JP2011186042A - Active energy ray curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray curable resin composition having superior heat resistance and being capable of patterning with a dilute aqueous alkaline solution, using a normal organic solvent as a solvent, and reducing a development residue in alkali development. <P>SOLUTION: The active energy ray curable resin composition contains: a branched polyimide resin (1) having a carboxy group, and/or an acid anhydride group, and a (meth)acryloyl group; a polymerizable resin (2) having a carboxy group obtained by reacting an esterified product of an epoxy compound (2a) and an unsaturated monocarboxylic acid (2b) to an acid anhydride (2c) of a polycarboxylic acid having at least two carboxy groups; and an organic solvent (3). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an active energy ray-curable polyimide resin composition that is excellent in heat resistance, solvent solubility, low thermal expansibility, and moisture resistance at high temperatures and can be developed with a dilute aqueous alkali solution. More specifically, various types of negative resists such as solder resist, plating resist, build-up method active energy ray-curable polyimide that can be optimally used for patterning materials such as printed circuit boards and resists for insulating layers of semiconductor elements. The present invention relates to a resin composition.

  Active energy ray-curable resins that are cured by ultraviolet rays or electron beams have a high curing rate and are preferable from the viewpoint of environmental protection. Therefore, replacement with conventional thermosetting resins and thermoplastic resins is progressing. Under such circumstances, improvements in heat resistance and electrical properties of active energy ray-curable resins are required in various fields. At present, there are a wide variety of active energy ray curable resins such as ester acrylate resins, epoxy acrylate resins, urethane acrylate resins, etc., but there is a limit in improving heat resistance.

  An active energy ray-curable resin with improved heat resistance is a photosensitive resin having a carboxyl group obtained by reacting an esterified product of an epoxy compound and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride. A production method is known in which a photosensitive polyamide resin having a carboxyl group and a photosensitive polyamideimide resin having a carboxyl group are reacted with the resin (Patent Document). However, since the photosensitive resin composition has a flexible skeleton such as polybutadiene, polypropylene glycol, and polycarbonate, thermal expansion is large.

  Examples of the active energy ray-curable resin having improved heat resistance include, for example, trifunctional or higher functional aromatic carboxylic acids and / or anhydrides thereof, polyisocyanate compounds, polymerizable double bonds, hydroxyl groups and / or epoxies. A method for producing an active energy ray-curable polyimide resin that reacts with a compound having a group is known (Patent Document 2). In Patent Document 2, a polyimide resin excellent in heat resistance, solvent solubility, active energy ray curability, developability, and the like can be obtained. As a polyisocyanate compound used in this production method, a buret body or a nurate body is also used. There is a description that it is possible to obtain an imide resin excellent in solvent solubility and curability, and that an aliphatic or alicyclic polyisocyanate is preferable. Moreover, the Example of this gazette describes the manufacturing method of the polyimide resin using cycloaliphatic diisocyanate as a polyisocyanate compound.

  However, although the polyimide resin obtained by the Example of the said patent document 2 has favorable heat resistance compared with ester acrylate resin, epoxy acrylate resin, urethane acrylate resin, etc., it was not yet enough.

  Therefore, in order to improve heat resistance, it contains a polymerizable polyimide resin (I) having an isocyanurate ring, a cycloaliphatic structure, an imide ring, and a (meth) acryloyl group and capable of patterning with a dilute alkaline aqueous solution. An active energy ray-curable polyimide resin composition is provided (Patent Document 3).

JP-A-11-288090 JP 2000-344889 A JP 2003-221429 A

  However, the polyimide resin obtained in Examples in Patent Document 3 has better heat resistance than the ester acrylate resin, epoxy acrylate resin, urethane acrylate resin, etc., but generated undeveloped residue during development. . Therefore, the problem to be solved by the present invention is that it has excellent heat resistance, can be patterned with a dilute alkaline aqueous solution, and an ordinary organic solvent can be used as a solvent. Provided is an active energy ray-curable resin composition capable of reducing development residues during development.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have excellent heat resistance by using an acid pendant type epoxy (meth) acrylate and a branched polyimide resin in combination, and a dilute alkaline aqueous solution. In addition, an active energy ray-curable resin composition that can be used for patterning, can be used as a solvent, and can reduce a development residue during alkali development, has been found. It came to be completed. That is, the present invention
A branched polyimide resin (1) having a carboxy group and / or an acid anhydride group and a (meth) acryloyl group, an esterified product of an epoxy compound (2a) and an unsaturated monocarboxylic acid (2b), and two or more carboxy groups Provided is an active energy ray-curable resin composition containing a polymerizable resin (2) having a carboxy group and an organic solvent (3) obtained by reacting an acid anhydride (2c) of a polycarboxylic acid having a group. .

  The active energy ray-curable resin composition of the present invention has a high development speed and is good even by dilute alkali development, and can reduce development residues. In particular, the development residue on the copper substrate can be suitably reduced. Moreover, it is possible to form a cured coating film having excellent heat resistance and excellent mechanical strength, particularly breaking strength and breaking elongation.

  The active energy ray-curable resin composition of the present invention is an esterified product of a branched polyimide resin (1) having an carboxy group and / or an anhydride group thereof, an epoxy compound (a) and an unsaturated monocarboxylic acid (b). It contains a polymerizable resin (2) having a carboxy group obtained by reacting an acid anhydride (c) of a polycarboxylic acid having two or more carboxy groups and an organic solvent (3). . The present invention is described in detail below.

■ Branched polyimide resin (1)
The branched polyimide resin (1) used in the present invention may be any one as long as it has a carboxy group and / or an acid anhydride group and a (meth) acryloyl group and has a branched structure in the molecule. Preferably, for the following branched polyimide resin (1α) or (1β), the branched polyimide resin (1α) or (1β) has a carboxy group and / or an acid anhydride group, a (meth) acryloyl group and a hydroxyl group. And a branched polyimide resin (1γ) having a carboxy group and / or an acid anhydride group obtained by reacting a compound (1f) having a carboxyl group and / or a compound (1g) having an (meth) acryloyl group and an epoxy group. it can.

◆ Branched polyimide resin (1α)
As the branched polyimide resin (1) used in the present invention, a polyisocyanate compound (1a) having three or more isocyanate groups and a polycarboxylic acid anhydride (1b) having three or more carboxy groups are used as an organic solvent. Examples thereof include branched polyimide resins (1α) having a carboxy group and / or an acid anhydride group, which are obtained by reacting them in the inside.

-Polyisocyanate compound (1a) having three or more isocyanate groups
The polyisocyanate compound (1a) may be any known polyisocyanate compound having three or more isocyanate groups. For example, a diisocyanate compound containing a cyclic aliphatic diisocyanate compound is used as the fourth compound. Isocyanurate ring-containing polyisocyanate compound obtained by isocyanuration in the presence or absence of an isocyanuration catalyst such as a quaternary ammonium salt, for example, an isocyanurate comprising a trimer of a cyclic aliphatic diisocyanate compound Preference is given to isocyanurates consisting of pentamers, isocyanurates consisting of heptamers, and the like, and mixtures of these isocyanurates because of their excellent heat resistance and moisture resistance. Among these polyisocyanate compounds, isocyanurates composed of trimers of cycloaliphatic diisocyanate compounds, that is, triisocyanate compounds containing one isocyanurate ring are preferable. Examples of the cycloaliphatic diisocyanate compound include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, and norbornene diisocyanate. Among these, isophorone diisocyanate and tolylene diisocyanate are preferable.
The proportion of the polyisocyanate compound in the isocyanate component is preferably 30% by weight or more from the viewpoint of heat resistance and moisture resistance. Furthermore, the polyimide resin can be easily produced, and the heat resistance of the cured product and moisture resistance under high temperature and high pressure From the standpoint of superiority, those containing 50% by weight or more, for example 50 to 95% by weight, are particularly preferred, and when obtaining a branched polyimide resin having excellent solvent solubility as well as heat resistance of the cured product, those containing 100% by weight are used. It is preferable.
Examples of the isocyanate component other than the polyisocyanate compound include known and commonly used aromatic diisocyanates and acyclic aliphatic diisocyanates.

