JP2003221429A - Active ray-curing polyimide resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active ray-curing polyimide resin composition having heat resistance, capable of patterning with an aqueous dilution alkaline solution and soluble in organic solvents. <P>SOLUTION: The active ray-curing polyimide resin composition comprises (I) a polymerizable polyimide resin and, if necessary, (II) an organic solvent, (III) an epoxy resin and (IV) a photopolymerization initiator, wherein the polymerizable polyimide resin contains an isocyanurate ring, a cyclic aliphatic structure, an imide ring and a (meth)acryloyl group and allows of patterning with an aqueous dilution alkaline solution, preferably the isocyanurate ring having a concentration of 0.4-1.2 mmol/g, the (meth)acryloyl group having a concentration of 0.3-4 mmol/g, the polyimide resin having an acid value of 20-250, a number-average molecular weight of 1,000-20,000 and a weight-average molecular weight of 1,500-30,000. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable polyimide resin composition which has excellent heat resistance, solvent solubility, and moisture resistance at high temperatures and which can be developed with a dilute aqueous alkali solution. More specifically, active energy ray curable polyimide that can be optimally used for various negative type resists such as solder resists, plating resists, patterning materials such as build-up method printed circuit boards and resists for insulating layers of semiconductor elements. It relates to a resin composition.

[0002]

2. Description of the Related Art Active energy ray curable resins that are cured by ultraviolet rays or electron beams have a fast curing rate and are preferable from the viewpoint of environmental protection. Therefore, they are being replaced by conventional thermosetting resins and thermoplastic resins. I'm out. Under these circumstances, improvement in heat resistance and electric characteristics of active energy ray-curable resins is required in various fields. Currently, there are a wide variety of active energy ray curable resins such as ester acrylate resins, epoxy acrylate resins, and urethane acrylate resins, but there is a limit to the improvement of heat resistance.

Examples of the active energy ray curable resin having improved heat resistance include, for example, JP-A-2000-344889.
Japanese Patent Laid-Open Publication No. 2003-242242, an active energy ray-curable polyimide for reacting a tri- or more functional aromatic carboxylic acid and / or its anhydride, a polyisocyanate compound, and a compound having a polymerizable double bond and a hydroxyl group and / or an epoxy group. A method of making a resin is disclosed. In this publication, it is possible to obtain a polyimide resin having excellent heat resistance, solvent solubility, active energy ray curability, developability, etc., and as the polyisocyanate compound used in this production method, a buret body or a nurate body can also be used. There is a description that an aliphatic or alicyclic polyisocyanate is preferable because an imide resin excellent in solvent solubility and curability can be obtained. In addition, the examples of this publication describe a method for producing a polyimide resin using a cycloaliphatic diisocyanate as a polyisocyanate compound.

However, the above-mentioned Japanese Patent Laid-Open No. 2000-344889.
The polyimide resin obtained in the examples of the publication has better heat resistance than ester acrylate resin, epoxy acrylate resin, urethane acrylate resin, etc.
There is a problem that it is not enough.

[0005]

The object of the present invention is to have sufficient heat resistance, patterning with a dilute alkaline aqueous solution is possible, and a solvent containing a usual organic solvent such as a nitrogen atom and a sulfur atom. Another object of the present invention is to provide an active energy ray-curable polyimide resin composition which can also use a polar solvent which does not.

[0006]

Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventors have an isocyanurate ring, a cycloaliphatic structure, an imide ring, and a (meth) acryloyl group, The polymerizable polyimide resin (I) capable of patterning with a dilute aqueous alkali solution has particularly good heat resistance, excellent solubility in organic solvents, can be patterned with a dilute aqueous alkali solution, and can be used even at a high temperature of 120 ° C. or higher. They have found that an active energy ray-curable polyimide resin composition suitable for applications such as resists can be easily obtained by containing it as a resin having excellent moisture resistance, and completed the present invention.

That is, the present invention contains a polymerizable polyimide resin (I) which has an isocyanurate ring, a cycloaliphatic structure, an imide ring and a (meth) acryloyl group and which can be patterned with a dilute aqueous alkaline solution. The present invention provides an active energy ray-curable polyimide resin composition.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
As the polymerizable polyimide resin (I) used in the present invention,
A polymerizable polyimide resin (I) which has an isocyanurate ring, a cycloaliphatic structure, an imide ring, and a (meth) acryloyl group and can be patterned with a dilute alkaline aqueous solution, may be any polymerizable polyimide resin, and is not particularly limited. For example, the concentration of the isocyanurate ring is 0.4 to 1.
2 mmol / g (resin solid content conversion), (meth) acryloyl group concentration is 0.3 to 4 mmol / g (resin solid content conversion), acid value is 20 to 250 (resin solid content conversion), number average A polymerizable polyimide resin having a molecular weight of 1,000 to 20,000 and a weight average molecular weight of 1,500 to 30,000 can be used.

Among these polymerizable imide resins, the solubility of the organic solvent and the heat resistance are good, and the patterning with a dilute alkaline aqueous solution is easy when used as a resist. 6 to 1.1 mm
ol / g, the concentration of the (meth) acryloyl group is 0.7 to
A polyimide resin having 3 mmol / g, an acid value of 50 to 180, a number average molecular weight of 1,500 to 6,000, and a weight average molecular weight of 3,000 to 15,000 is particularly preferable.

The isocyanurate ring in the polyimide resin (I) is preferably an isocyanurate ring derived from an isocyanurate ring-containing polyisocyanate compound derived from a cycloaliphatic diisocyanate compound. In this case, the polymerizable polyimide resin used in the present invention usually has 2 to 3 moles of the cycloaliphatic structure derived from the cycloaliphatic diisocyanate compound with respect to 1 mole of the isocyanurate ring. Above all, it is more preferable that the amount of the cyclic aliphatic structure is 2.5 to 3 times, and the more the amount is the better.

In the present invention, the isocyanurate ring concentration, the (meth) acryloyl group concentration, the acid value, the number average molecular weight, and the weight average molecular weight of the aliphatic structure polymerizable imide resin (I) are as follows. It was measured by the method.

(1) Concentration of isocyanurate ring: ¹³ C-
NMR analysis [solvent: deuterated dimethyl sulfoxide (D
_{MSO-d 6)} performed to determine the concentration of isocyanurate ring of the polymerizable polyimide resin (I) per 1g using a calibration curve from the spectral intensity of carbon atoms due to isocyanurate ring (mmol) in 149 ppm. In addition,
Similarly, the concentration of the imide ring can be determined from the spectral intensity of carbon atoms originating from the imide ring at 169 ppm by ¹³ C-NMR analysis. (2) Concentration of (meth) acrylate group: Polymerization was performed by measuring the bromine number in the polyimide resin (I) by utilizing the relationship that 160 g of bromine is theoretically added to 1 mol of unsaturated bond. The concentration (mmol) of the (meth) acryloyl group per 1 g of the polyimide resin (I) is calculated. The bromine number is measured by the method described in JIS K-2605,
Generally, it is expressed by the number of grams of bromine added to the unsaturated bond in 100 g of the sample, and thus the value of the bromine number obtained is divided by 16 to determine the concentration of the (meth) acrylate group.
Calculate (mmol / g). (3) Acid value: measured according to JIS K-5601-2-1. As a diluent 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 anhydrous acid can be measured. (4) Number average molecular weight and weight average molecular weight: The polystyrene equivalent number average molecular weight and weight average molecular weight are determined by gel permeation chromatography (GPC).

