JP2004269895A - Method for producing curable imide resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide active energy ray-curable resins having improved heat resistance and electric characteristics, and to provide a method for producing a new curable imide resin soluble in a solvent, having increased photocurable properties and easily producible. <P>SOLUTION: The method for producing the curable imide resin comprises reacting (a) a tetracarboxylic acid dianhydride represented by formula (1) (wherein, Ar is an organic group containing an aromatic ring), (b) a compound having at least one (meth)acryloyl group and hydroxy group with (c) a compound having at least two isocyanate groups. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a novel method for producing a curable imide resin. More specifically, the present invention provides a method for producing a curable imide resin which is particularly urethane acrylate containing an imide group in the molecule and has excellent heat resistance, electrical properties, and the like.

  In recent years, active energy ray-curable resins that are cured by ultraviolet rays or electron beams are increasingly being replaced with thermosetting resins and thermoplastic resins from the viewpoint of curing speed and environmental protection. Under these circumstances, there is a demand in various fields to improve the heat resistance and electrical properties of active energy ray-curable resins.

  At present, there are a wide variety of active energy ray-curable resins such as ester acrylate, epoxy acrylate, and urethane acrylate, but their performance is limited.

  In addition, conventionally, as an active energy ray-curable resin and a composition to be a heat-resistant polymer, a resin containing an imide group as a component thereof has been studied. For example, a composition in which a compound containing a dimerizable or polymerizable carbon-carbon double bond, an amino group or a quaternized salt thereof is introduced into a polyamic acid which is a polyimide precursor of the component through actinic radiation via an ionic bond. (See, for example, Patent Document 1), a composition in which a photosensitive group is introduced into a carboxyl group of a polyamic acid by an ester bond (see, for example, Patent Documents 2 and 3), an ester bond to a carboxyl group of a polyamic acid, There is a composition in which a methacryloyl group is introduced by ionic bonding (for example, see Patent Documents 1 and 4).

  In such a conventional technique, the imide precursor is ring-closed and imidized by heat treatment after polymerization or reaction by light in order to generate an imide bond. However, in this case, there is a problem that the photosensitive group is separated and volatilizes, resulting in voids and pinholes, a decrease in film thickness, and a lack of flatness.

  In addition, a composition containing an unsaturated ester imide containing a hydroxyl group at a molecular terminal by using a dibasic acid having an imide group and a dibasic acid having a double bond capable of crosslinking in a molecule in combination and performing condensation esterification with a polyol compound. A technology relating to a product is disclosed (for example, refer to Patent Literature 5 and Patent Literature 6).

  In these methods, since the imide group is already present in the molecule and there is no need to perform imide ring closure in a subsequent step, the above problem can be avoided, but the method has a reactive double bond in the rigid molecular main chain. Therefore, there is a problem that the reactivity with light is inferior, and since it originally has an imide bond, it is necessary to use a toxic polar solvent such as N-methylpyrrolidone, and further, the remaining polyol must be removed. Have problems that must be addressed.

  Further, compounds having an amide / imide group and having a reactive double bond in the molecule have been disclosed (for example, see Patent Documents 7 and 8), but similarly, photoreactivity and solubility are also known. In addition, there is a problem in production, such as complicated purification and reaction during production.

  Further, compounds having an imide group and having a reactive double bond in the molecule have been disclosed (for example, see Patent Document 9), but similarly have problems in photoreactivity and solubility. In addition, there is a problem that a Michael addition reaction with a double bond occurs and stability is poor because purification at the time of production and use of an amine as a raw material for producing an imide group occur.

  Also disclosed are compounds having an amide imide group, having 20% or more of cyclohexanedicarboxylic acid in the resin, and further having a reactive double bond in the composition and / or the resin (for example, Patent However, this technique requires the use of special toxic solvents such as γ-butyrolactone and dimethyl imidazolidine in the synthesis. Further, a method of directly introducing a double bond into the resin skeleton has not been clarified, and the diluent is used in Examples. For this reason, the amide imide resin hardly contributes to the curing reaction, and when cured, there is a problem that the properties of the cured product are greatly influenced by the properties of the diluent.