  Furthermore, as said polyisocyanate compound (1a), it is a thing containing 5-30 weight% of isocyanate groups with respect to the said polyisocyanate compound, and a branched polyimide resin with favorable curability and solvent solubility is obtained. It is more preferable from the above, and it is particularly preferable that the isocyanate group contains 10 to 20% by weight.

-Acid anhydride (1b) of polycarboxylic acid having 3 or more carboxy groups
The acid anhydride (1b) of the polycarboxylic acid used in the method for producing the branched polyimide resin is not particularly limited as long as it is an acid anhydride derived from a polycarboxylic acid having 3 or more carboxy groups. Tricarboxylic acid anhydrides and tetracarboxylic acid anhydrides are preferred. Examples of the acid anhydride of tricarboxylic acid include trimellitic anhydride and naphthalene-1,2,4-tricarboxylic acid anhydride. Examples of the acid anhydride of tetracarboxylic acid include pyromellitic dianhydride; benzophenone-3,4,3 ′, 4′-tetracarboxylic dianhydride, diphenyl ether-3,4,3 ′, 4′- Tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,4.3 ', 4'-tetracarboxylic dianhydride, biphenyl-2,3,2 ', 3'-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1, 8,4,5-tetracarboxylic dianhydride, decahydronaphthalene-1,8,4,5-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7- Hexahydronaphthalene-1,2,5 6-tetracarboxylic dianhydride; 2,6-dichloronaphthalene-1,8,4,5-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,8,4,5-tetracarboxylic acid dianhydride Anhydride, 2,3,6,7-tetrachloronaphthalene-1,8,4,5-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, berylene-3 , 4,9,10-tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-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 2,3-bis 3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride And tetracarboxylic anhydride having a group. In addition to these dianhydrides, there are monoanhydrides as tetracarboxylic acid anhydrides, which can be used alone or in combination with dianhydrides. Examples of the monoanhydride include those obtained by opening one of the anhydride groups of the dianhydride with an alcohol or the like. Moreover, what hydrogenated the acid anhydride which has said aromatic ring can be used individually or together with the acid anhydride which has said aromatic ring. Examples of such a compound include cyclohexanetricarboxylic acid and its anhydride. The acid anhydride (1b) of the polycarboxylic acid may be used alone or in combination of two or more. If necessary, an aromatic dicarboxylic acid compound and / or an anhydride thereof may be used in combination as long as the effects of the present invention are exhibited. Among these, it is more preferable to use trimellitic anhydride.

-Manufacturing method As a preferable manufacturing method of the said branched polyimide resin (1 (alpha)), a well-known and usual method may be sufficient, for example, the said polyisocyanate compound (1a) and the said acid anhydride (1b) are made into temperature in an organic solvent. Examples include a method of producing a carboxy and / or acid anhydride group-containing polyimide resin (Iα) by reacting at 50 to 250 ° C. for 1 to 30 hours.

  In the said manufacturing method, since reaction is easy to control especially, it is made to react with polyisocyanate compound (1a) using what contains the acid anhydride which has a carboxy group as acid anhydride (1b) of polycarboxylic acid. The method is preferred.

Furthermore, in the production method, in order to obtain a branched polyimide resin having sufficient solvent solubility, heat resistance, and alkali developability, the total moles of carboxylic acid anhydride groups and carboxy groups in the acid anhydride (1b) The ratio (n _b ) / (n _a ) of the number (n _b ) and the number of moles (n _a ) of the isocyanate groups in the polyisocyanate compound (1a) is preferably 0.3 to 2.0, It is especially preferable that it is 0.6-1.8.

  Here, as the organic solvent, various polar organic solvents can be used. Among them, a solvent that can dissolve the branched polyimide resin (1) used in the present invention, and does not contain a nitrogen atom and a sulfur atom. Solvents such as ether solvents, ester solvents and ketone solvents are preferred, and ether solvents are particularly preferred. In addition, it is preferable that the organic solvent (3) mentioned later and the organic solvent used with the manufacturing method of the said branched polyimide resin are what has the same or the same solvent as a main component.

  Various ether solvents can be used, such as ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether; polyethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether acetate. Polyethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate; Polypropylene glycol dialkyl ethers such as propylene glycol dimethyl ether; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate; Dipropylene glycol monomethyl ether Polypropylene glycol monoalkyl ether acetates such as Le acetate, and the like. Among them, polyethylene glycol monoalkyl ether acetates, polypropylene glycol monoalkyl ether acetates are preferred.

  Examples of the ester solvent include ethyl acetate and butyl acetate, and examples of the ketone solvent include acetone, methyl ethyl ketone, and cyclohexanone.

  The amount of the organic solvent used in the method for producing the branched polyimide resin is uniform in the system and can be reacted at a suitable reaction rate. Therefore, the content in the system after the reaction is 10 to 70% by weight. A range of 20 to 60% by weight is particularly preferable.

  In the method for producing the branched polyimide resin, a polyisocyanate compound (1a) and a polycarboxylic acid anhydride (1b) are reacted to obtain a polyimide resin (1α) containing a carboxy group and / or an acid anhydride group. In obtaining, the molecular weight and acid value of the resulting polyimide resin (1α) can be adjusted by changing the weight ratio of the polyisocyanate compound (1a) to the polycarboxylic acid anhydride (1b). Moreover, an imidation catalyst or the like may be used in the reaction of the polyisocyanate compound (1a) with the polycarboxylic acid anhydride (1b), and an antioxidant or a polymerization inhibitor is used in combination. Also good.

  In the production method of the active branched polyimide resin (1), an acid anhydride group and / or a carboxy group in the acid anhydride (1b) of the polycarboxylic acid are present at the molecular terminal, but an acid anhydride group is present at the molecular terminal. In this case, the ring may be opened using water or the like to generate a carboxylic acid.

◆ Branched polyimide resin (1β)
As the branched polyimide resin (1) used in the present invention, a polyisocyanate compound (1e) containing a urethane prepolymer (1d) having an isocyanate group at the terminal obtained from the polyisocyanate compound (1a) and the polyol compound (1c). ) And a polycarboxylic acid anhydride (1b) having three or more carboxy groups described above, and a branched polyimide resin having a carboxy group and / or an acid anhydride group (1b). 1β).

・ Urethane prepolymer (1d)
The urethane prepolymer (1d) that can be used in the present invention includes the polyisocyanate compound (1a) and the polyol compound (1c), and the isocyanate group in the polyisocyanate compound (1e) is the polyol compound (1c). The urethane prepolymer which has an isocyanate group at the terminal obtained after making it react by the molar ratio which becomes excess with respect to the hydroxyl group in the inside etc. are mentioned.

