲ_３として前記一般式（１４）で表される構造がさらに連結して分岐を繰り返している構造であってもよい。〕

[In general formula (14), r represents 1 to 50 repeating units, and R in the r repeating units independently represents a linking group represented by the structural formula (1) or (2). . Further, Ar in the r repeating units each independently represents a structure represented by the general formula (12) or (13), and R ₃ in the general formula (12) or (13) A structure in which the structure represented by the general formula (14) is further connected to repeat branching may be used. ]

In the case of the branched polyether resin (Y2), R ₁ in the general formulas (4), (12) and (13) [two glycidyl ether groups from the aromatic bifunctional epoxy resin (B) The aromatic linking group having a structure excluded is preferably a naphthylene group or an aromatic linking group having a structure represented by the general formula (10).

  Examples of the branched polyether resin (X) in the resin composition (I) used in the production of the branched polyether resin composition (II) include a hydroxyl group, an acryloyl group, an epoxy group, and the general formula ( Examples thereof include branched polyether resins (X1) having a structure represented by 3) and a structure represented by the general formula (4) and having a weight average molecular weight of 3,000 to 1,000,000.

  As the branched polyether resin (X1), the number average molecular weight is 1,500 to 10,000, and the weight average molecular weight is 3 because it is excellent in touch drying at the time of film formation and flexibility of the cured coating film. It is preferable that the epoxy equivalent is 500 to 10,000 g / equivalent, respectively, the number average molecular weight is 1,500 to 8,000, the weight average molecular weight is 3,000 to 50,000, and the epoxy equivalent Are more preferably 800 to 8,000 g / equivalent.

  Moreover, as said branched polyether resin (X1), since it is excellent in the touch-drying property at the time of film forming and the softness | flexibility of a cured coating film, unsaturated group content per 1g of resin is 0.2-3. It is preferable that the hydroxyl group content per 5 g of resin is 5 to 3.5 mmol, the unsaturated group content is 0.3 to 3.3 mmol, and the hydroxyl group content is 0.3. More preferably, it is -3.3 mmol.

  Further, the branched polyether resin (X1) is preferably a branched polyether resin (X2) represented by the following general formula (15).

〔一般式（１５）中、ｎは２〜１００の繰り返し単位数を表し、このｎ個の繰り返し単位中のＲはそれぞれ独立に前記構造式（１）または（２）で表される連結基を示す。また、前記ｎ個の繰り返し単位中および繰り返し単位外におけるＡrはそれぞれ独立に下記一般式（１６）または（１７）で表される構造を示す。〕

[In General Formula (15), n represents the number of repeating units of 2 to 100, and R in the n repeating units independently represents a linking group represented by Structural Formula (1) or (2). Show. Further, Ar in the n repeating units and outside the repeating units each independently represents a structure represented by the following general formula (16) or (17). ]

〔一般式（１６）、（１７）中、Ｒ_１は芳香族二官能エポキシ樹脂（Ｂ）から２個のグリシジルエーテル基を除いた構造の芳香族連結基を示し、ｐ、ｑはそれぞれ独立に０〜２０の繰り返し単位を示す。また、Ｒ_３は水素原子または下記一般式（１８）で表される構造を示す。〕

[In the general formulas (16) and (17), R ₁ represents an aromatic linking group having a structure obtained by removing two glycidyl ether groups from the aromatic bifunctional epoxy resin (B), and p and q are each independently 0 to 20 repeating units are shown. R ₃ represents a hydrogen atom or a structure represented by the following general formula (18). ]

〔一般式（１８）中、ｒは１〜５０の繰り返し単位を示し、このｒ個の繰り返し単位中のＲはそれぞれ独立に前記構造式（１）または（２）で表される連結基を示す。また、前記ｒ個の繰り返し単位中のＡrはそれぞれ独立に前記一般式（１６）または（１７）で表される構造を示すが、この一般式（１６）または（１７）中のＲ_３として前記一般式（１８）で表される構造がさらに連結して分岐を繰り返している構造であってもよい。〕

[In the general formula (18), r represents 1 to 50 repeating units, and R in the r repeating units each independently represents a linking group represented by the structural formula (1) or (2). . Further, Ar in the r repeating units each independently represents a structure represented by the general formula (16) or (17), and R ₃ in the general formula (16) or (17) A structure in which the structure represented by the general formula (18) is further connected to repeat branching may be used. ]

In the case of the branched polyether resin (X2), R ₁ in the general formulas (4), (16) and (17) [two glycidyl ether groups from the aromatic bifunctional epoxy resin (B) The aromatic linking group having a structure excluded is preferably a naphthylene group or an aromatic linking group having a structure represented by the general formula (10).

  In the branched polyether resin composition (II) obtained by the production method of the present invention, if necessary, the reaction of an epoxy compound other than the aromatic bifunctional epoxy resin (B) with an unsaturated monocarboxylic acid In this case, the content of the branched polyether resin (Y) in 100% by weight of the total resin component is 20 to 90% by weight. It is preferable because of the excellent flexibility of the cured coating film. In addition, it is also possible to add another epoxy compound (b) to the branched polyether resin composition (II).

  In addition, the acid pendant branched polyether resin composition (III) obtained by the production method of the present invention further includes the other epoxy compound or the reaction of the other epoxy compound with an unsaturated monocarboxylic acid as necessary. In this case, the content of the acid pendant branched polyether resin (Z) in 100% by weight of the total resin component is 20 to 90% by weight. It is preferable because of its excellent properties and flexibility of the cured coating film.

  The epoxy compound other than the aromatic bifunctional epoxy resin (B) is not particularly limited, and any of a mono-epoxy compound and a polyfunctional epoxy resin can be used. Specific examples of the other epoxy compounds include monoepoxy compounds such as phenyl glycidyl ether and alkylphenyl glycidyl ether; biphenol type epoxy resins; bisphenol type epoxy resins such as bisphenol A, bisphenol F and bisphenol S; and various bisphenols. Various novolak epoxy resins such as novolak type epoxy resin, cresol novolak type epoxy resin, phenol novolak type, xylenol novolak; dicyclopentadiene-modified aromatic epoxy resin; dihydroxynaphthalene type epoxy resin obtained by epoxidizing dihydroxynaphthalenes Epoxy resin obtained by epoxidizing a novolak body of naphthalene; glycidyl ester type resin of polyvalent carboxylic acid; Examples include epoxy resins derived from xylenol, phenol aralkyl epoxy resins, naphthalene aralkyl epoxy resins, other zylock type epoxy resins; hydrogenated products of the above aromatic epoxy compounds; epoxy resins such as aliphatic, alicyclic, and ether skeletons. be able to.

  Examples of the unsaturated monocarboxylic acid used for the reaction with the other epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, monomethyl malate, monoethyl malate, monopropyl malate, and monobutyl malate. . Mono (2-ethylhexyl) malate, sorbic acid and the like can be mentioned.

  Both the branched polyether resin composition (II) and the acid pendant branched polyether resin composition (III) obtained by the production method of the present invention may be used as they are as resins for heat curing and / or photocuring. Often, urethanization and other chemical modifications can be applied.

  When the branched polyether resin composition (II) and the acid pendant type branched polyether resin composition (III) are used as a resin for heat curing and / or photocuring, they may further contain a curing agent.

  The curing agent is not particularly limited. For example, when photocuring the branched polyether resin composition (II) or the acid pendant type branched polyether resin composition (III), a photoinitiator or a photosensitizer. Can be contained. Moreover, when making these heat-harden, radical generators, such as a peroxide, can be added. Furthermore, an epoxy resin can be added as a thermosetting component, and the epoxy resin curing agent can be used in combination for thermosetting. In particular, when the acid pendant type branched polyether resin composition (III) is used as a photo patterning material, development is performed with a dilute alkaline aqueous solution after photocuring with a combination of epoxy resin and / or epoxy resin and epoxy resin curing agent. After the pattern is formed, a cured product having excellent heat resistance and durability can be obtained by thermosetting. It is also possible to perform urethane curing by adding a curing agent containing an isocyanate group.