JP-B-59-052822 JP-B-55-030207 JP-B-55-041422 JP-A-58-038038 JP-A-58-013657 JP-A-57-133108 JP-A-54-089623 JP-A-54-009218 JP-A-05-232701 JP-A-08-283356

  The present invention has been made in view of the problems of the prior art as described above, and improves the heat resistance and electrical properties of the active energy ray-curable resin, and is soluble in a solvent, and has a light curability. An object of the present invention is to provide a novel method for producing a curable imide resin which is improved and easy to produce.

The present inventor has conducted intensive studies to solve the above-mentioned problems, and as a result, the following general formula (1)
And a compound (b) having at least one (meth) acryloyl group and a hydroxyl group, and a compound (c) having at least two isocyanate groups. The present inventors have found that a curable imide resin can solve the above problems, and have completed the present invention.

  That is, the present invention provides the following general formula (1)

（式中のＡｒは芳香環を含む有機基を表す。）
で示されるテトラカルボン酸二無水物（ａ）と、少なくとも１つの（メタ）アクリロイル基及び水酸基を有する化合物（ｂ）と、少なくとも２つのイソシアネート基を有する化合物（ｃ）とを反応させることを特徴とする硬化型イミド樹脂の製造法に関する。

(Ar in the formula represents an organic group containing an aromatic ring.)
(A), a compound (b) having at least one (meth) acryloyl group and a hydroxyl group, and a compound (c) having at least two isocyanate groups. And a method for producing a curable imide resin.

  According to the production method of the present invention, a curable imide resin which is excellent in curability, heat resistance, electric properties and the like and is soluble in a solvent can be easily produced.

  The method for producing a curable imide resin of the present invention comprises: a tetracarboxylic dianhydride (a) represented by the general formula (1); a compound (b) having at least one (meth) acryloyl group and a hydroxyl group; This is a method of reacting a compound (c) having at least two isocyanate groups. In this case, a compound (c1) having two isocyanate groups in the molecule is used in order to generate a repeating unit of an imide group as necessary. Is preferred.

  In this case, the tetracarboxylic dianhydride (a), the compound (b), and the compound (c) may be simultaneously reacted, or two compounds may be reacted once, and then another compound may be reacted. .

  That is, a compound having a (meth) acryloyl group, a urethane bond and an isocyanate group in the molecule by reacting a compound (b) having at least one (meth) acryloyl group and a hydroxyl group with a compound (c) having at least two isocyanate groups And then reacting the compound with a tetracarboxylic dianhydride (a) represented by the general formula (1) to obtain a desired curable imide resin. Also, in this case, a compound (c1) having two isocyanate groups in the molecule may be used in combination in order to generate a repeating unit of an imide group as required. Further, an imide bond is formed in advance by reacting the tetracarboxylic dianhydride (a) represented by the general formula (1) with the compound (c) having at least two isocyanate groups, and the remaining isocyanate group and at least one isocyanate group are formed. The compound (b) having a (meth) acryloyl group and a hydroxyl group may be reacted to form a urethane bond to obtain a desired curable imide resin.

  As the curable imide resin obtained by the production method of the present invention, for example, the following general formula (2)

で示される数平均分子量が３００〜５０，０００の硬化性イミド樹脂が挙げられる。

And a curable imide resin having a number average molecular weight of 300 to 50,000.

  Here, Ar in the formula represents an organic group containing an aromatic ring. By having an aromatic ring in the resin, the effect of improving the heat resistance and physical properties of the imide resin can be obtained. The number of aromatic rings is not particularly limited, but is preferably 1-2.

