JP2007009071A - Method for manufacturing branched type of polyether resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a branched type of a polyether resin composition which is excellent in the tack-free property at the time of forming a film, the developability, and the flexibility of a cured coat film. <P>SOLUTION: The method for manufacturing a branched type of a polyether resin composition comprises forming a resin composition, which contains a branched type of a polyether resin that is polymerized by reacting hydroxyl groups and acryloyl groups in an aromatic bifunctional epoxy resin di(meth)acrylate and an aromatic bifunctional epoxy resin mono(meth)acrylate in the reaction system containing an aromatic bifunctional epoxy resin di(meth)acrylate and an aromatic bifunctional epoxy resin mono(meth)acrylate and/or an aromatic bifunctional epoxy resin and including mixedly acryloyl groups and methacryloyl groups, in the presence of a phosphor-based catalyst, and which contains an unreacted component of resins of one or more kinds selected from the group consisting of an aromatic bifunctional di(meth)acrylate, an aromatic bifunctional epoxy resin mono(meth)acrylate and an aromatic epoxy compound. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention has excellent dryness to touch, developability, and flexibility of a cured coating film, particularly a branched type capable of thermal curing and energy ray curing suitable for coatings, inks, and adhesives. The present invention relates to a method for producing a polyether resin composition.

  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 the interlayer insulating layer and the conductor circuit layer of the multilayer printed wiring board, an acid anhydride is added to the novolac type epoxy (meth) acrylate resin as the resin component. There has been proposed a resin composition containing an acid pendant epoxy (meth) acrylate resin and an epoxy resin which are reacted as essential components (see, for example, 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.

JP2001-094261 (page 4-6)

  An object of the present invention is to provide a method for producing a branched polyether resin composition excellent in dryness to touch during film formation, 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 (5).
(1) In the production of mono- and / or di (meth) acrylate (aromatic bifunctional epoxy (meth) acrylate resin) of an aromatic bifunctional epoxy resin in which an aromatic bifunctional epoxy resin is reacted with acrylic acid and methacrylic acid, If necessary, the reaction is carried out in the presence of an organic solvent under the condition that the epoxy group in the aromatic bifunctional epoxy resin is excessive with respect to the carboxyl group in acrylic acid and methacrylic acid, and acrylic acid and methacrylic acid in the reaction system are reacted. After consumption, a reaction system containing di (meth) acrylate of aromatic bifunctional epoxy resin and mono (meth) acrylate of aromatic bifunctional epoxy resin and / or unreacted aromatic bifunctional epoxy resin Furthermore, if this reaction system is maintained in the presence of a phosphorus-based catalyst, a monofunctional aromatic bifunctional epoxy resin can be obtained. Reaction of hydroxyl group in di (meth) acrylate (hydroxyl group formed by reaction of epoxy group in aromatic bifunctional epoxy resin and carboxyl group in acrylic acid) to carbon-carbon double bond of acryloyl group Proceeding repeatedly to increase the molecular weight, a new branched polyether resin into which (meth) acryloyl groups and / or epoxy groups are introduced is produced.

(2) By the reaction in which the hydroxyl group in the mono- and di (meth) acrylate of the aromatic bifunctional epoxy resin described in (1) is added to the carbon-carbon double bond of the acryloyl group, the reaction system is ) Novel branched polyether resins having acryloyl and / or epoxy groups introduced, and di (meth) acrylates of aromatic bifunctional epoxy resins, mono (meth) acrylates and aromatic bifunctionals of aromatic bifunctional epoxy resins A branched polyether resin composition containing at least one unreacted resin component selected from the group consisting of epoxy resins.

(3) The reaction in which the hydroxyl group in the mono- and di (meth) acrylate of the aromatic bifunctional epoxy resin is added to the carbon-carbon double bond of the acryloyl group in the presence of the phosphorus-based catalyst described in the above (1) When the epoxy group in the aromatic bifunctional epoxy resin is not excessive with respect to the carboxyl group in acrylic acid, the mono (meth) acrylate of the aromatic bifunctional epoxy resin and / or the unreacted aromatic diester is contained in the reaction system. When there is no epoxy group-containing aromatic compound such as a functional epoxy resin, it should not proceed in a system using all methacrylic acid, not an acrylic acid / methacrylic acid mixed system.

(4) The branched polyether resin composition obtained by this production method is capable of both thermosetting and energy ray curing, and is curable resin that is superior in aerobic dryness, curability, and mechanical properties of the cured product. The composition is highly flexible, for example, the molecular weight of the aromatic bifunctional epoxy resin, the molar ratio of the epoxy group in the aromatic bifunctional epoxy resin to the carboxyl group in acrylic acid and methacrylic acid, By changing the mixing ratio of acrylic acid / methacrylic acid, the amount of phosphorus catalyst used, the reaction temperature, the reaction time, etc., the molecular weight of the resulting polyether resin, the introduction amount and introduction density of (meth) acryloyl groups and epoxy groups The ratio of the introduced (meth) acryloyl group to the epoxy group can be adjusted over a wide range.

(5) Branched poly by reaction similar to the reaction in which the hydroxyl group in the mono- and di (meth) acrylate of the aromatic bifunctional epoxy resin described in (1) is added to the carbon-carbon double bond of the acryloyl group. The production of the ether resin composition comprises di (meth) acrylate of aromatic bifunctional epoxy resin, mono (meth) acrylate of aromatic bifunctional epoxy resin and / or unreacted aromatic bifunctional epoxy resin, And if it is a reaction system in which an acryloyl group and a methacryloyl group are mixed and a phosphorus-based catalyst exists, it should proceed. For this reason, the branched polyether resin composition does not need to be produced continuously from the reaction of the aromatic bifunctional epoxy resin, acrylic acid and methacrylic acid as described in (1). Di (meth) acrylate of aromatic bifunctional epoxy resin with mixed acryloyl group and methacryloyl group (however, it contains mono (meth) acrylate and / or aromatic bifunctional epoxy resin of aromatic bifunctional epoxy resin) And a mono (meth) acrylate of an aromatic bifunctional epoxy resin produced separately and / or an unreacted aromatic bifunctional epoxy resin and a phosphorus-based catalyst. The branched polyether resin, di (meth) acrylate of aromatic bifunctional epoxy resin, and aromatic bifunctional epoxy resin module. A resin composition containing at least one unreacted resin component selected from the group consisting of (meth) acrylates and aromatic epoxy compounds is obtained (however, in this reaction, the reaction system is further divided into (It may contain a mono (meth) acrylate of an epoxy compound and / or an aromatic monoepoxy compound).