  As the epoxy resin curing agent, any of various epoxy resin curing agents can be used. For example, aliphatic polyamines such as triethylenetetramine; alicyclic rings such as bis (3-methyl-4-aminocyclohexyl) methane Polyamines; aromatic polyamines such as diaminodiphenylmethane and diaminodiphenylsulfone; novolac-type phenol resins; polybasic acid anhydrides such as methylhexahydrophthalic anhydride and benzophenonetetracarboxylic dianhydride; And modified products thereof; latent curing agents such as imidazole, dicyandiamide, boron trifluoride-amine complex, and guanidine derivatives. Among these curing agents, diaminodiphenylmethane, diaminodiphenylsulfone, novolac type phenol resin, dicyandiamide, and polybasic acid anhydrides are preferable. These curing agents may be used alone or in combination of two or more.

  The amount of the curing agent for epoxy resin used is the above-mentioned branched polyether resin composition (II) or acid pendant type in the case of a curing agent having active hydrogen such as amino group or imino group or phenolic hydroxyl group in the curing agent. The active hydrogen is preferably used in an amount of 0.3 to 1.2 equivalents per equivalent of epoxy group in the epoxy resin added to the branched polyether resin composition (III). In the case of acid anhydrides, there are acid anhydride groups per equivalent of epoxy groups in the epoxy resin added to the branched polyether resin composition (II) or the acid pendant type branched polyether resin composition (III). It is preferable to use in the range which becomes 0.3-1.2 equivalent.

  Moreover, when using the hardening | curing agent for epoxy resins, a hardening accelerator can be used suitably. The curing accelerator that can be used is not particularly limited, and any of those usually used as a curing accelerator for an epoxy resin can be used. For example, a tertiary amine such as dimethylbenzamine, 2-thymer. Examples include imidazole compounds such as imidazole, and organic phosphorus compounds such as triphenylphosphine.

  Examples of the photoinitiator include acetophenones, benzophenone derivatives, Michler's ketone, benzine, benzyl derivatives, benzoin derivatives, benzoin methyl ethers, α-acyloxime esters, thioxanthones, anthraquinones, and various derivatives thereof. Etc.

  Specific examples of the photoinitiator include 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, alkoxyacetophenone, benzyldimethyl ketal, benzophenone, alkyl benzoylbenzoate, bis (4-dialkylaminophenyl) ketone, benzyl Benzoin; benzoin benzoate, benzoin alkyl ether, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 2,4,6-trimethylbenzoyldiphenoylphosphine oxide, bis (2,6 ) -Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; 2-methyl-1- [ - (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) - butanone-1, metallocene compounds, and the like.

  Furthermore, various photosensitizers can be used in combination with these photoinitiators, such as amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, or other nitrogen-containing compounds. Is mentioned.

  The amount of the photoinitiator used is in the range of 0.5 to 25 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the resin in the composition.

  The branched polyether resin composition obtained by the production method of the present invention may further include various additives such as a filler, a colorant, a flame retardant, a release agent, and a thermoplastic resin silane coupling agent as necessary. It can be added and blended.

  Typical examples of the filler include silica powder, zirconium zirconium silicate, alumina, calcium carbonate, quartz powder, zirconium oxide, talc, clay, barium sulfate, asbestos powder, and milled glass. Also, representative examples of colorants include carbon black, typical examples of flame retardants include antimony trioxide, and typical release agents include carnauba wax. Typical examples of the silane coupling agent include aminosilane and epoxysilane.

  In addition, the branched polyether resin composition obtained by the production method of the present invention comprises an electrical insulating material such as an electrical / electronic component sealing material, an insulating varnish, a laminated board, and an insulating powder paint; a laminated board for a printed wiring board; Adhesives for structural materials such as prepregs, conductive adhesives and honeycomb panels; fiber reinforced plastics using various reinforcing fibers such as glass fibers, carbon fibers and aramid fibers and their prepregs; can be used for resist inks, etc. .

  When the acid pendant branched polyether resin composition (III) is used as a photo patterning material such as resist ink, for example, the optical patterning using the acid pendant branched polyether resin composition (III) on the substrate to be used is used. The material is applied to a dry film thickness of about 5 to 100 μm, and if necessary, solvent drying is performed, and then ultraviolet rays are irradiated through a photomask. A portion that has passed through the photomask undergoes a curing reaction due to the ultraviolet rays, and a portion where the ultraviolet rays do not pass through the photomask does not cause a curing reaction. The desired film can be formed by developing the coating film irradiated with ultraviolet rays through the mask with a developer of a dilute alkaline aqueous solution. At this time, as the developer, an aqueous solution of an inorganic alkali such as sodium carbonate, potassium carbonate, sodium hydroxide, or potassium hydroxide, or an organic alkaline aqueous solution such as tetramethylammonium hydroxide can be used. Moreover, the density | concentration of a developing solution can be used at about 0.2 to 5 weight%, and you may contain surfactant. Such development can be performed by application by immersion, shaking immersion or spray application for image formation.

  Next, the present invention will be specifically described with reference to examples and comparative examples. In the following,% and parts are based on weight unless otherwise specified. The units of viscosity, acid value, and epoxy equivalent in the following table are Pa · S, mgKOH / g, and g / equivalent, respectively.

Example 1
Into a flask equipped with a thermometer, a stirrer and a reflux condenser, 24.9 g of ethyl carbitol acetate is put, and 188 g of bisphenol A type epoxy resin (epoxy equivalent 188 g / equivalent; EPICLON 850 manufactured by Dainippon Ink & Chemicals, Inc.) is dissolved. Then, after adding 1 g of hydroquinone as a polymerization inhibitor, 36.1 g (0.5 mol) of acrylic acid was charged. 0.446 g (0.2% of resin content) of triphenylphosphine was added as a catalyst, and the temperature was raised to 130 ° C. in 2 hours while stirring. The reaction was continued for 10 hours at the same temperature while sampling at 0, 2, 6, 8 and 10 hours after the time when the temperature reached 130 ° C. was 0 hours, and the light containing the branched polyether resin (X1) A yellow transparent resinous reaction mixture (I-1) was obtained. The five samples sampled were measured for viscosity [E-type viscometer (25 ° C.)], acid value (solid content), and epoxy equivalent (solid content), respectively, and from molecular weight distribution measurement results by GPC. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined. The obtained results are shown in Table 1-1 below.

  The obtained reaction mixture (I-1) had the composition shown in Table 1-2 below from the GPC. Moreover, the branched polyether resin computed from the content rate of each component in following Table 1-2, and the epoxy equivalent (solid content) of the reaction mixture (I-1) after the elapsed time 10 hours in the said Table 1-1. The epoxy equivalent (solid content) of (X1) was 1,148 g / equivalent. The epoxy equivalent (solid content) of this branched polyether resin (X1) is 100 / [epoxy equivalent of reaction mixture (I-1)] = {(content of bisphenol A type epoxy resin) / (epoxy equivalent thereof) ) + (Epoxy group-containing bisphenol A type epoxy monomethacrylate content) / (epoxy equivalent) + [content of branched polyether resin (X1)] / (epoxy equivalent)}, that is, 100/533 = [(19 .3 / 188) + (15.5 / 448) + (57.8 / epoxy equivalent of branched polyether resin (X1))].

