WO2002090418A1

WO2002090418A1 - Unsaturated multibranched compounds, curable compositions containing the same, and cured articles of the compositions

Info

Publication number: WO2002090418A1
Application number: PCT/JP2002/004377
Authority: WO
Inventors: Tadatomi Nishikubo; Atsushi Kameyama; Hidekazu Miyabe; Masaki Sasaki; Masatoshi Kusama
Original assignee: Kanagawa University; Taiyo Ink Manufacturing Co., Ltd.
Priority date: 2001-05-02
Filing date: 2002-05-01
Publication date: 2002-11-14
Also published as: TWI314935B; JP4148781B2; JPWO2002090418A1

Abstract

An unsaturated multibranched compound (A-1) capable of being speedily cured by irradiation with actinic radiation, which is prepared by reacting (a) a compound having two or more oxetane rings in the molecule with (b) a compound having in the molecule two or more carboxyl groups (with the proviso that when the compound (a) has two oxetane rings, the compound (b) has three or more carboxyl groups) and (c) an unsaturated monocarboxylic acid; an alkali-soluble unsaturated multibranched compound (A-2) prepared by the reaction of the compound (A-1) with (d) a polybasic acid anhydride; a curable composition comprising as the essential components (A) the unsaturated multibranched compound (A-1 and/or A-2) and (B) a polymerization initiator; and a curable composition comprising the components (A) and (B) and (C) a thermosetting component.

Description

Description Unbranched compound containing unsaturated group, curable composition containing the same, and cured product thereof

The present invention relates to an unsaturated group-containing multibranched compound which can be advantageously used as a photocurable component and / or a thermosetting component in various fields. Further, the present invention provides the above-mentioned unsaturated group-containing multibranched compound, which is rapidly cured by irradiation with an active energy ray such as an ultraviolet ray or an electron beam, or is further cured by heating, and has an adhesive property to a substrate. The present invention relates to a curable composition that provides a cured product having excellent mechanical properties, chemical resistance, etc., and a cured product obtained therefrom. The composition is used in the production of adhesives, coating agents, and printed wiring boards. It can be used in a wide range of applications, such as solder resists, etching resists, interlayer insulating materials for build-up substrates, plating resists, and dry films.

Background art

The curing of resins by irradiation with active energy rays is widely used in metal coating, wood coating, printing inks, electronic materials, etc. due to their high curing speed and no solvent. The photocurable composition used in these fields generally contains a prepolymer having an unsaturated double bond, a polymerizable monomer, and a photopolymerization initiator as essential components. Examples of the prepolymer used mainly as a photocurable component include polyester acrylate, urethane acrylate, and epoxy acrylate. Since these prepolymers have a polymerizable unsaturated group, they can be crosslinked by mixing with a compound (photopolymerization initiator) that generates a radical upon irradiation with active energy rays.

However, these radically polymerizable blepolymers generally have small molecular weights and are instantaneously cured by irradiation with active energy rays, so they remain in the coating film. There was a problem that stress was generated and the adhesion to the substrate and the mechanical properties were reduced. To solve such problems, studies have been made to increase the molecular weight of the radical polymerizable prepolymer, but a large amount of a reactive diluent is required to adjust the viscosity to a level that allows coating. Therefore, such active energy ray-curable compositions are poor in toughness, mechanical properties, chemical resistance, and the like, and their applications are currently limited.

In order to solve the above problems, Japanese Patent Application Laid-Open No. 11-193321 proposes a multibranched compound containing an amino group in the molecule. This hyperbranched compound has the advantage of requiring a small amount of low molecular weight components when preparing a curable composition because the solution viscosity is low even though it has a high molecular weight. Its use is limited because it contains a group and does not have a chemically modifiable substituent on the side chain.

In addition, a composition using cationic polymerization of oxetane as a curing reaction has recently been reported, since cured products with low curing shrinkage and excellent adhesion can be obtained.However, compared with radical polymerizable prepolymers or monomers, Therefore, it was difficult to achieve desired cured product properties because there were few types of materials that could be used.

Recently, from the viewpoint of creating new organic reactions and applying them to polymer reactions, organic synthesis using ring-opening addition reaction of oxetane ring, which is a 4-membered ether, has been reported. Synthesis of polyesters with primary hydroxyl groups in the side chain by addition reaction with active esters (T. Nishikubo and K. Sato, Chem. Lett., 697 (1992)) and polyaddition reaction of bisoxetane with dicarboxylic acid ( T. Nishikubo, A. Kameyama, and A. Suzuki, Reactive & Functional Polymers, 37, 19 (1998)).

However, even in the above-mentioned known documents, there is no description about the unsaturated group-containing multibranched compound of the present invention and the curable resin composition using the same.

The present invention has been made in view of the above-mentioned problems of the related art, and its purpose is to cure quickly by irradiation with active energy rays such as ultraviolet rays and electron beams, or to further cure by heating, The material has good adhesion to the substrate and mechanical Provide unsaturated group-containing multi-branched compounds having excellent properties and which can be advantageously used as photo-curable and / or thermo-curable components in various fields, or alkali-soluble unsaturated group-containing multi-branched compounds. Is to do.

Further, an object of the present invention is to rapidly cure by irradiation with active energy rays such as ultraviolet rays or electron beams, or to further cure by heating, and to have excellent adhesion to a substrate, as well as mechanical properties, heat resistance, and thermal stability. An object of the present invention is to provide a curable composition from which a cured product excellent in various properties such as chemical resistance and electrical insulation can be obtained, and a cured product thereof. Disclosure of the invention

In order to achieve the above object, according to a first aspect of the present invention, there is provided an unsaturated group-containing hyperbranched compound, wherein the first embodiment comprises: (a) two or more oxetane rings in a molecule; (B) a compound having two or more carboxyl groups in the molecule (however, in the case where the component (a) has two oxetane rings, three or more), and (c) a compound having It is an unsaturated group-containing hyperbranched compound (A-1) obtained by a reaction with a saturated monocarboxylic acid.

This unsaturated group-containing hyperbranched compound (A-1) has a specific structure having both a primary hydroxyl group generated by a ring-opening reaction of an oxetane ring and a polymerizable unsaturated bond at a terminal, and has one molecule. The content of the polymerizable group per unit is high, so that it can be quickly cured by irradiation with active energy rays for a short time and cured by heating, and the cured product obtained by the hydrogen bonding property of the primary hydroxyl group Has excellent adhesion to various base materials and has a multi-branched structure with ether bond and ester bond, so it has low curing shrinkage and can be used to obtain a cured product with excellent mechanical properties such as strength and toughness. give. In addition, due to the multi-branched structure, it has high solubility in various solvents, and can reduce solution viscosity.

The second embodiment is characterized in that (a) a compound having two or more oxetane rings in the molecule, and (b) two or more oxetane rings in the molecule (provided that the component (a) has two oxetane rings). A compound having a carboxyl group). (c) the unsaturated group-containing multibranched compound obtained by reacting the hydroxyl group of the unsaturated group-containing multibranched compound obtained by the reaction with the unsaturated monocarboxylic acid with (d) a polybasic acid anhydride, A—2).

The unsaturated group-containing multi-branched compound (A-2) having a carboxyl group is a resin excellent in photocurability because of having a large amount of polymerizable groups at the terminal as described above, and also contains the unsaturated group-containing compound. Since it has a carboxyl group introduced by reacting a polybasic acid anhydride with the primary hydroxyl group of the side chain of the hyperbranched compound (A_l), it shows excellent solubility in aqueous solutions It is useful as an all-developed photosensitive resin.

Further, according to the second aspect of the present invention, there is also provided a curable composition containing the unsaturated group-containing multibranched compound, wherein the first basic aspect is (A) the unsaturated group-containing compound. It is characterized by containing a multi-branched compound ((A-1) and / or (A-2)), and (B) a polymerization initiator as an essential component.

Further, a second embodiment of the curable composition of the present invention is characterized in that the composition further comprises (C) a thermosetting component in addition to the components (A) and (B). The curable composition of the present invention may be used in a liquid state, or may be used as a dry film.

The curable composition of the present invention is rapidly cured by irradiation with active energy rays such as ultraviolet rays or electron beams, or is further cured by heating, and has excellent adhesiveness to a substrate, as well as strength and toughness. A cured product with excellent properties such as mechanical properties, heat resistance, thermal stability, chemical resistance, and electrical insulation can be obtained.

Furthermore, according to the third aspect of the present invention, there is also provided a cured product obtained by curing the curable composition by irradiating with active energy rays and / or heating, and can be applied to various fields. It can be advantageously applied to the formation of a solder resist layer or an interlayer insulating layer of a printed wiring board. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows the IR spectrum of the unsaturated group-containing hyperbranched compound produced in Example 1. 6 is a graph showing a graph.