The present invention is based on such knowledge.
That is, the present invention relates to di (meth) acrylate (A2) of aromatic bifunctional epoxy resin, mono (meth) acrylate (A1) of aromatic bifunctional epoxy resin and / or aromatic bifunctional epoxy resin (B). And a di (meth) acrylate (A2) and an aromatic difunctional bifunctional epoxy resin in the presence of a phosphorus catalyst (C) in a reaction system in which an acryloyl group and a methacryloyl group are mixed. Branched polyether resin (X) and aromatic bifunctional di (meth) acrylate (A2) obtained by increasing the molecular weight by reacting the hydroxyl group and acryloyl group in mono (meth) acrylate (A1) of the functional epoxy resin One or more selected from the group consisting of mono (meth) acrylate (A1) and aromatic epoxy compound (B) of an aromatic bifunctional epoxy resin There is provided a method for producing a branched polyether resin composition characterized in that a resin composition containing the unreacted resin component.

  By the production method of the present invention, it is possible to provide a branched polyether resin composition having excellent touch drying properties during film formation, developability, and flexibility of a cured coating film.

  In the di (meth) acrylate (A2) of the aromatic bifunctional epoxy resin used in the production method of the present invention, the two epoxy groups in the aromatic bifunctional epoxy resin (B) are acrylic acid (a) and / or methacrylic. It is (meth) acrylated with an acid. Examples of the aromatic bifunctional epoxy resin (B) used here include biphenol type epoxy resins such as tetramethylbiphenol type epoxy resins; bisphenols such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol S type epoxy resins. Type epoxy resin; dicyclopentadiene-modified aromatic bifunctional epoxy resin; dihydroxynaphthalene type epoxy resin obtained by epoxidizing dihydroxynaphthalene; glycidyl ester type resin of aromatic divalent carboxylic acid; bifunctional epoxy derived from xylenol Resins, naphthalene aralkyl epoxy resins; epoxy resins obtained by modifying these aromatic bifunctional epoxy resins with dicyclopentadiene; ester-modified epoxy resins obtained by modifying these aromatic bifunctional epoxy resins with dibasic acids Resins.

  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 dibasic acid. Examples of dibasic 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, hexahydro Phthalic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, maleic anhydride, phthalic anhydride, succinic anhydride, dodecenyl succinic anhydride, tetrahydrophthalic anhydride, 4-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride And dibasic acid anhydrides such as hexahydrophthalic anhydride.

  The dibasic 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 dibasic 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 di (meth) acrylate (A2) of the aromatic bifunctional epoxy resin is an aromatic bifunctional epoxy resin (B) used in the production method of the present invention described later. ) May be the same or different.

  Examples of the mono (meth) acrylate (A1) and / or aromatic epoxy compound (B) of the aromatic bifunctional epoxy resin used in the production method of the present invention include, for example, 2 in the aromatic bifunctional epoxy resin (B). A mono (meth) acrylate (A1) of an aromatic bifunctional epoxy resin in which one of the epoxy groups is (meth) acrylated with acrylic acid or methacrylic acid, the aromatic bifunctional epoxy Either the resin (B) alone or a mixture thereof can be used.

  In order to obtain a branched polyether resin composition by the production method of the present invention, for example, di (meth) acrylate (A2) of an aromatic bifunctional epoxy resin produced separately and an aromatic bifunctional epoxy resin produced separately, respectively. The mono (meth) acrylate (A1) and / or the unreacted aromatic bifunctional epoxy resin (B) are appropriately selected so that acryloyl groups and methacryloyl groups are mixed in the reaction system, and these are phosphorus-based In the presence of the catalyst (C), if necessary, in the presence of an organic solvent or a reactive diluent, the reaction is usually performed at 100 to 170 ° C., preferably 100 to 150 ° C., usually for 1 to 20 hours, preferably 2 to 15 hours. That's fine. In this case, di (meth) acrylate (A2) of aromatic bifunctional epoxy resin is mono (meth) acrylate (A1) and / or aromatic bifunctional epoxy resin (B) of aromatic bifunctional epoxy resin. In addition, a (meth) acrylate of an aromatic polyfunctional epoxy resin having a functionality of 3 or more may be used in combination as long as it does not cause gelation. In this case, a monoacrylate of an aromatic monoepoxy compound and / or an aromatic monoepoxy compound may be used in combination.

  Di (meth) acrylate (A2) of the aromatic bifunctional epoxy resin, mono (meth) acrylate (A1) and / or aromatic bifunctional epoxy resin (B) of the aromatic bifunctional epoxy resin, The reaction system in which acryloyl group and methacryloyl group are mixed is, for example, as shown below, di (meth) acrylate of aromatic bifunctional epoxy resin (A2) mono (meth) acrylate of aromatic bifunctional epoxy resin ( A1) can be selected and mixed.

(1) Aromatic bifunctional epoxy resin di (meth) acrylate (A2) having an acryloyl group is used, and an aromatic bifunctional epoxy resin mono (meth) acrylate (A1) having a methacryloyl group is used. The reaction system. At this time, if necessary, an aromatic bifunctional epoxy resin mono (meth) acrylate (A1) having an acryloyl group or an aromatic bifunctional epoxy resin (B) may be used.

(2) Aromatic bifunctional epoxy resin di (meth) acrylate (A2) having a methacryloyl group is used, and an aromatic bifunctional epoxy resin mono (meth) acrylate (A1) having an acryloyl group is used. The reaction system. At this time, if necessary, a mono (meth) acrylate (A1) of an aromatic bifunctional epoxy resin having a methacryloyl group or an aromatic bifunctional epoxy resin (B) may be used.

(3) A di (meth) acrylate (A2) of an aromatic bifunctional epoxy resin having both an acryloyl group and a methacryloyl group, and an acryloyl group as a mono (meth) acrylate (A1) of the aromatic bifunctional epoxy resin Or a compound having a methacryloyl group is used as the reaction system. At this time, you may use an aromatic bifunctional epoxy resin (B) as needed.

(4) As a di (meth) acrylate (A2) of an aromatic bifunctional epoxy resin, a reaction system using both an acryloyl group and a methacryloyl group and an aromatic bifunctional epoxy resin (B) is used. At this time, what has an acryloyl group and what has a methacryloyl group as mono (meth) acrylate (A1) of an aromatic bifunctional epoxy resin may be used as needed.

In addition, the di (meth) acrylate (A2) of the aromatic bifunctional epoxy resin and the mono (meth) acrylate (A1) and / or the aromatic bifunctional epoxy resin (B And a reaction system in which an acryloyl group and a methacryloyl group are mixed.
(5) Aromatic bifunctional epoxy resin (B), acrylic acid (a) and methacrylic acid, and the epoxy group in aromatic bifunctional epoxy resin (B) is the total of acrylic acid (a) and methacrylic acid. The reaction is carried out under an excess condition with respect to the carboxyl group, and the di (meth) acrylate (A2) of the aromatic bifunctional epoxy resin and the mono (meth) acrylate (A1) and / or fragrance of the aromatic bifunctional epoxy resin. A reaction system containing a group II functional epoxy resin (B) is used.