  Next, 30.4 g of acrylic acid (0.42 mol: equivalent to 1 mol per 1 mol of the remaining epoxy groups) and ethylcarby are obtained with respect to 224.1 g of the solid content of the reaction mixture (I-1). 38.7 g of tall acetate was added and reacted at 130 ° C. for 5 hours to obtain a pale yellow transparent resinous branched polyether resin composition (II-1) containing the branched polyether resin (Y1). At this time, the epoxy equivalent (solid content) of the branched polyether resin composition (II-1) was 18500 g / equivalent, and the acid value (solid content) was 0.2 (mg KOH / g). From the molecular weight distribution measurement result by GPC, the composition of the branched polyether resin composition (II-1), the number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of polystyrene standard sample were determined. The obtained results are shown in Table 1-3 below.

Example 2
Into a flask equipped with a thermometer, a stirrer and a reflux condenser, 26.5 g of ethyl carbitol acetate is put, and 188 g of bisphenol A type epoxy resin (epoxy equivalent 188 g / equivalent; EPICLON 850 manufactured by Dainippon Ink & Chemicals, Inc.) is dissolved. Then, after adding 1 g of hydroquinone as a polymerization inhibitor, 50.68 g (0.7 mol) of acrylic acid was charged. 0.477 g of triphenylphosphine (0.2% of resin content) was added as a catalyst, and the temperature was raised to 130 ° C. in 2 hours while stirring. The time at which the temperature reached 130 ° C. was defined as 0 hour, and the reaction was continued at the same temperature for 10 hours while sampling 6 times after 0, 2, 4, 6, 8, and 10 hours, and branched polyether resin (X2 ) Containing a pale yellow transparent resinous reaction mixture (I-2). The six samples sampled were measured for viscosity [E-type viscometer (25 ° C.)], acid value (solid content), and epoxy equivalent (solid content), respectively, and from the molecular weight distribution measurement result by GPC. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined. The obtained results are shown in Table 2-1 below.

  The obtained reaction mixture (I-2) had the composition shown in Table 2-2 below from its GPC. Moreover, it computed similarly to Example 1 from the content rate of each component in following Table 2-2, and the epoxy equivalent (solid content) of the reaction mixture (I-2) 10 hours after the elapsed time in the said Table 2-1. The epoxy equivalent (solid content) of the branched polyether resin (X2) thus obtained was 2,240 g / equivalent.

Further analysis by IR was conducted. An infrared absorption spectrum of the reaction mixture (I-2) is shown in FIG. From Figure 1, the hydroxyl group of the reaction mixture to compare the relative intensity of the absorption of alkyl group absorption and 2800～3100Cm ^-1 broad hydroxyl group of 3300~3600cm ^-1 (I-2) is small, a hydroxyl group is consumed I understand that. Further, when the relative strengths of the 1410 cm ⁻¹ acryloyl group and the 755 cm ⁻¹ monosubstituted benzene ring were compared, it was found that almost 50% of the acryloyl group had disappeared. Similarly, the absorption of ether near 1120 cm ⁻¹ is increased, and it can be seen that an ether bond is formed by the reaction between the acryloyl group and the hydroxyl group. Next, as a result of measuring the hydroxyl group equivalent and the concentration of acryloyl group, it was confirmed that 50 mol% of the hydroxyl group and acryloyl group reacted as in the infrared spectrum.

  Next, 17.3 g of acrylic acid (0.24 mol: equivalent to 1 mol per 1 mol of the remaining epoxy groups) and ethylcarby are added to 238.7 g of the solid content of the reaction mixture (I-2). 37.5 g of tall acetate was added and reacted at 130 ° C. for 5 hours to obtain a light yellow transparent resinous branched polyether resin composition (II-2) containing the branched polyether resin (Y2). At this time, the epoxy equivalent (solid content) of the branched polyether resin composition (II-2) was 21100 g / equivalent, and the acid value (solid content) was 0.15 (mg KOH / g). From the molecular weight distribution measurement result by GPC, the composition, average molecular weight (Mn) and weight average molecular weight (Mw) of the branched polyether resin composition (II-2) were determined. The obtained results are shown in Table 2-3 below.

Furthermore, 78.5 g of ethyl carbitol acetate was added to 256 g of the solid content of the branched polyether resin composition (II-2), the temperature in the system was lowered to 100 ° C., and then tetrahydrophthalic anhydride 76 was added. .6 g (0.504 mol) was added and the reaction was carried out at 100 ° C. for 8 hours. From the infrared absorption spectrum, 1780 cm ⁻¹ absorption due to the acid anhydride has disappeared, and tetrahydrophthalic anhydride is branched polyether resin (Y2) and bisphenol A in the branched polyether resin composition (II-2). It confirmed that it reacted with the diacrylate of a type epoxy resin, and an acid pendant type branched polyether resin composition (III-2) containing an acid pendant type branched polyether resin (Z2) was obtained. The acid pendant branched polyether resin composition (III-2) had an acid value (solid content) of 84.8 (mgKOH / g). From the molecular weight distribution measurement result by GPC, the composition, average molecular weight (Mn) and weight average molecular weight (Mw) of the acid pendant branched polyether resin composition (III-2) were determined. The obtained results are shown in Table 2-4.

Example 3
In a flask equipped with a thermometer, a stirrer and a reflux condenser, 27.32 g of ethyl carbitol acetate was put, and 188 g of bisphenol A type epoxy resin (epoxy equivalent 188 g / equivalent; EPICLON 850 manufactured by Dainippon Ink & Chemicals, Inc.) was dissolved. After adding 1 g of hydroquinone as a polymerization inhibitor, 57.92 g (0.8 mol) of acrylic acid was charged. 0.49 g (0.2% of resin content) of triphenylphosphine was added as a catalyst, and the temperature was raised to 110 ° C. over 2 hours while stirring. When the temperature reaches 110 ° C., 0 hour is set as 0 hour, and the reaction is continued at the same temperature for 8 hours while sampling 4 times after 2, 4, 6 and 8 hours, and the branched polyether resin (X3) is contained. A pale yellow transparent resinous reaction mixture (I-3) was obtained. The four samples sampled were measured for viscosity [E-type viscometer (25 ° C.)], acid value (solid content), and epoxy equivalent (solid content), respectively, and from the results of molecular weight distribution measurement by GPC. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined. The obtained results are shown in Table 3-1 below.

  The obtained reaction mixture (I-3) had the composition shown in Table 3-2 below from its GPC. Moreover, it computed similarly to Example 1 from the content rate of each component in following Table 3-2, and the epoxy equivalent (solid content) of the reaction mixture (I-3) after the elapsed time 8 hours in the said Table 3-1. The epoxy equivalent (solid content) of the branched polyether resin (X3) thus obtained was 4,448 g / equivalent.

  Next, 9.3 g of acrylic acid (0.128 mol: 1 mol to the remaining epoxy group to 1 mol) with respect to the solid content of 245.9 g (273.2 g as a resin solution) of the reaction mixture (I-3) And 36.5 g of ethyl carbitol acetate are added and reacted at 130 ° C. for 5 hours to form a pale yellow transparent resinous branched polyether resin composition (II) containing the branched polyether resin (Y3). -3) was obtained. At this time, the epoxy equivalent (solid content) of the branched polyether resin composition (II-3) was 24200 g / equivalent, and the acid value (solid content) was 0.16 (mg KOH / g). The composition of the branched polyether resin composition (II-3), the number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined from the molecular weight distribution measurement result by GPC. The obtained results are shown in Table 3-3 below.

Further, 78.3 g of ethyl carbitol acetate was added to 255.2 g of the solid content of the branched polyether resin composition (II-3), and the temperature in the system was lowered to 100 ° C. 76.4 g (0.502 mol) of acid was added and the reaction was carried out at 100 ° C. for 8 hours. From the infrared absorption spectrum, 1780 cm ^−1, which is absorption due to the acid anhydride, has disappeared, and the tetrahydrophthalic anhydride is branched polyether resin (Y3) and bisphenol A in the branched polyether resin composition (II-3). It confirmed that it reacted with the diacrylate of a type epoxy resin, and an acid pendant type branched polyether resin composition (III-3) containing an acid pendant type branched polyether resin (Z3) was obtained. The acid pendant branched polyether resin composition (III-3) had an acid value (solid content) of 85.8 (mgKOH / g). From the molecular weight distribution measurement result by GPC, the composition, average molecular weight (Mn), and weight average molecular weight (Mw) of the acid pendant branched polyether resin composition (III-3) were determined. The obtained results are shown in Table 3-4.