FIG. 2 shows the unsaturated group-containing multibranched compound before the introduction of the carboxyl group (shown by the abbreviation HBP) and the unsaturated group-containing multibranched compound after the introduction of the carboxyl group (abbreviation: HBP (C a)) produced in Example 9. 3 is a graph showing each IR spectrum of FIG. BEST MODE FOR CARRYING OUT THE INVENTION

The present inventors have conducted intensive studies in order to solve the above-mentioned problems. As a result, (a) a compound having two or more oxetane rings in a molecule (hereinafter referred to as a polyfunctional oxetane compound); (B) a compound having a carboxy group (hereinafter, referred to as a polycarboxylic acid) having two or more (however, when the component (a) is a bisoxetane compound having two oxetane rings, three or more); The unsaturated group-containing hyperbranched compound (A-1) obtained by the polyaddition reaction with a saturated monocarboxylic acid is a specific compound having both a primary hydroxyl group generated by the ring-opening reaction of the oxetane ring and an unsaturated double bond at the terminal. Structure, and the content of polymerizable groups per molecule is large, so that it is quickly cured by irradiation with active energy rays for a short time, and heat radiated due to the presence of unsaturated double bonds. Heat-curing by calcination, and heat-curing by adding a curing agent (for example, isocyanates) capable of reacting with a hydroxyl group due to the presence of a primary hydroxyl group in the side chain. Due to the hydrogen bonding property of the hydroxyl group, the resulting cured product shows excellent adhesion to various substrates, and contains a multi-branched structure having an ether bond and an ester bond. It has been found that the composition has a low curing shrinkage and gives a cured product excellent in mechanical properties such as strength and toughness and heat resistance. In addition, since it has a multi-branched structure, compared to a linear polymer having the same molecular weight, the molecules are not entangled with each other, so that it has high solubility in various solvents and can lower the solution viscosity.

Further, according to the study of the present inventors, it is obtained by further reacting (d) a polybasic acid anhydride with a primary hydroxyl group of the unsaturated group-containing multibranched compound (A-11). The unsaturated group-containing multibranched compound having a carboxyl group (A-2) is a resin having excellent photocurability due to having a large amount of polymerizable group at the terminal, and the presence of a carboxyl group introduced into a side chain. As a result, the resin exhibits excellent solubility in aqueous solutions, and becomes an alkali developing type photosensitive resin.

Accordingly, the unsaturated group-containing multibranched compounds (A-1) and (A-2) of the present invention have the excellent properties as described above, and therefore have a photocurable component and / or a thermosetting property in various fields. It can be used advantageously as a component.

Hereinafter, the present invention will be described in detail.

First, the unsaturated group-containing multibranched compound (A-1) of the present invention comprises a polyfunctional oxetane compound (a), a polycarboxylic acid (b) and an unsaturated monocarboxylic acid (c) in the presence of a reaction accelerator. )).

For example, when one of the polyfunctional oxetane compound (a) and the polycarboxylic acid (b) is a bifunctional compound and the other is a trifunctional compound, for example, X is represented by using tricarboxylic acid as the polycarboxylic acid. When a bisoxetane compound is represented by Y as a functional oxetane compound and an unsaturated monocarboxylic acid is represented by Z, a polymer having a multi-branched structure represented by the following general formula (1) is obtained.

Z

Y

χζ ヽ ζ Ζ

— Υ-X X "-(1)

Υ ヽ / Υγ,

χ ^/ヽ

場合 When the bifunctional compound and the trifunctional compound are reversed, that is, in the case of a polyaddition reaction between a trioxetane compound having three oxetane rings in one molecule and a dicarboxylic acid having two carboxyl groups in one molecule Has the same multi-branched structure, but the unsaturated monocarboxylic acid acts as a reaction terminator and reacts with the oxetane ring, so that the unsaturated monocarboxylic acid is added to the oxetane ring at the terminal. There are unsaturated groups introduced. Similarly, when the polyfunctional oxetane compound (a) and the polycarboxylic acid (b) are both trifunctional or higher compounds, the state of branching is further complicated, but the compound has a multibranched structure.

The above can be more specifically described by using a chemical formula. For example, a bisoxetane compound represented by the following general formula (9) is used as the polyfunctional oxetane compound (a), and the polycarboxylic acid (b) When a tricarboxylic acid represented by the following general formula (12) is used, for example, an unsaturated group-containing multibranched compound (A-1) having a skeleton structural unit represented by the following general formula (2) Is obtained. For example, when a trixoxane compound is used as the polyfunctional oxetane compound (a) and a dicarboxylic acid is used as the polycarboxylic acid (b), for example, a skeleton structural unit represented by the following general formula (3) Thus, the unsaturated group-containing multibranched compound (A-1) having

In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ² represents a polyfunctional oxetane residue, and R ³ represents a polycarboxylic acid residue. n is an integer of 1 or more, and the upper limit can be appropriately controlled according to the desired molecular weight.

In the general formulas (2) and (3), the terminal group is represented by the following general formula (4) It becomes a group as shown in (8).

0- C one ^{C = C (4) -R 2} - 0- CH 2 - C (5)

II I

0 R '

₇ C OOH one OOC \

-OOC-R ³ (6)) R ³ -C OOH (7)

\

C OOH one OOC

-OOC-R ³ -COOH (8) In the formula, R ¹ to R ³ have the same meaning as described above, and R ⁴ , R ⁵ , and R ^{6 each} represent a hydrogen atom, a carbon number of 1 to 6 Represents an alkyl group, an aryl group, an aralkyl group, a cyano group, a fluorine atom, or a furyl group.

That is, the terminal of the portion where the unsaturated monocarboxylic acid is added to the terminal oxetane ring to introduce the unsaturated group becomes the terminal group represented by the general formula (4). In addition, the terminal of the portion where the unsaturated monocarboxylic acid is not added to the oxetane ring at the terminal is a terminal group represented by the general formula (5). Furthermore, if the polyfunctional oxetane compound (a) and the unreacted carboxy group remain in the polycarboxylic acid (b), the terminal of that portion is represented by the general formula (6), (7) or It becomes the terminal group represented by (8). However, the general formulas (6) and (7) are for the case where tricarboxylic acid is used, and the general formula (8) is for the case where dicarboxylic acid is used.

The reaction is carried out by mixing the polyfunctional oxetane compound (a), the polycarboxylic acid (b) and the unsaturated monocarboxylic acid (c) at once and reacting them (one-pot method); After the completion of the polyaddition reaction between a) and the polycarboxylic acid (b), an unsaturated monocarboxylic acid (c) is added and reacted (sequential method). However, in consideration of workability, a one-pot method in which three components of a multifunctional oxetane compound (a), a polycarboxylic acid (b), and an unsaturated monocarboxylic acid (c) are mixed and reacted at a time is preferable. In the above reaction, the polyfunctional oxetane compound (a) and the polycarboxylic acid (b) Is preferably in the range of 0.1≤ (b) / (a) ≤1, more preferably 0.2 (b) /, in terms of the molar ratio of the functional groups in each reaction mixture. (a) The range is ≤ 0.8. If the above-mentioned equivalent ratio is 0.1 or less, the amount of the polycarboxylic acid skeleton introduced into the resulting multi-branched compound becomes small, and a resin having a desired molecular weight cannot be obtained, and sufficient coating film properties are obtained. It is not preferable because it cannot be obtained. On the other hand, when the above equivalent ratio exceeds 1, the terminal of polymerization tends to be a carboxy group in the polyaddition reaction, so that the subsequent addition reaction of the unsaturated monocarboxylic acid (c) is difficult to proceed, and the introduction of a polymerizable group is difficult. It is not preferable because it becomes difficult. That is, regardless of the valency of the polyfunctional oxetane compound (a) and the polycarboxylic acid (b), the functional group (oxenyl group) of the polyfunctional oxetane compound (a) is changed to the functional group of the polycarboxylic acid (b). The reaction is carried out in excess of (carboxyl group) so that the oxetane ring is located at the end, and unsaturated monocarbonic acid (c) is added to this to introduce a large amount of unsaturated groups. can do. By changing the reaction conditions such as the reaction time and the reaction temperature, and by controlling the amount of the polycarboxylic acid (b) used within the above-mentioned equivalence ratio, the molecular weight and the branched state of the resulting multi-branched compound can be changed. It is possible to control to some extent. Furthermore, the ratio of the unsaturated monocarboxylic acid (c) to the polyfunctional oxetane compound (a) (the charge ratio in the reaction mixture) is 0.1≤ (c) / (a) ≤10 is preferred, and more preferably 0.2≤ (c) / (a) ≤5. By controlling the amount of unsaturated monocarboxylic acid (c) used and the reaction method (one-pot method or sequential method), it is possible to control the ratio and molecular weight of the unsaturated group introduced.