  In the production method of the present invention, when the reaction system obtained by the method (5) (hereinafter, this step may be abbreviated as “step 1”) is used, the subsequent branched polyether resin composition This is preferable because the production can be carried out subsequently.

  In this step 1, since it can be easily performed, a reaction system containing di (meth) acrylate (A2) of an aromatic bifunctional epoxy resin and mono (meth) acrylate (A1) of an aromatic bifunctional epoxy resin [ However, you may contain the unreacted aromatic bifunctional epoxy resin (B). 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 carry out the production method of the present invention using the reaction system obtained in Step 1, di (meth) acrylate of an aromatic bifunctional epoxy resin in the reaction system in which an acryloyl group and a methacryloyl group coexist ( A2) and a hydroxyl group in a mono (meth) acrylate (A1) of an aromatic bifunctional epoxy resin and a (meth) acryloyl group are reacted in the presence of a phosphorus catalyst (C) to obtain an aromatic bifunctional epoxy resin Di (meth) acrylate (A2), or branched poly-polymers obtained by increasing the molecular weight of di (meth) acrylate (A2) of aromatic bifunctional epoxy resin and mono (meth) acrylate (A1) of aromatic bifunctional epoxy resin Ether resin (X) and di (meth) acrylate (A2) of aromatic bifunctional epoxy resin, mono (meth) acrylate of aromatic bifunctional epoxy resin A resin composition containing at least one unreacted resin component selected from the group consisting of (A1) and an aromatic bifunctional epoxy resin (B) may be used (hereinafter, this step is abbreviated as “step 2”). To do.) In this case, the phosphorus catalyst (C) may be added after the completion of the step 1, but it is preferable to add it in the reaction of the step 1.

  As the aromatic bifunctional epoxy resin (B) used in the step 1, since a polyether resin composition having excellent curability is obtained, it is preferable that the epoxy equivalent is 135 to 2,000 g / equivalent, More preferably, the epoxy equivalent is 135 to 500 g / equivalent. Moreover, since a branched polyether 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 Bisphenol type epoxy resins such as epoxy resins and dihydroxynaphthalene type epoxy resins obtained by epoxidizing dihydroxynaphthalenes are preferred, and bisphenol A type epoxy resins or 1,6-dihydroxynaphthalene type epoxy resins (dihydroxynaphthalene type epoxy resins) are more preferred. Bisphenol A epoxy resin is most preferred.

  In addition, when manufacturing a branched polyether resin composition by the process of the said process 1 and 2, the ester modified aromatic two which modified the aromatic bifunctional epoxy resin with the dibasic acid as an aromatic bifunctional epoxy resin (B). Instead of using a functional epoxy resin, the aromatic bifunctional epoxy can be obtained by using a dibasic acid for modification in combination with the aromatic bifunctional epoxy resin (B), acrylic acid (a), and methacrylic acid (b) in Step 1 above. The resin (B) may be modified with dibasic acids.

  In 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 acrylic acid (a) and methacrylic acid (b) is not particularly limited. However, in Step 2, the reaction between the hydroxyl group and the (meth) acryloyl group in the di (meth) acrylate (A2) of the aromatic bifunctional epoxy resin and the mono (meth) acrylate (A1) of the aromatic bifunctional epoxy resin is smooth. Since the process proceeds, the equivalent ratio of epoxy groups in the aromatic bifunctional epoxy resin (B) to the total carboxyl groups in the acrylic acid (a) and methacrylic acid (b) (epoxy group equivalent / carboxyl group equivalent) is 1. It is preferable that it is the range used as 0.1-5.5. Moreover, since the molecular weight adjustment of the obtained branched polyether resin is facilitated, the equivalent ratio (epoxy group equivalent / carboxyl group equivalent) is more preferably in the range of 1.25 to 3.0. preferable.

  Furthermore, the use ratio [(a) / (b)] of acrylic acid (a) and methacrylic acid (b) is 0.1 to 9 in terms of molar ratio, and the heat resistance of the resulting coating film is good. Therefore, 0.25 to 4 is more preferable. By the way, in the present invention, it is necessary to use a system in which an acryloyl group and a methacryloyl group are mixed. This is because when a system has only a methacryloyl group, molecular growth due to reaction with a hydroxyl group does not proceed. It is because it is not preferable, and when the system is a system having only an acryloyl group, the heat resistance of the coating film obtained using the obtained polyether resin composition tends to be inferior.

  In the reaction in the coexistence system of the aromatic bifunctional epoxy resin (B) with acrylic acid (a) and methacrylic acid (b), the molecular growth reaction when focusing on the acryloyl group is as shown in the following diagram, for example. It is considered that the reaction proceeds with a simple reaction scheme.

〔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（Ｉ）または（II）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 (I) or (II) Either of two types of linking groups. ]

  The catalyst used in Step 1 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, and phosphorus catalysts such as phosphines and phosphonium salts are preferable. Of these, phosphorus catalysts such as phosphines and phosphonium salts are more preferred, and phosphines are most preferred because they can be used as essential catalysts in Step 2 above.

  Further, the catalyst used in Step 2 is essentially a phosphorus catalyst, and is preferably a non-halogen catalyst. As such a catalyst, phosphorus-based catalysts such as the phosphines and phosphonium salts are more preferable, and phosphines are most preferable. Examples of the phosphine 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), acrylic acid (a), and methacrylic acid (b). 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 Step 1, the reaction between the hydroxyl group and the carbon-carbon double bond of the acryloyl group hardly proceeds during the reaction of the aromatic bifunctional epoxy resin (B), acrylic acid (a) and methacrylic acid (b). Hydroxyl and acryloyl at the end of step 1 when acrylic acid (a) and methacrylic acid (b) and carboxyl groups in methacryloyl groups were consumed by reaction with epoxy groups in aromatic bifunctional epoxy resin (B) By the reaction with the carbon-carbon double bond of the group, an ether bond is formed to increase the molecular weight, and Step 2 is started.