Example 4
Into a flask equipped with a thermometer, a stirrer and a reflux condenser, 58.5 g of ethyl carbitol acetate is put, and 476 g of bisphenol A type epoxy resin (epoxy equivalent 476 g / equivalent; EPICLON 1050 manufactured by Dainippon Ink & Chemicals, Inc.) is dissolved. Then, after adding 1 g of hydroquinone as a polymerization inhibitor, 50.68 g (0.7 mol) of acrylic acid was charged. As a catalyst, 1.05 g of triphenylphosphine (0.2% of resin content) was added, and the temperature was raised to 130 ° C. in 2 hours while stirring. The time when the temperature reached 130 ° C. was defined as 0 hour, and the reaction was continued at the same temperature for 8 hours while sampling 5 times after 0, 2, 4, 6 and 8 hours, and the branched polyether resin (X4) was obtained. A pale yellow transparent resinous reaction mixture (I-4) was obtained. In addition, each of the five samples sampled was measured for acid value (solid content) and epoxy equivalent (solid content), and the number average molecular weight (Mn) and weight average molecular weight (Mw) from the molecular weight distribution measurement result by GPC. Asked. The obtained results are shown in Table 4-1 below.

  The obtained reaction mixture (I-4) had the composition shown in Table 4-2 below from the GPC. Moreover, it computed similarly to Example 1 from the content rate of each component in following Table 4-2, and the epoxy equivalent (solid content) of the reaction mixture (I-4) after the elapsed time 8 hours in the said Table 4-1. The epoxy equivalent (solid content) of the branched polyether resin thus obtained was 3,895 g / equivalent.

  Next, with respect to the solid content of 526.7 g (585.2 g as a resin solution) of the reaction mixture (I-4), 17.7 g of acrylic acid (0.245 mol: 1 mol per 1 mol of the remaining epoxy groups) And 77.6 g of ethyl carbitol acetate are added and reacted at 130 ° C. for 5 hours to form a pale yellow transparent resinous branched polyether resin composition containing a branched polyether resin (Y4) ( II-4) was obtained. At this time, the epoxy equivalent (solid content) of the branched polyether resin composition (II-4) was 19800 g / equivalent, and the acid value (solid content) was 0.11 (mg KOH / g). From the molecular weight distribution measurement result by GPC, the composition of the branched polyether resin composition (II-4), the number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined. The obtained results are shown in Table 4-3 below.

Further, 167.0 g of ethyl carbitol acetate was added to 544.4 g of the solid content of the branched polyether resin composition (II-4), and the temperature in the system was lowered to 100 ° C. The acid 162.9g (1.072mol) was added, and reaction was performed at 100 degreeC for 8 hours. The branched polyether resin (Y4) and bisphenol A in the branched polyether resin composition (II-4) in which 1780 cm ^−1, which is absorption due to the acid anhydride, has disappeared from the infrared absorption spectrum and the tetrahydrophthalic anhydride is converted into the branched polyether resin composition (II-4). After confirming that it reacted with the diacrylate of the epoxy resin, an acid pendant branched polyether resin composition (III-4) containing an acid pendant branched polyether resin (Z4) was obtained. The acid pendant branched polyether resin composition (III-4) had an acid value (solid content) of 85.2 (mgKOH / g). From the molecular weight distribution measurement result by GPC, the composition, average molecular weight (Mn) and weight average molecular weight (Mw) of the acid pendant branched polyether resin composition (III-4) were determined. The results obtained are shown in Table 4-4.

Example 5
Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 26.3 g of ethyl carbitol acetate is put, and 186 g of tetramethylbiphenyl type epoxy resin (epoxy equivalent 186 g / equivalent; YX-4000 manufactured by Japan Epoxy Resin Co., Ltd.) is dissolved. After adding 1 part of hydroquinone as a polymerization inhibitor, 50.4 g (0.7 mol) of acrylic acid was charged. As a catalyst, 0.236 g of triphenylphosphine (0.1% of resin content) was added, and the temperature was raised to 130 ° C. in 2 hours while stirring, and 4 hours and 7 hours after the temperature reached 130 ° C. Later, another 0.236 g of triphenylphosphine was added. Sampling was performed at the same temperature for 10 hours while sampling was performed five times after 0, 1, 5, 8, and 10 hours, with the time when the temperature reached 130 ° C. being 0 hours, and branched polyether resin. A pale yellow transparent resinous reaction mixture (I-5) containing (X5) was obtained. The five samples sampled were measured for viscosity [E-type viscometer (25 ° C.)], acid value (solid content), and epoxy equivalent (solid content), respectively, and from molecular weight distribution measurement results by GPC. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined. The obtained results are shown in Table 5-1 below.

  The obtained reaction mixture (I-5) had a composition shown in Table 5-2 below from the GPC. Moreover, it computed similarly to Example 1 from the content rate of each component in following Table 5-2, and the epoxy equivalent (solid content) of the reaction mixture (I-5) after the elapsed time 10 hours in the said Table 5-1. The epoxy equivalent (solid content) of the branched polyether resin (X5) thus obtained was 1,776 g / equivalent.

  Next, with respect to the solid content of 236.4 g (262.7 g as a resin solution) of the reaction mixture (I-5), 17.2 g of acrylic acid (0.238 mol: 1 mol relative to 1 mol of the remaining epoxy group) And 37.1 g of ethyl carbitol acetate were added and reacted at 130 ° C. for 5 hours to give a pale yellow transparent resinous branched polyether resin composition containing a branched polyether resin (Y5) ( II-5) was obtained. At this time, the epoxy equivalent (solid content) of the branched polyether resin composition (II-5) was 20900 g / equivalent, and the acid value (solid content) was 0.20 (mgKOH / g). From the molecular weight distribution measurement result by GPC, the composition, number average molecular weight (Mn) and weight average molecular weight (Mw) of the branched polyether resin composition (II-5) were determined. The obtained results are shown in Table 5-3 below.

Further, 77.8 g of ethyl carbitol acetate was added to 253.6 g of the solid content of the branched polyether resin composition (II-5), and the temperature in the system was lowered to 100 ° C. 75.9 g (0.5 mol) of acid was added and the reaction was carried out at 100 ° C. for 8 hours. The branched polyether resin (Y5) and bisphenol A in the branched polyether resin composition (II-5) in which 1780 cm ^−1, which is an absorption due to the acid anhydride, disappears from the infrared absorption spectrum and the tetrahydrophthalic anhydride is the branched polyether resin composition (II-5). After confirming reaction with the diacrylate of the epoxy resin, an acid pendant branched polyether resin composition (III-5) was obtained. The acid pendant branched polyether resin composition (III-5) had an acid value (solid content) of 85.7 (mgKOH / g). From the molecular weight distribution measurement result by GPC, the composition, average molecular weight (Mn), and weight average molecular weight (Mw) of the acid pendant branched polyether resin composition (III-5) were determined. The results obtained are shown in Table 5-4.

Example 6
The solid content of 238.7 g of the reaction mixture (I-2) obtained in Example 2 is further 20.6 g of methacrylic acid (0.24 mol: equivalent to 1 mol per 1 mol of the remaining epoxy groups). ) And ethyl carbitol acetate 38.3 g, reacted at 130 ° C. for 5 hours, and a pale yellow transparent resinous branched polyether resin composition (II-6) containing a branched polyether resin (Y6) Got. At this time, the epoxy equivalent (solid content) was 24100 g / equivalent, and the acid value (solid content) was 0.25 (mg KOH / g). From the molecular weight distribution measurement result by GPC, the composition, number average molecular weight (Mn) and weight average molecular weight (Mw) of the branched polyether resin composition (II-6) were determined. The obtained results are shown in Table 6-1 below.