In this way, the unsaturated group-containing hyperbranched compound (A-1) ranging from liquid to solid can be synthesized according to the molecular weight.

Among the polyfunctional oxetane compounds (a) used in the present invention, representative examples of compounds having two oxetane rings in one molecule include bisoxetanes represented by the following general formula (9). H ₂ C— CH 2 (9)

0—

0 In the above general formula (9), R ¹ is a hydrogen atom or an alkyl group having 16 carbon atoms, and R ² is a linear or branched saturated hydrocarbon having 11 carbon atoms, 1 carbon atom. To 12 linear or branched unsaturated hydrocarbons, aromatic hydrocarbons represented by the following formulas (A), (B), (C), (D) and (E), formulas (F) and A divalent selected from linear or cyclic alkylenes containing a carbonyl group represented by (G), and aromatic hydrocarbons containing a carboxy group represented by the formulas (H) and (I); Is a group having the valence of

One CH, one (B)

(E)

Wherein, R ⁷ is a hydrogen atom, an alkyl group of from 1 to 1 2 carbon atoms, Ariru group, or represents a Ararukiru group, R ⁸ is one ^{^{0-, _ S -, - CH}} 2 one, One ^NH one , 1 S0 H ₃ ) ₂ or 1 C (CF ₃ ) ₂ — represents an alkyl group in Tables 6 to 6.

one

II

0

In the formula, m represents an integer of 1 to 12.

Representative examples of compounds having three or more oxetane rings in one molecule include trisoxetanes represented by the following general formula (10), and oxetane and novo Lacquer resin, poly (p-hydroxystyrene), cardo-type bisphenols, calixarenes, dextrin resorcinarenes, or etherified products thereof with a resin having a hydroxyl group such as silsesquioxane. Is received. Other examples include a copolymer of an unsaturated monomer having an oxetane ring with an alkyl (meth) acrylate. H ₂ (10)

In the above general formula (10), R ¹ has the same meaning as described above, and R ^{1 Q} is a hydroxyl group-containing resin residue of the above-mentioned etherified product, represented by the following formulas (J), (K) and (L). And a branched alkylene group having 1 to 12 carbon atoms, and aromatic hydrocarbons represented by formulas (M), (N), and (0). P is residue R ¹ . Represents the number of functional groups bonded to the compound, and is an integer of 3 or more, preferably an integer of 3 to 500.

One (J)

CH _2-

H 2 C 1 C H 2 (K)

CH _2-

■ CH ₂ -CH ₂ -CH-CH ₂ -CH-CH ₂ -CH _2- … (L)

R 11

In the formula, R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group.

Among the polycarboxylic acids (b) used in the present invention, representative examples of compounds having two carboxyl groups in one molecule include dicarboxylic acids represented by the following general formula (11).

HOOC- R in ³ -COOH (11) formula, R ³ is as defined above.

Specific examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glucuric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, pendelic acid, dodecanedioic acid Linear aliphatic dicarboxylic acids having 2 to 20 carbon atoms, such as tridecandioic acid, tetradecandioic acid, pentadecanoic acid, hexadecanedioic acid, octadecanedioic acid, nonadecandioic acid, and eicosandioic acid. A branched form having 3 to 20 carbon atoms such as methylmalonic acid, ethylmalonic acid, n-propylmalonic acid, butylmalonic acid, methylsuccinic acid, ethylsuccinic acid, 1,1,3,5-tetramethyloctylsuccinic acid; Aliphatic dicarboxylic acids; maleic acid, fumaric acid, Linear or branched aliphatic unsaturated dicarboxylic acids such as citraconic acid, methylcitraconic acid, mesaconic acid, methylmesaconic acid, itaconic acid, and glutaconic acid; hexahydrofluric acid, hexahydroisophthalic acid, and hexahydro Terephthalic acid, cyclohexene-1,2-dicarboxylic acid, cyclohexene-1,6-dicarboxylic acid, cyclohexene-1,4-dicarboxylic acid, cyclohexene-1,4,5-dicarboxylic acid, formula (P ), And tetrahydrofuroic acid such as methylhexahydroisophthalic acid and methylhexahydroterephthalic acid.

Furthermore, tetrahexyl isofuric acid such as cyclohexene-1,3-dicarboxylic acid, cyclohexene-1,5-dicarboxylic acid, cyclohexene-1,3,5-dicarboxylic acid; cyclohexene-1,1, 4-dicarboxylic acid, cyclohexene — tetrahydroterephthalic acid such as 3,6-dicarboxylic acid; 1,3-cyclohexadiene 1,2-dicarboxylic acid, 1,3-cyclohexadiene 1,6 dicarboxylic acid Acid, 1,3-cyclohexadiene_2,3-dicarboxylic acid, 1,3-cyclohexadiene 5,6-dicarboxylic acid, 1,4-cyclohexadiene 1,2-dicarboxylic acid, 1, 4-cyclohexadiene 1,6-dicarboxylic acid and other dihydrofuroic acids; 1,3-cyclohexadiene 1,3-dicarboxylic acid, 1,3-cyclohexadiene 3,5-dicarboxylic acid Etc. Acid; 1,3-cyclohexadiene 1,4-dicarboxylic acid, 1,3-cyclohexadiene 2,5-dicarboxylic acid, 1,4-cyclohexadiene 1,4-dicarboxylic acid, 1,4 —Dihydroxyterephthalic acid such as cyclohexadiene-3,6-dicarboxylic acid; methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, and endo-cis-bicyclo represented by the formula (Q) [2.2.1] Heptaw 5-ene-1,2,3-dicarboxylic acid (trade name: Saturated or unsaturated alicyclic dicarboxylic acids such as nadic acid) and methylend-cis-bicyclo [2.2.1] hept-15-ene-2,3-dicarboxylic acid (trade name: methylnadidic acid) Can be

Furthermore, phthalic acid, isophthalic acid, terephthalic acid, 3-methylphthalic acid,

3-alkylfuric acids such as 3-ethylphthalic acid, 3-n-propylfuric acid, 0.3-sec-butylphthalic acid, 3-isobutylphthalic acid, and 3-tert-butylphthalic acid; 2-methylisophthalic acid Acid, 2-ethylisophthalic acid, 2-propylisophthalic acid, 2-isopropylisophthalic acid, 2-n-butylisophthalic acid, 2-sec-butylisophthalic acid, 2-tert-butylisophthalic acid, etc. 2-alkylisofluric acid; 4-methylisophthalic acid, 4-ethylisophthalic acid, 4-propylisophthalic acid, 4-isopropylisophthalic acid, 4-n-butylisophthalic acid, 41 sec-butylisophthalic acid Luic acid,

4-alkylisophthalic acid such as 4-tert-butylisophthalic acid: methyl terephthalic acid, ethyl terephthalic acid, propyl terephthalic acid, isopropyl terephthalic acid, n-butyl terephthalic acid, sec-butyl terephthalic acid, tert-butyl terephthalic acid, etc. Alkyl terephthalic acid; naphthylene-1,2-dicarboxylic acid, naphthylene-1,3-dicarboxylic acid, naphthylene-1,4-dicarboxylic acid, naphthylene-1,5-dicarboxylic acid, naphthylene Yu Renichi 1,

6-dicarboxylic acid, naphthalene-1, 7-dicarboxylic acid, naphthalene-1, 8-dicarboxylic acid, naphthalene-1,2,3-dicarboxylic acid, naphthylene-1,

7-dicarboxylic acid, anthracene-1,3-dicarboxylic acid, anthracene-1,4-dicarboxylic acid, anthracene-1,5-dicarboxylic acid, anthracene-1,9-dicarboxylic acid, anthracene-1,2,3- And aromatic dicarboxylic acids such as dicarboxylic acid and anthracene-9,10-dicarboxylic acid. In the present invention, in addition to the above, a dicarboxylic acid represented by the following general formula (R) can be used as the dicarboxylic acid.

In the formula, R ¹² is — 0—, — S—, one CH ₂ —, _NH—, one S 0 ₂ —, — CH (CH ₃ ) —, — C (CH ₃ ) ₂ —, or — C ( CF ₃ ) ₂ —.