  The polyol compound (1c) is introduced into the resin via the polyisocyanate compound (1a) and a urethane bond. Thus, by introducing the polyol compound (1c) into the imide resin skeleton, the solvent of the polyimide resin is dissolved. And the performance such as development speed and development stability during development is improved.

  In general, introduction of a urethane bond is considered to cause deterioration of heat resistance, but in the urethane modification with the polyol compound (1c) as described above, it directly binds to an isocyanurate type polyisocyanate compound and has an imide bond. As a result, deterioration of the heat resistance of the imide resin is prevented, and good heat resistance can be maintained.

Polyol compound (1c)
The polyol compound (1c) used in the present invention is not particularly limited as long as it is a polyol compound having two or more hydroxyl groups in one molecule. Among them, a compound having 2 to 6 hydroxyl groups is preferable, and a diol compound It is particularly preferred that Examples of the polyol compound (1c) include alkyl polyols, polyester polyols, polyether polyols, polycarbonate polyols, urethane polyols, silicon polyols, acrylic polyols, and epoxy polyols.

  Among them, as the polyol compound (1c), a polyol compound containing the polyol compound (1c-1) having a carboxy group, that is, the polyol compound (1c-1) having a carboxy group alone or the polyol compound (1c- It is preferable to use a mixture of 1) and other polyol compounds because there is an improvement in development performance and compatibility with other compounding components such as various curing agents.

  As the polyol compound (1c-1) having a carboxy group, a compound represented by the following general formula (1) is more preferable.

（但し、式中のＲ_１は、直接結合又は炭素原子数１〜６の炭化水素鎖、Ｒ_２とＲ_３は、異なっていても同一であっても良く、炭素原子数１〜６の炭化水素鎖である。また、Ｒ_４は、水素原子又は炭素原子数１〜１２のアルキル基を示す。）

(However, R ₁ in the formula is a direct bond or a hydrocarbon chain having 1 to 6 carbon atoms, R ₂ and R ₃ may be different or the same, and carbon atoms having 1 to 6 carbon atoms. (It is a hydrogen chain. R ₄ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.)

  Examples of the compound represented by the general formula (1) include dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolpentanoic acid, dimethylolhexanoic acid, and tartaric acid.

  Furthermore, as the polyol compound (1c), an ester compound obtained by reacting the compound represented by the general formula (1) with ε-caprolactone, the compound represented by the general formula (1), and the polyol compound ( An ester compound obtained by reacting a polyol compound (1c-2) or dicarboxylic acid compound (1c-3) other than 1c-1), a compound represented by the general formula (1) and an alkyl ester compound (1c-4) ) Or an ester compound obtained by transesterification, or a compound represented by the general formula (1), the polyol compound (1c-2), and an alkyl ester compound (1c-4) A compound having two or more hydroxyl groups, such as an ester compound obtained, can also be used.

  Examples of the polyol compound (1c-2) include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, 1,4. -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, hydroxypivalic acid neopentyl glycol ester, cyclohexane dimethylol, 1,4-cyclohexanediol, spiroglycol, tricyclodecane dimethylol, hydrogenated bisphenol A, ethylene Diols such as xide-added bisphenol A, propylene oxide-added bisphenol A, dimethylolpropionic acid and dimethylolbutanoic acid; trimethylolethane, trimethylolpropane, ditrimethylolethane, ditrimethylolpropane, glycerin, diglycerol, 3-methyl Pentane-1,3,5-triol, pentaerythritol, dipentaerythritol, tripentaerythritol, 2,2,6,6-tetramethylolcyclohexanol-1, tris-2-hydroxyethyl isocyanurate, mannitol, sorbitol, inositol And trifunctional or higher functional polyol compounds such as glucose.

  Moreover, as said dicarboxylic acid compound (1c-3), various dicarboxylic acids or those acid anhydrides can be used, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, het acid, Highmic acid, chlorendic acid, dimer acid, adipic acid, succinic acid, alkenyl succinic 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 sulfoisophthalic acid; orthophthalic acid, 4-sulfophthalic acid, 1,10-decamethylenedicarboxylic acid, muconic acid, oxalic acid Acid, malonic acid, glutamic acid, trimellitic acid, Sahidorofutaru acid, tetrabromophthalic acid, methyl cyclohexene tricarboxylic acid, pyromellitic acid, or an anhydride, and the like.

  Furthermore, examples of the alkyl ester compound (1c-4) include alkyl ester compounds such as methanol, ethanol, and butanol of the dicarboxylic acid compound (1c-3).

-Reaction in organic solvent As a manufacturing method of the said branched polyimide resin (1 (beta)), a well-known and usual method may be sufficient, for example, the said polyisocyanate compound (1a) and the said polyol (1c) in the said organic solvent, Reaction is carried out at a temperature of 50 to 110 ° C. for 1 to 20 hours to produce a polyisocyanate compound (1e) containing a urethane prepolymer (1d) having an isocyanate group at the terminal, and subsequently the polyisocyanate compound (1a) and In the same manner as when the acid anhydride (1b) is reacted in an organic solvent, the polyisocyanate compound (1e) is reacted with the acid anhydride (1b) to contain a carboxy group and / or an acid anhydride group. A method for producing the resin (1β) can be mentioned.

However, in order to obtain an imide resin having sufficient solvent solubility, heat resistance, and alkali developability, the carboxylic acid anhydride group and carboxy group in the polycarboxylic acid anhydride (1b) and the polyisocyanate compound (1e) ) The ratio (n _be ) / (n _a ) of the total number of moles (n _be ) of carboxy groups in () to the number of moles of isocyanate groups (n _a ) in the polyisocyanate compound (1a) is 0.3 to 3.0. It is preferable that

◆ Branched polyimide resin (1γ)
As the branched polyimide resin (1) used in the present invention, a compound having a (meth) acryloyl group and a hydroxyl group in the carboxy group and / or acid anhydride group of the aforementioned branched polyimide resin (1α) and / or (1β) ( 1f) and / or a branched polyimide resin (1γ) containing a carboxy group and / or an acid anhydride group obtained by reacting a compound (1 g) having a (meth) acryloyl group and an epoxy group in an organic solvent. . Since the branched polyimide resin (1γ) has a (meth) acryloyl group in the molecule, it has polymerizability and can be used as a thermosetting or active energy ray-curable polyimide resin.

-Compound (1f) having (meth) acryloyl group and hydroxyl group
Examples of the compound (1f) having a (meth) acryloyl group and a hydroxyl group used in the present invention include 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, trimethylolpropane di (meth) acrylate , Trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) (Meth) acrylate compounds having various hydroxyl groups such as acrylate, dipentaerythritol penta (meth) acrylate, glycidyl (meth) acrylate- (meth) acrylic acid adduct, 2-hydroxy-3-phenoxypropyl (meth) acrylate, or Examples thereof include a ring-opening reaction product of the above-described (meth) acrylate compound having a hydroxyl group and ε-caprolactone.

  Moreover, the epoxy (meth) acrylate by which various epoxy compounds and (meth) acrylic acid were made to react and the (meth) acrylic acid ester and the hydroxyl group were produced | generated can be used. Especially, the compound which has 2-5 (meth) acrylate groups and one hydroxyl group is preferable.

・ Compound having (meth) acryloyl group and epoxy group (1 g)
Examples of the compound (1g) having a (meth) acryloyl group and an epoxy group used in the present invention include glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate glycidyl ether, hydroxypropyl (meth) acrylate glycidyl ether, 4 -Hydroxybutyl (meth) acrylate glycidyl ether, 6-hydroxyhexyl (meth) acrylate glycidyl ether, 5-hydroxy 3-methylpentyl (meth) acylate glycidyl ether, (meth) acrylic acid 3,4-epoxycyclohexyl, lactone modified ( And (meth) acrylic acid 3,4-epoxycyclohexyl, vinylcyclohexene oxide, and the like.