Furthermore, 72.7 g of ethyl carbitol acetate was added to 259 g of the solid content of the branched polyether resin composition (II-6), the temperature in the system was lowered to 100 ° C., and then hexahydrophthalic anhydride 61 0.5 g (0.4 mol) was added and the reaction was carried out at 100 ° C. for 8 hours. From the infrared absorption spectrum, 1780 cm ^−1, which is absorption due to the acid anhydride, has disappeared, and the hexahydrophthalic anhydride is the branched polyether resin (Y6) and bisphenol A in the branched polyether resin composition (II-6). After confirming that it reacted with the di (meth) acrylate of the epoxy resin, an acid pendant branched polyether resin composition (III-6) was obtained. The acid pendant branched polyether resin composition (III-6) had an acid value (solid content) of 71.1 (mgKOH / g). From the molecular weight distribution measurement result by GPC, the composition, average molecular weight (Mn), and weight average molecular weight (Mw) of the acid pendant branched polyether resin composition (III-6) were determined. The obtained results are shown in Table 6-2.

Example 7
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 188 g of a bisphenol A type epoxy resin (epoxy equivalent 188 g / equivalent; EPICLON 850 manufactured by Dainippon Ink & Chemicals, Inc.) was dissolved, and BHT (2,6) was used as a polymerization inhibitor. After adding 1 g of (ditertiary butyl-4-methylphenol), 28.8 g (0.4 mol) of acrylic acid and 34.4 g (0.4 mol) of methacrylic acid were charged. 1.26 g of triphenylphosphine (0.5% of resin content) was added as a catalyst, and the temperature was raised to 130 ° C. over 1 hour while stirring. The time when the temperature reached 130 ° C. was defined as 0 hour, and the reaction was continued at the same temperature for 5 hours while sampling at 0, 1, 3, 5 hours later, and the pale yellow transparent containing the branched polyether resin (X7) A resinous reaction mixture (I-7) was obtained. Each sampled sample was measured for viscosity [Gardner method (25 ° C., using E-type viscometer)], acid value (solid content), and epoxy equivalent (solid content), and GPC (gel permeation). The number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined from the molecular weight distribution measurement results by chromatography. The obtained results are shown in Table 7-1 below.

  The obtained reaction mixture (I-7) had a composition shown in Table 7-2 below from its GPC. Moreover, the branched polyether resin (X7) calculated from the content of each component in the following Table 7-2 and the epoxy equivalent of the reaction mixture (I-7) after 10 hours elapsed in the Table 7-1. The epoxy equivalent was 2604. The epoxy equivalent of this branched polyether resin (X7) is 100 / (epoxy equivalent of branched polyether resin composition 1) = [(content of bisphenol A type epoxy resin) / (its epoxy equivalent) + (epoxy Group-containing bisphenol A type epoxy mono (meth) acrylate content) / (epoxy equivalent) + (content of branched polyether resin (X1)) / (epoxy equivalent)], that is, 100/1570 = [(1. 4/188) + (13.1 / 455) + (71.5 / epoxy equivalent of branched polyether resin (X1))]. However, the epoxy equivalent of the epoxy group-containing bisphenol A type epoxy mono (meth) acrylate was calculated as an average epoxy equivalent on the assumption that bisphenol A type epoxy monoacrylate and bisphenol A type epoxy monomethacrylate exist in an equimolar molecule.

Furthermore, analysis by IR (infrared absorption spectrum) was performed. As a result of the analysis, the amount of hydroxyl groups of the reaction mixture to compare the relative intensity of the absorption of alkyl group absorption and 2800～3100Cm ^-1 broad hydroxyl group of 3300~3600cm ^-1 (I-7) is small, a hydroxyl group is consumed I found out. Also, it was found from the relative strength of the acryloyl group at 1410 cm ⁻¹ that almost 50% of the acryloyl group had disappeared. Similarly, the absorption of ether near 1120 cm ⁻¹ was increased, and it was found that an ether bond was formed by the reaction between the acryloyl group and the hydroxyl group.

  Next, 66.2 g of ethyl diglycol acetate (EDGA) and 13.7 g (0.16 mol) of methacrylic acid were added to this reaction mixture (I-7), and the reaction was carried out at 130 ° C. for 8 hours. A branched polyether resin composition (II-7) containing Y7) was obtained. At this time, the epoxy equivalent (solid content) of the branched polyether resin composition (II-7) was 23000 g / equivalent, and the acid value (solid content) was 0.5 (mg KOH / g). The composition, number average molecular weight (Mn) and weight average molecular weight (Mn) of the branched polyether resin composition were determined from the measurement results of molecular weight distribution by GPC. The obtained results are shown in Table 7-3 below.

  3 g of ethyl diglycol acetate, 28 g of an aromatic petroleum solvent (Sorvesso 150) and 30 g of tetrahydrophthalic anhydride were added to 100 g of the resin solid content of this branched polyether resin composition (II-7). A time reaction was performed to obtain an acid pendant branched polyether resin composition (III-7). From the infrared absorption spectrum, the absorption of the acid anhydride group at 1850 cm −1 completely disappeared. Moreover, the acid value of solid content conversion was 86 mg-KOH / g. From the molecular weight distribution measurement result by GPC, the composition, number average molecular weight and weight average molecular weight (Mn) of the acid pendant branched polyether resin composition were determined.

Comparative Example 1
Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 28.9 g of ethyl carbitol acetate was put, and 188 g of bisphenol A type epoxy resin (epoxy equivalent 188 g / equivalent; EPICLON 850 manufactured by Dainippon Ink & Chemicals, Inc.) was dissolved. Then, after adding 0.5 g of hydroquinone as a polymerization inhibitor, 72 g (1 mol) of acrylic acid and 0.52 g of triphenylphosphine (0.2% of resin content) were added, and the mixture was stirred up to 130 ° C. in 2 hours. The temperature rose. The time when the temperature reached 130 ° C. was defined as 0 hour, and the reaction was continued at the same temperature for 10 hours while sampling 6 times after 1, 3, 4.5, 6, 8 and 10 hours, and then removed from the flask. A light yellow transparent resinous resin (R-1) was obtained. The six samples sampled were measured for viscosity [E-type viscometer (25 ° C.)], acid value (solid content), and epoxy equivalent (solid content), respectively, and from the molecular weight distribution measurement result by GPC. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined. From the GPC analysis results, no significant change was observed in the molecular weight immediately after the start of the reaction and 10 hours after the start of the reaction, and the resin (R-1) had an epoxy group at the end of the bisphenol A type epoxy resin and acrylic acid. It was found to be a reacted diacrylate. That is, only the diacrylate of the aromatic bifunctional epoxy resin exists in the reaction system, and the monoacrylate of the aromatic bifunctional epoxy resin or the aromatic bifunctional epoxy resin does not exist. The reaction mixture (I-2) obtained by the production method of the present invention does not cause the reaction between the hydroxyl group in the acrylate and the acryloyl group, does not cause the synthesis of a branched polyether resin having a hydroxyl group, an acryloyl group, and an epoxy group. It was a different resin. The obtained results are shown in Table 1'-1.