Further, _one of Z ₁ and Z ₂ is a carboxyl group and the other is an organic group other than a carboxyl group, both are carboxyl groups, or Z ₁ and Z ₂ combine to form an acid anhydride. And represents a residue of the tetracarboxylic dianhydride (a) represented by the above general formula (1) of the resin raw material or a group obtained by ring-opening this anhydride.

  n is an integer of 1 to 10, and m is 0 or an integer of 1 to 10. If n and m exceed 10, the solubility of the imide resin deteriorates and the synthesis of the imide resin becomes difficult. Particularly, n is preferably an integer of 1 to 3, and m is preferably 0 or an integer of 1 to 8.

R ₁ represents an organic group, and represents a residue of the compound (c1) having two isocyanate groups in the molecule of the resin raw material. The organic group is not particularly limited, and examples thereof include compounds having aliphatic, alicyclic, aromatic, heterocyclic, and the like. Among these, those having a cyclic structure are preferable from the viewpoint of heat resistance.

R ₂ represents an organic group consisting of a residue of the compound (c1) having two isocyanate groups in the molecule similarly to R _1, and its specific functional group is also the same as R ₁ .

  Y is the following general formula (3)

（ただし、式中Ｒ_３は、Ｈ又はメチル基であり、Ｒ_４は樹脂原料の少なくとも１つの（メタ）アクリロイル基及び水酸基を有する化合物（ｂ）の（メタ）アクリロイル基部分を除いた残基からなる有機基であり、脂肪族、脂環族、芳香族、ヘテロ環状等含んでいるもので エーテル、エステル、ウレタン、アミド等の結合基を含んでいても良い。またｋは、１〜１０の整数である。）
で示される（メタ）アクリロイル基を一個以上有する有機基である。

(However, in the formula, R ₃ is H or a methyl group, and R ₄ is a residue of the compound (b) having at least one (meth) acryloyl group and a hydroxyl group of the resin raw material excluding the (meth) acryloyl group part. Organic group consisting of aliphatic, alicyclic, aromatic, heterocyclic, etc., and may contain a linking group such as ether, ester, urethane, amide, etc., and k is 1 to 10. Is an integer.)
Is an organic group having one or more (meth) acryloyl groups.

  When k exceeds 10, the solubility of the imide resin of the present invention is deteriorated or the synthesis of the resin becomes difficult.

  Examples of the tetracarboxylic dianhydride (a) represented by the general formula (1) used in the production method of the present invention include pyromellitic dianhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic acid Acid dianhydride, diphenyl ether-3,3 ', 4,4'-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3', 4, 4′-tetracarboxylic dianhydride, biphenyl-2,2 ′, 3,3′-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1, 2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, , 8-dimethyl-1,2,3,5 , 7-Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene -1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,3,9 , 10-Tetracarboxylic dianhydride, berylen-3,4,9,10-tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 1,1-bis (2 3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2 , 2-bis (3,4- Tetracarboxylic acids having an aromatic organic group in the molecule such as carboxyphenyl) propane dianhydride, bis (3,4-carboxyphenyl) sulfone dianhydride and bis (3,4-dicarboxyphenyl) ether dianhydride Anhydrides. One or more of these compounds can be used. Among these anhydrides of tetracarboxylic acid, pyromellitic dianhydride and benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride can be preferably used.

  Further, an anhydride of tricarboxylic acid can be used in combination as a part of the acid anhydride. Examples of the tricarboxylic anhydride include trimellitic anhydride, naphthalene-1,2,4-tricarboxylic anhydride and the like.

  As the compound (b) having at least one (meth) acryloyl group and a hydroxyl group used in the production method of the present invention, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, trimethylol Propane di (meth) acrylate, trimethylol ethane di (meth) acrylate, pentaerythritol tri (meth) acrylate or glycidyl (meth) acrylate- (meth) acrylic acid addition And various hydroxy-containing (meth) acrylate compounds such as 2-hydroxy-3-phenoxypropyl (meth) acrylate, and ring-opening reaction products of the above-mentioned hydroxyl-containing (meth) acrylate compound with ε-caprolactone. Can be.