The method for producing the polymerizable polyimide resin (I) used in the present invention is not particularly limited, but for example, isocyanurate ring-containing polyisocyanate compound (A1) derived from a cycloaliphatic diisocyanate compound,
And / or a polyisocyanate compound (A) containing a urethane prepolymer (A2) having an isocyanate group at the terminal obtained from the polyisocyanate compound (A1) and the polyol compound (a2), and three or more carboxyl groups With an acid anhydride (B) of a polycarboxylic acid having a compound (C) having a (meth) acryloyl group and a hydroxyl group and / or a compound having a (meth) acryloyl group and an epoxy group. (C
The method of reacting 2) is mentioned.

The polyisocyanate compound (A) used in this production method is an isocyanurate ring-containing polyisocyanate compound (A1) derived from a cycloaliphatic diisocyanate compound, and / or the polyisocyanate compound (A1) and a polyol. Any compound containing a urethane prepolymer (A2) having an isocyanate group at the terminal obtained from the compound (a2) may be used, but if necessary, the polyisocyanate compound (A1) and / or
Alternatively, it may contain a polyisocyanate compound (A3) other than the urethane prepolymer (A2).

As the polyisocyanate compound (A1), for example, a diisocyanate compound containing a cycloaliphatic diisocyanate compound is isocyanurate in the presence or absence of an isocyanurate-forming catalyst such as a quaternary ammonium salt. As a result, an isocyanurate mixture such as an isocyanurate consisting of a trimer of a cycloaliphatic diisocyanate compound, an isocyanurate consisting of a pentamer, an isocyanurate consisting of a heptamer, and the like. Among these polyisocyanate compounds (A1), isocyanurate composed of a trimer of a cycloaliphatic diisocyanate compound, that is, a compound containing 30% by weight or more of a triisocyanate compound containing one isocyanurate ring is heat resistant. , Because it is possible to obtain a polymerizable polyimide resin having excellent moisture resistance,
Furthermore, since it is easy to produce and a polymerizable polyimide resin having excellent heat resistance and humidity resistance under high temperature and high pressure is obtained, 50
Those containing more than 50% by weight, for example 50 to 95% by weight, are particularly preferable.

As the diisocyanate compound containing the above-mentioned cycloaliphatic diisocyanate compound, a diisocyanate compound other than the cycloaliphatic diisocyanate compound, for example, an acyclic aliphatic diisocyanate compound is used.
Those containing in the range of less than or equal to wt% and those containing the aromatic diisocyanate in the range of less than or equal to 30% by weight, among others, since a polymerizable polyimide resin excellent in solvent solubility with heat resistance is obtained, It is preferable that the content of the cycloaliphatic diisocyanate compound is high, and normally, the content of the cycloaliphatic diisocyanate compound is 10 or less.
0% by weight is used. Examples of the cycloaliphatic diisocyanate compound include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbonylene diisocyanate and the like. Further, examples of the acyclic aliphatic diisocyanate include hexamethylene diisocyanate, lysine diisocyanate, trimethylhexane diisocyanate, and the like. These may be used alone or in combination of two or more.

Further, the polyisocyanate compound (A1) contains 5 to 30% by weight of an isocyanate group.
It is more preferable that the resin composition contains the polymerizable polyimide resin having good curability and solvent solubility, and it is particularly preferable that the resin composition contains 10 to 20% by weight of an isocyanate group.

The urethane prepolymer (A used in the present invention
As 2), the polyisocyanate compound (A1)
And a polyol compound (a2) are reacted at a molar ratio such that the isocyanate group in the polyisocyanate compound (A1) is in excess of the hydroxyl group in the polyol compound (a2), and an isocyanate group is formed at the terminal. Examples thereof include urethane prepolymers.

The above-mentioned polyol compound (a2) is not particularly limited as long as it is a polyol compound having two or more hydroxyl groups in one molecule, and above all, it has 2 to 6 hydroxyl groups.
A compound having an individual group is preferable, and a diol compound is particularly preferable. The polyol compound (a2) is introduced into the resin via the urethane bond with the polyisocyanate compound (A1).
By introducing 2) into the imide resin skeleton, the cohesiveness, crystallinity, solvent solubility, etc. of the imide resin are improved,
Further, performances such as development speed and development stability during development are improved.

Generally, the introduction of urethane bond is considered to cause deterioration of heat resistance, but in the urethane modification with the polyol compound (a2) as described above, direct bonding with an isocyanurate type polyisocyanate compound and imide By having a bond, deterioration of heat resistance of the imide resin is prevented, and good heat resistance can be maintained.

Examples of the polyol compound (a2) include alkyl polyols, polyester polyols, polyether polyols, polycarbonate polyols, urethane polyols, silicone polyols, acrylic polyols, epoxy polyols and the like.

Among them, the polyol compound (a2) has a carboxyl group-containing polyol compound (a2).
When a polyol compound containing 1), that is, a polyol compound (a21) having a carboxyl group alone or a mixture of the polyol compound (a21) and another polyol compound is used, development performance is improved and various curing agents are used. It is preferable because it improves the compatibility with other compounding ingredients such as.

As the polyol compound (a21) having a carboxyl group, a compound represented by the following general formula (1) is more preferable.

[Chemical 1] (However, R in the formula₁Is a direct bond or 1 to 6 carbon atoms
Hydrocarbon chain of R_TwoAnd R _ThreeAre the same even if they are different
It may be a hydrocarbon chain having 1 to 6 carbon atoms. Well
R_FourIs a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
Represents a radical. )

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

Further, as the polyol compound (a2), 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 above An ester compound obtained by reacting a polyol compound (a22) other than the polyol compound (a21) or a dicarboxylic acid compound (a23), or a transesterification of the compound represented by the general formula (1) with an alkyl ester compound (a24). The ester compound obtained by the reaction, or the compound represented by the general formula (1) and the polyol compound (a2
It is also possible to use a compound having two or more hydroxyl groups, such as an ester compound obtained by transesterification of 2) with an alkyl ester compound (a24).

Examples of the polyol compound (a22) 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, cyclohexanedimethylol, 1,4-cyclohexanediol, spiroglycol, tricyclodecanedimethylol, hydrogenated bisphenol A, Bifunctional diol such as ethylene oxide-added bisphenol A, propylene oxide-added bisphenol A, dimethylolpropionic acid, and dimethylolbutanoic acid;

Trimethylolethane, trimethylolpropane, ditrimethylolethane, ditrimethylolpropane, glycerin, diglycerol, 3-methylpentane-1,3,5-triol, pentaerythritol, dipentaerythritol, tripentaerythritol, 2 , 2,6,6-tetramethylol cyclohexanol-1, tris 2 hydroxyethyl isocyanurate, mannitol, sorbitol, inositol, trifunctional or higher functional polyol compounds such as glucose.