Representative examples of the compound (b) having at least three carboxyl groups in one molecule include tricarboxylic acids represented by the following general formula (12). -C00H-(12)

Specific examples of tricarboxylic acids include methanetricarboxylic acid, 1,2,3-propanetricarboxylic acid, 1,3,5-pentantricarboxylic acid, aconic acid, 3-butene-1,2,3- Examples thereof include saturated or unsaturated aliphatic tricarboxylic acids having 1 to 18 carbon atoms such as tricarboxylic acids, and aromatic tricarboxylic acids such as hemimelenic acid, trimesic acid and trimeric acid.

Also, tricarboxylic acids represented by the following general formula (13) can be mentioned.

C00H

… 3)

Wherein, R ¹³ is one 0-, One S-, one CH ₂ -, One NH-, One S_〇 ₂ - one CH (CH ₃₎ -, one C (CH ₃₎ ₂ -, or one C Represents (CF ₃ ) ₂ —.

Furthermore, tricarboxylic acids represented by the following general formula (14) can also be mentioned.

In the formula, R ¹⁴ represents an alkyl group having 1 to 12 carbon atoms, an aryl group, or an aralkyl group.

As the unsaturated monocarboxylic acid (c) used in the reaction, known compounds can be used as long as they have both a polymerizable unsaturated bond and a carboxyl group in the molecule. Specific examples include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, sorbic acid, hyanocyanoic acid, and polystyrylacrylic acid. Also, a half ester of a dibasic acid anhydride and a (meth) acrylate having a hydroxyl group may be used. More specifically, acid anhydrides such as hydrofluoric acid, tetrahydrofuroic acid, hexahydroplophthalic acid, maleic acid, and succinic acid, and hydroxethyl acrylate, hydroxethyl methacrylate, and hydroxy Examples thereof include half esters with hydroxy group-containing (meth) acrylates such as propyl acrylate and hydroxypropyl methacrylate. These unsaturated monocarboxylic acids may be used alone or in combination of two or more. In this specification, the term “(meth) acrylate” is a general term for acrylate and methyl acrylate, and the same applies to other similar expressions.

Examples of the reaction accelerator used in the synthesis of the unsaturated group-containing multibranched compound (A-1) include a tertiary amine, a tertiary amine salt, a quaternary onium salt, a tertiary phosphine, a crown ether complex, or It is possible to arbitrarily select from phosphonimides, and these may be used alone or in combination of two or more. Tertiary amines include triethylamine, tributylamine, DBU (1,8-diazabicyclo [5.4.0]), and DBN (1,5). —Diazabicyclo [4.3.0] nona-5-ene), DABCO (1,4-diazabicyclo [2.2.2] octane), pyridine, N, N-dimethyl-14-aminopyridine Can be

Examples of the tertiary amine salt include U-CAT series manufactured by Sanpro Corporation.

Examples of the quaternary salt include an ammonium salt, a phosphonium salt, an arsonium salt, a stibonium salt, an oxonium salt, a sulfonium salt, a selenonium salt, a stannonium salt, and a sodium salt. Particularly preferred are ammonium and phosphonium salts. Specific examples of ammonium salts include tetra-n-butylammonium chloride (TBAC), tetra-n-butylammonium bromide (TBAB), and tetra-n-butylammonium chloride (ド ΤΒΑ). Tetra η-butylammonium halide and Tetra η-butylammonium acetate (TBAAc). Specific examples of the phosphonium salt include tetra-n-butylphosphonium chloride (TBPC), tetra-n-butylphosphonium bromide (TBPB), tetra-n-butylphosphonium iodide (TBBI) and the like. Tetra-n-butylphosphonium halide, tetraphenylphosphonium chloride (TPPC), tetraphenylphosphonium bromide (TPPB), tetraphenylphosphonium iodide (TPP I), etc. Examples include phosphonium halide, ethyl refenylphosphonium bromide (ETPPB), and ethyl refenylphosphonium acetate (ETPPAc). The tertiary phosphine may be any trivalent organic phosphorus compound having an alkyl group having 1 to 12 carbon atoms or an aryl group. Specific examples include triethylphosphine, tributylphosphine, triphenylphosphine and the like.

Furthermore, a quaternary onium salt formed by an addition reaction of a tertiary amine or tertiary phosphine with a carboxylic acid or a strongly acidic phenol can also be used as a reaction accelerator. These form quaternary salts before being added to the reaction system, Alternatively, any method may be used in which quaternary salts are formed in the reaction system by adding them separately. Specific examples include tributylamine acetate obtained from tributylamine and acetic acid, and triphenylphosphine acetate formed from triphenylphosphine and acetic acid.

Further, specific examples of crown ether complexes include 12—crown 4, 15—crown 5, 18—crown 6, dibenzo 18—crown 6, 21, 1—crown 7, 24— Crown ethers such as Crown-18, and other compounds such as lithium chloride, lithium bromide, lithium iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, and potassium iodide A complex with a alkali metal salt is exemplified.

As the phosphonimide, a known compound can be used as long as it is a compound obtained by reacting a phosphonium salt with a base, but a compound having high stability is preferable because of easy handling. Specific examples include (formylmethylene) triphenylphosphine, (acetylmethylene) triphenylphosphine, (bivaloylmethylene) triphenylphosphine, (benzoylmethylene) triphenylphosphine. , (P-methoxybenzoylmethylene) triphenylphosphine, (p-methylbenzoylmethylene) triphenylphosphine, (p-nitrobenzoylmethylene) triphenylphosphine, (naphthyl) Triphenyl phosphine, (methoxycarbonyl) triphenyl phosphine, (diacetyl methylene) triphenyl phosphine, (acetyl cyano) triphenyl phosphine, (dicyan methylene) triphenyl phosphine, and the like. .

The amount of the reaction accelerator used is desirably about 0.1 to 25 mol%, preferably 0.5 to 0.5 mol%, per 1 mol of the oxenyl group of the polyfunctional oxetane compound (a). The ratio is 20 mol%, and more preferably the ratio is 1 to 15 mol%. When the amount of the reaction accelerator used is less than 0.1 mol% with respect to the oxenyl group, the reaction hardly proceeds at a practical rate, whereas the reaction accelerator is present in a large amount exceeding 25 mol%. No significant reaction promoting effect was seen Therefore, it is not preferable in terms of economy.

The reaction temperature for the synthesis of the unsaturated group-containing multibranched compound (A-1) is preferably in the range of about 100 to 200 ° C, more preferably 120 to 160 ° C. . If the reaction temperature is lower than 100 ° C., the reaction does not easily proceed, which is not preferable. On the other hand, when the temperature exceeds 200 ° C., it is not preferable because the double bond of the product reacts to easily cause thermal polymerization, and the low-boiling unsaturated monocarboxylic acid evaporates. The reaction time may be appropriately selected depending on the reactivity of the raw materials and the reaction temperature, but is preferably about 5 to 72 hours.

The reaction proceeds even in the absence of a solvent, but may be carried out in the presence of a diluent to improve the stirring efficiency during the reaction. The diluent to be used is not particularly limited as long as it can maintain the reaction temperature, but is preferably one that dissolves the raw materials. When an organic solvent is used as a diluent at the time of synthesis, the solvent may be removed by a known method such as distillation under reduced pressure. Furthermore, it can be carried out in the presence of a reactive diluent (D) described later during production.

Known organic solvents can be used as long as they do not adversely affect the reaction and can maintain the reaction temperature. Specifically, alcohols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether; ethylene glycol monomethyl ether acetate, and ethylene glycol monomethyl Glycol esters such as ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate ; Diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, etc. Ketones such as methyl isobutyl ketone and cyclohexanone; amides such as dimethylformamide, dimethylacetamide, N-methylbiopenidone, and hexamethylphosphoric triamide; toluene and xylene Hydrocarbons Is mentioned.

Next, the synthesis of the unsaturated group-containing multibranched compound (A-2) having a carboxyl group will be described.

In the present invention, the amount of the hydroxymethyl group in the unsaturated group-containing hyperbranched compound (A-1) having an ethylenically unsaturated group at the terminal and a hydroxymethyl group at the side chain generated as described above is one equivalent of the chemical equivalent. Then, the polybasic acid anhydride (d) is reacted in 0.1 to 1.0 mol to produce the unsaturated group-containing multibranched compound (A-2) having a carboxyl group. In the unsaturated group-containing hyperbranched compound (A-2), a hydroxymethyl group formed by an addition reaction between the oxenyl group of the polyfunctional oxetane compound (a) and the carboxyl group of the polycarboxylic acid (b) is contained. The carboxyl group is introduced by the addition reaction between the hydroxyl group and the polybasic acid anhydride (d), so that it becomes soluble.