  Moreover, as a compound (1g) which has a (meth) acryloyl group and an epoxy group, an epoxy group equivalent is converted into an acryloyl group by a reaction between an epoxy compound (1g-1) having two or more epoxy groups and (meth) acrylic acid. It is possible to use an epoxy acrylate in which an epoxy group obtained by reacting in excess of the equivalent amount remains.

  Examples of the epoxy compound (1g-1) include bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolac epoxy resin, cresol novolac type epoxy resin; dicyclopentadiene and various phenols. Epoxy products of various dicyclopentadiene-modified phenol resins obtained by reaction; epoxidized products of 2,2 ', 6,6'-tetramethylbiphenol; aromatic epoxy resins such as naphthalene skeleton epoxy and fluorene skeleton epoxy; neo Aliphatic epoxy resins such as pentyl glycol diglycidyl ether and 1,6-hexanediol diglycidyl ether; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate Bis - (3,4-epoxy human cyclohexyl) adipate alicyclic epoxy resins such as; for such heterocycle-containing triglycidyl isocyanurate epoxy resins.

  The compound (1f) having a (meth) acryloyl group and a hydroxyl group and / or the compound (1g) having a (meth) acryloyl group and an epoxy group can be used alone or in combination of two or more. .

-Reaction in an organic solvent The production method of the branched polyimide resin (1γ) used in the present invention may be a known and conventional method. For example, a polyimide resin containing a carboxy group and / or an acid anhydride group in the organic solvent. After synthesizing (Iα) and / or (1β), and then adjusting the temperature to 50 to 150 ° C., the compound (1f) having a (meth) acryloyl group and a hydroxyl group and / or (meth) acryloyl group and epoxy A group-containing compound (1 g) is added and reacted for 1 to 30 hours to produce a polyimide resin (Iγ) containing a carboxyl group and / or an acid anhydride group in the molecule and having a (meth) acryloyl group. Methods and the like.

  Further, in the organic solvent, the polyisocyanate compound (1a) to the polyisocyanate compound (1e), the acid anhydride (1b) of the polycarboxylic acid, the compound (1f) having a (meth) acryloyl group and a hydroxyl group. And / or (meth) acryloyl group and a compound having an epoxy group (1 g) are added and reacted at a temperature of 50 to 160 ° C. for 1 to 40 hours to produce a branched polyimide resin (Iγ).

  In the said manufacturing method, the compound (1f) which has a (meth) acryloyl group and a hydroxyl group, and the compound (1g) which has a (meth) acryloyl group and an epoxy group are the acid of the said polyisocyanate compound (1a) and the said polycarboxylic acid. The same resin can be obtained by adding and reacting during or after the reaction of the anhydride (1b).

After completion of the reaction of the polyisocyanate compounds (1a) to (1e) and the acid anhydride (1b) of the polycarboxylic acid, a compound (1f) having a (meth) acryloyl group and a hydroxyl group or a (meth) acryloyl group and an epoxy group When adding and reacting the compound which has (1g), it is necessary to avoid the danger of gelatinization. Therefore, the molar ratio (n _b ) / (n _a ) or (n _be ) / (n _a ) of the polyisocyanate compound (1a) and the acid anhydride (1b) of the polycarboxylic acid is 0. It is preferable to use in the range which does not become .9-1.1.

  Moreover, when adding the compound (1f) which has a (meth) acryloyl group and a hydroxyl group in the middle of reaction, and the compound (1g) which has a (meth) acryloyl group and an epoxy group, for example, (i) an isocyanate group and / or an acid The compound (1f) is added to the system in the middle of the reaction in which an anhydride group remains, and a hydroxyl group in the compound (1f) is reacted with an isocyanate group and / or an acid anhydride group to form a urethane bond and / or When a polyimide resin is formed by forming an ester bond and a reactive double bond is introduced, or (ii) the compound (1 g) is added to the system in the middle of the reaction in which the carboxy group remains, (1g) The epoxy group and carboxy group in (1g) are reacted to form an epoxy ester bond, and a polyimide resin into which a reactive double bond is introduced is mentioned. For the (i) it is preferred.

In the case of (i), the compound (1f) having a (meth) acryloyl group and a hydroxyl group is composed of the number of moles of the hydroxyl group (n _f ) in the compound (1f), the acid anhydride group and the isocyanate group remaining in the reaction system. range ratio _{(n f) / (n ab} ) is 0.5 or more of the total number of moles _{(n ab),} is preferably added in a range among them becomes 0.9 to 2.0. In the case of (ii), the compound (1g) having a (meth) acryloyl group and an epoxy group is composed of the number of moles of carboxy group (n _COOH ) remaining in the reaction system and the epoxy group in the compound (1g). moles _{(n g)} ratio of _{(n COOH) / (n g} ) range of 1 or more, it is preferably added in a range among them becomes 1.5 to 20.

  The reaction between the branched polyimide resins (1α) to (1β) containing the carboxyl group and / or the acid anhydride group and the compound (1f) having a (meth) acryloyl group and a hydroxyl group includes (a) Compound (1f) Ring-opening esterification reaction (half-esterification reaction) between the hydroxyl group in the resin and the acid anhydride group remaining in the polyimide resin (1α), (b) the hydroxyl group in the compound (1f) and the carboxy group in the polyimide resin (1α) And (c) reaction of an isocyanate group remaining in the polyimide resin (1α) with a hydroxyl group in the compound (1f). By these reactions, the polyimide resin (1α) is converted to (meta ) An acryloyl group is introduced to obtain a branched polyimide resin (1γ-1).

  Moreover, as reaction of the polyimide resin (1 (alpha)) thru | or (1 (beta)) containing the said carboxy group and / or an acid anhydride group, and the compound (1g) which has a (meth) acryloyl group and an epoxy group, (d) Compound ( Ring-opening esterification reaction between the epoxy group in 1 g) and the acid anhydride remaining in the polyimide resins (1α) to (1β), and (e) the epoxy group in the compound (1g) and the polyimide resin (1α) Thru | or esterification reaction with the carboxy group in (1β) is mentioned. By these reactions, a (meth) acryloyl group is introduced into the polyimide resins (1α) to (1β) to obtain a branched polyimide resin (1γ-2). It is done.

  Moreover, the branched polyimide resin obtained by making the polyimide resin (1 (alpha)) thru | or (1 (beta)) containing the said carboxy group and / or an acid anhydride group react with the compound (1g) which has a (meth) acryloyl group and an epoxy group. (1γ-2) generates a hydroxyl group as the epoxy group is opened. It is possible to adjust the developability when used as a resist resin composition by further reacting this hydroxyl group with a polybasic acid anhydride to make a half ester.

  Examples of such polybasic acid anhydrides include maleic anhydride, succinic anhydride, dodecenyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 3-methylhexahydrate. Examples thereof include hydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, and the acid anhydride (1b) of the polycarboxylic acid described above.

  In the method for producing the branched polyimide resin (1), an acid anhydride group and / or a carboxy group in the acid anhydride (1b) of the polycarboxylic acid is present at the molecular end of the polyimide resin, but the acid anhydride group is a molecule. When present at the terminal, the ring may be opened using water or the like to generate a carboxylic acid.