Further, the dicarboxylic acid compound (a23)
As various dicarboxylic acids, or those acid anhydrides can be used, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, het acid,
Hymic 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, malonic acid, glutaric acid, trimellitic acid, hexahydrophthalic acid, tetrabromophthalic acid, methylcyclohexene tricarboxylic acid, pyromellitic acid, and acid anhydrides thereof.

Further, the alkyl ester compound (a
As 24), for example, the dicarboxylic acid compound (a
23) Alkyl ester compounds such as methanol, ethanol and butanol.

In the method for producing the polymerizable polyimide resin, it is usually preferable to use only the polyisocyanate compound (A1) and / or the urethane prepolymer (A2) as the polyisocyanate compound (A), but if necessary, Thus, one or more polyisocyanate compounds (A3) other than these may be used in combination.

The polyisocyanate compound (A3) is preferably a diisocyanate compound, for example, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate. , 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4'-diisocyanate, m-xylene diisocyanate, p-
Aromatic diisocyanates such as xylene diisocyanate and naphthalene diisocyanate; isophorone diisocyanate, hexamethylene diisocyanate, 4,4 '
And aliphatic diisocyanates such as dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbonylene diisocyanate and lysine diisocyanate. Of these, aliphatic diisocyanates are particularly preferable.

When the polyisocyanate compound (A3) is used in combination as the polyisocyanate compound (A),
The number of moles of isocyanate groups (n ₁₂ ) in the polyisocyanate compound (A1) and / or the urethane prepolymer (A2), and the polyisocyanate compound (A
3) the ratio (n ₁ ) of the number of moles (n ₃ ) of isocyanate groups in
₂ ) / (n ₃ ) is used in combination with the polyisocyanate compound (A3) in a range of 1.0 or more, but is 1.5 or more.
It is preferably used in the range of 10.5.

The polycarboxylic acid anhydride (B) used in the method for producing the polymerizable polyimide resin is not particularly limited as long as it is a polycarboxylic acid anhydride having three or more carboxyl groups. Of these, tricarboxylic acid anhydrides and tetracarboxylic acid anhydrides are preferable.

Examples of the acid anhydride of tricarboxylic acid include trimellitic anhydride, naphthalene-1,2,4-tricarboxylic acid anhydride and the like.

Examples of the acid anhydride of tetracarboxylic acid include pyromellitic dianhydride; benzophenone-3,
3 ', 4,4'-tetracarboxylic dianhydride, diphenyl ether-3,3', 4,4'-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride , Biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, biphenyl-2,2', 3,3'-
Tetracarboxylic acid dianhydride, naphthalene-2,3,6
7-tetracarboxylic dianhydride, naphthalene-1,2,
4,5-tetracarboxylic dianhydride, naphthalene-1,
4,5,8-Tetracarboxylic acid dianhydride, Decahydronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 4,8-Dimethyl-1,2,3,5,6,7- Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride;

2,6-dichloronaphthalene-1,4
5,8-Tetracarboxylic dianhydride, 2,7-Dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-Tetrachloronaphthalene-1,
4,5,8-Tetracarboxylic dianhydride, Phenanthrene-1,3,9,10-tetracarboxylic dianhydride, 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-
Aroma in the molecule of bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride An anhydride of a tetracarboxylic acid having a group organic group may be mentioned. Further, as the tetracarboxylic acid anhydride, there are monoanhydrides other than these dianhydrides, which can be used alone or in combination with the dianhydride. Examples of the monoanhydride include those obtained by ring-opening one of the anhydrous groups of the dianhydride with alcohol or the like.

The polycarboxylic acid anhydride (B) is
One kind or two or more kinds can be used. If necessary,
Further, an aromatic dicarboxylic acid compound and / or its anhydride may be used in combination.

Examples of the compound (C1) having a (meth) acryloyl group and a hydroxyl group used in the above-mentioned method for producing a polymerizable polyimide resin include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 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, trimethylolethanedi (meth) acrylate, Pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycidyl (meth) acrylate- (meth) acrylic acid adduct, 2 -Hydroxy-3-
(Meth) acrylate compounds having various hydroxyl groups such as phenoxypropyl (meth) acrylate, or the above-mentioned (meth) acrylate compounds having hydroxyl groups and ε
-A ring-opening reaction product with caprolactone and the like.

Further, as the compound (C1) having a (meth) acryloyl group and a hydroxyl group, various epoxy compounds are reacted with (meth) acrylic acid to form a (meth) acrylic acid ester and an epoxy (meth) group having a hydroxyl group. Acrylate can be used. Among them, compounds having 2 to 5 (meth) acrylate groups and one hydroxyl group are preferable.

Examples of the compound (C2) having a (meth) acryloyl group and an epoxy group used in the method for producing the polymerizable polyimide resin include, for example, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate glycidyl ether, and hydroxy. Propyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, 6-hydroxyhexyl (meth) acrylate glycidyl ether, 5-hydroxy 3 methylpentyl (meth) acrylate glycidyl ether, (meth) acrylic acid 3 , 4-
Examples thereof include epoxycyclohexyl, lactone-modified (meth) acrylic acid 3,4-epoxycyclohexyl, and vinylcyclohexene oxide.

As the compound (C2) having a (meth) acryloyl group and an epoxy group, the epoxy group equivalent is changed to acryloyl by the reaction of an epoxy compound (c21) having two or more epoxy groups with (meth) acrylic acid. It is possible to use an epoxy acrylate in which the epoxy group obtained by the reaction in excess of the group equivalent remains.

Examples of the epoxy compound (c21) 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. Epoxidized products of various dicyclopentadiene-modified phenolic resins obtained by reacting with
Epoxy compound of 2 ', 6,6'-tetramethylbiphenol; Aromatic epoxy resin such as epoxy of naphthalene skeleton, epoxy of fluorene skeleton; Fat such as neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether Group epoxy resin; 3,
Alicyclic epoxy resins such as 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis- (3,4-epoxyhicyclohexyl) adipate; heterocyclic epoxy resins such as triglycidyl isocyanurate. To be

The compound (C1) having a (meth) acryloyl group and a hydroxyl group and / or the compound (C2) having a (meth) acryloyl group and an epoxy group is 1 respectively.
They may be used alone or in combination of two or more.

As a preferred method for producing the polymerizable polyimide resin, for example, the polyisocyanate compound (A) and the polycarboxylic acid anhydride (B) are heated in an organic solvent at a temperature of 50 to 250 ° C. At 1 to 30 hours to synthesize a carboxyl group and / or acid anhydride group-containing imide resin (X), and then, after adjusting the temperature to 50 to 150 ° C., a compound having a (meth) acryloyl group and a hydroxyl group ( C1) and / or (meth) acryloyl group and a compound (C2) having an epoxy group are added and reacted for 1 to 30 hours to prepare an active energy ray-curable imide resin having a (meth) acryloyl group in the molecule. Methods and the like.