  Further, as the compound (b) having at least one (meth) acryloyl group and hydroxyl group, an epoxy (meth) acrylate obtained by reacting various epoxy compounds with (meth) acrylic acid can also be used. The epoxy ring is opened by the reaction between the epoxy group and (meth) acrylic acid, and at this time, a (meth) acrylic ester and a hydroxyl group are generated.

  Examples of such epoxy compounds include phenylglycidyl ether, bisphenol A epoxy, bisphenol S epoxy, bisphenol F epoxy, phenol novolak epoxy, cresol novolak epoxy resin, and various diphenols obtained by reacting dicyclopentadiene with various phenols. Aromatic epoxy resins such as epoxidized cyclopentadiene-modified phenolic resin, epoxidized 2,2 ', 6,6'-tetramethylbiphenol, neopentyl glycol diglycidyl ether and 1,6-hexanediol diglycidyl ether Alicyclic rings such as aliphatic epoxy resins, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis- (3,4-epoxycyclohexyl) adipate Epoxy resins, heterocycle-containing epoxy resins such as triglycidyl isocyanurate can also be used.

  As the compound (c) having at least two isocyanate groups, a compound having two or more isocyanate groups in a molecule can be used, and as an isocyanate compound used for generating a repeating unit of an imide group, 2 Functional ones are preferred from the standpoint of synthesis stability.

  Examples of the compound (c) having at least two isocyanate groups include o-tolylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4'-diisocyanate, m-xylene diisocyanate , P-xylene diisocyanate, aromatic isocyanates such as naphthalene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diiso Aneto, hydrogenated xylene diisocyanate, nor Bonu diisocyanate, aliphatic such as lysine diisocyanate, etc. alicyclic isocyanate.

  In addition, one or more kinds of such isocyanate compounds such as a burette or a polyisocyanate material such as a nurate can be used, and an adduct obtained by a urethanization reaction between the above isocyanate compound and various polyols can be used. You can also. Among these isocyanate raw materials, aliphatic and alicyclic isocyanates are preferable in terms of solubility and reactivity, and can be suitably used.

  Further, as the various polyols used in producing the above-mentioned adduct, a bifunctional or higher functional polyol can be used. The reaction is preferably carried out with an excess of isocyanate in a molar ratio as a reaction ratio between hydroxyl groups and isocyanate groups of the polyol. The polyol having a molecular weight of 5,000 or less can be used.

  Representative examples of such polyols include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, and 1,4-propylene glycol. Butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, 3-methyl-1,5-pentanediol, Dichloroneopentyl glycol, dibromoneopentyl glycol, neopentyl glycol hydroxypivalate, cyclohexane dimethylol, 1,4-cyclohexanediol, spiro glycol, tricyclodecane dimethylol, hydrogenated bisphenol A, ethylene oxide Side added bisphenol - Le A, propylene oxide addition bisphenol - Le A, dimethylol propionic acid, dimethylol butanoic acid, and the like.

  Examples of the trifunctional or higher functional polyol compound include trimethylolethane, trimethylolpropane, ditrimethylolethane, ditrimethylolpropane, glycerin, diglycerol, 3-methylpentane-1,3,5-triol, pentaerythritol, and dipentaerythritol. , Tripentaerythritol, 2,2,6,6-tetramethylolcyclohexanol-1, tris-2-hydroxyethylisocyanurate, mannitol, sorbitol, inositol, glucose and the like. . Of these, dipentaerythritol is particularly preferably used.

  Further, as the polyol compound mentioned here, polyester polyol, polyether polyol, polycarbonate polyol and the like can be used, and they may be used alone or in combination of two or more kinds. Although there is no limitation on the molecular weight of the polyol compound, those having a molecular weight of 100 to 5,000 are preferable.