-Molecular weight adjustment The carboxy group and acid anhydride group which remain | survive at the terminal of the said polyimide resin (1) can be made to react with the epoxy resin which has a 2 or more epoxy group in a molecule | numerator, and molecular weight can be adjusted. As the epoxy resin, an epoxy compound (1g-1) described later can be used.

・ Other polyisocyanate compound components (1h)
In the branched polyimide resin (1), the polyisocyanate compound (1a), the polyisocyanate compound (1a), and the urethane prepolymer (1c) are used as the polyisocyanate compound component. You may use together 1 type (s) or 2 or more types of polyisocyanate compounds (1h) other than.

  Among the polyisocyanate compounds (1h), diisocyanate compounds are preferable, and examples thereof include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2, Aromatics such as 6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4'-diisocyanate, naphthalene diisocyanate Diisocyanates; isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornylene diisocyanate Sulfonates, aliphatic diisocyanates such as lysine diisocyanate. Of these, aliphatic diisocyanates are particularly preferred.

When the polyisocyanate compound (1h) is used in combination as a polyisocyanate component, the number of moles of isocyanate groups (n _ac ) in the polyisocyanate compound (1a) and / or the urethane prepolymer (1c) and the polyisocyanate compound ( The polyisocyanate compound (1h) is used in combination so that the ratio (n _ac ) / (n _h ) of the number of moles (n _h ) of isocyanate groups in 1h) is 1.0 or more. It is preferable to use in the range of ˜10.5.

As the branched polyimide resin (1) used in the present invention, one having an isocyanurate ring concentration of 0.6 to 1.1 mmol / g (in terms of resin solid content) is preferably used. Moreover, it is preferable to use what (meth) acryloyl group concentration is 0.7-3 mmol / g (resin solid content conversion). Furthermore, it is preferable to use what has an acid value of 50-180 (resin solid content conversion). Furthermore, it is preferable to use a polyimide resin having a number average molecular weight of 1,500 to 6,000 and a weight average molecular weight of 3,000 to 15,000.
The organic solvent solubility and heat resistance are good in the above range, and patterning with a dilute alkaline aqueous solution can be easily performed when used for resist.

  However, the values of the preferred ranges of the concentration of the isocyanurate ring, the concentration of the (meth) acryloyl group, the acid value, the number average molecular weight, and the weight average molecular weight of the branched polyimide resin (1) described above were measured by the following methods. Is.

1. Concentration of isocyanurate ring: 13C-NMR analysis [solvent: deuterated dimethyl sulfoxide (DMSO-d6), and using a calibration curve from the spectral intensity of the carbon atom due to the isocyanurate ring at 149 ppm, 1) Obtain the concentration (mmol) of isocyanurate ring per gram. In addition, the concentration of the imide ring can be similarly determined from the spectral intensity of the carbon atom resulting from the imide ring at 169 ppm by 13C-NMR analysis.

2. Concentration of (meth) acrylate groups: The branched polyimide resin (1) is measured by measuring the bromine number in the polyimide resin (1) using the relationship that theoretically 160 g of bromine is added per 1 mol of unsaturated bonds. ) Calculate the concentration (mmol) of (meth) acryloyl groups per gram. The bromine number is measured by the method described in JIS K-2605, and is generally expressed as the number of grams of bromine added to the unsaturated bond in 100 g of the sample. The concentration (mmol / g) of the (meth) acrylate group is determined by dividing by 16.

3. Acid value: Measured according to JIS K-5601-2-1. As a dilution solvent for the sample, a mixed solvent of acetone / water (9/1 volume ratio) having an acid value of 0 is used so that the acid value of the acid anhydride can also be measured.

4). Number average molecular weight and weight average molecular weight: The number average molecular weight and weight average molecular weight in terms of polystyrene are determined by gel permeation chromatography (GPC).

■ Polymerizable resin (2)
The polymerizable resin (2) having a carboxy group used in the present invention is an acid anhydride of a polycarboxylic acid having two or more carboxy groups in an esterified product of an epoxy compound (2a) and an unsaturated monocarboxylic acid (2b). It can be obtained by reacting product (2c).

・ Epoxy compound (a)
As the epoxy compound (2a) used in the present invention, for example, a novolac type obtained by reacting novolaks obtained by reacting phenol, cresol, halogenated phenol or alkylphenols with formaldehyde in the presence of an acidic catalyst and epichlorohydrin. There are epoxy compounds, YDCN-701, 704, YDPN-638, 602 manufactured by Tohto Kasei Co., Ltd., DEN-431, 439 manufactured by Dow Chemical Co., EPN-1299 manufactured by Ciba Geigi Co., Ltd., and N-730 manufactured by Dainippon Ink & Chemicals, Inc. 770, 865, 665, 673, VH-4150, 4240, Nippon Kayaku Co., Ltd. EOCN-120, BREN, and the like. In addition to the novolac type epoxy compound, for example, an epoxy compound (EPPN502H, FAE2500, etc., manufactured by Nippon Kayaku Co., Ltd.) obtained by reacting epichlorohydrin with a reaction product of salicylaldehyde and phenol or cresol is preferably used. Further, for example, Epicoat 828, 1007, 807 manufactured by Yuka Shell Co., Ltd., Epicron 840, 860, 3050 manufactured by DIC, DER-330, 337, 361 manufactured by Dow Chemical Company, Celoxide 2021, manufactured by Daicel Chemical Industries, Ltd., manufactured by Mitsubishi Gas Chemical Company, Inc. TETRAD-X, C, EPB-13, 27 manufactured by Nippon Soda Co., Ltd., GY-260, 255, XB-2615 manufactured by Ciba Geigy Co., Ltd., bisphenol A type, bisphenol F type, hydrogenated bisphenol A type, brominated bisphenol A Epoxy compounds such as molds, amino group-containing types, and alicyclic glycidyl ether types are also used. Also, rubber-modified epoxy compounds such as epoxidized polybutadiene PB3600, PB4700 (manufactured by Daicel Chemical Industries, Ltd.), epoxidized butadiene-styrene Epoblend T014 (manufactured by Daicel Chemical Industries, Ltd.), or polydimethylsiloxane epoxy compounds X22-163B, KF100T (Manufactured by Shin-Etsu Silicon). Further, an epoxy compound obtained by reacting an epoxy compound such as that described above with Α, Ω-polybutadienedicarboxylic acid, an acrylonitrile-butadiene rubber having a carboxylic acid at both terminals, and one of the bisphenol F-type epoxy resin and bisphenol-type epoxy resin described above. Epoxy compounds obtained by reacting parts are also used. Among these, a rubber-modified epoxy resin or a bisphenol F-type epoxy resin is preferable from the viewpoint of mechanical properties such as flexibility and warping.

Unsaturated monocarboxylic acid (2b)
Examples of the unsaturated monocarboxylic acid (2b) used in the present invention include (meth) acrylic acid, crotonic acid, and cinnamic acid. Also, saturated or unsaturated polybasic acid anhydrides and (meth) acrylates having one hydroxyl group in one molecule, or half-ester compounds of saturated or unsaturated dibasic acids and unsaturated monoglycidyl compounds Reactants such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid and hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, tris (hydroxyethyl) isocyanurate di (meth) acrylate, Examples include a reaction product obtained by reacting glycidyl (meth) acrylate with an equimolar ratio by a conventional method. These unsaturated monocarboxylic acids can be used alone or in combination. Of these, acrylic acid is preferred.