Specific examples of the polybasic acid anhydride (d) include phthalic anhydride, succinic anhydride, octenyl anhydride, pentadodecenyl succinic anhydride, maleic anhydride, tetrahydrofuranoic anhydride, and hexahydrohydric acid. Phthalic anhydride, methyl tetrahydrofluoric anhydride, 3,6-Endomethylene tetrahydrofluoric anhydride, methylene tetramethylene tetrahydrofluoric anhydride, tetrabromofluoric anhydride, trime Dibasic acid anhydrides such as littic acid, or biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyltetrateric carboxylic dianhydride, cyclopentanetracarboxylic acid Examples thereof include tetrabasic dianhydrides such as acid dianhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride. These can be used alone or as a mixture of two or more.

The reaction between these polybasic acid anhydrides and the unsaturated group-containing hyperbranched compound (A-1) is carried out at a mixing ratio of about 50 to 150 ° C, preferably 80 to 130 ° C. It can be performed in the temperature range of C. The amount of the polybasic acid anhydride to be used is preferably 0.1 to 1.0 mol per 1 chemical equivalent of the hydroxymethyl group in the unsaturated group-containing hyperbranched compound (A-1). Less than 0.1 mole introduced This is not preferred because the amount of carboxyl groups decreases and the solubility of the carboxylic acid decreases significantly. On the other hand, if it is added in a large amount exceeding 1.0 mol, unreacted polybasic anhydride remains in the resin, which deteriorates properties such as durability and electric properties, which is not preferable.

Examples of the reaction accelerator in the reaction with the polybasic acid anhydride include the above-mentioned tertiary amine, tertiary amine salt, quaternary ammonium salt, tertiary phosphine, phosphorylide, clathane ether complex, and tertiary amine or Adducts of tertiary phosphines with carboxylic acids or strongly acidic phenols can be used. The amount used is in the range of 0.1 to 25 mol%, more preferably 0.5 to 20 mol%, and more preferably 1 to 15 mol%, based on the polybasic acid anhydride. . However, when the catalyst used in the production of the unsaturated group-containing multibranched compound (A-1) remains in the system, the reaction can be promoted without newly adding a catalyst. The reaction proceeds in the presence of an organic solvent or in the absence of a solvent, but can be performed in the presence of the diluent in order to improve the stirring efficiency during the reaction.

In the above reaction, air may be blown or a polymerization inhibitor may be added for the purpose of preventing gelation due to polymerization of the unsaturated double bond. Examples of polymerization inhibitors include hydroquinone, tolquinone, methoxyphenol, phenothiazine, triphenylantimony, copper chloride and the like.

Photo-radical polymerization as a polymerization initiator (B) is carried out with one or a mixture of two or more of the unsaturated group-containing hyperbranched compounds (A_1 and A-2) of the present invention obtained as described above. By mixing an initiator and / or a thermal radical polymerization initiator, a photo-curable and / or thermo-curable composition is obtained, which is rapidly cured by irradiation with active energy rays such as ultraviolet rays or electron beams, or Further, the composition can be cured by heating to form a cured product excellent in adhesion to a substrate, mechanical properties, chemical resistance, and the like.

Further, together with the unsaturated group-containing hyperbranched compound (A-1 and / or A-2) and the polymerization initiator (B), a thermosetting component (C), for example, two or more oxysilane groups per molecule. And / or by mixing a compound having an oxenyl group. Thus, a photocurable and thermosetting composition is obtained. This photo-curable and thermo-curable composition can form an image by exposing and developing the coating film, and by heating after development, it does not cause curing shrinkage and adherence to the substrate. A cured film with excellent properties such as mechanical properties, heat resistance, electrical insulation, chemical resistance, and crack resistance can be formed.

Furthermore, the photocurability can be improved by adding a reactive monomer as described below as the diluent (D) to the curable composition or the photocurable and thermosetting composition. The amount of the unsaturated group-containing multibranched compound (A-1 and / or A-2) contained in the curable composition or the photocurable and thermosetting composition of the present invention is not particularly limited. There is no.

As the photo-radical polymerization initiator used as the polymerization initiator (B), known compounds that generate radicals upon irradiation with active energy rays can be used. Specific examples thereof include benzoin, benzoin methyl ether, and benzoin methyl ether. Benzoines such as benzoethyl ethers and their alkyl ethers; acetophenone, 2,2-dimethoxy-1-2-phenylacetophenone, 4- (1-tert-butyldioxy-1-methylmethyl) acetophenone, etc. Acetophenones; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diisopropyl Thioxanthones such as thioxanthone and 2 monocloth thioxanthone; Ketals such as tophenone dimethyl ketone and benzyl dimethyl ketal; benzophenone, 4- (1_t-butyldioxy-1- 1-methylethyl) benzophenone, 3,3 ', 4,4'-tetrakis (t-butylyl) Benzophenones such as xycarbonyl) benzophenone; 2-methylthio-1— [4- (methylthio) phenyl] —2—morpholino-1-propane-1-one, 2-benzyl-2-dimethylamino-1-_ (4-morpholinov) Enyl) aminoacetophenones such as 1-butan-1-one; 2,4,6—alkyl phosphines such as trimethylbenzoylphosphonoxide; acridines such as 9-phenylacridine. Can be

These photoradical polymerization initiators can be used alone or in combination of two or more. The compounding amount of the photoradical polymerization initiator is preferably 0.1 to 30 parts by mass per 100 parts by mass of the unsaturated group-containing hyperbranched compound (A-1 and / or A-2). If the amount of the photo-radical polymerization initiator is less than the above range, the composition does not cure even when irradiated with active energy rays, or the irradiation time needs to be increased, and it is difficult to obtain appropriate coating film properties. Become. On the other hand, even if the photo-radical polymerization initiator is added in a larger amount than the above range, the curability does not change, which is not economically preferable.

In the curable composition or the photo-curable and thermo-curable composition of the present invention, in order to promote curing by active energy rays, a curing accelerator and / or a sensitizer is used to initiate photo-radical polymerization as described above. You may use together with an agent. Examples of curing accelerators that can be used include triethylamine, triethanolamine, 2-dimethylaminoethanol, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate. And tertiary amines such as thiodiglycol; and the like. Examples of the sensitizer include sensitizing dyes such as (keto) coumarin and thioxanthene; and alkylborates of dyes such as cyanine, rhodamine, safranine, malachite green, and methylene bull. These curing accelerators and / or sensitizers can be used alone or in combination of two or more. The amount used is preferably from 0.1 to 30 parts by mass per 100 parts by mass of the unsaturated group-containing hyperbranched compound (A-1 and Z or A-2).

Examples of the thermal radical polymerization initiator used as the polymerization initiator (B) include benzoyl peroxide, acetyl peroxide, methylethyl ketone peroxide, lauroyl peroxide, dicumyl peroxide, and dimethyl peroxide. Organic peroxides such as t-butyl peroxide, t-butyl hydroperoxide and cumene hydroperoxide; 2,2'-azobisisobutyronitrile Ryl, 2, 2'-azobis- 2-methylbutyronitrile, 2,2'-azobis- 1,2-divaleronitrile, 1, 1'-azobis (1-acetoxyl- 1-phenylene), 1 '-Azobis-1-1-cyclohexanecarbonitrile, dimethyl-2,2'-Azobisisobutyrate, 4,4'-Azobis-141-cyanonolic acid, 2-Methyl-1-2,2'-Azobispropane Examples include azo-based initiators such as nitrile, and more preferred are 1,1′-azobis (1-acetoxy-11-phenylethane) of non-cyanide and non-halogen types. The thermal radical polymerization initiator is used in an amount of 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, per 100 parts by mass of the unsaturated group-containing multibranched compound (A-1 and / or A-2). Used in proportion.

When an organic peroxide having a low curing rate among organic peroxides is used as the thermal radical polymerization initiator, a compound such as triptylamine, triethylamine, dimethyl p-toluidine, dimethylaniline, triethanolamine, diethanolamine, or the like may be used. Tertiary amines or metal stones such as cobalt naphthenate, cobalt octoate and manganese naphthenate can be used as accelerators.

The thermosetting component (C) added to the photocurable and thermosetting composition of the present invention includes at least two or more oxysilane groups and / or oxenyl groups in one molecule. The polyfunctional epoxy compound (C-1) and / or the polyfunctional oxide compound (C-2) can be suitably used.