  Examples of such polyester polyols include polyester polyols obtained by the reaction of the above-mentioned polyol components and carboxylic acid-containing compounds, alcohol ester compounds such as methanol and ethanol, and lactone polyols obtained by a ring-opening reaction between ε-caprolactone and the above-mentioned polyol components. And the like.

  As such a carboxylic acid-containing compound, various known and commonly used carboxylic acids or acid anhydrides thereof can be used. Among them, maleic acid, fumaric acid, maleic acid, Itaconic acid, citraconic acid, tetrahydrophthalic acid, heptic acid, hymic acid, chlorendic acid, dimer acid, adipic acid, succinic acid, alkenylsuccinic acid, sebacic acid, azelaic acid,

2,2,4-trimethyladipic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, 2-sodium sulfoterephthalic acid, 2-potassium sulfoterephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalate Acids or di-lower alkyl esters of 5-sodium-sulfoisophthalic acid, such as dimethyl or diethyl ester,

Or, orthophthalic acid, 4-sulfophthalic acid, 1,10-decamethylenedicarboxylic acid, muconic acid, oxalic acid, malonic acid, glutanic acid, trimellitic acid, hexahydrophthalic acid, tetrabromophthalic acid, methylcyclohexentricarboxylic acid or Pyromellitic acid or acid anhydrides thereof are exemplified.

  As the polyether polyol, known and commonly used ones can be used. Of those, if only typical ones are exemplified, polytetramethylene glycol, propylene oxide-modified polytetramethylene glycol, ethylene oxide-modified polytetramethylene glycol can be used. An ether glycol such as methylene glycol, polypropylene glycol, polyethylene glycol, or a cyclic ether such as tetrahydrofuran substituted with an alkyl group such as ethylene oxide, propylene oxide, tetrahydrofuran or methyl is used as an initiator. And polyether polyols formed by ring polymerization.

  In addition, as the polycarbonate polyol referred to herein, particularly only typical ones are exemplified, and diphenyl carbonate, bischlorophenyl carbonate, dinaphthyl carbonate, phenyl-toluyl-carbonate, phenyl-chlorophenyl-carbonate or 2-tolyl Polyesters such as -4-tolyl-carbonate, or diaryl- or dialkylcarbonates such as dimethylcarbonate or diethylcarbonate; various polyols as listed above and the reaction products of polycarboxylic acids as described above. Examples include carbonate derivatives and the like obtained by reaction with diols and polyols obtained by transesterification.

  The imide bond in the curable imide resin obtained by the production method of the present invention is formed by a reaction between an anhydride group and an isocyanate group of the tetracarboxylic dianhydride (a) represented by the general formula (1). The reaction temperature is 30 to 180 ° C., and preferably 80 to 150 ° C. in view of side reaction and reaction rate.

  The synthesis of imides by the reaction between acid anhydrides and isocyanates is described in RAMeyers (1969), Reters. Carleton, et al. (Journal of applied polymer science Vol. 16, PP.2983-2989 (1972), NDGhatge et al. (.Journal of polymer science Polymer Chemistry Edition, Vol. 18, 1905-1909 (1980) and the like.

  In the production method of the present invention, when an imide bond is previously formed by reacting the tetracarboxylic dianhydride (a) represented by the general formula (1) with the compound (c) having at least two isocyanate groups, A urethane bond is formed by adding at least one compound (b) having a (meth) acryloyl group and a hydroxyl group while containing an isocyanate group and an anhydride group during the reaction, and reacting the isocyanate group and the hydroxyl group. Thus, the desired compound can be obtained. At this time, it is preferable that the imidization reaction is carried out under the condition that the molar ratio of the acid anhydride group and the isocyanate group in the imide formation reaction is (molar anhydride number) / (molar number of isocyanate) of 2 or less. It is more preferable to carry out the reaction in the range of 0.6 to 1.2 from the viewpoint of not remaining. Thereafter, a urethane bond can be formed by reacting the remaining isocyanate group with the hydroxyl group of the compound (b) having at least one (meth) acryloyl group and hydroxyl group. At this time, the mole of the hydroxyl group is at least equivalent to the remaining isocyanate group. It is preferable to add at least one compound (b) having a (meth) acryloyl group and a hydroxyl group as a number to carry out a urethanization reaction. At this time, the compound (b) having at least one (meth) acryloyl group and a hydroxyl group undergoes an esterification reaction with a partially remaining acid anhydride group.