-Esterified product of epoxy compound (2a) and unsaturated monocarboxylic acid (2b) The esterified product of epoxy compound (2a) and unsaturated monocarboxylic acid (2b) may be a known and commonly used production method. The epoxy compound (2a) and the unsaturated monocarboxylic acid (2b) in the presence of a catalyst at a molar ratio of epoxy group to carboxy group of about 1: 0.9 to 1: 1. The target ester compound (epoxy acrylate) can be obtained by reacting at a temperature of about 1 hour to about 20 hours. At this time, the reaction may be carried out in a solvent, or a polymerization inhibitor may be used in combination. As a reaction catalyst of an epoxy group and a carboxy group, known and conventional ones can be used. For example, tertiary amine catalyst, quaternary ammonium salt catalyst, imidazole, phosphine catalyst such as triphenylphosphine, organic metal salt, etc. are used. it can.

・ Acid anhydride (2c)
As the acid anhydride (2c) of a polycarboxylic acid having two or more carboxy groups, anhydrides such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, trimellitic acid and the like are used.

Reaction of esterified product with acid anhydride (2c) Acid ester of polycarboxylic acid having two or more carboxy groups (2c) to esterified product of epoxy compound (2a) and unsaturated monocarboxylic acid (2b) ). For example, the acid anhydride (2c) can be obtained by reacting the hydroxyl group generated by the reaction of the epoxy compound and the unsaturated carboxylic acid with the hydroxyl group at a ratio of 0.1 to 1 with respect to 1 mol. The reaction temperature at this time is preferably 50 to 150 ° C., and the reaction time can be obtained by reacting for about 1 to 10 hours. At this time, an esterification catalyst or a polymerization inhibitor may be used in combination, and the reaction may be carried out in various solvents.

Others In addition to the above-mentioned polymerizable resin (2) having a carboxy group, isocyanate ethyl (meth) acrylate, or tolylene diisocyanate or isophorone diisocyanate and (meth) acrylates having one or more hydroxyl groups in one molecule, such as hydroxy A compound obtained by reacting an equimolar reaction product with ethyl (meth) acrylate to introduce an unsaturated bond via a urethane bond can also be used as the polymerizable resin (2) having a carboxy group.

  The polymerizable resin (2) having a carboxy group preferably has an acid value (KOH mg / g) of 40 to 250, preferably 50 to 150, in view of the balance between alkali developability, electrical characteristics and other characteristics.

  The resin composition of the present invention includes, in addition to the polymerizable resin (2) having a carboxy group, JP-B-7-92603 or JP-A-63-205649 having a carboxy group and a (meth) acrylate group. You may mix | blend acrylic type and styrene type resin shown by these.

  ZFER1179 is commercially available from Nippon Kayaku Co., Ltd. as the above-mentioned polymerizable resin (2) having a carboxy group.

  The composition ratio between the branched polyimide resin (1) and the polymerizable resin (2) is resin (1) / resin (2) = 2/98 to 98/2, preferably 2/98 to 60 / on a weight basis. The range is 40, more preferably 2/98 to 50/50, and still more preferably 2/98 to 40/60.

■ Organic solvent (3)
As the organic solvent (II) contained in the active energy ray-curable resin composition of the present invention, the same organic solvent used in the method for producing the branched polyimide resin can be used.

The organic solvent (3) is used in an amount of 10 to 80% by weight in the active energy ray-curable polyimide resin composition of the present invention because a composition excellent in coating suitability and the like is obtained. A range is preferable, and a range of 20 to 70% by weight is particularly preferable.
■ Other Components / Epoxy Resin The active energy ray-curable resin composition of the present invention comprises the epoxy resin listed above in addition to the branched polyimide resin (1), the polymerizable resin (2) and the organic solvent (3). And can be used as a thermosetting component. When the epoxy resin is used as a thermosetting component, it acts as a curing agent in this final process by painting → pre-drying → UV exposure → development → thermosetting. The thermosetting reaction is a reaction in which the carboxy group of the polymerizable resin (2) and the epoxy group of the epoxy resin react to further perform thermal crosslinking other than the reaction at the time of UV exposure. Improvements can be made. In addition, the reaction with the carboxylic acid of the polymerizable resin (2) is effective in improving water resistance. As the epoxy resin that can be used, various epoxy resins listed above can be used. Preferably, an aromatic epoxy resin having two or more epoxy groups in the molecule is preferable in terms of heat resistance and the like.

Curing agent or curing accelerator The active energy ray-curable resin composition containing the polymerizable resin (2) can use a curing agent or a curing accelerator, such as melamine, dicyandiamide, guanamine resin and the like. Derivatives, amines, phenols, organic phosphines, phosphonium salts, quaternary ammonium salts, polybasic acid anhydrides, photocationic catalysts, cyanate compounds, isocyanate compounds, blocked isocyanate compounds, and the like.

-Photoinitiator Moreover, in order to harden an active energy ray hardening-type resin composition by light irradiation, a photoinitiator can be used. Examples of the photoinitiator include acetophenones, benzophenone derivatives, Michler's ketone, benzine, benzyl derivatives, benzoin derivatives, benzoin methyl ethers, α-acyloxime esters, thioxanthones, anthraquinones, and various derivatives thereof. Can be mentioned.

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

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

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

-Reactive diluent Furthermore, a reactive diluent can be used for the purpose of adjusting curability by an active energy ray, and examples thereof include (meth) acrylate compounds, vinyl compounds, acrylamide compounds, maleimide compounds, and the like. Especially, the compound which has a (meth) acryloyl group and a hydroxyl group from the point which improves the developability of a resist composition.

  Examples of the compound having a (meth) acryloyl group and a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl (meth). Acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane ( (Meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipe (Meth) acrylate compounds having various hydroxyl groups such as taerythritol penta (meth) acrylate, glycidyl (meth) acrylate- (meth) acrylic acid adduct, 2-hydroxy-3-phenoxypropyl (meth) acrylate; And a ring-opening reaction product of (meth) acrylate compound and ε-caprolactone.

  Moreover, the epoxy (meth) acrylate obtained by making various epoxy compounds and (meth) acrylic acid react as a compound which has the said (meth) acryloyl group and a hydroxyl group can also be used. The epoxy ring is opened by the reaction of the epoxy group and (meth) acrylic acid, and at this time, a (meth) acrylic acid ester and a hydroxyl group are generated.

  The amount of the reactive diluent used is 10 to 200 parts by weight with respect to 100 parts by weight of the polyimide resin (1) because an active energy ray-curable resin composition having excellent photocurability and the like is obtained. A range is preferable, and a range of 10 to 100 parts by weight is particularly preferable.

Filler The active energy ray-curable resin composition can be added with various inorganic fillers as necessary. For example, barium sulfate, barium titanate, silicon oxide powder, fine particles Examples thereof include silicon oxide, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica.

-Pigment Furthermore, an inorganic pigment, an organic pigment, etc. can be added to the said active energy ray hardening-type resin composition as needed. Inorganic pigments include, for example, chromates such as chrome lead, zinc chromate, molybdate orange; ferrocyanides such as bitumen, titanium oxide, zinc white, bengara, iron oxide; metal oxides such as chromium carbide green, cadmium Yellow, cadmium red; metal sulfides such as mercury sulfide; selenides; sulfates such as lead sulfate; silicates such as ultramarine; carbonates, cobalt violet; phosphates such as manganese purple; aluminum powder, zinc dust, Examples thereof include metal powders such as brass powder, magnesium powder, iron powder, copper powder and nickel powder; carbon black and the like.