In the above-mentioned production method, the polyisocyanate compound (A) containing the acid anhydride having a carboxyl group as the acid anhydride (B) of the polycarboxylic acid is used because the reaction is easy to control. And then reacting a compound (C1) having a (meth) acryloyl group and a hydroxyl group and / or a compound (C2) having a (meth) acryloyl group and an epoxy group, or an acid anhydride of a polycarboxylic acid ( A method in which an acid anhydride having no carboxyl group is used as B) to react with the polyisocyanate compound (A), and then a compound (C1) having a (meth) acryloyl group and a hydroxyl group is reacted is preferable.

Further, in order to obtain a polymerizable polyimide resin having sufficient solvent solubility, heat resistance and alkali developability in the above production method, the carboxylic acid anhydride group in the polycarboxylic acid anhydride (B) is used. and the total number of moles of carboxyl groups _{(n b)} a polyisocyanate compound the number of moles of isocyanate groups in (a) the ratio of _{(n a) (n b)} / (n
_a ) is preferably 0.3 to 2.0, and particularly preferably 0.6 to 1.8. However, a polyisocyanate compound (A2) is used as the polyisocyanate compound (A), and this polyisocyanate compound (A2) is reacted with a polyisocyanate compound (A1) and a polyol compound containing a polyol (a21) having a carboxyl group. In the case of a urethane prepolymer having an isocyanate group at the terminal obtained as described above, in order to obtain an imide resin having sufficient solvent solubility, heat resistance, and alkali developability, in the acid anhydride (B) of polycarboxylic acid, the ratio of carboxylic acid anhydride group and a carboxyl group and a polyisocyanate compound (A2) the total number of moles of carboxyl groups in the (n _ba2) and the number of moles of isocyanate groups in the polyisocyanate compound _{(a) (n a) (} n
_ba2) / _{(n a)} is preferably a 0.3 to 3.0.

In the above production method, the compound (C1) having a (meth) acryloyl group and a hydroxyl group or the compound (C2) having a (meth) acryloyl group and an epoxy group is
It can be added during or after the reaction of the polyisocyanate compound (A) and the acid anhydride (B) of the polycarboxylic acid.

However, when a compound (C1) having a (meth) acryloyl group and a hydroxyl group or a compound (C2) having a (meth) acryloyl group and an epoxy group is added after completion of the reaction, the risk of gelation is avoided. , the polyisocyanate compound having an acid anhydride (a) and the polycarboxylic acid (B) and, said the molar ratio _{(n b) / (n a} ) or _{(n ba2) / (n a} ) is 0.9 It is preferable to use in a range that does not result in ~ 1.1.

When a compound (C1) having a (meth) acryloyl group and a hydroxyl group or a compound (C2) having a (meth) acryloyl group and an epoxy group is added during the reaction, for example, an isocyanate group and / or an acid group is used. The compound (C1) is added into the reaction system in which an anhydrous group remains, and the hydroxyl group in the compound (C1) is reacted with an isocyanate group and / or an acid anhydride group to form a urethane bond and / or When a polyimide resin in which an ester bond is formed and a reactive double bond is introduced, or when the compound (C2) is added to the system in the middle of the reaction where the carboxyl group remains, the compound (C2) is added. The case where the epoxy group and the epoxy group in the inside are reacted to form an epoxy ester bond to form a polyimide resin having a reactive double bond introduced, among others, In the case of the serial it is preferred.

In the above case, the compound (C1) having a (meth) acryloyl group and a hydroxyl group means that the number of moles of the hydroxyl group in the compound (C1) (n _c1 ) and the acid anhydride group and the isocyanate group remaining in the reaction system. range ratio _{(n c1) / (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. Further, in the above-mentioned case, the compound (C2) having a (meth) acryloyl group and an epoxy group is the number of moles of the carboxyl group (n _COOH ) remaining in the reaction system and the number of moles of the epoxy group in the compound (C2). (N _c2 ) and the ratio (n
_COOH ) / (n _{c 2} ) is preferably added in a range of 1 or more, particularly in a range of 1.5 to 20.

The active energy ray-curable polyimide resin composition of the present invention may be one containing the polymerizable polyimide resin (I). For example, the polymerizable polyimide resin (I) and the organic solvent (II). And the like. The active energy ray-curable polyimide resin composition contains the polymerizable polyimide resin (I), an organic solvent (II), an epoxy compound (III), and a photoinitiator (IV) to form a resist. It can be used as a composition. At this time, a reactive diluent (V) can be further contained.

As the organic solvent (II) and the organic solvent used in the method for producing the polymerizable polyimide resin, various polar organic solvents can be used, but among them,
A solvent capable of dissolving the polymerizable polyimide resin (I) used in the present invention, a polar solvent containing no nitrogen atom and no sulfur atom, for example, an ether solvent, an ester solvent, a ketone solvent or the like is preferable, Ether solvents are particularly preferred. The organic solvent (II) and the organic solvent used in the method for producing the polymerizable polyimide resin are preferably the same or a solvent containing the same solvent as a main component.

As the ether solvent, various ones can be used. For example, ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether; polyethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate and the like. Ethylene glycol monoalkyl ether acetates; Polyethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate;
Examples include polypropylene glycol dialkyl ethers such as propylene glycol dimethyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate; polypropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate; Glycol monoalkyl ether acetates and polypropylene glycol monoalkyl ether acetates are preferred.

Examples of ester solvents include:
Examples thereof 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 (II) used is 10 to 80% by weight in the active energy ray-curable polyimide resin composition of the present invention because a composition having excellent coating suitability and the like can be obtained. % Is preferable, and a range of 20 to 70% by weight is particularly preferable. Also,
As the amount of the organic solvent used in the method for producing the polymerizable polyimide resin, the content in the system after completion of the reaction is 10 to 70% by weight because the system can be reacted uniformly and at a suitable reaction rate. Is preferable, and a range of 20 to 60% by weight is particularly preferable.

In the above-mentioned method for producing a polymerizable polyimide resin, the polyisocyanate compound (A) is reacted with the polycarboxylic acid anhydride (B) to give a carboxyl group- and / or acid anhydride group-containing polyimide resin (X ) Is obtained by changing the weight ratio of the polyisocyanate compound (A) and the polycarboxylic acid anhydride (B),
The molecular weight and acid value of the resulting imide resin (X) can be adjusted. Further, an imidization catalyst or the like may be used in the reaction between the polyisocyanate compound (A) and the polycarboxylic acid anhydride (B), and an antioxidant or a polymerization inhibitor may be used in combination. Good.

Further, the molecular weight can be adjusted by reacting the carboxylic acid or anhydride remaining at the terminal of the polyimide resin (X) with an epoxy resin having two or more epoxy groups in the molecule. As such an epoxy resin,
The epoxy compound (c21) described above can be used.