Further, in the above design, the acid anhydride group is present at the terminal, but the acid anhydride group may be opened with water or the like to generate a carboxylic acid group. In this case, both Z ₁ and Z ₂ in the general formula (1) are carboxylic acid groups, and are represented by the following general formula (4).

（ただし、式中のＹ、Ａｒ、Ｒ_１、Ｒ_２、ｍ、ｎは、上記と同様である。）

(However, Y, Ar, R ₁ , R ₂ , m, and n in the formula are the same as described above.)

When the acid anhydride group is opened, the ring may be opened with a compound having a hydroxyl group or the like. In this case, Z ₁ or Z ₂ in the general formula (1) has a structure represented by the following general formula (5), and an organic group is connected to Ar via an ester bond. In this case, the general formula (1) becomes the following general formula (6).

However, R ₅ in the formula is an organic group, and can be used irrespective of saturation or unsaturation, and examples thereof include aliphatic, alicyclic, and aromatic compounds. It may contain a bonding group. R ₅ is preferable since solubility is improved. When a hydroxyl group-containing compound is used for ring-opening of an acid anhydride group, R ₅ represents a residue of the compound. When a compound having a (meth) acryloyl group and a hydroxyl group is used as the hydroxyl group-containing compound, R ₅ is a group containing a (meth) acryloyl group, and the curability is preferably improved.

（ただし、式中のＹ、Ａｒ、Ｒ_１、Ｒ_２、Ｒ_５、ｍ、ｎは、上記と同様である。）

(However, Y, Ar, R ₁ , R ₂ , R ₅ , m, and n in the formula are the same as described above.)

  The compound having a hydroxyl group used at this time can be used without limitation as long as it has at least one alcoholic hydroxyl group. For example, monovalent compounds such as methanol, ethanol, propyl alcohol and butyl alcohol can be used. And the above-mentioned polyol raw materials, the compound (b) having at least one (meth) acryloyl group and a hydroxyl group, and the like can be used.

Further, as the compound having a hydroxyl group when opening the acid anhydride group, the compound (b) having at least one (meth) acryloyl group and a hydroxyl group described above may be used. In this case, Z ₁ or Z ₂ in the general formula (1) has a structure represented by the following general formula (7), which is preferable because the curability by irradiation with active energy rays is improved. In this case, the general formula (1) becomes the following general formula (8).

（ただし、式中のＲ_３、ｋは上記と同様であり、Ｒ_６は有機基である。）

(However, R ₃ and k in the formula are the same as described above, and R ₆ is an organic group.)

（ただし、式中のＹ、Ａｒ、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_６、ｍ、ｎ、ｋは、上記と同様である。）

(However, Y, Ar, R ₁ , R ₂ , R ₃ , R ₆ , m, n, and k in the formula are the same as described above.)

When a raw material having three or more functional groups is used as the compound (c) having at least two isocyanate groups, a compound having a branched structure represented by the following general formula (9) may be synthesized. it can. At this time, in the general formula (9), as the polyisocyanate raw material used for R ₂ , an isocyanurate-type polyisocyanate is preferable in terms of solubility and physical properties.

（ただし、式中のＹ、Ａｒ、Ｒ_１、Ｒ_２、ｍ、ｎは、上記と同様であり、ｊは１〜１０の整数である。）

(However, Y, Ar, R ₁ , R ₂ , m, and n in the formula are the same as described above, and j is an integer of 1 to 10.)