  In the step 2, the di (meth) acrylate (A2) of the aromatic bifunctional epoxy resin, the mono (meth) acrylate (A1) and / or the aromatic bifunctional epoxy resin (B) of the aromatic bifunctional epoxy resin, And a di (meth) acrylate (A2) and an aromatic difunctional bifunctional epoxy resin in the presence of a phosphorus catalyst (C) in a reaction system in which an acryloyl group and a methacryloyl group are mixed. Di (meth) acrylate (A2) and aromatic bifunctional epoxy resin by reacting the hydroxyl group in mono (meth) acrylate (A1) of functional epoxy resin with the carbon-carbon double bond of acryloyl group The bifunctional epoxy resin mono (meth) acrylate (A1) is a new multifunctional branched polyether resin (X) with a high molecular weight. Diversified polyether resin (X), di (meth) acrylate (A2) of aromatic bifunctional epoxy resin, mono (meth) acrylate (A1) of aromatic bifunctional epoxy resin and aromatic bifunctional epoxy resin (B A branched polyether resin composition containing one or more unreacted resin components selected from the group consisting of:

  In addition, the reaction in Steps 1 and 2 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 amount of the organic solvent and the reactive diluent with respect to the resin component consisting of (X) and one or more unreacted resin components selected from the group consisting of (A2), (A1) and (B) is large. As a result, the reaction rate in the steps 1 and 2 is slowed down, and therefore the ratio of the resin component during the 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 steps 1 and 2 is the equivalent of the total carboxyl groups in the epoxy group, acrylic acid (a) and methacrylic acid in the aromatic bifunctional epoxy resin (B). It is influenced by the ratio (epoxy group equivalent / carboxyl group equivalent), catalyst type, catalyst amount, reaction temperature, reaction time, and the like. 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, although the reaction time of the step 1 and the step 2 is affected by the temperature, in the above temperature range, the step 1 is 0.5 to 10 hours, preferably 1 to 5 hours, and the step 2 is 1 to 20 hours, preferably 2 to 15 hours.

  In order to adjust the molecular weight of the branched polyether resin composition or branched polyether resin (X) obtained by the production method of the present invention, for example, di (meth) acrylate (A2) of an aromatic bifunctional epoxy resin. The molar ratio of the mono (meth) acrylate (A1) of the aromatic bifunctional epoxy resin to the acrylic acid (a) and methacrylic acid (b) of the epoxy group in the aromatic bifunctional epoxy resin (B) in step 1 The excess ratio relative to the total carboxyl groups], the ratio of acrylic acid (a) and methacrylic acid (b), the amount of phosphorus catalyst (C) used, the reaction temperature, the reaction time, and the like may be appropriately adjusted. For example, the molar ratio (A1 / A2) of the mono (meth) acrylate (A1) of the aromatic bifunctional epoxy resin to the di (meth) acrylate (A2) of the aromatic bifunctional epoxy resin is reduced (for example, the molar ratio is reduced). 0 to 1) [molar ratio of epoxy group in aromatic bifunctional epoxy resin (B) in step 1 to total carboxyl group in acrylic acid (a) and methacrylic acid (b) (B / (a + b )) Is reduced (for example, B / (a + b)) = 1.25-3], the amount of acrylic acid (a) used is larger than the amount of methacrylic acid (b) used, phosphorus The branched type polyether having a higher molecular weight can be obtained by increasing the amount of the catalyst (C) used, increasing the reaction temperature, increasing the reaction time, and increasing the concentration of the resin component in the reaction system. Resin is obtained.

  In order to adjust the introduction amount of the (meth) acryloyl group and the epoxy group in the branched polyether resin (X) obtained by the production method of the present invention, for example, an excess of the epoxy group in the reaction system relative to the carboxyl group The size of the epoxy equivalent of the di (meth) acrylate (A2) of the aromatic bifunctional epoxy resin and the mono (meth) acrylate (A1) of the aromatic bifunctional epoxy resin may be appropriately adjusted. For example, di (meth) acrylate (A2) of aromatic bifunctional epoxy resin and mono (meth) acrylate (A1) of aromatic bifunctional epoxy resin, di (meth) of aromatic bifunctional epoxy resin having a small epoxy equivalent By using acrylate or mono (meth) acrylate, a branched polyether resin having a high introduction amount (content) of (meth) acryloyl group and epoxy group can be obtained, and carboxyl of epoxy group in the reaction system can be obtained. The introduction amount of (meth) acryloyl groups and epoxy groups in the polyether resin can be adjusted by adjusting the excess ratio relative to the groups.

  The branched polyether resin composition and the branched polyether resin (X) obtained by the production method of the present invention can be synthesized so as to have a molecular weight sufficient to satisfy performance required in various applications. However, in order to satisfy various application suitability, the resin component in the branched polyether resin composition [branched polyether resin (X) and aromatic difunctional di (meth) acrylate (A2), aromatic The composition which consists of 1 or more types of unreacted resin components chosen from the group which consists of the mono (meth) acrylate (A1) of a group bifunctional epoxy resin, and an aromatic epoxy compound (B). The same applies below. ] Is preferably in the range of 800 to 10,000 in terms of polystyrene-equivalent number average molecular weight (Mn), and in the range of 1,000 to 50,000 in terms of weight average molecular weight (Mw). More preferably, the molecular weight (Mn) is in the range of 800 to 5,000, and the weight average molecular weight (Mw) is in the range of 2,000 to 30,000. The molecular weight of the branched polyether resin (X) is within the range of 1,500 to 10,000 in terms of polystyrene-equivalent number average molecular weight (Mn) and 3,000 to 100,000 in terms of weight average molecular weight (Mw). The number average molecular weight (Mn) is preferably in the range of 1,500 to 8,000, and the weight average molecular weight (Mw) is more preferably in the range of 3,000 to 50,000.

  The epoxy equivalent of the resin component in the branched polyether resin composition obtained in the present invention is preferably 250 to 10,000 g / equivalent, and further, the branched polyether resin composition having excellent curability and mechanical properties of the cured product. It is more preferable that the epoxy equivalent is 400 to 5,000 g / equivalent because it becomes a product. Further, the epoxy equivalent of the branched polyether resin (X) is preferably 500 to 10,000 g / equivalent, and since it becomes a branched polyether resin composition excellent in curability and mechanical properties of the cured product, it is epoxy. More preferably, the equivalent is 800 to 8,000 g / equivalent.

  Further, the branched polyether resin composition obtained in the present invention has a (meth) acryloyl group content of 0.2 to 4 mmol per 1 g of the resin component and a hydroxyl group content of 0.2 to 4 g of the resin component. 4 mmol is preferable, the (meth) acryloyl group content per 1 g of the resin component is 0.3 to 3.5 mmol, and the hydroxyl group content per 1 g of the resin component is 0.3 to 3.5 mmol. Is more preferable. The branched polyether resin (X) has a (meth) acryloyl group content of 0.2 to 3.5 millimoles per gram of resin and a hydroxyl group content of 0.2 to 3.5 millimoles per gram of resin. Preferably, the (meth) acryloyl group content per 1 g of resin is 0.3 to 3.3 mmol, and the hydroxyl group content per 1 g of resin is more preferably 0.3 to 3.3 mmol.

  The branched polyether resin composition obtained in the present invention contains the branched polyether resin (X) as an essential component, and the branched polyether resin is contained in a total of 100% by weight of the contained resin components. What contains 20 to 90 weight% of (X) is preferable. In addition to the branched polyether resin (X), this branched polyether resin composition includes di (meth) acrylate (A2) of an aromatic bifunctional epoxy resin, mono (meta) of an aromatic bifunctional epoxy resin. 1) One or more unreacted resin components selected from the group consisting of acrylate (A1) and aromatic epoxy compound (B). 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 branched polyether resin composition. 5 to 50% by weight of di (meth) acrylate (A2) and 5 to 30% by weight of mono (meth) acrylate (A1) of aromatic bifunctional epoxy resin [however, di (meth) of the above aromatic bifunctional epoxy resin ) Acrylate (A2) and aromatic bifunctional epoxy resin mono (meth) acrylate (A1) in total 10 to 80 wt%], and aromatic bifunctional epoxy resin (B) containing 0 to 30 wt% preferable. In addition, when making this branched polyether resin composition 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%. It is more preferable.