An infrared absorption spectrum of the comparative resin (R-1) is shown in FIG. From Figure 2, comparing the relative intensity of the absorption of alkyl group broad hydroxyl absorption and 2800～3100Cm ^-1 of 3300～3600Cm ^-1, compared to the absorption intensity of the hydroxyl groups of the reaction mixture (I-2) 2 shows that the comparative resin (R-1) shown in FIG. 2 has high hydroxyl group absorption strength, and a larger amount of hydroxyl group remains than the reaction mixture (I-2). Further, comparing the relative intensities of the 1410 cm ⁻¹ acryloyl group and the 755 cm ⁻¹ monosubstituted benzene ring, it was found that most of the acryloyl groups remained unreacted.

Subsequently, 79.8 g of ethyl carbitol acetate was added to 260 g of the solid content of the resin for comparison (R-1), the temperature in the system was lowered to 100 ° C., and then 77. 8 g (0.512 mol) was added and the reaction was carried out at 100 ° C. for 8 hours. From the infrared absorption spectrum, it was confirmed that 1780 cm ^{−1, which} was absorption due to the acid anhydride, had disappeared, and tetrahydrophthalic anhydride reacted with the comparative control resin (R-1). An epoxy acrylate resin (RZ-1) was obtained. The acid value (solid content) of RZ-1 was 85.1 (mgKOH / g). As a result of obtaining the average molecular weight (Mn) and the weight average molecular weight (Mw) of the acid pendant bisphenol A type epoxy acrylate resin (RZ-1) from the molecular weight distribution measurement result by GPC, the number average molecular weight is 780 and the weight average molecular weight. Was 960.

Comparative Example 2
Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 428 g of ethyl carbitol acetate was added, and 188 g of bisphenol A type epoxy resin (epoxy equivalent 188 g / equivalent; EPICLON 850 manufactured by Dainippon Ink & Chemicals, Inc.) was dissolved and polymerized. After adding 0.5 g of hydroquinone as an inhibitor, 144 g (2 mol) of acrylic acid and 0.52 g of triphenylphosphine (0.2% of resin content) are added, and the temperature is raised to 130 ° C. in 2 hours while stirring. did. After reaching the temperature of 130 ° C., gelation occurred with an intense exotherm about 1 hour.

Comparative Example 3
Into a flask equipped with a thermometer, a stirrer and a reflux condenser, 72 g of ethyl carbitol acetate was added, and 215 g of cresol novolac type epoxy resin (epoxy equivalent 215 g / equivalent; EPICLONN-673 manufactured by Dainippon Ink & Chemicals, Inc.) was dissolved. Then, after adding 0.5 g of hydroquinone as a polymerization inhibitor, 72 g (1 mol) of acrylic acid and 0.52 g of triphenylphosphine (0.2% of resin content) were added, and the temperature was increased to 120 ° C. in 2 hours while stirring. The temperature rose. After the temperature reached 120 ° C., the reaction was carried out for about 15 hours to obtain a cresol novolac type epoxy acrylate resin. Next, after the temperature was lowered to 100 ° C., 91.2 g (0.6 mol) of tetrahydrophthalic anhydride was added, and the reaction was carried out at this temperature for 10 hours. After confirming that the absorption of the anhydride disappeared in the infrared spectrum, the acid pendant type epoxy acrylate resin (RZ-3) was obtained. The acid value (solid content) was 91 mgKOH / g.

Application Examples 1-7 and Comparative Application Examples 1-2
Acid pendant branched polyether resin compositions (III-2) to (III-7) obtained in Examples 2 to 7, resins (RZ-1) and resins (RZ-3) obtained in Comparative Examples 1 and 3 , A cresol novolac type epoxy resin [EPICLON N-680: epoxy equivalent 214 g / equivalent (hereinafter abbreviated as N680)] ethyl carbitol acetate non-volatile content 70% solution, dipentaerythritol hexaacrylate (hereinafter abbreviated as DPHA). And resist ink compositions (W-1) to (W-6) and (RW-1) having the formulations shown in Table 8 and Table 9 below using Irgacure 907 (a photopolymerization initiator manufactured by Ciba Geigy) (RW-2) was prepared. In addition, since the resin in Comparative Example 2 was gelled, it could not be evaluated as a comparative application example.

  Next, dryness to touch of the obtained resist ink compositions (W-1) to (W-5) and (RW-1) to (RW-2), developability, sensitivity, stability during solvent drying, The flexibility of the coating film and the heat resistance of the coating film were evaluated. The evaluation method is shown below.

(1) Dryness to touch 1
Each resist ink composition is coated on a glass epoxy substrate with an applicator so that the dry film thickness of the coating film becomes 40 μm, dried at 80 ° C. for 30 minutes, cooled to room temperature (23 ° C.), and then touched to the coating film. The tackiness at the time was evaluated according to the following criteria.
Evaluation criteria ○: No tack.
Δ: Tack is slightly present.
X: There is tackiness.

(2) Dryness to touch 2
Each resist ink composition is coated with an applicator so that the dry film thickness of the coating film is 40 μm on a glass epoxy substrate, dried at 80 ° C. for 30 minutes, cooled to room temperature (23 ° C.), and then a step for sensitivity evaluation. A tablet (Step Tablet No. 2 manufactured by Kodak Co., Ltd.) was placed on the surface of the dried coating film, and ultraviolet irradiation was performed in this state. Ultraviolet irradiation is performed under a vacuum under reduced pressure using a 7 KW metal halide lamp (HTE-106-M07 manufactured by Hitech Co., Ltd.), after returning to normal pressure after irradiation with ultraviolet light with an integrated light amount of 800 mJ / cm ² , the step tablet is removed from the coating surface. The tackiness generated when peeling was evaluated according to the following criteria.
Evaluation criteria ○: The step tablet can be easily peeled off without any tackiness.
Δ: There is a slight tackiness, and the step tablet is caught but can be peeled off.
X: Tackiness, ink adheres to the step tablet and hardly peels off.

(3) Developability Each resist ink composition was applied to a tinplate substrate with an applicator so that the dry film thickness was 40 μm, and left in an oven at 80 ° C. for 30 minutes to evaporate the solvent and left at room temperature. Thereafter, the film was immersed in a 1% sodium carbonate aqueous solution at 30 ° C. for 120 seconds, and the degree of the coating film remaining on the substrate was evaluated according to the following criteria.
Evaluation criteria ○: No coating film remains on the substrate.
Δ: Part of the coating film on the substrate remains.
X: The coating film on the substrate is not dissolved and almost remains.

(4) Sensitivity (sensitivity of resist ink)
A sample obtained by screen-printing each resist ink composition on a glass epoxy substrate was allowed to stand in an oven at 80 ° C. for 30 minutes to volatilize the solvent, and a step tablet (Step Tablet No. 2 manufactured by Kodak Co., Ltd.) was applied on the coating film. was loaded, using the 7KW metal halide lamp (manufactured Hightech Co. HTE-106-M07), after irradiation with ultraviolet light at an accumulated light intensity of ^{400mJ / cm 2, 600mJ / cm} 2, 800mJ / cm 2, the sample surface the step tablet The sample was immersed in a 1% sodium carbonate aqueous solution at 30 ° C. for 120 seconds and evaluated by the step tablet method. The numbers in the table indicate the number of steps of the step tablet, and the larger the number, the better the curability (sensitivity).

(5) Stability during solvent drying (drying control width)
A tin plate (test piece) coated with an applicator so that the dry film thickness was 40 μm was left in a 90 ° C. dryer for 30 minutes, 40 minutes, and 50 minutes to volatilize the solvent, Development was performed by immersing in a 1% sodium carbonate aqueous solution at 30 ° C. for 120 seconds, and the drying control width (stability at the time of solvent drying) was visually evaluated according to the following criteria based on the following criteria.
Evaluation criteria ○: No coating film remains on the substrate.
Δ: Part of the coating film on the substrate remains.
X: The coating film on the substrate is not dissolved and almost remains.