  As the organic solvent used in the production of the imide resin of the present invention, any solvent containing no hydroxyl group, no active proton, or the like can be used. For example, ether solvents, ester solvents, ketone solvents and the like can be mentioned. In addition to these solvents, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone, and the like can be used in combination as polar solvents.

  In the reaction, a urethanation catalyst, an imidation catalyst, or the like may be used, and an antioxidant, a polymerization inhibitor, or the like may be used. As a method for curing the imide resin obtained by the production method of the present invention, curing by irradiation with active energy rays is desirable, but curing can also be performed by heat. When curing with active energy rays, ultraviolet rays or electron beams can be used. As the ultraviolet light, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, a metal halide lamp and the like can be used. As the ultraviolet wavelength, a wavelength of 1900 to 3800 angstroms is mainly used. When curing is carried out with ultraviolet light, a photoinitiator or a photosensitizer can be used.

  When curing with an electron beam is performed, an apparatus having an irradiation source such as various electron beam accelerators can be used, and electrons having an energy of 100 to 1000 KeV are irradiated. In the case of curing by heat, a catalyst for initiating thermal polymerization or an additive can be used. Of course, curing can be performed by using both active energy rays and heat.

  The curable imide resin of the present invention can be widely used for applications such as coating and bonding.

  Hereinafter, the present invention will be specifically described based on examples.

Example 1
A flask equipped with a stirrer, a thermometer, and a condenser was charged with 222 parts by weight of isophorone diisocyanate (hereinafter referred to as IPDI) and heated to 65 ° C. Into this, 116 parts by weight of 2-hydroxyethyl acrylate (hereinafter referred to as HEA) was added dropwise over 1 hour while paying attention to heat generation. After the dropwise addition, the temperature in the flask was raised to 80 ° C., and the reaction was performed for 5 hours. The NCO% in the system was measured to be 12.4% by weight. As a result of the analysis, the IPA had an acrylate component of one end isocyanate group in which HEA was connected to one end of the IPDI by a urethane bond and 60% by weight of free IPDI. It was 20% by weight.

  264.2 parts by weight of DMF was added thereto, and the temperature of the flask was raised to 70 ° C. Then, 152.6 parts by weight of pyromellitic anhydride was added, and 0.73 part by weight of water was added while paying attention to heat generation and foaming, and the temperature was raised to 120 ° C. in 2 hours. The contents of the flask gradually became transparent from about 80 ° C. while foaming. The reaction was carried out at 120 ° C. for 10 hours to obtain a light brown transparent liquid.

Results of measurement of the characteristic absorption at IR (see Fig. 1), 2270 cm ^-1 which is the characteristic absorption of an isocyanate group was disappeared completely, absorption and 1860cm imide groups 725 cm ^-1 and 1780 cm ^-1 and 1720 cm ^{-1 - 1} and 910 cm ^-1 had absorption of an acid anhydride, and GPC and NMR confirmed that the acrylate was an imide group-containing acrylate represented by the following general formula (10).

  In the molecular weight distribution measurement by GPC, the number average molecular weight was 630 in terms of polystyrene. Further, the acid value was 99.5 KOH-mg / g (solid content conversion).

Example 2
A flask equipped with a stirrer, a thermometer, and a condenser was charged with 100 parts by weight of a DMF solution (resin content: 65% by weight) of the compound of the general formula (10) obtained in Example 1 and heated to 80 ° C. 370 parts by weight of pentaerythritol triacrylate (hydroxyl value 160 KOH-mg / g) was added dropwise thereto. After the dropwise addition, the temperature in the flask was raised to 100 ° C., and the reaction was performed for 3 hours.

Results of measurement of the characteristic absorption at IR, 1860 cm ^-1 and 910 cm ^-1 which is the characteristic absorption of an acid anhydride group disappeared, the absorption of an imide group was observed at 725 cm ^-1 and 1780 cm ^-1 and 1720 cm ^-1 .