  Examples of the branched polyether resin (X) in the branched polyether resin composition obtained through the steps 1 and 2 include a (meth) acryloyl group, an epoxy group, a hydroxyl group, and the following general formula (1). Examples thereof include a branched polyether resin (X1) having a structure shown and a structure represented by the following general formula (4) and having a weight average molecular weight of 3,000 to 100,000.

〔一般式（１）中、Ｒは下記構造式（２）または（３）で表される連結基を示す。〕

[In the general formula (1), R represents a linking group represented by the following structural formula (2) or (3). ]

〔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 branched polyether resin (X1) has a number average molecular weight of 1,500 to 10,000, a weight average molecular weight of 3,000 to 100,000, and an epoxy equivalent of 500 to 10,000 g / equivalent branch. Type polyether resins are preferable, and branched polyether resins having a number average molecular weight of 1,500 to 8,000, a weight average molecular weight of 3,000 to 50,000, and an epoxy equivalent of 800 to 8,000 g / equivalent are more preferable. .

  The branched polyether resin (X1) includes 0.2 to 3.5 mmol (meth) acryloyl groups and 0.2 to 3.5 mmol per 1 g of the branched polyether resin (X1). It preferably has a hydroxyl group, more preferably 0.3 to 3.3 mmol of (meth) acryloyl group and 0.3 to 3.3 mmol of hydroxyl group per 1 g of branched polyether resin (X1).

  Further, the branched polyether resin (X1) is preferably a branched polyether resin (X2) 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（２）または（３）で表される連結基を示す。また、Ｒ１は、水素原子および／またはメチル基である。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 (2) or (3). Show. R1 is a hydrogen atom and / or a methyl group. 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_２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（８）で表される構造を示す。〕

[In the general formulas (6) and (7), R ₂ 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 independently selected. 0 to 20 repeating units are shown. R ₃ represents a hydrogen atom or a structure represented by the following general formula (8). ]

〔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（２）または（３）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_２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 general formula (8), r represents 1 to 50 repeating units, and R in the r repeating units independently represents a linking group represented by the structural formula (2) or (3). . Ar in the r repeating units independently represents a structure represented by the general formula (6) or (7), and R ₂ 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. ]

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 (9) is preferable.

〔一般式（４）中、Ｒ_４は単結合又は２価の連結基を表し、Ｒ_５はそれぞれ同一でも異なっていても良い水素原子または炭素数１〜５のアルキル基を表す。〕

[In General Formula (4), R ₄ represents a single bond or a divalent linking group, and R ₅ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, which may be the same or different. ]

  In addition, in the branched polyether resin composition obtained by the production method of the present invention, if necessary, another epoxy compound (b) other than the aromatic bifunctional epoxy resin (B) or other epoxy compound A reaction product of (b) and unsaturated carboxylic acid (c) may be added, but even in that case, the content of the branched polyether resin (X) in 100% by weight of the total resin component is 20 to 90% by weight. % Is preferable from the viewpoint of excellent drying properties and the like.

  The other epoxy compound (b) is not particularly limited, and any of a monoepoxy compound and a polyfunctional epoxy resin can be used. Specific examples of the other epoxy compound (b) 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; various bisphenols Novolac epoxy resin, cresol novolac epoxy resin, phenol novolac type, xylenol novolak, and other novolac epoxy resins; dicyclopentadiene-modified aromatic epoxy resins; dihydroxynaphthalene epoxy obtained by epoxidizing dihydroxynaphthalenes An epoxy resin obtained by epoxidizing a novolak resin or a dihydroxynaphthalene; a glycidyl ester type resin of a 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 carboxylic acid (c) 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.

  Moreover, you may add other polyether resins other than polyether resin (X) to the branched polyether resin composition obtained by the manufacturing method of this invention as needed. Examples of other polyether resins include polyether resins obtained by the following method.

  1. In the reaction system containing monomethacrylate of aromatic bifunctional epoxy resin and further containing dimethacrylate and / or aromatic bifunctional epoxy resin of aromatic bifunctional epoxy resin, or aromatic bifunctional epoxy In a reaction system containing a resin dimethacrylate and an aromatic bifunctional epoxy resin, in the presence of a nitrogen-based catalyst, the aromatic bifunctional epoxy resin monomethacrylate and / or the aromatic bifunctional epoxy resin dimethacrylate By reacting the hydroxyl group with the epoxy group in the monomethacrylate and / or aromatic bifunctional epoxy resin of the aromatic bifunctional epoxy resin, the dimethacrylate and / or aromatic bifunctional epoxy resin of the aromatic bifunctional epoxy resin is reacted. A branched polyether resin obtained by increasing the molecular weight of methacrylate.

  2. Aromatic difunctional epoxy resin diacrylate, aromatic bifunctional epoxy resin monoacrylate and / or aromatic bifunctional epoxy resin, and reaction system containing phosphorus catalyst, aromatic bifunctional epoxy resin diacrylate And a branched polyether resin obtained by reacting a hydroxyl group and an acryloyl group in a monoacrylate of an aromatic bifunctional epoxy resin to increase the molecular weight by this reaction.

  The branched polyether resin composition of the present invention obtained by the production method of the present invention may be used as it is as a heat curing and / or photocuring resin utilizing the remaining epoxy group, or the remaining epoxy It may be used after synthesizing acrylic acid or methacrylic acid to synthesize a polyfunctional acrylate resin, and after reacting an acid anhydride with a hydroxyl group in this polyfunctional acrylate resin to synthesize an acid pendant type epoxy acrylate. It is also possible to use it. It is also possible to apply urethanization and other chemical modifications.

  When the branched polyether resin composition obtained by the production method of the present invention is used as a resin for heat curing and / or photocuring, the branched polyether resin composition may further contain a curing component. . The curing component is not particularly limited, and various curing agents for epoxy resins can be used. Moreover, you may contain a photoinitiator and a photosensitizer as a hardening | curing agent. Further, when the branched polyether resin composition obtained by the production method of the present invention is used as a developable resin composition, a cresol novolac epoxy acrylate or an acid pendant resin thereof may be contained.

  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 epoxy resin curing agent used is a branched polyether resin composition obtained by the production method of the present invention 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 contained in the product. In the case of an acid anhydride, the acid anhydride group is used in a range of 0.3 to 1.2 equivalent per 1 equivalent of epoxy group contained in the branched polyether resin composition obtained by the production method of the present invention. It is preferable to do.