Examples of the polyfunctional epoxy compound (C-1) include novolak type epoxy resins (for example, novolak obtained by reacting phenols such as phenol, cresol, halogenated phenol, and alkylphenol with formaldehyde in the presence of an acid catalyst. And EOCN—103, EOCN—104S, and EOCN available from Nippon Kayaku Co., Ltd. — 102, EOCN— 107, EP PN— 201, BREN—S; DEN—431, DEN—438, manufactured by Dow Chemical Company; manufactured by Dainippon Ink and Chemicals, Inc. N-- 730, N-- 770, N-- 865, N-- 665, N-- 673, N-- 695, VH Bisphenol A epoxy resin (e.g., reaction of epichlorohydrin and / or methylepichlorohydrin with bisphenols such as bisphenol, bisphenol, bisphenol, and tetrabromobisphenol) And commercially available products, such as Epicoat 104 and Epicoat 1002, manufactured by Yuka Shell Epoxy Co., Ltd .; DER-330, DER- manufactured by Dow Chemical Co., Ltd. 333, etc.), trisphenol-enoxy epoxy resins (for example, those obtained by reacting epichlorohydrin and / or methylepichlorohydrin with trisphenol methane, trischloromethane, etc.) There are commercial products such as Nippon Kayaku Co., Ltd.'s EPPN-501, EPPN-502, etc., and Tris (2,3-epoxypropyl) Known and common epoxy resins such as cyanurate, biphenol diglycidyl ether, other alicyclic epoxy resins, amino group-containing epoxy resins, copolymerized epoxy resins, epoxy resins, epoxy resins, and epoxy resins Or a combination of two or more.

Representative examples of the polyfunctional oxetane compound (C-2) used as the thermosetting component in the photocurable and thermosetting composition of the present invention include two oxetane rings in the molecule as exemplified above. Bisoxetanes, and trisoxetanes having three or more oxetane rings in the molecule. These can be used alone or in combination of two or more.

The compounding amount of the polyfunctional epoxy compound (C-1) and / or the polyfunctional oxetane compound (C-2) is determined by the amount of the unsaturated group-containing hyperbranched compound (A-1 and / or A-2) 1. A ratio of 5 to 100 parts by mass to 100 parts by mass is appropriate, and preferably 15 to 60 parts by mass.

Further, in order to accelerate the thermosetting reaction, a known curing accelerator such as a tertiary amine, a quaternary salt, a tertiary phosphine, a crown ether complex, an imidazole derivative, or dicyandiamide is used. A small amount can be used together. The curing accelerator can be arbitrarily selected from these, and these may be used alone or in combination of two or more. Others, such as phosphonimulide, Known curing accelerators can be used.

Examples of imidazole derivatives include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylmidazole, 4-phenylmidazole, Examples thereof include 1-cyanoethyl-1-phenylphenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-4-methylimidazole, and the like. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2Ρ4Η, 2Ρ4ΒΗ, and 2Ρ4ΜΗ made by Shikoku Chemicals. To improve the stability over time, Asahi Chiba Co., Ltd. Novakiure 3—3721, ΗΧ—3748, ΗΧ_3741, ΗΧ-3088, 3—3722, 3-3742 , HX-39 21 HP, 3-394 1 ΗΡ, ΗΧ-36 13 and the like.

The curing accelerator is used in an amount of 0.1 to 2 with respect to 1 mol of the oxysilane group and / or the oxesinyl group of the polyfunctional epoxy compound (C-1) and / or the polyfunctional oxetane compound (C-2). It is in the range of 5 mol%, preferably 0.5 to 20 mol%, and more preferably 1 to 15 mol%. If the amount of the curing accelerator used is less than 0.1 mol with respect to the oxysilane group / oxenyl group, the curing reaction hardly proceeds at a practical rate, while the curing accelerator is present in an amount greater than 25 mol%. Even so, no remarkable reaction-accelerated curing is observed, which is not preferable in terms of economy. The diluent (D) can be added to the curable composition or photocurable / thermocurable composition of the present invention during or after the synthesis. As the diluent (D), in addition to the organic solvent described above, a compound having a polymerizable group capable of participating in a curing reaction can be suitably used. Monofunctional (meth) acrylates and Known reactive diluents such as polyfunctional (meth) acrylates can be used. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, η-propyl (meth) acrylate, isopropyl (meth) acrylate, η-butyl (meth) acrylate, and isobutyl (meth) acrylate. Rate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, Stearyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isoboronyl (meth) acrylate, benzyl

(Meth) acrylate, 2-hydroxyhexyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, ethylene glycol diethylene glycol (Meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, trimethylolpropane triacrylate (Meth) acrylate, glycerin di (meta) acrylate, pen erythritol

(Meth) acrylate, pentaerythritol lutetra (meth) acrylate, dipentyl erythritol hexa (meth) acrylate, polyester (meth) acrylate, and dibasic acid anhydride and at least one in one molecule Reaction products with the above alcohol having an unsaturated group can be exemplified. The diluent (D) is used alone or in a mixture of two or more types, and the amount of the diluent is not limited. The curable composition or photo-curable and thermo-curable composition of the present invention may further include, if necessary, known and common fillers such as barium sulfate, silica, talc, clay, and calcium carbonate, phthalocyanine blue, and phthalocyanine green. And various known additives such as color pigments such as carbon black, antifoaming agents, adhesion-imparting agents, and leveling agents.

The curable composition or photo-curable / thermo-curable composition obtained in this manner is adjusted in viscosity by adding a diluent, and then subjected to screen printing, force coating, roll coating, and the like. The organic solvent contained in the composition is removed by applying a coating method such as a dip coating method and a spin coating method, and temporarily drying the coating solution at a temperature of, for example, about 60 to 120 ° C. To form If it is in the form of a dry film, it may be laminated as it is. After that, it is quickly cured by irradiating with active energy rays. In addition, the unsaturated group containing a carboxyl group as a photocurable component In the case of the composition containing the compound, the resist pattern can be formed by selectively exposing the active energy ray through a photomask on which a predetermined exposure pattern has been formed, and developing the unexposed portion with an aqueous solution of alkali.

Furthermore, in the case of a photocurable and thermosetting composition containing a thermosetting component, the composition is heated and cured at a temperature of about 140 to 200 ° C. after the exposure and development. A cured film with excellent properties such as adhesion, mechanical strength, solder heat resistance, chemical resistance, electrical insulation, and corrosion resistance can be formed. Further, various properties can be further improved by performing the UV curing before or after the thermal curing.

As the aqueous alkali solution used for the development, an aqueous solution of sodium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, ammonia, organic amine, tetramethylammonium hydroxide, or the like can be used. The concentration of the alkali in the developer may be about 0.1 to 5 wt%. Known development methods such as dip development, paddle development, and spray development can be used.

As an irradiation light source for curing the curable composition or the photocurable and thermosetting composition, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, and the like are suitable. In addition, a laser beam or the like can also be used as an active light source for exposure. In addition, electron beam, corrugated wire,? -Ray, a-ray, X-ray neutron beam, etc. can be used. Hereinafter, the present invention will be described in more detail with reference to Examples. However, it goes without saying that the present invention is not limited to the following Examples. In the following, “parts” and “%” are all based on mass unless otherwise specified.

Example 1

In a 20 O ml four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 10.0 parts of 1,4-bis (3-ethyl-3-oxenylmethyl) benzene was added. 3.3 parts of 3,5-benzenetricarboxylic acid, 0.56 parts of tetraphenylphosphonidine chloride, and 20 ml of N-methylbipyridine were charged and reacted at 140 ° C. for 24 hours. Thereafter, 12.9 parts of methacrylic acid and 0.05 part of methquinone were added, and the mixture was further reacted at the same temperature for 6 hours. After the reaction solution was cooled to room temperature, it was poured into a large amount of water, and a precipitated solid was recovered. Furthermore, this solid was dissolved in tetrahydrofuran and purified by pouring into a large amount of hexane. The obtained precipitate was separated by filtration and dried under reduced pressure to obtain 4.6 parts of an unsaturated group-containing hyperbranched compound (a).

The structure of the resulting unsaturated group-containing hyperbranched compound (a) was confirmed by iH-NMR and IR spectrum. The introduction ratio of methacrylic acid determined by ¹ H-NMR was 33%. The weight average molecular weight was 12000 as measured by GPC (gel / permeation / chromatography). Figure 1 shows the IR spectrum of the resulting unsaturated group-containing hyperbranched compound. The absorption of the hydroxyl group generated by the ring-opening addition reaction of oxetane and the absorption derived from the unsaturated double bond were detected, indicating that the target structure was obtained.

Example 2

In a 200 ml four-necked flask equipped with a stirrer, reflux condenser and thermometer, 10.0 parts of 1,4-bis (3-ethyl-13-oxenylmethyl) benzene, 10.0 parts, 1,3,5-benzene Charge 3.3 parts of carboxylic acid, 2.60 parts of methacrylic acid, 0.56 parts of tetraphenylphosphonium chloride, 0.05 parts of methquinone, and 20 ml of N-methylpyrrolidone, and bring to 140 ° C. For 24 hours. After cooling the reaction solution to room temperature, it was poured into a large amount of water, and the precipitated solid was collected. Further, this solid was dissolved in tetrahydrofuran and purified by pouring into a large amount of hexane. The obtained precipitate was separated by filtration and dried under reduced pressure to obtain 8.6 parts of an unsaturated group-containing hyperbranched compound (b).