  Examples of the organic pigments include azo pigments; copper phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, and quinacridone pigments.

-Others Furthermore, a rust preventive, an extender, etc. can be further added to the said active energy ray hardening-type resin composition as needed. These may be used alone or in combination of two or more. However, when ultraviolet rays are used as an active energy ray source, it is necessary to use them in a range having transparency necessary for curing.

  Furthermore, the active energy ray-curable resin composition may contain various (meth) acrylate compounds and vinyl compounds in order to improve photocuring characteristics and physical properties.

■ Application (resist material)
-Usage method The active energy ray-curable resin composition is suitably used as a resist composition, and is applied to a substrate by a screen printing method, a spray method, an electrostatic spray method, an airless spray method, a curtain coater method, a roll coat method. The film is applied at a film thickness of 60 to 160 μm by a conventionally known method, and the solvent is dried at 60 to 110 ° C., and then irradiated with active energy rays such as ultraviolet rays through a mask having a desired negative pattern. A pattern is formed by dissolving and removing (developing) the exposed portion with a dilute alkaline aqueous solution, and further, usually irradiation with active energy rays and / or heating at about 100 to 200 ° C. is performed for about 0.5 to 1 hour, Sufficient curing can be performed to obtain a cured coating film.

  As the dilute alkaline aqueous solution, a known and commonly used alkaline aqueous solution can be used, and representative examples thereof include aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and tetramethylammonium hydroxide. Alternatively, an aqueous solution of tetraethylammonium hydroxide, tetramethylphosphonium hydroxide, or the like can be used. Examples of the concentration of the alkaline aqueous solution include 0.2 to 5% by weight. The developing method can be carried out by dipping the coating sample into the developer and shaking, or by spraying the developer onto the sample with a spray. Moreover, the temperature of a developing solution is 10-50 degreeC.

  Examples of the active energy rays used for curing the active energy ray-curable resin composition include electron beams, α rays, γ rays, X rays, neutron rays, and ionizing radiation and light such as ultraviolet rays.

  Next, this invention is based on an Example and a comparative example. Specifically, in the following, all parts and% are based on weight unless otherwise specified.

(Synthesis Example 1)
In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 4332.0 g of diethylene glycol monoethyl ether acetate, 2772 g of IPDI-N (molar number of isocyanate group: 12 mol), and 1536.0 g (8 mol) of trimellitic anhydride The temperature was raised to 160 ° C. while charging and stirring. Foaming started vigorously from around 60 ° C., and the flask contents gradually became transparent. The reaction was carried out at 160 ° C. for 4 hours, and the system was cooled to 80 ° C. when the isocyanate group content in the system reached 2.0%. Next, 935.0 g of diethylene glycol monoethyl ether acetate and 3.51 g of methylhydroquinone were added, and further 935.0 g (2 mol) of pentaerythritol triacrylate (hydroxyl value 120) was added thereto, and 80 ° C. while paying attention to heat generation. It was made to react with. After reacting at 80 ° C. for 4 hours, it was confirmed by IR that the absorption of 2270 cm ⁻¹ isocyanate group had disappeared, and a light yellow transparent branched polyimide resin solution (1γ-1) was obtained.

(Synthesis Example 2)
In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 4332.0 g of diethylene glycol monoethyl ether acetate and an isocyanurate ring-containing polyisocyanate compound derived from isophorone diisocyanate (hereinafter abbreviated as IPDI-N. Isocyanate group). Content: 18.2%, content of isocyanurate ring-containing triisocyanate compound: 952) 2772 g (12 mol of isocyanate group) and trimellitic anhydride 1536.0 g (8 mol) were charged at 160 ° C. while stirring. The temperature was raised to. Foaming started vigorously from around 60 ° C., and the flask contents gradually became transparent. The reaction was carried out at 160 ° C. for 4 hours, and the system was cooled to 80 ° C. when the isocyanate group content in the system reached 2.0%. Next, 935.0 g of diethylene glycol monoethyl ether acetate and 3.51 g of methylhydroquinone were added, and further 284.3 g (2 mol) of glycidyl methacrylate was added, and the reaction was carried out at 80 ° C. while paying attention to heat generation. After reacting at 80 ° C. for 4 hours, it was confirmed by IR that the absorption of 2270 cm ⁻¹ isocyanate group had disappeared, and a light yellow transparent branched polyimide resin solution (1γ-2) was obtained.

(Synthesis Example 3)
A flask equipped with a thermometer, a stirrer and a condenser was charged with 322.2 g of ethyl carbitol acetate, and orthocresol novolac type epoxy resin EPICLON N-680 [manufactured by DIC Corporation, epoxy equivalent 212 g / eq] 954.0 g. (Epoxy group 4.5 mol) was dissolved. Next, 1.3 g of hydroquinone was added, and then 325.8 g of acrylic acid (4.5 mol of carboxy group) and 2.1 g of triphenylphosphine were added while stirring, and esterified at 130 ° C. while blowing air. Reaction was performed. The reaction end point was the point where the acid value became 1 mgKOH / g or less. Thereafter, 61.2 g of ethyl bicarbitol acetate and 444.6 g of tetrahydrophthalic anhydride were added and reacted at 90 ° C. for 5 hours to obtain a light yellow color having an acid value of 82.4 and an acryloyl group concentration of 2.61 mmol. An acid pendant type epoxy acrylate resin solution (2) was obtained.

(Example / Comparative Example)
As the polyimide resin (1) component, the branched polyimide resin solution obtained in Synthesis Examples 1 and 2, the acid pendant type epoxy acrylate resin solution (2) obtained in Synthesis Example 3 as the polymerizable resin (2) component, In addition, ortho-cresol novolac type epoxy resin as epoxy resin Epoxy equivalent 212 g / eq Softening point 80 ° C. diluted with EDGA to 60% nonvolatile content (however, the numerical values in the table are solid content values), photoinitiator (Irgacure 907) (Manufactured by Ciba Specialty Chemical Co., Ltd.)), DPHA (dipentaerythritol hexaacrylate), and thermosetting catalyst (2-ethyl-4-methyl-imidazole) in the mixing ratio (parts by weight) described in Tables 1 and 2. The active energy ray-curable resin composition was obtained by blending. Each curable resin composition was subjected to various measurements according to the test method described later. The results are also shown in Tables 1 and 2.