  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. .

  Next, the present invention will be specifically described with reference to examples and comparative examples. In addition,% described below is 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
A flask equipped with a thermometer, a stirrer and a reflux condenser was charged with 188 g of a bisphenol A type epoxy resin (epoxy equivalent 188 g / equivalent; EPICLON 850 manufactured by Dainippon Ink & Chemicals, Inc.), and BHT (2,6- 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 after 0, 1, 3, 5 hours, and then taken out from the flask and branched polyether resin (X1) A pale yellow transparent resinous branched polyether resin composition 1 containing 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 1-1 below.

  The obtained branched polyether resin composition 1 had the composition shown in Table 1-2 below from its GPC. The branched polyether resin (X1) calculated from the content of each component in Table 1-2 below and the epoxy equivalent of the branched polyether resin composition 1 after 10 hours elapsed in Table 1-1 The epoxy equivalent of 2604 was 2604. The epoxy equivalent of this branched polyether resin (X1) is 100 / (epoxy equivalent of branched polyether resin composition 1) = [(content of bisphenol A type epoxy resin) / (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 equimolar molecules of bisphenol A type epoxy monoacrylate and bisphenol A type epoxy monomethacrylate exist.

Furthermore, analysis by IR (infrared absorption spectrum) was performed. An infrared absorption spectrum of the branched polyether resin composition 1 is shown in FIG. From FIG. 1, broad hydroxyl group content of the branched polyether resin composition 1 and comparing the relative intensity of the absorption of alkyl group absorption and 2800～3100Cm ^-1 hydroxyl groups 3300～3600Cm ^-1 less, consumes hydroxyl You can see that 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 is increased, and it can be seen that an ether bond is formed by the reaction between the acryloyl group and the hydroxyl group.

Example 2
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 188 g of EPICLON850, and further with 1 g of BHT, 21.6 g (0.3 mol) of acrylic acid and 51.6 g (0.6 mol) of methacrylic acid were charged. . 1.57 g of triphenylphosphine (0.6% of resin content) was added, and the temperature was raised to 130 ° C. in 2 hours while stirring. The reaction was continued at the same temperature for 10 hours while sampling at 0, 2, 4, 6 and 8 hours after the time when the temperature reached 130 ° C. was taken as 0 hours, and then taken out from the flask and branched polyether resin ( A pale yellow transparent resinous branched polyether resin composition 2 containing X2) was obtained. For the sampled samples, the viscosity, acid value (solid content), epoxy equivalent (solid content) number average molecular weight (Mn) and weight average molecular weight (Mw) were determined in the same manner as in Example 1. The obtained results are shown in Table 2-1 below.

  The obtained branched polyether resin composition 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 of the branched-type polyether resin composition 2 after the elapsed time 10 hours in the said Table 2-1. The epoxy equivalent of the branched polyether resin was 7115. However, the epoxy equivalent of the epoxy group-containing bisphenol A type epoxy mono (meth) acrylate is an average on the assumption that the molecules exist in a ratio of 1: 2 moles of bisphenol A type epoxy monoacrylate and bisphenol A type epoxy monomethacrylate. Calculated as epoxy equivalent.

Comparative Example 1
Into a flask equipped with a thermometer, a stirrer and a reflux condenser, 28.9 g of ethyl carbitol acetate was added, 188 g of EPICLON 850 was dissolved therein, 0.5 g of hydroquinone was added, and then 72 g (1 mol) of acrylic acid and triphenyl were added. Phosphine 0.52 g (0.2% of resin content) was added, and the temperature was raised to 130 ° C. in 2 hours while stirring. The reaction was continued at the same temperature for 10 hours while sampling at 1, 3, 4.5, 6, 8 and 10 hours after the time when the temperature reached 130 ° C. was taken as 0 hours, and then taken out from the flask and pale yellow A transparent control resin (Y-1) was obtained. For the sampled samples, the viscosity, acid value (solid content), epoxy equivalent (solid content) number average molecular weight (Mn) and weight average molecular weight (Mw) were determined in the same manner as in Example 1. The obtained results are shown in Table 1′-1.

  As can be seen from Table 1'-1, the epoxy equivalent of the obtained resin (Y-1) is very large, and the epoxy groups are almost disappeared, and the oxidation is extremely small and almost no carboxyl groups remain. Also, the molecular weight does not change greatly even after 10 hours from the GPC analysis results, and the resin (Y-1) is a diacrylate obtained by reacting the epoxy group at the end of the bisphenol A type epoxy resin with acrylic acid. Thus, the resin was different from the branched polyether resin composition (X-2) obtained by the method for producing a branched polyether resin composition of the present invention.

An infrared absorption spectrum of the comparative resin (Y-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, absorption of hydroxyl groups of the branched polyether resin composition (X-2) Compared to the strength, it can be seen that the comparative resin (Y-1) shown in FIG. 2 has higher hydroxyl group absorption strength, and more hydroxyl groups remain than the above (X-2). Further, comparing the relative intensities of 1410 cm ⁻¹ acryloyl groups, it was found that most of the acryloyl groups remained unreacted.

Example 3
In a flask equipped with a thermometer, a stirrer and a reflux condenser, 500 g of ethyl carbitol acetate was added, 1504 g of EPICLON 850 was dissolved therein, 5.9 g of BHT was further added, and then 166 g (1 mol) of isophthalic acid and acrylic acid were added. 180 g (2.5 mol) and 43 g (0.5 mol) of methacrylic acid were charged. 3.95 g of triphenylphosphine (0.2% of resin content) was added, and the temperature was raised to 130 ° C. in 2 hours while stirring. The reaction was continued for 2 hours with the temperature reaching 130 ° C. as 0 hour, then taken out from the flask, and a pale yellow transparent resinous branched polyether resin composition containing the branched polyether resin (X3) 3 was obtained. For the sampled samples, the viscosity, acid value (solid content), epoxy equivalent (solid content) number average molecular weight (Mn) and weight average molecular weight (Mw) were determined in the same manner as in Example 1. The obtained results are shown in Table 3-1 below.

  The obtained branched polyether resin composition 3 had the composition shown in Table 3-2 below from its GPC. Moreover, it is the same as that of Example 1 from the content rate of each component in following Table 3-2, and the epoxy equivalent of the branched-type polyether resin composition (X-3) after the elapsed time 8 hours in the said Table 3-1. The calculated epoxy equivalent of the branched polyether resin was 1523. However, the epoxy equivalent of the epoxy group-containing bisphenol A type epoxy mono (meth) acrylate is an average on the assumption that bisphenol A type epoxy monoacrylate and bisphenol A type epoxy monomethacrylate are present in a ratio of 5: 1 mol. Calculated as epoxy equivalent.