The structure of the resulting unsaturated group-containing multibranched compound (b) was confirmed by iH-NMR and IR spectrum. — The introduction rate of methacrylic acid determined by NMR was 24%. The weight average molecular weight is 1 It was 2000.

Example 3

The procedure was performed in the same manner as in Example 2 except that the amount of methacrylic acid was changed to 12.9 parts. As a result, 9.6 parts of unsaturated group-containing hyperbranched compound (c) was obtained.

The structure of the resulting unsaturated group-containing hyperbranched compound (c) was confirmed by —NMR and IR spectrum. — The introduction rate of methacrylic acid determined by NMR was 83%. The weight average molecular weight was 6

It was 300.

Table 1 shows the raw materials used in the following examples.

table 1

Examples 4 to 8

Each component was blended at the blending ratio shown in Table 2 and kneaded using a three-roll mill to prepare an active energy ray-curable composition, which was subjected to the following performance evaluation. Table 2

(1) Photocurable

Each active energy ray-curable composition prepared as described above is applied on a copper foil at a film thickness of 10 / zm using a bar coater, irradiated with light using a high-pressure mercury lamp, and tack-free. The time until it became was measured.

(2) Double bond conversion

Each of the active energy ray-curable compositions of Examples 4 to 8 was applied to a KBr plate so as to have a film thickness of 10 m, and irradiated with light for 120 seconds with a high-pressure mercury lamp to obtain an IR spectrum. The conversion of the double bond was measured in torr.

(3) Toughness

Each of the active energy ray-curable compositions of Examples 4 to 8 was applied to an aluminum foil at a film thickness of 10 m using a barco all day, and irradiated with light for 120 seconds with a high-pressure mercury lamp, A cured coating was formed. The presence or absence of cracks when this coating film was bent at 90 ° was visually observed.

〇: No crack is observed

Δ: Cracks were slightly observed

X: Cracks observed on the entire coating film

Table 3 summarizes the above test results. Table 3

As is clear from the results shown in Table 3, the active energy ray-curable compositions of Examples 4 to 8 using the unsaturated group-containing multibranched compounds produced according to Examples 1 to 3 of the present invention were: The ability to provide a cured product with excellent curability and toughness o

Example 9

In a 200 ml four-necked flask equipped with a stirrer, reflux condenser, and thermometer, add 1,4-bis (3-ethyl-3-oxenylmethyl) benzene 10.0 parts, 1,3,5-benzene Charge 2.1 parts of tricarboxylic acid, 2.6 parts of methacrylic acid, 0.56 parts of tetraphenylphosphonium chloride, 0.05 parts of methquinone and 20 ml of N-methylpyrrolidone at 140 ° C. The reaction was performed for 24 hours. After cooling the reaction solution to room temperature, it was poured into a large amount of water, and the precipitated solid was collected. Further, this solid was dissolved in tetrahydrofuran and purified by pouring into a large amount of hexane. The resulting precipitate was separated by filtration and dried under reduced pressure to obtain an unsaturated group-containing hyperbranched compound. The hydroxyl group equivalent of the obtained unsaturated group-containing hyperbranched compound was 199 mgKOH / OH group, and the acid value was 42 mgKOH / g.

Next, using 0.26 parts of tetraphenylphosphonium chloride as a catalyst, the addition reaction of 9.80 parts of the above-mentioned unsaturated group-containing hyperbranched compound with 7.6 parts of tetrahydrofluoric anhydride was carried out by radicals. The reaction was carried out in dioxane at 80 ° C for 3 hours in the presence of 0.1 part of hydroquinone as a polymerization inhibitor.

The powdered solid obtained was subjected to structural confirmation by NMR and IR spectra. As a result of NMR, it was found that tetrahydrofuroic anhydride was found. The resulting methine and methylene protons were identified at 2.30 and 2.94 ppm, and the vinyl proton at 5.57 ppm. In the IR spectrum, v C = 0 due to the ester bond, which indicates that the addition reaction of phthalic anhydride at the tetrahedral port has progressed, and the absorption of C — 0—C is 177 cm. — ¹ and 1 289, ¹ 198, 1160 cm — Newly found at ¹ Also, broad absorption due to the carboxyl group was observed, confirming that the carboxyl group was introduced into the side chain. Furthermore, acid value measurement showed that the acid value of the unsaturated group-containing hyperbranched compound before introduction of the carboxyl group was 42 mg K◦Hg, but increased to 187 mg KOH / g after introduction. .

FIG. 2 shows, in comparison, the IR spectra of the unsaturated group-containing hyperbranched compound before the introduction of the carboxyl group (indicated by the abbreviation HBP) and after the introduction (indicated by the abbreviation HBP (Ca)).

In addition, the dissolution characteristics of the unsaturated group-containing multibranched compound after carboxyl group introduction obtained as described above in various aqueous solutions were examined. The results are shown in Table 4.

Table 4

As is evident from Table 4, the unsaturated group-containing multibranched compound obtained after the introduction of the carboxyl group obtained in the manner described above contains various aqueous alkali solutions including a 1.0 wt% aqueous sodium hydrogen carbonate solution. Was soluble at room temperature. This is because the acid value of the unsaturated group-containing hyperbranched compound after the introduction of the carboxyl group is 1 This is probably because the concentration increased to 87mgKOH / g (carboxyl group content: 15%).

Example 10

In a 200 ml four-necked flask equipped with a stirrer, reflux condenser and thermometer, 10.0 parts of 1,4-bis (3-ethyl-3-oxenylmethyl) benzene, 10.0 parts, 1,3,5-benzenebenzene 2.1 parts of acid, 2.6 parts of methacrylic acid, 0.56 parts of tetraphenylphosphonium chloride, 0.05 parts of methquinone and 20 ml of N-methylpyrrolidone, 140 ° C For 24 hours. After cooling the reaction solution to room temperature, it was poured into a large amount of water, and the precipitated solid was collected. Further, this solid was dissolved in tetrahydrofuran and purified by pouring into a large amount of hexane. The resulting precipitate was separated by filtration and dried under reduced pressure to obtain an unsaturated group-containing hyperbranched compound. The obtained unsaturated group-containing multibranched compound had a hydroxyl equivalent of 39.3 mg K 0 H / 0 H group and an acid value of 26.2 mg K 0 H Z g. Next, using 0.26 parts of tetraphenylphosphonium chloride as a catalyst, the addition reaction of 9.60 parts of the above-mentioned unsaturated group-containing hyperbranched compound with 2.8 parts of tetrahydrofuronic anhydride was carried out. The reaction was carried out in dioxane at 80 ° C for 6 hours in the presence of 0.1 part of hydroquinone as a radical polymerization inhibitor.

The obtained powdered solid was subjected to ¹ H-NMR and IR spectra to confirm its structure. As a result, NMR revealed that methineprotone and methyleneprotone caused by tetrahydrofuroic anhydride were different from each other. 30 ppm and 2.

94 ppm and vinyl proton were confirmed at 5.57 ppm. Furthermore, in the IR spectrum, it is attributed to C = 0 of tetrahydrofuroic anhydride.

1778 absorption of c ^m-1 completely disappeared, by wide absorption due to carboxyl groups was observed around 3000 cm- ^1, the carboxyl group in the side chain is introduced was confirmed. As a result of acid value measurement, the acid value of the unsaturated group-containing hyperbranched compound before the introduction of the carboxyl group was 26.2 mgKOH / g, but increased to 100 mgKOH / g after the introduction. Hereinafter, the carboxyl-containing unsaturated group-containing hyperbranched compound obtained as described above is subjected to hyperbranched compound. It is called object d.

Example 1 1

In a 200-ml four-necked flask equipped with a stirrer, reflux condenser, and thermometer, add 4,4'-bis (3-ethyl-1-3-oxenilylmethoxy) biphenol 10.6 parts, 1,3,5- 2.1 parts of benzenetricarboxylic acid, 0.63 parts of tetraphenylphosphonium bromide and 60 ml of N-methylpyrrolidone were charged and reacted at 140 ° C for 12 hours. Thereafter, 0.05 parts of methquinone and 5.6 parts of methacrylic acid were added to the reaction system, and the mixture was further reacted at 140 ° C for 12 hours. After the reaction solution was cooled to room temperature, it was poured into a large amount of water, and the precipitated solid was collected. Further, this solid was dissolved in tetrahydrofuran and purified by pouring into a large amount of hexane. The resulting precipitate was separated by filtration and dried under reduced pressure to obtain 9.9 parts of a multibranched compound having an unsaturated group. The hydroxyl group equivalent of the obtained unsaturated group-containing hyperbranched compound was 173.5 mgKOH / OH group, and the acid value was 6.4 mg KOH /.