The reaction of the above-mentioned carboxyl group- and / or acid anhydride group-containing polyimide resin (X) with the compound (C1) having a (meth) acryloyl group and a hydroxyl group is (1)
Ring-opening esterification reaction (semi-esterification reaction) between the hydroxyl group in compound (C1) and the acid anhydride group remaining in polyimide resin (X), (2) Hydroxyl group in compound (C1) and polyimide resin (X) Esterification reaction with the carboxyl group in
And (3) a reaction between an isocyanate group remaining in the polyimide resin (X) and a hydroxyl group in the compound (C1), and a (meth) acryloyl group is introduced into the polyimide resin (X) by these reactions. , A polymerizable polyimide resin is obtained.

The reaction of the carboxyl group- and / or acid anhydride group-containing polyimide resin (X) with the compound (C2) having a (meth) acryloyl group and an epoxy group includes (1) compound (C2) Ring-opening esterification reaction between the epoxy group of (1) and the acid anhydride remaining in the polyimide resin (X), and (2) ester of the epoxy group in the compound (C2) and the carboxyl group in the polyimide resin (X) And a (meth) acryloyl group is introduced into the polyimide resin (X) to obtain a polymerizable polyimide resin.

A polymerizable polyimide resin obtained by reacting the carboxyl group- and / or acid anhydride group-containing polyimide resin (X) with a compound (C2) having a (meth) acryloyl group and an epoxy group is A hydroxyl group is generated along with the ring opening of the epoxy group. By further reacting this hydroxyl group with a polybasic acid anhydride for half-esterification,
It is possible to adjust the developability when used as a resist resin composition.

Examples of such polybasic acid anhydrides include:
Maleic anhydride, succinic anhydride, dodecenyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride Examples thereof include acids, 4-methylhexahydrophthalic anhydride, and the above-mentioned polycarboxylic acid anhydrides (B).

In the method for producing the active-polymerizable polyimide resin, the acid anhydride group and / or carboxyl group in the acid anhydride (B) of polycarboxylic acid is present at the molecular end of the imide resin, but the acid anhydride group is When it exists at the terminal of the molecule, it may be opened by using water or the like to generate a carboxylic acid.

The resist composition using the active energy ray-curable polyimide resin composition of the present invention has the epoxy compound (III) as described above in order to obtain a cured product excellent in heat resistance, mechanical properties and durability. ) Can be included. In this case, the epoxy compound (III) is hardened by irradiating it with an active energy ray and then hardening it. The epoxy compound (c21) described above can be used as the epoxy compound (III).

The epoxy compound (III) is used in an amount of 10 to 300 parts by weight based on 100 parts by weight of the polymerizable polyimide resin (I) since a resist composition having excellent heat resistance and moist heat resistance can be obtained. The range of 10 parts by weight is preferable, and the range of 15 to 200 parts by weight is particularly preferable.

A curing agent or a curing accelerator can be used in the resist composition containing the epoxy compound (III), and examples thereof include melamine, dicyandiamide, and the like.
Guanamine resin and its derivatives, amines, phenols, organic phosphines, phosphonium salts, quaternary ammonium salts, polybasic acid anhydrides, photocation catalysts,
Examples thereof include cyanate compounds, isocyanate compounds, blocked isocyanate compounds, and the like.

A photoinitiator (IV) can be used to cure the resist composition by light irradiation. Examples of the photoinitiator (IV) include acetophenones, benzophenone derivatives, Michler's ketone, benzine, benzyl derivatives, benzoin derivatives, benzoin methyl ethers, α-acyloxime esters, thioxanthones, anthraquinones and various kinds thereof. Examples include derivatives.

Specific examples of the photoinitiator (IV) include 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, alkoxyacetophenone, benzyldimethylketal, benzophenone, alkyl benzoylbenzoate and bis (4-dialkylamino). Phenyl) 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-
Examples thereof include benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, metallocene compounds and the like.

Further, various photosensitizers can be used in combination with these photoinitiators (IV). For example, amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds or nitriles or Other nitrogen-containing compounds are included.

The amount of the photoinitiator (IV) used is 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.

The reactive diluent (V) is used for the purpose of adjusting the curability by active energy rays, and for example,
(Meth) acrylate compounds, vinyl compounds, acrylamide compounds, maleimide compounds and the like can be mentioned. Among them, from the viewpoint of improving the developability of the resist composition,
A compound having a (meth) acryloyl group and a hydroxyl group is preferable.

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, trimethylol Ethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate (Meth) acrylate compounds having various hydroxyl groups such as bisphenol, dipentaerythritol penta (meth) acrylate, glycidyl (meth) acrylate- (meth) acrylic acid adduct, 2-hydroxy-3-phenoxypropyl (meth) acrylate; or Examples thereof include ring-opening reaction products of the above-mentioned (meth) acrylate compound having a hydroxyl group and ε-caprolactone.

Epoxy (meth) obtained by reacting various epoxy compounds with (meth) acrylic acid as the compound having a (meth) acryloyl group and a hydroxyl group.
Acrylate can also be used. The reaction between the epoxy group and (meth) acrylic acid opens the epoxy ring, at which time a (meth) acrylic acid ester and a hydroxyl group are generated.

Regarding the amount of the reactive diluent (V) used, an active energy ray-curable imide resin (I) 10 is used because a resist composition having excellent photocurability can be obtained.
The range of 10 to 200 parts by weight is preferable with respect to 0 parts by weight, and the range of 10 to 100 parts by weight is particularly preferable.

If desired, various inorganic fillers can be added to the resist composition. For example, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, Examples thereof include silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide and mica.

Further, an inorganic pigment, an organic pigment or the like can be added to the resist composition, if necessary. Examples of the inorganic pigments include chromates such as yellow lead, zinc chromate and molybdate orange; ferrocyanides such as navy blue, titanium oxide, zinc oxide, red iron oxide, iron oxide; metal oxides such as chromium carbide green and cadmium. Yellow, cadmium red; metal sulfides such as mercury sulfide, selenides; sulfates such as lead sulfate; silicates such as ultramarine blue; carbonates, cobalt violet, phosphates such as manganese purple; aluminum powder, zinc dust, Brass powder,
Metal powders such as magnesium powder, iron powder, copper powder and nickel powder; carbon black and the like.

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

The resist composition may be used, if desired.
Further, a rust preventive agent, an extender pigment and the like can be added. These may be used alone or in combination of two or more, but 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.

The resist composition may contain various (meth) acrylate compounds or vinyl compounds in order to improve photocuring characteristics and physical properties.

The resist composition is coated on a substrate, dried with a solvent, irradiated with energy rays such as ultraviolet rays through a mask having a desired negative pattern, and developed with a dilute alkaline aqueous solution. Can be formed.