Example 4
Into a flask equipped with a thermometer, a stirrer and a reflux condenser, 58.6 g of ethyl carbitol acetate was placed, and 476 g of bisphenol A type epoxy resin (epoxy equivalent 476 g / equivalent; EPICLON 1050 manufactured by Dainippon Ink & Chemicals, Inc.) was added. After dissolving and adding 1.58 g of BHT, 43.2 g (0.6 mol) of acrylic acid and 8.6 (0.1 mol) of methacrylic acid were charged. Further, 1.58 g of triphenylphosphine (0.3% of resin content) was added, and the temperature was raised to 130 ° C. in 2 hours while stirring. The reaction was continued at the same temperature for 8 hours while sampling at 0, 2, 4, 6 and 8 hours after the time when the temperature reached 130 ° C. was taken as 0 hours, and then taken out from the flask and branched polyether resin ( A pale yellow transparent resinous branched polyether resin composition 4 containing X4) was obtained. For the sampled samples, the viscosity, acid value (solid content), epoxy equivalent (solid content) number average molecular weight (Mn) and weight average molecular weight (Mw) were determined in the same manner as in Example 1. The obtained results are shown in Table 4-1.

  The obtained branched polyether resin composition 4 had the composition shown in Table 4-2 below from its GPC. Moreover, the branch calculated similarly to Example 1 from the content rate of each component in following Table 4-2, and the epoxy equivalent of the branched polyether resin composition 4 after the elapsed time 8 hours in the said Table 4-1. The epoxy equivalent of the type polyether resin was 4275. However, the epoxy equivalent of the epoxy group-containing bisphenol A type epoxy mono (meth) acrylate is an average on the assumption that bisphenol A type epoxy monoacrylate and bisphenol A type epoxy monomethacrylate are present in a ratio of 6: 1 mol. Calculated as epoxy equivalent.

Example 5
Into a flask equipped with a thermometer, a stirrer and a reflux condenser, 26.6 g of ethyl carbitol acetate was put, and 186 g of tetramethylbiphenyl type epoxy resin (epoxy equivalent 186 g / equivalent; YX-4000 manufactured by Japan Epoxy Resin Co., Ltd.) was added here. After dissolving and further adding 1 g of BHT, 36 g (0.5 mol) of acrylic acid and 17.2 g (0.2 mol) of methacrylic acid were charged. 1.2 g of triphenylphosphine (0.5% of resin content) was added, the temperature was raised to 130 ° C. in 2 hours while stirring, and 4 hours and 7 hours after the temperature reached 130 ° C. Further, 0.236 g of triphenylphosphine was added. The reaction was continued for 10 hours while sampling at 0, 1, 5, 8 and 10 hours after the time when the temperature reached 130 ° C. was taken as 0 hours, and then taken out from the flask, and branched polyether resin (X5 A light yellow transparent resinous branched polyether resin composition 5 was obtained. For the sampled samples, the viscosity, acid value (solid content), epoxy equivalent (solid content) number average molecular weight (Mn) and weight average molecular weight (Mw) were determined in the same manner as in Example 1. The obtained results are shown in Table 5-1.

  The obtained branched polyether resin composition 5 had a composition shown in Table 5-2 below from the GPC. Moreover, it is the same as that of Example 1 from the content rate of each component in following Table 5-2, and the epoxy equivalent of the branched-type polyether resin composition (X-5) after the elapsed time 10 hours in the said Table 5-1. The calculated epoxy equivalent of the branched polyether resin was 2193. However, the epoxy equivalent of the epoxy group-containing bisphenol A type epoxy mono (meth) acrylate is an average on the assumption that bisphenol A type epoxy monoacrylate and bisphenol A type epoxy monomethacrylate are present in a ratio of 5: 2 moles. Calculated as epoxy equivalent.

Comparative Example 2
Into a flask equipped with a thermometer, a stirrer and a reflux condenser, 428 g of ethyl carbitol acetate was added, 188 g of EPICLON 850 was dissolved therein, 0.5 g of hydroquinone was further added, and then 144 g (2 mol) of acrylic acid and triphenylphosphine were added. 0.52 g (0.2% of resin content) was added, and the temperature was raised to 130 ° C. over 2 hours while stirring. After reaching the temperature of 130 ° C., gelation occurred with an intense exotherm about 1 hour.

Synthesis Example 1 (Synthesis of acid pendant type epoxy acrylate resin)
In 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. After adding 0.5 g of hydroquinone, 72 g (1 mol) of acrylic acid and 0.52 g of triphenylphosphine (0.2% of resin content) were added, and the temperature was raised to 120 ° C. over 2 hours while stirring. After the temperature reached 120 ° C., the reaction was carried out for about 15 hours, and then the temperature was lowered to 100 ° C., then 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 epoxy acrylate resin (Z-1) was obtained. The acid value was 91 mgKOH / g in terms of solid content.

Test example 1
Each raw material was mix | blended with the compounding ratio shown in Table 6, and the active energy ray hardening-type resin composition 1 (resist ink 1) was prepared. The resist ink 1 was evaluated for finger touch drying property, developability, sensitivity, stability during solvent drying, and flexibility of the coating film. The evaluation method is shown below.

(1) Dryness to touch 1
Each resist ink 1 is applied with an applicator so that the dry film thickness of the coating film is 40 μm on the glass epoxy substrate, dried at 80 ° C. for 30 minutes, and the coated film after cooling to room temperature (23 ° C.) is touched The tackiness of 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
Apply resist ink 1 with an applicator so that the coating film has a dry film thickness of 40 μm on a glass epoxy substrate, dry at 80 ° C. for 30 minutes, cool to room temperature (23 ° C.), and then step tablet for sensitivity evaluation ( Step tablet No. 2) manufactured by Kodak Co., Ltd. was placed on the surface of the dried coating film and irradiated with ultraviolet rays 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 a feeling of tack.
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 sample coated with resist ink 1 with an applicator so that the dry film thickness is 40 μm on the tinplate is 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 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 resist ink 1 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 placed on the coating film. , a metal halide lamp of 7 ^kW, after irradiation with ultraviolet rays of ^{400mJ / cm 2, 600mJ / cm} 2, 800mJ / cm 2, 120 seconds step tablet removed from the sample surface, the sample in 1% sodium carbonate aqueous solution 30 ° C. It was immersed 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 resist ink 1 with an applicator so that the dry film thickness was 40 μm was left in a 90 ° C. dryer for 30 minutes, 40 minutes, 50 minutes to volatilize the solvent, and 30 ° C. The sample was immersed in a 1% aqueous solution of sodium carbonate for 120 seconds for development, and visually 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.

(6) Coating film flexibility test (Eriksen test)
A tin plate (test piece) coated with resist ink 1 with an applicator so that the dry film thickness is 40 μm is dried for 30 minutes in a dryer at 90 ° C., and then irradiated with UV light at 800 mJ / cm ² with a 7 KW metal halide lamp. Further, heat curing was performed at 150 ° C. for 1 hour. This sample was cut together with a tin plate to a size of 5 cm square, and subjected to an Erichsen test at 23 ° C. using an automatic Eriksen tester 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.