(6) Coating film flexibility (Erichsen test)
A tin plate (test piece) coated with each resist ink composition with an applicator so as to have a dry film thickness of 40 μm was dried in a 90 ° C. drier for 30 minutes, and then a 7 KW metal halide lamp (manufactured by Hitec Corporation). HTE-106-M07) was irradiated with ultraviolet light with an integrated light amount of 800 mJ / cm ² and further heat-cured at 150 ° C. for 1 hour. The sample was cut together with a tin plate to a size of 5 cm square, and an Erichsen test was performed under the condition of 23 ° C. using an automatic Erichsen manufactured by Ueshima Seisakusho. When the coating film is pushed out by a punch and floats or peels off from the tinplate substrate or cracks are generated, the lift of the punch is stopped, the height of the punch is read from the device, and the average value of four times is obtained as a result. It was.

(7) Heat resistance of coating film (solder heat resistance)
After drying a test piece on which a resist ink composition 1 is applied by screen printing on a glass epoxy substrate with a copper foil to which a test pattern has been applied so as to have a dry film thickness of 20 μm, in a dryer at 80 ° C. for 30 minutes. The film was irradiated with ultraviolet light at 800 mJ / cm ² with a 7 KW metal halide lamp, and further heat-cured at 150 ° C. for 1 hour. Next, rosin-based flux is applied to the cured test piece, immersed in a solder bath melted at 260 ° C. for 30 seconds, and the performance is observed by a peel test in which the appearance is observed and the peel operation is performed three times using an adhesive tape. evaluated.
Evaluation Criteria A: No abnormality in appearance and no part of peeling with cello tape (registered trademark).
○: No abnormality in appearance, some peeling with cello tape (registered trademark) is observed.
X: Appearance abnormalities such as swelling and peeling, and peeling is noticeable with cello tape (registered trademark).

  Resist ink compositions (W-1) to (W-6) obtained using the acid pendant branched polyether resin compositions (III-2) to (III-7) obtained in Examples 2 to 7 ) Was dry to the touch and all the formulations showed good results, and the developability was also good. Furthermore, the sensitivity is at a pass level, and the drying control range is also able to be developed for approximately 50 minutes or more. Regarding Eriksen, it is 4 mm or more in the examples, and the results of excellent adhesion and elongation of the coating film are obtained. On the other hand, the resist ink compositions (RW-1) and (RW-2) obtained using the resins (RZ-1) and resins (RZ-3) obtained in Comparative Examples 1 and 3 are the above items. A balanced composition could not be obtained.

Application examples 7-9 and comparative application examples 3-4
Using the branched polyether resin compositions (II-1) to (II-3) obtained in Examples 1 to 3 and the resins (R-1) and resins (R-3) obtained in Comparative Examples 1 and 3 The photocurable compositions shown in Table 12 below were prepared, and the touch-drying properties and bending resistance of the obtained photocurable resin compositions were evaluated according to the following evaluation methods. The results obtained are shown in Table 12.

(7) Dryness to touch 3
Each photocurable resin composition is applied to a tinplate substrate with an applicator so that the dry film thickness of the coating film becomes 40 μm, dried at 90 ° C. for 30 minutes, and the coating film after cooling to room temperature (23 ° C.) is designated. The tackiness at the time of touch was evaluated according to the following criteria.
Evaluation criteria ○: No tack.
Δ: Tack is slightly present.
X: There is tackiness.
(8) Bending resistance After a tin plate (test piece) coated with an applicator so that each photocurable resin composition had a dry film thickness of 40 μm was dried in a 90 ° C. dryer for 30 minutes, 7 kW of After irradiating with a metal halide lamp (HTE-106-M07, manufactured by Hitec Co., Ltd.) with ultraviolet light with an integrated light quantity of 1000 mJ / cm ² and confirming curability with a finger, a cured coating film is formed in a strip shape with a width of 1 cm and a length of 5 cm. Cut out and isolated from tinplate. The presence or absence of breakage when this strip-like cured coating film was folded at 180 ° so that the coating film surface overlapped in the longitudinal direction was evaluated according to the following criteria.
Evaluation criteria ○: All of the four strip-shaped cured coating films do not break.
Δ: One or two of the four strip-shaped cured coatings were broken.
X: Three or more of the four strip-shaped cured coatings were broken.

Reference example 1
The results of the reaction of phenylglycidyl ether and acrylic acid as a model substance are shown below.

  Step 1: In a flask equipped with a stirrer, 150 g (1 mol) of phenylglycidyl ether, 57.92 g (0.8 mol) of acrylic acid and BHT (2,6-ditertiarybutyl-4-methylphenol) as a polymerization inhibitor 0.667g was added and it heated up to 130 degreeC, stirring. When the temperature reached 130 ° C., the acid value became 0.3 mg KOH / g, and acrylic acid almost disappeared.

  Step 2: Further, when the reaction was continued, the viscosity of the system increased. Infrared absorption spectra after 2, 3 and 4 hours after the start of the reaction are shown in FIG. As in Example 2, it can be seen that hydroxyl groups and carbon-carbon double bonds are decreased, and ether bonds are increased. Reaction was performed at 130 ° C. for 5 hours, and a polyether resin composition (PPGE-A) containing a polymer of phenyl glycidyl ether acrylate (polyether resin, hereinafter abbreviated as PPGE-A) was taken out. As a result of GPC analysis, it was confirmed that the PPGE-A was subjected to a high molecular weight reaction to produce a pentamer or higher component.

Furthermore, as a result of structural identification by C ¹³ -NMR, it was found that the acrylated phenyl glycidyl ether was increased in molecular weight by the reaction shown in the reaction scheme shown below.

〔式中、Ｒは、それぞれ独立に下記構造式（１）または（２）で表される２種の連結基のいずれかである。〕

[Wherein, R is independently any one of two linking groups represented by the following structural formula (1) or (2). ]

Comparative Reference Example 1
For comparison, 150 g (1 mol) of phenylglycidyl ether, 72.4 g (1 mol) of acrylic acid, and 0.667 g of BHT (2,6-ditertiarybutyl-4-methylphenol) as a polymerization inhibitor were added and stirred. The temperature was raised to 130 ° C. Three hours after the temperature reached 130 ° C., the acid value became 0.35 mg KOH / g, and acrylic acid disappeared. Further, the viscosity did not increase even when the reaction was continued.

2 is an infrared absorption spectrum of the resinous material obtained in Example 2. 2 is an infrared absorption spectrum of the resinous material obtained in Comparative Example 1. 4 is an infrared absorption spectrum showing a change with time of the reaction product in Reference Example 1.

Claims (17)