  Furthermore, GPC and NMR confirmed that the imide group-containing acrylate represented by the following general formula (11) was the main component. In the molecular weight distribution measurement by GPC, the number average molecular weight was 500 in terms of polystyrene. Further, the acid value was 58 KOH-mg / g (in terms of solid content). FIG. 2 shows an IR chart.

Example 3
A flask equipped with a stirrer, a thermometer, and a condenser was charged with 564 parts by weight of H6XDI [1,3-bis (isocyanatomethyl) cyclohexane] and 1,530 parts by weight of DMF, heated to 65 ° C., and completely dissolved. .

  966 parts by weight of benzophenonetetracarboxylic dianhydride and 7.6 parts by weight of water were added thereto. The temperature was raised to 120 ° C. while paying attention to heat generation and foaming, and the reaction was carried out for 5 hours. The isocyanate reaction rate in the system was 79% by weight from the IR chart.

After the temperature of the flask was lowered to 60 ° C., 463 parts by weight of pentaerythritol triacrylate (hydroxyl value 160 KOH-mg / g) was added dropwise. The temperature was raised to 80 ° C., and the reaction was carried out for 8 hours, and it was confirmed by IR that the absorption of isocyanate groups was eliminated. Furthermore, absorption of an imide group was confirmed at 725 cm ⁻¹ , 1780 cm ⁻¹ and 1720 cm ⁻¹ .

  Further, GPC and NMR confirmed that the imide group-containing acrylate represented by the following general formula (12) was the main component. In the molecular weight distribution measurement by GPC, the number average molecular weight was 3200 in terms of polystyrene and the weight average molecular weight was 26,000. Further, the acid value was 44 KOH-mg / g (in terms of solid content). FIG. 3 shows an IR chart.

FIG. 2 is a chart of an infrared absorption spectrum of the curable imide resin obtained in Example 1. 5 is a chart of an infrared absorption spectrum of the curable imide resin obtained in Example 2. FIG. 5 is a chart of an infrared absorption spectrum of the curable imide resin obtained in Example 3. FIG.

Claims (7)

The following general formula (1)

(Ar in the formula represents an organic group containing an aromatic ring.)
(A), a compound (b) having at least one (meth) acryloyl group and a hydroxyl group, and a compound (c) having at least two isocyanate groups. A method for producing a curable imide resin. A compound having a (meth) acryloyl group, a urethane bond and an isocyanate group in a molecule by reacting a compound (b) having at least one (meth) acryloyl group and a hydroxyl group with a compound (c) having at least two isocyanate groups And then reacting the compound with a tetracarboxylic dianhydride (a) represented by the general formula (1). The tetracarboxylic dianhydride (a) represented by the general formula (1) is reacted with the compound (c) having at least two isocyanate groups to form an imide bond, and then the remaining isocyanate group and at least one ( The method for producing a curable imide resin according to claim 1, wherein the compound (b) having a (meth) acryloyl group and a hydroxyl group is reacted. The method for producing a curable imide resin according to claim 1, wherein the compound (c1) having two isocyanate groups is used as the compound (c) having at least two isocyanate groups. The tetracarboxylic dianhydride (a) represented by the general formula (1) is pyromellitic dianhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride. Or a method for producing a curable imide resin according to item 3. A tetracarboxylic dianhydride (a) represented by the general formula (1), a compound (b) having at least one (meth) acryloyl group and a hydroxyl group, and a compound (c) having at least two isocyanate groups. The method for producing a curable imide resin according to claim 1, wherein the imide resin having an acid anhydride group at a terminal is reacted to react with a compound having a hydroxyl group to open the acid anhydride group. A tetracarboxylic dianhydride (a) represented by the general formula (1), a compound (b) having at least one (meth) acryloyl group and a hydroxyl group, and a compound (c) having at least two isocyanate groups. The imide resin having an acid anhydride group at a terminal by a reaction, and then reacting with at least one compound (b) having a (meth) acryloyl group and a hydroxyl group to open the acid anhydride group. Production method of curable imide resin.

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