(Evaluation methods)
■ Developing speed The curable resin compositions obtained in Examples and Comparative Examples were applied to a glass substrate using an applicator so that the film thickness was 30 μm after drying, and the obtained test piece was placed in a dryer at 80 ° C. For 30 minutes to evaporate the solvent and measure the weight (W ₀ ). The test piece was immersed and shaken for 30 seconds using a 1% aqueous sodium carbonate solution at 30 ° C., washed with tap water, and then weighed again (W ₁ ). The development rate (t) was calculated from the following formula using the weight loss by development (W ₁ -W ₀ ), resin specific gravity (1.2 g / cm ² ), and coating area (S).
◇ Developing speed [μm / min]: [{(W ₁ −W ₀ ) /1.2} / (S)] / 0.5

■ Development residue The curable resin compositions obtained in Examples and Comparative Examples were applied to a glass substrate using an applicator so that the film thickness was 30 μm after drying, and the obtained test piece was placed in a dryer at 80 ° C. For 30 minutes to evaporate the solvent. This test piece was immersed and shaken for 120 seconds using a 1% sodium carbonate aqueous solution at 30 ° C. as a developer, and washed with tap water. The test piece in which the development trace (residue of the resin composition that could not be developed) was confirmed by visually confirming the development trace, the weight (W2) of the residue area transferred to tracing paper and cut into the residue Was compared with the weight (W3) of the tracing paper of the same area as the area (S) applied at the initial stage, and the residual area relative to the initial coating area was calculated and evaluated.
◇ Development residue [%]: W2 / W3

■ Tackiness (dryness to touch)
The curable resin compositions obtained in Examples and Comparative Examples were applied to a glass substrate using an applicator so as to have a film thickness of 50 μm after drying, and the obtained test pieces were placed in a dryer at 80 ° C. for 30 minutes. The solvent was stripped on standing. After cooling to room temperature (25 ± 2 ° C.), the surface was pushed with a finger, and tackiness was evaluated as follows.
○: No tackiness at all, and no finger marks are left.
Δ: There is no stickiness, but a finger mark remains.
×: There is stickiness.

■ Mechanical strength <Preparation of test specimen for measurement>
The curable resin compositions obtained in Examples and Comparative Examples were coated on a mirror aluminum substrate so that the film thickness after curing was 25 μm, and the temperature was further raised to 100 ° C. for 30 minutes with a 50 ° C. dryer. After drying for 30 minutes, the dryer was heated to 170 ° C. and cured for 60 minutes to produce a cured coating film. After cooling to room temperature, the cured coating film was cut into a predetermined size, isolated from the substrate, and used as a measurement sample.
<Measurement method of tensile test>
Four samples for measurement were prepared and subjected to a tensile test under the following conditions to determine the breaking strength and breaking elongation. It represents that it is a coating film which is excellent in mechanical physical property, so that the value of breaking strength and breaking elongation is high.
Measuring instrument: Tensilon 1210A manufactured by A & D
Sample shape: 10mm x 100mm
Between chucks: 20 mm
Tensile speed: 10 mm / min
Measurement atmosphere: 23 ° C., 50% RH

■ Heat resistance <Preparation of test specimen for measurement>
The curable resin compositions obtained in Examples and Comparative Examples were coated on a mirror aluminum substrate so that the film thickness after curing was 25 μm, and the temperature was further raised to 100 ° C. for 30 minutes with a 50 ° C. dryer. After drying for 30 minutes, the dryer was heated to 170 ° C. and cured for 60 minutes to produce a cured coating film. After cooling to room temperature, the cured coating film was cut into a predetermined size, isolated from the substrate, and used as a measurement sample.
<Heat resistance test method>
Measurement was performed using a TG-DTA differential calorific value simultaneous measurement apparatus. The resin coating film was weighed in a deep aluminum pan container, heated from room temperature to 500 ° C., and heat resistance was evaluated by weight change. It represents that it is a coating film which is excellent in heat resistance, so that weight reduction is small.
Measuring device: SIINT TG / DTA6200
Measurement temperature: RT to 500 ° C
Temperature increase rate: 10 ° C / min

■ Thermal expansion coefficient <Preparation of test specimen for measurement>
The curable resin compositions obtained in Examples and Comparative Examples were coated on a mirror aluminum substrate so that the film thickness after curing was 25 μm, and the temperature was further raised to 100 ° C. for 30 minutes with a 50 ° C. dryer. After drying for 30 minutes, the dryer was heated to 170 ° C. and cured for 60 minutes to produce a cured coating film. After cooling to room temperature, the cured coating film was cut into a predetermined size, isolated from the substrate, and used as a measurement sample piece.
<Thermal expansion test method>
Using a thermal analysis system TMA-SS6000 manufactured by Seiko Electronics Co., Ltd., measurement was performed by the TMA (Thermal Mechanical Analysis) method under the conditions of a test length of 10 mm, a heating rate of 10 ° C./min, and a load of 6 mN. In addition, the temperature range used for the linear expansion coefficient was calculated | required from the displacement of the test length of 20-100 degreeC. Note that the smaller the value of the linear expansion coefficient, the smaller the thermal expansion coefficient, and the better. The unit is ppm / K.

  The resist composition of the present invention has a good and fast development speed even by dilute alkali development, and can reduce development residues. In particular, in Examples 1 to 8, development residues could be eliminated as compared with Comparative Examples 2 and 3. Moreover, the cured product of the resist composition of the present invention formed a cured coating film having excellent heat resistance and excellent mechanical strength, particularly breaking strength and breaking elongation. Moreover, the tackiness with the photomask in the contact-type UV exposure step was also good, and in particular, even when the proportion of the branched polyimide resin (1) was small, good tackiness was exhibited.

  The active energy ray-curable resin composition of the present invention is optimally used for various negative type resists, for example, patterning materials such as solder resists, plating resists, build-up printed circuit boards, and resists for insulating layers of semiconductor elements. Can do.

Claims (9)

A branched polyimide resin (1) having a carboxy group and / or an acid anhydride group and a (meth) acryloyl group, an esterified product of an epoxy compound (2a) and an unsaturated monocarboxylic acid (2b), and two or more carboxy groups An active energy ray-curable resin composition containing a polymerizable resin (2) having a carboxy group obtained by reacting an acid anhydride (2c) of a polycarboxylic acid having a group and an organic solvent (3). The composition ratio between the branched polyimide resin (1) and the polymerizable resin (2) is in the range of resin (1) / resin (2) = 2/98 to 60/40 on a weight basis. An active energy ray-curable resin composition. The branched polyimide resin (1) is
A carboxy group obtained by reacting a polyisocyanate compound (1a) having 3 or more isocyanate groups with an acid anhydride (1b) derived from a polycarboxylic acid having 3 or more carboxy groups in an organic solvent; Branched polyimide resin (1α) having acid anhydride groups
Or
A polyisocyanate compound (1e) containing a urethane prepolymer (1d) having an isocyanate group at the terminal obtained from the polyisocyanate compound (1a) and a polyol compound (1c), and a polycarboxylic acid having three or more carboxy groups Branched polyimide resin (1β) having a carboxy group and / or an acid anhydride group, obtained by reacting an acid anhydride (1b) of an acid in an organic solvent
Carboxy group and / or acid anhydride group possessed by reacting a compound (1f) having a (meth) acryloyl group and a hydroxyl group and / or a compound (1 g) having a (meth) acryloyl group and an epoxy group. The active energy ray-curable resin composition according to claim 1 or 2, which is a branched polyimide resin (1γ) having a group and / or an acid anhydride group. The activated energy ray-curable resin composition according to claim 3, wherein the acid anhydride (1b) contains an acid anhydride having a carboxy group. The active energy ray-curable composition according to claim 3, wherein the polyisocyanate compound (1a) is an isocyanurate ring-containing polyisocyanate compound obtained by isocyanurating a cyclic aliphatic isocyanate compound. The active energy ray-curable resin composition according to claim 5, wherein the cycloaliphatic isocyanate compound is isophorone diisocyanate or tolylene diisocyanate. The active energy ray-curable resin composition according to claim 3, wherein the acid anhydride (1b) is trimellitic anhydride or hydrogenated trimellitic acid. The active energy ray-curable resin composition according to any one of claims 1 to 7, wherein the epoxy compound (2a) is a bisphenol type epoxy compound or a novolac type epoxy compound. Hardened | cured material obtained by hardening | curing the active energy ray-curable resin composition as described in any one of Claims 1-8.