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 the like, and tetramethyl. An aqueous solution of ammonium hydroxide, tetraethylammonium hydroxide, tetramethylphosphonium hydroxide or the like can be used.
The concentration of the alkaline aqueous solution may be 0.2 to 5% by weight. The developing method can be carried out by dipping the coated sample in a developing solution and shaking it, or spraying the developing solution onto the sample. The temperature of the developing solution is 10 to 50 ° C.

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

[0083]

EXAMPLES Next, the present invention will be described with reference to Examples and Comparative Examples. Although specifically described below, all parts and% are by weight unless otherwise specified.

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 and an isocyanurate ring-containing polyisocyanate compound derived from isophorone diisocyanate (hereinafter referred to as IPDI-N Isocyanate group content rate 18.2%, isocyanurate ring-containing triisocyanate compound content rate 95%) 2772 g (isocyanate group mole number 12 mol) and trimellitic anhydride 1536.0 g (8 mol) were charged, The temperature was raised to 160 ° C. with stirring. Vigorous foaming started at around 60 ° C, and the contents of the flask gradually became transparent.
The reaction was carried out at 160 ° C for 4 hours, and when the isocyanate group content in the system reached 2.0%, the system was cooled to 80 ° C.
Next, 935.0 g of diethylene glycol monoethyl ether acetate and 3.51 of methylhydroquinone
In addition, 935.0 g (2 mo) of pentaerythritol triacrylate (hydroxyl value 120) was added.
1) was added and the reaction was carried out at 80 ° C. while paying attention to the exotherm.
After reacting at 80 ° C. for 4 hours, it was confirmed by infrared absorption spectrum (hereinafter abbreviated as IR) that the absorption of the isocyanate group at 2270 cm ⁻¹ disappeared,
A light yellow transparent polymerizable polyimide resin solution was obtained.

This polyimide resin solution was coated on a KBr plate and the IR of a sample in which the solvent was volatilized was measured.
Absorption of imide ring at 780 cm ⁻¹ and 735 cm ⁻¹ , 1
Absorption of amide group at 660 cm ⁻¹ , absorption of acid anhydride group at 1850 cm ⁻¹ and 1780 cm ⁻¹ and 720 cm ⁻¹ ,
Absorption of carboxyl group at 3390 cm ^-1 , further 16
Absorption of acryloyl group at 38cm ^-1 and 810 cm ^-1 was confirmed, respectively. Moreover, the concentration of isocyanurate ring was 0.87 mmol / g from ¹³ C-NMR analysis.
It was confirmed (in terms of resin solid content) that it was an acrylate containing an imide ring and an amide group. In the molecular weight measurement by GPC, the number average molecular weight (hereinafter abbreviated as Mn) was 2,000 in terms of polystyrene, and the weight average molecular weight (hereinafter abbreviated as Mw) was 4,020 in terms of polystyrene. . Acid value is 76.7 (resin solid content conversion) and acryloyl group concentration is 1.25 mmol / g.
(Converted to resin solid content). Hereinafter, this polyimide resin solution is abbreviated as resin solution P1.

The resin solution P1 thus obtained was blended with the composition shown in Table 1 (1) and kneaded with a homodisper to prepare a resist ink. Next, using this resist ink, a test piece having a resist ink coating film on a tin plate or on a glass epoxy printed circuit board on which a circuit pattern that has been etched in advance is formed is prepared, and the following (1) to ( The evaluation test of 4) was performed. The evaluation results are shown in Table 2 (1).

<Evaluation Test Method> (1) Resolubility Test A resist ink was applied onto a tin plate using an applicator of 0.076 mil so as to have a film thickness of 30 μm after drying, and a test piece was obtained. In an oven at 80 ° C for 3
After leaving for 0 minutes, a test piece having a resist ink coating film in which the solvent was volatilized was prepared, its weight and coating area were measured, and then the test piece was placed in a 1% aqueous sodium carbonate solution and a 1% aqueous sodium hydroxide solution at 50 ° C. Then, the coating is redissolved by shaking for 120 seconds, dried, and weighed.
From the weight before re-dissolution, the weight after re-dissolution, the coating area, and the specific gravity of the coating film (provided that the specific gravity is 1.2), 12
The thickness of the coating film redissolved in 0 seconds was calculated, and then the film reduction speed was determined. The larger the value of the film-reducing speed, the better the resolubility.

(2) Evaluation of UV curability and patterning property A resist ink was applied onto a tin plate using an applicator of 0.076 mil so as to have a film thickness of 30 μm after drying, and a test piece was obtained. In an oven at 80 ° C for 3
After leaving for 0 minutes, a test piece having a resist ink coating film in which the solvent was volatilized was prepared, and the step tablet No. 2 (made by Kodak Co., Ltd.) and 500 mJ / cm ² and 1000 mJ / c using an ultra-high pressure mercury lamp
After irradiating the coating film of each different test piece with m ² of ultraviolet ray, the coating film was redissolved by immersing and shaking in 1% sodium hydroxide aqueous solution at 50 ° C. for 60 seconds, and remained without being redissolved. The evaluation was performed using the number of steps. The evaluation is indicated by the number of steps of the step tablet, and the larger the number of steps, the better the ultraviolet curing property and the patterning property.

(3) Measurement of glass transition temperature and coefficient of linear expansion A resist ink was applied onto a tin plate with an applicator of 0.076 mil so as to have a thickness of 30 μm after drying, and a test piece was obtained. In an oven at 80 ° C for 3
A test piece having a resist ink coating film in which the solvent was volatilized was left for 0 minutes, and the coating film was irradiated with ultraviolet rays of 500 mJ / cm ² using an ultra-high pressure mercury lamp, and then 1
Separate test pieces were left to cure in a dryer at 50 ° C and 170 ° C for 60 minutes, the cured coating film was peeled off, and then the thermal analysis system TMA-S manufactured by Seiko Denshi KK
Using S6000, sample length 10 mm, heating rate 10 ° C
/ Min, load 49mN (5g) under the conditions of TMA (Therm
The glass transition temperature (Tg) and the linear expansion coefficient (α1) of the obtained cured coating film were measured by the al mechanical analysis method. Glass transition temperature (Tg)
The value of indicates that the higher the temperature, the better the heat resistance.
The linear expansion coefficient (α1) is the glass transition temperature (Tg).
The dimensional stability at the previous temperature is shown. The smaller the value, the better the thermal dimensional stability.