Next, using 0.24 parts of triphenylphosphine as a catalyst, the addition reaction of 10.4 parts of the above unsaturated group-containing hyperbranched compound with 3.7 parts of tetrahydrophthalic anhydride was inhibited by radical polymerization. The test was carried out in carbitol acetate at 80 ° C for 6 hours in the presence of 0.1 part of hydroquinone as an agent.

As a result of confirming the structure of the obtained resin solution by IR spectroscopy, the absorption of 1 778 cm- ¹ attributable to C = 0 of tetrahydrofuroic anhydride was completely disappeared, and 3000 Broad absorption due to the carboxyl group was observed around cm- ¹ and it was confirmed that the carboxyl group was introduced into the side chain. In addition, acid value measurement showed that the acid value of the unsaturated group-containing hyperbranched compound before the introduction of the carboxyl group was 6.4 mgKOH / g, but increased to 100 mgKOH / g after the introduction. Hereinafter, the unsaturated group-containing multi-branched compound having a carboxyl group obtained as described above is referred to as a multi-branched compound e. In addition, the solubility characteristics of the unsaturated group-containing hyperbranched compounds d and e obtained after the introduction of the carboxyl group in various alkaline aqueous solutions were also examined. did. The results were similar to those shown in Table 4.

Table 5 shows the raw materials used in the following examples.

Table 5

Examples 12 and 13 and Comparative Example 1

Using the unsaturated group-containing hyperbranched compounds d and e obtained in Examples 10 and 11, the respective components were blended at the blending ratios shown in Table 6, and kneaded using a three-roll mill to obtain a light-curing property. · A thermosetting composition was prepared, and the properties of the cured coating film were evaluated by the following methods.

For comparison, a coating film using a general nopolak type epoxy acrylate resin was similarly evaluated.

Table 6

Preparation of test piece:

The above-mentioned photo-curable and thermo-curable composition was applied to a polyester film using Apliquet overnight and dried at 80 ° C. for 30 minutes to evaporate the organic solvent. The dried coating film was irradiated with ultraviolet rays at 50 OmJ / cm ² , and subsequently thermally cured at 150 ° C. for 60 minutes. The cured coating film was peeled from the polyester film, cut into a predetermined size, and subjected to the following test.

Measurement of modulus, stress at break, strain at break:

A cured film having a thickness of 40 zm was prepared, cut into a size of 1 O mm x 60 mm, and measured with an Autograph AG S-G 100 ON manufactured by Shimadzu Corporation.

Measurement of glass transition point Tg:

A cured film having a thickness of 40 μm was prepared, cut into a size of 5 mm × 40 mm, and measured with DMS 6100 manufactured by Seiko Instruments Inc.

Measurement of dielectric constant and dielectric loss tangent:

A cured film having a thickness of 40 m was prepared, cut into a size of 15 mm x 15 mm, and measured with an HP 4291 A RF impedance / material analyzer manufactured by Hurret Packard.

Bending test: The photocurable and thermosetting composition was applied to a 25 / m-thick Kapton film so as to have a dry film thickness of 25 μm. The dried coating film was entirely exposed to ultraviolet light at 50 OmJ / cm ² , and then subjected to a thermosetting reaction at 150 ° C. for 60 minutes to produce a cured coating film. This coating film was bent at 180 degrees, and the presence or absence of cracks was visually observed.

〇: No cracks occur

△: Slightly cracked

X: Cracks are observed on the entire coating film

Table 7 summarizes the above test results.

Table 7

As is evident from the results shown in Table 7, the photocuring properties of Examples 12 and 13 obtained using the unsaturated group-containing hyperbranched compounds produced according to Examples 10 and 11 of the present invention · It can be seen that the thermosetting composition gives a cured product having excellent toughness as compared with Comparative Example 1 in which a general epoxy acrylate resin is used. Industrial applicability

As described above, the unsaturated group-containing hyperbranched compound (A-1) of the present invention can be rapidly cured by irradiation with active energy rays for a short time, can be cured by heating, and The cured product obtained has excellent adhesion to various substrates It gives a cured product that exhibits good properties, has low curing shrinkage, and has excellent mechanical properties such as strength and toughness. In addition, the unsaturated group-containing branched compound having a carboxyl group (A-2) of the present invention is a resin having excellent photocurability, exhibits excellent solubility in aqueous alkali solutions, Useful as a developing type photosensitive resin 型) -έ> o

Therefore, the unsaturated group-containing hyperbranched compounds (A-1) and (Α-2) of the present invention have the above-mentioned excellent properties, and therefore, have photocurable components and / or thermosetting properties in various fields. It can be used advantageously as a component.

Furthermore, the curable composition of the present invention containing the unsaturated group-containing hyperbranched compound (A-1) and / or (Α_2) together with a polymerization initiator, or a thermosetting composition further containing a thermosetting component The photocurable composition is rapidly cured by irradiation with active energy rays such as ultraviolet rays or electron beams, or is further cured by heating, has excellent adhesion to a substrate, and has mechanical properties such as strength and toughness. Since a cured product with excellent properties such as heat resistance, heat stability, chemical resistance, and electrical insulation can be obtained, it can be used for manufacturing adhesives, coating agents, and printed wiring boards. It can be used in a wide range of applications, including etching resists, interlayer insulating materials for build-up substrates, plating resists, and dry films.

Claims

The scope of the claims

1. (a) a compound having two or more oxetane rings in the molecule; and (b) a compound having two or more oxetane rings in the molecule (however, in the case where the component (a) is a compound having two oxetane rings, (C) a compound having a carboxyl group, and (c) an unsaturated group-containing multibranched compound obtained by reaction with an unsaturated monocarboxylic acid.

2. The unsaturated group-containing multibranched compound according to claim 1, which has a skeleton structural unit represented by the following general formula (2) or (3).

(Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ² represents a polyfunctional oxetane residue, R ³ represents a polycarboxylic acid residue, and n is an integer of 1 or more. Is.)

3. In the general formula (2) or (3), the terminal group is at least one of the groups represented by the following general formulas (4) to (8), and at least one of the following general formula (4) 3. The unsaturated group-containing branched compound according to claim 2, which has a terminal group represented by the formula: o

R ⁴ R ⁵

oc = R ¹

^{(4) -R 2 - 0- CH} 2 - C (5) c

R c I OOC-R ³ OOH (7)

-OOC-R ³ -C OOH (8)

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ² represents a polyfunctional oxetane residue, R ³ represents a polycarboxylic acid residue, R ⁴ , R ⁵ , And R ^{6 each} represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, a cyano group, a fluorine atom, or a furyl group.

4. (a) a compound having two or more oxetane rings in the molecule; and (b) a compound having two or more oxetane rings in the molecule (however, in the case where the component (a) is a compound having two oxetane rings, (C) a compound having a carboxyl group, and (c) a hydroxyl group of an unsaturated group-containing multibranched compound obtained by reaction with an unsaturated monocarboxylic acid, and (d) a polybasic acid anhydride. Unsaturated group-containing hyperbranched compounds.

5. A curable composition comprising (A) the unsaturated group-containing multi-branched compound according to any one of claims 1 to 4, and (B) a polymerization initiator as essential components.

6. The curable composition according to claim 5, further comprising (C) a thermosetting component.

7. The curable composition according to claim 5, wherein the polymerization initiator (B) is a photoradical polymerization initiator and / or a thermal radical polymerization initiator.

8. The method according to claim 6, wherein the thermosetting component (C) is a compound having two or more oxysilane groups and / or oxenyl groups in one molecule. The curable composition according to the above.

9. 0.1 to 30 parts by mass of the polymerization initiator (B) in the case of a photo-radical polymerization initiator with respect to 100 parts by mass of the unsaturated group-containing hyperbranched compound (A), and a thermal radical polymerization initiator 6. The curable composition according to claim 5, wherein the curable composition is contained in an amount of 0.1 to 10 parts by mass.

10. The thermosetting component (C) is contained in a proportion of 5 to 100 parts by mass with respect to 100 parts by mass of the unsaturated group-containing multibranched compound (A). Curable composition.

1. The curable composition according to claim 5, further comprising a curing accelerator.

12. The curable composition according to claim 5, further comprising a reactive diluent.

13. A cured product obtained by curing the curable composition according to claim 5 or 6 by irradiation with active energy rays and / or heating.