(1-1) Diacrylate (A2) of an aromatic bifunctional epoxy resin,
(1-2) (1-2-1) Aromatic bifunctional epoxy resin monoacrylate (A1)
And / or
(1-2-2) Other than (A1) and (A2)
Aromatic bifunctional epoxy resin (B),
And (1-3) phosphorus catalyst (C)
In the diacrylate (A2) of the aromatic bifunctional epoxy resin in the mixture containing the diacrylate (A2) of the aromatic bifunctional epoxy resin and the monoester of the aromatic bifunctional epoxy resin. Reacting the hydroxyl group and acryloyl group in the acrylate (A1),
(1-A) having a hydroxyl group, an acryloyl group and an epoxy group
Branched polyether resin (X) and (1-B) (1-B-1) aromatic difunctional epoxy resin diacrylate (A2),
(1-B-2) Aromatic bifunctional epoxy resin monoacrylate (A1) and
(1-B-3) Other than (A1) and (A2)
Aromatic bifunctional epoxy resin (B)
A first step of obtaining a reaction mixture containing one or more resin components selected from the group consisting of:
A branched polysiloxane comprising a second step of mixing the reaction mixture with an unsaturated monocarboxylic acid and reacting an epoxy group in the reaction mixture with a carboxyl group in the unsaturated monocarboxylic acid. A method for producing an ether resin composition.   The mixture used in the first step, the aromatic bifunctional epoxy resin (b) and the acrylic acid (a) in the presence of the phosphorus catalyst (C), the epoxy group in the aromatic bifunctional epoxy resin (b) The manufacturing method of the branched polyether resin composition of Claim 1 obtained by making it react on the conditions which become excessive with respect to the carboxyl group in acrylic acid (a). In the first step, the aromatic bifunctional epoxy resin (b) and the acrylic acid (a) are mixed as a mixture, and the epoxy group in the aromatic bifunctional epoxy resin (b) is added in the presence of the phosphorus catalyst (C). The reaction is carried out under an excess condition with respect to the carboxyl group in the acrylic acid (a),
(1-1) Diacrylate (A2) of an aromatic bifunctional epoxy resin,
(1-2-1) Monoacrylate (A1) of aromatic bifunctional epoxy resin
And (1-3) phosphorus catalyst (C)
And a hydroxyl group and an acryloyl group in the diacrylate (A2) of the aromatic bifunctional epoxy resin and the monoacrylate (A1) of the aromatic bifunctional epoxy resin in the mixture are reacted (1- A) having a hydroxyl group, an acryloyl group and an epoxy group
Of branched polyether resin (X) and (1-B) (1-B-1) aromatic bifunctional epoxy resin
Diacrylate (A2) and
(1-B-2) of aromatic bifunctional epoxy resin
Monoacrylate (A1)
The method for producing a branched polyether resin composition according to claim 1, which is a step of obtaining a reaction mixture containing at least one resin component selected from the group consisting of:   The method for producing a branched polyether resin composition according to claim 1, wherein a mixture further containing a methacryloyl group is used as the mixture used in the first step. In the first step, the aromatic bifunctional epoxy resin (b), acrylic acid (a) and methacrylic acid (a ′) are mixed as a mixture in the presence of a phosphorus catalyst (C). (B) The epoxy group in (b) is reacted under the condition that it is excessive with respect to the total carboxyl groups in acrylic acid (a) and methacrylic acid (a ′),
(1-1) Di (meth) acrylate (A2 ′) of an aromatic bifunctional epoxy resin,
(1-2) (1-2-1) of aromatic bifunctional epoxy resin
Mono (meth) acrylate (A1 ′) and / or
(1-2-2) Other than (A1 ′) and (A2 ′)
Aromatic bifunctional epoxy resin (B ')
And (1-3) phosphorus catalyst (C)
A hydroxyl group and an acryloyl group in the aromatic difunctional epoxy resin di (meth) acrylate (A2 ′) and the mono (meth) acrylate (A1 ′) of the aromatic bifunctional epoxy resin in the mixture. To have (1-A) hydroxyl group, (meth) acryloyl group and epoxy group
Of branched polyether resin (X) and (1-B) (1-B-1) aromatic bifunctional epoxy resin
Di (meth) acrylate (A2 ′),
(1-B-2) of aromatic bifunctional epoxy resin
Mono (meth) acrylate (A1 ′) and
(1-B-3) Other than (A1 ′) and (A2 ′)
Aromatic bifunctional epoxy resin (B ')
The method for producing a branched polyether resin composition according to claim 3, which is a step of obtaining a reaction mixture containing at least one resin component selected from the group consisting of: In the first step, an aromatic bifunctional epoxy resin (b), acrylic acid (a) and methacrylic acid (a ′) are mixed as a mixture in the presence of a phosphorus catalyst (C). b) the epoxy group in the reaction is allowed to react with the total amount of carboxyl groups in acrylic acid (a) and methacrylic acid (a ′) in an excess condition,
(1-1) Di (meth) acrylate (A2 ′) of an aromatic bifunctional epoxy resin,
(1-2-1) Mono (meth) acrylate (A1 ′) of aromatic bifunctional epoxy resin
And (1-3) phosphorus catalyst (C)
A hydroxyl group and an acryloyl group in the aromatic difunctional epoxy resin di (meth) acrylate (A2 ′) and the mono (meth) acrylate (A1 ′) of the aromatic bifunctional epoxy resin in the mixture. To have (1-A) hydroxyl group, (meth) acryloyl group and epoxy group
Of branched polyether resin (X) and (1-B) (1-B-1) aromatic bifunctional epoxy resin
Di (meth) acrylate (A2 ') and
(1-B-2) of aromatic bifunctional epoxy resin
Mono (meth) acrylate (A1 ')
The method for producing a branched polyether resin composition according to claim 3, which is a step of obtaining a reaction mixture containing at least one resin component selected from the group consisting of:   In the second step, the reaction mixture and the unsaturated monocarboxylic acid are mixed, and the equivalent ratio of the epoxy group in the reaction mixture to the carboxyl group in the unsaturated monocarboxylic acid (epoxy group / carboxyl group) is 0.9 / 1. The method for producing a branched polyether resin composition according to claim 1, which is a step of reacting in a range of ˜1 / 0.9.   The method for producing a branched polyether resin composition according to claim 6, wherein acrylic acid and / or methacrylic acid is used as the unsaturated monocarboxylic acid.   The branched polyfunctional resin according to claim 1, wherein an aromatic bifunctional epoxy resin (B1) having an epoxy equivalent of 135 to 500 g / equivalent is used as the aromatic bifunctional epoxy resin (B) and / or the aromatic bifunctional epoxy resin (b). A method for producing an ether resin composition.   The method for producing a branched polyether resin composition according to claim 8, wherein a dihydroxynaphthalene type epoxy resin or a bisphenol type epoxy resin is used as the aromatic bifunctional epoxy resin (B1).   The aromatic bifunctional epoxy resin (b) and acrylic acid (a) are mixed with an equivalent ratio of an epoxy group in the aromatic bifunctional epoxy resin (b) and a carboxyl group in the acrylic acid (a) [(epoxy group The method for producing a branched polyether resin composition according to claim 2, wherein the reaction is performed within a range of 1.1 to 5.5 in terms of (equivalent) / (carboxyl group equivalent).   The aromatic bifunctional epoxy resin (b) and acrylic acid (a) methacrylic acid (a ′) are combined with the epoxy group in the aromatic bifunctional epoxy resin (b), acrylic acid (a) and methacrylic acid (a ′). Of the branched polyether resin composition according to claim 3, wherein the equivalent ratio of (epoxy group equivalent) / (carboxyl group equivalent) is 1.1 to 5.0. Production method.   The method for producing a branched polyether resin composition according to claim 1, wherein a phosphine catalyst is used as the phosphorus catalyst (C).   Resin component in the reaction mixture [from branched polyether resin (X) and aromatic difunctional diacrylate (A2), aromatic bifunctional epoxy resin monoacrylate (A1) and aromatic epoxy compound (B) The one or more selected resin components] have a weight average molecular weight of 1,000 to 50,000 and an epoxy equivalent of 250 to 10,000 so that the aromatic bifunctional diacrylate (A2) and the aromatic two The method for producing a branched polyether resin composition according to claim 1, wherein a hydroxyl group and an acryloyl group in the monoacrylate (A1) of the functional epoxy resin are reacted.   A branched polyether resin composition obtained by the method for producing a branched polyether resin composition according to claim 1 and a polycarboxylic acid anhydride are mixed, a hydroxyl group in the branched polyether resin composition, and a polycarboxylic acid A method for producing an acid pendant branched polyether resin composition, characterized by reacting a hydroxyl group in an anhydride.   The acid pendant branch according to claim 14, wherein the hydroxyl group in the branched polyether resin composition and the hydroxyl group-free in the polycarboxylic acid anhydride are reacted until the acid value of the resin solid content is 50 to 120 mgKOH / g. A method for producing a polyether resin composition. The method for producing an acid pendant branched polyether resin composition according to claim 14, wherein an aliphatic dicarboxylic acid anhydride is used as the polycarboxylic acid anhydride.

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