Test Examples 2 and 3 and Comparative Test Examples 1 to 3
Resist inks 2 and 3 and comparative resist inks 1 'to 3' were prepared in the same manner as in Test Example 1 except that the blending ratios shown in Table 6 were used. Evaluation was performed in the same manner as in Test Example 1, and the results are shown in Table 7.

Footnotes in Table 6 EP20: EPICLON 2055: Epoxy equivalent 640 g / equivalent [Dai Nippon Ink Chemical Co., Ltd. bisphenol A type epoxy resin].
EP8: EPICLON 850: Epoxy equivalent 188 g / equivalent [Bisphenol A type epoxy resin manufactured by Dainippon Ink & Chemicals, Inc.]
DPHA: dipentaerythritol hexaacrylate.
Irgacure 907: Photopolymerization initiator manufactured by Ciba Geigy

  In addition, since the resin in Comparative Example 2 was gelled, it could not be evaluated as a comparative application example. In addition, the compositions of the examples were 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, in the result of the comparative example, a balanced composition in the above items was not obtained.

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（Ｉ）または（II）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 (I) or (II). ]

Comparative Example 3
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 1. 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 (12)

A di (meth) acrylate (A2) of an aromatic bifunctional epoxy resin, a mono (meth) acrylate (A1) and / or an aromatic bifunctional epoxy resin (B) of an aromatic bifunctional epoxy resin, and In a reaction system in which acryloyl group and methacryloyl group are mixed, di (meth) acrylate (A2) of an aromatic bifunctional epoxy resin and mono (2) of an aromatic bifunctional epoxy resin in the presence of a phosphorus catalyst (C) Branched polyether resin (X), aromatic bifunctional di (meth) acrylate (A2), aromatic bifunctional epoxy formed by increasing the molecular weight by reacting a hydroxyl group and acryloyl group in (meth) acrylate (A1) One or more unreacted resin components selected from the group consisting of resin mono (meth) acrylate (A1) and aromatic epoxy compound (B) Method for producing a branched polyether resin composition characterized in that a resin composition having. Aromatic bifunctional epoxy resin (B), acrylic acid (a) and methacrylic acid (b), and the epoxy group in aromatic bifunctional epoxy resin (B) is in acrylic acid (a) and methacrylic acid (b) And di (meth) acrylate (A2) of the aromatic bifunctional epoxy resin, mono (meth) acrylate (A1) of the aromatic bifunctional epoxy resin, and And / or a reaction system containing the aromatic bifunctional epoxy resin (B), and then in the presence of the phosphorus catalyst (C), the aromatic bifunctional epoxy resin diacrylate (A2) and the aromatic bifunctional epoxy resin mono ( The method for producing a branched polyether resin composition according to claim 1, wherein a hydroxyl group in the (meth) acrylate (A1) is reacted with an acryloyl group. Aromatic bifunctional epoxy resin (B), acrylic acid (a) and methacrylic acid (b), and the epoxy group in aromatic bifunctional epoxy resin (B) is in acrylic acid (a) and methacrylic acid (b) The reaction is carried out in an excess condition with respect to the total carboxyl group of the above, and 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. And then in the presence of the phosphorus catalyst (C), the aromatic bifunctional epoxy resin di (meth) acrylate (A2) and the hydroxyl group in the mono (meth) acrylate (A1) of the aromatic bifunctional epoxy resin; The manufacturing method of the branched polyether resin composition of Claim 1 made to react with an acryloyl group. Aromatic bifunctional epoxy resin (B), acrylic acid (a) and methacrylic acid (b), and the epoxy group in aromatic bifunctional epoxy resin (B) is acrylic acid in the presence of phosphorus catalyst (C) (A) and di (meth) acrylate (A2) of an aromatic bifunctional epoxy resin and an aromatic bifunctional epoxy resin that are reacted under an excess condition with respect to the total carboxyl groups in methacrylic acid (b) Of the mono (meth) acrylate (A1) and / or the aromatic bifunctional epoxy resin (B), followed by the hydroxyl group and acryloyl group in the aromatic bifunctional epoxy resin di (meth) acrylate (A2) The method for producing a branched polyether resin composition according to claim 1. Aromatic bifunctional epoxy resin (B), acrylic acid (a) and methacrylic acid (b), and the epoxy group in aromatic bifunctional epoxy resin (B) is acrylic acid in the presence of phosphorus catalyst (C) (A) and methacrylic acid (b) are reacted under an excess condition with respect to the total carboxyl groups, and the aromatic bifunctional epoxy resin di (meth) acrylate (A2) and the aromatic bifunctional epoxy resin Hydroxyl group in mono (meth) acrylate (A1) of aromatic bifunctional epoxy resin di (meth) acrylate (A2) and aromatic bifunctional epoxy resin, followed by reaction system containing mono (meth) acrylate (A1) The manufacturing method of the branched polyether resin composition of Claim 1 which makes an acryloyl group react. The branched type according to any one of claims 2 to 5, wherein the use ratio [(a) / (b)] of acrylic acid (a) and methacrylic acid (b) is 0.25 to 4 in molar ratio. A method for producing a polyether resin composition. The branched polyether resin composition according to any one of claims 1 to 5, wherein the aromatic bifunctional epoxy resin (B) is an aromatic bifunctional epoxy resin (B1) having an epoxy equivalent of 135 to 500 g / equivalent. Production method. The method for producing a branched polyether resin composition according to claim 7, wherein the aromatic bifunctional epoxy resin (B1) is a dihydroxynaphthalene type epoxy resin or a bisphenol type epoxy resin. Aromatic bifunctional epoxy resin (B), acrylic acid (a) and methacrylic acid (b), epoxy group in aromatic bifunctional epoxy resin (B), acrylic acid (a) and methacrylic acid (b) The equivalent ratio of total carboxyl groups in the [polyepoxy group equivalent) / (carboxyl group equivalent) is used in a range of 1.1 to 5.5. A method for producing an ether resin composition. The method for producing a branched polyether resin composition according to any one of claims 1 to 5, wherein the phosphorus catalyst (C) is a phosphine. Selected from the group consisting of branched polyether resin (X) and aromatic bifunctional di (meth) acrylate (A2), mono (meth) acrylate (A1) of aromatic bifunctional epoxy resin and aromatic epoxy compound (B) The resin component comprising one or more unreacted resin components is reacted until the weight average molecular weight is 1,000 to 50,000 and the epoxy equivalent is 250 to 10,000. A method for producing the branched polyether resin composition according to item 1. The branched type according to any one of claims 1 to 5, wherein the polyether resin (X) is reacted until the weight average molecular weight is 3,000 to 100,000 and the epoxy equivalent is 500 to 10,000. A method for producing a polyether resin composition.

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