(4) Pressure Cooker (PCT) Resistance Test 0.076 on a glass epoxy printed circuit board having a circuit pattern formed by pre-etching a resist ink.
Test using a mill applicator so as to have a film thickness of 30 μm after drying, and leave the resulting test piece in a dryer at 80 ° C. for 30 minutes to evaporate the solvent and have a resist ink coating film As a piece, after irradiating the coating film with ultraviolet rays of 500 mJ / cm ² using an ultra-high pressure mercury lamp, separate test pieces were left for 60 minutes in a dryer at 150 ° C. and 170 ° C. to form a cured coating film. The test piece thus obtained is used as a test piece
After treating with a T tester (PC-304RIII, Hirayama Seisakusho Co., Ltd.) under a saturated vapor pressure of 121 ° C. and 100% RH for 50 hours, the temperature was returned to room temperature and the change in appearance was visually evaluated. In addition, according to the JISD-0202 cellophane tape peeling test, a grid-like cross cut is put in the obtained coating film at 1 mm intervals, and a peeling test is performed with cellophane tape to count the number of peeled coating films. The adhesion of the coating film was evaluated according to the following criteria. Appearance evaluation criteria ⊚: Changes before and after the PCT test, the above is not seen. Good: After the PCT test, coating film abnormalities such as blister, whitening, and dissolution can be confirmed within a range of less than 10% of the coating film area. Δ: After the PCT test, abnormality of the coating film such as blister, whitening and dissolution can be confirmed in the range of 10% or more and less than 50% by weight of the coating film area. X: After the PCT test, coating film abnormalities such as blister, whitening, and dissolution can be confirmed in a range of 50% or more of the coating film area. Adhesion evaluation ◎: No cross-cutting. ◯: The number of cross-cuts separated from 100 cross-cuts is less than 20. Δ: The number of cross-cuts separated from 100 cross-cuts is 20 or more and less than 70. X: The number of cross-cuts was 70 or more with respect to 100 cross-cuts.

Example 2 3979.5 g of diethylene glycol monoethyl ether acetate and IPDI-N2097.0 g were placed in a four-necked flask equipped with a stirrer, a thermometer and a condenser.
538.5 g (isocyanurate ring-containing polyisocyanate compound derived from hexamethylene diisocyanate (isocyanate group content 23.4%, isocyanurate ring-containing triisocyanate compound content 60%)) (3 mol of isocyanate groups) and trimellitic anhydride 1
344.0 g (7 mol) was charged, and the temperature was raised to 160 ° C. with stirring. Vigorous foaming started at around 60 ° C, and the contents of the flask gradually became transparent. 160 ° C
The reaction was carried out for 4 hours, and the system was cooled to 80 ° C when the isocyanate group content in the system reached 1.1%. Then
Diethylene glycol monoethyl ether acetate 9
35.0 g and 3.56 g of methyl hydroquinone were added, and further 935.0 g (2 mol) of pentaerythritol triacrylate (hydroxyl value 120) was added therein, and the mixture was reacted at 80 ° C. After reacting at 80 ° C. for 4 hours, it was confirmed by IR that absorption of isocyanate at 2270 cm ⁻¹ had disappeared, and a light yellow transparent polymerizable polyimide resin solution was obtained.

This polyimide resin solution was coated on a KBr plate, and the IR of a sample in which the solvent was volatilized was measured.
Absorption of imide ring at 780 cm ⁻¹ and 735 cm ⁻¹ , 1
Absorption of amide group at 660 cm ⁻¹ , absorption of acid anhydride group at 1850 cm ⁻¹ and 1780 cm ⁻¹ and 720 cm ⁻¹ ,
Absorption of carboxyl group at 3390 cm ^-1 , further 16
Absorption of acryloyl group at 38cm ^-1 and 810 cm ^-1 was confirmed, respectively. Also, Mn is 2,000, M
w was 4,600, the acid value was 76.7, and the concentration of the (meth) acryloyl group was 1.42 mmol / g. Furthermore, the concentration of isocyanurate ring is 0.96 mmol / g
Met. Hereinafter, this imide resin solution is used as a resin solution P
It is abbreviated as 2.

A resist ink was prepared in the same manner as in Example 1 except that the obtained resin solution P2 was used in place of the resin solution P1.
The evaluation test of (4) was performed. The evaluation results are shown in Table 2 (1).

Example 3 In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 4524.0 g of diethylene glycol monoethyl ether acetate and IPDI-N2797.0 g.
(12 mol of isocyanate groups) and 1728.0 g (9 mol) of trimellitic anhydride were charged, and the temperature was raised to 160 ° C. with stirring. Vigorous foaming started at around 60 ° C, and the contents of the flask gradually became transparent. The reaction was carried out at 160 ° C for 7 hours, and the system was cooled to 80 ° C when the isocyanate group content in the system reached 0.1%. Next, 355.0 g of diethylene glycol monoethyl ether acetate and methylhydroquinone 2.
18 g was added, and further, 355.0 g (2.5 mol) of glycidyl methacrylate and 10.0 g of triphenylphosphine were added thereto and reacted at 100 ° C.
After reacting at 100 ° C. for 5 hours, the epoxy equivalent is 150.
After confirming that the amount was 00 g / eq or more, a pale yellow transparent polymerizable polyimide resin solution was obtained.

This polyimide resin solution was coated on a KBr plate, and the IR of a sample in which the solvent was volatilized was measured.
Absorption of imide ring at 780 cm ⁻¹ and 735 cm ⁻¹ , 1
Absorption of amide group at 660 cm ⁻¹ , absorption of acid anhydride group at 1850 cm ⁻¹ and 1780 cm ⁻¹ and 720 cm ⁻¹ ,
Absorption of carboxyl group at 3390 cm ^-1 , further 16
Absorption of acryloyl group at 38cm ^-1 and 810 cm ^-1 was confirmed, respectively. Also, Mn is 2,900, M
The w was 6,500, the acid value was 74.2, and the concentration of the acryloyl group was 0.57 mmol / g. Furthermore, the isocyanurate ring concentration was 0.92 mmol / g. Hereinafter, this polymerizable polyimide resin solution is abbreviated as resin solution P3.

A resist ink was prepared in the same manner as in Example 1 except that the obtained resin solution P3 was used in place of the resin solution P1.
The evaluation test of (4) was performed. The evaluation results are shown in Table 2 (1).

Example 4 A four-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 4151.5 g of diethylene glycol monoethyl ether acetate and IPDI-N2077.0 g.
538.5 g (isocyanurate ring-containing polyisocyanate compound derived from hexamethylene diisocyanate (isocyanate group content 23.4%, isocyanurate ring-containing triisocyanate compound content 60%)) (3 mol of isocyanate groups) and trimellitic anhydride 1
536.0 g (8 mol) was charged, and the temperature was raised to 160 ° C. with stirring. Vigorous foaming started at around 60 ° C, and the contents of the flask gradually became transparent. 160 ° C
The reaction was carried out for 4 hours, and the system was cooled to 80 ° C when the isocyanate group content in the system reached 1.1%. Then
Diethylene glycol monoethyl ether acetate 9
35.0 g and 3.56 g of methylhydroquinone were added, and further 935.0 g (2 mol) of pentaerythritol triacrylate (hydroxyl value 120) was added therein, and the reaction was carried out at 80 ° C. while paying attention to heat generation. 80 ° C
After reacting for 4 hours at room temperature, it was confirmed by IR that absorption of the isocyanate at 2270 cm ^-1 had disappeared, and a light yellow transparent polymerizable polyimide resin solution was obtained.

This polyimide resin solution was coated on a KBr plate and the IR of a sample in which the solvent was volatilized was measured.
Absorption of imide ring at 780 cm ⁻¹ and 735 cm ⁻¹ , 1
Absorption of amide group at 660 cm ⁻¹ , absorption of acid anhydride group at 1850 cm ⁻¹ and 1780 cm ⁻¹ and 720 cm ⁻¹ ,
Absorption of carboxyl group at 3390 cm ^-1 , further 16
Absorption of acryloyl group at 38cm ^-1 and 810 cm ^-1 was confirmed, respectively. In addition, in the molecular weight distribution measurement by GPC, the number average molecular weight is 211 in terms of polystyrene.
0, and the weight average molecular weight was 4,400 in terms of polystyrene. The Mn is 2,110, the Mw is 4,400, the acid value is 77.6, and the acryloyl group concentration is 1.28 mm.
It was ol / g. Furthermore, the isocyanurate ring concentration was 0.93 mmol / g. Hereinafter, this polymerizable polyimide resin solution is abbreviated as resin solution P4.

A resist ink was prepared in the same manner as in Example 1 except that the obtained resin solution P4 was used instead of the resin solution P1.
The evaluation test of (4) was performed. The evaluation results are shown in Table 2 (1).

Comparative Example 1 In a flask equipped with a thermometer, a stirrer and a condenser,
Charge 322.2 g of ethyl carbitol acetate,
Orthocresol novolac type epoxy resin EP
ICLON N-680 [Dainippon Ink and Chemicals, Inc.
Manufactured, epoxy equivalent 212 g / eq] 954.0 g was dissolved. Then, after adding 1.3 g of hydroquinone,
With stirring, 325.8 g of acrylic acid and N, N-
Dimethylbenzylamine (4.25 g) was added, and the esterification reaction was carried out at 115 ° C while blowing air. The end point of the reaction was the point at which the acid value became 1 mgKOH / g or less. Then ethyl carbitol acetate 611.2
g and 444.6 g of tetrahydrophthalic anhydride are added,
The reaction was carried out at 90 ° C. for 5 hours to obtain a pale yellow acid pendant type epoxy acrylate resin solution. Acid value is 82.4
The concentration of acryloyl group was 2.61 mmol / g. Moreover, Mn was 3,500 and Mw was 9,800. Hereinafter, this epoxy acrylate resin solution is abbreviated as resin solution 1 '.

Using the resin solution 1'obtained, the composition shown in Table 1 (1) was blended and kneaded with a homodisper to prepare a resist ink. Then, using this resist ink, a test piece having a resist ink coating film is formed on a tin plate or a glass epoxy printed circuit board on which a circuit pattern that has been previously etched is formed. The evaluation test of 4) was performed. The evaluation results are shown in Table 2 (2).

Comparative Example 2 195.4 g of diethylene glycol monoethyl ether acetate and 11 of isophorone diisocyanate were placed in a four-necked flask equipped with a stirrer, a thermometer and a condenser.
1.0 g and trimellitic anhydride 134.4 g were charged, and the temperature was raised to 80 ° C. with stirring under a nitrogen atmosphere. Vigorous foaming started at around 60 ° C, and the contents of the flask gradually became transparent. After reacting at 80 ° C for 1 hour, the temperature was raised to 150 ° C. Further, the reaction was carried out at 150 ° C. for 7 hours. After cooling to 100 ° C and changing to an air atmosphere, 0.22 g of methylhydroquinone was added, and 100 ° C
The mixture is cooled to 100 ° C., charged with 37.4 g of pentaerythritol triacrylate (hydroxyl value 120), and heated at 100 ° C. for 3 days.
The reaction was carried out for a time to obtain a pale yellow polymerizable polyimide resin solution. The acid value was 100.9 and the acryloyl group concentration was 0.98 mmol / g. Also, Mn is 1,70
0 and Mw were 2,050. Hereinafter, this polyimide resin solution is abbreviated as resin solution 2 '.

A resist ink was prepared in the same manner as in Comparative Example 1 except that the obtained resin solution 2'was used in place of the resin solution 1 ', and then the above-mentioned (1) to (1) were repeated.
The evaluation test of (4) was performed. The evaluation results are shown in Table 2 (2).

[0104]

[Table 1]

[0105]

[Table 2]

Footnotes in Table 1 (1) to (2) * 1) EPICLON N-680; orthocresol novolac type epoxy resin (manufactured by Dainippon Ink and Chemicals,
Epoxy equivalent 212)

[0107]

[Table 3]

[0108]

[Table 4]

Example 5 In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 5200 g of diethylene glycol monoethyl ether acetate, 2772 g of IPDI-N (12 mol of isocyanate groups) and 148 g (1 mol) of dimethylolbutanoic acid were added. Was charged, the temperature was raised to 80 ° C. while stirring, and the reaction was carried out for 3 hours while paying attention to heat generation. Then, 1344 g (7 mol) of trimellitic anhydride was charged and the temperature was raised to 160 ° C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 4 hours. The inside of the system became a light brown clear liquid. Cool the solution temperature to 100 ° C,
Furthermore, 935 g (2 mol) of pentaerythritol triacrylate (hydroxyl value 120) and 15 g of methylhydroquinone were charged, and urethane reaction was carried out at this temperature for 5 hours, and absorption of the isocyanate group at 2270 cm ⁻¹ disappeared by IR. Then, a light brown transparent polymerizable polyimide resin solution was obtained.

This polyimide resin solution was coated on a KBr plate, and the IR of a sample in which the solvent was volatilized was measured.
Absorption of imide ring at 25 cm ^-1 and 1780 cm ^-1 and 1720 cm ^-1, characteristic absorption of isocyanurate ring at 1690 cm ^-1 and 1460 cm ^-1, further 1550cm
Absorption of urethane bond was confirmed at ^-1 . Also, Mn is 2,500, Mw is 5,200, and acid value is 9
8. The concentration of acryloyl group was 1.23 mmol / g. Furthermore, the isocyanurate ring concentration is 0.85 mm
It was ol / g. Hereinafter, this polymerizable polyimide resin solution is abbreviated as resin solution P5.

Using the resulting resin solution P5, the composition shown below was compounded and kneaded with a homodisper to prepare a negative type resist ink. Below (5)
The evaluation test of (9) was performed. The evaluation results are shown in Table 3.

Blending composition (1) Polymerizable polyimide resin solution (resin solids) 75 parts (2) EPICLON N-680 * 2) 25 parts (3) Dipentaerythritol hexaacrylate 10 parts (4) 2-Methyl-1 -[4- (Methylthio) phenyl] -2-morpholinopropan-1-one 5 parts (5) N, N-dimethylbenzylamine 1 part Footnote of formulation example * 2) EPICLON N-680; orthocresol novolac type epoxy Resin (manufactured by Dainippon Ink and Chemicals,
Epoxy equivalent 216)

<Evaluation Test Method> (5) Evaluation of Touch Dryness A resist ink was applied onto a glass substrate using an applicator so as to have a thickness of 30 μm after drying, and dried at 80 ° C. for 30 minutes. After obtaining the test piece, leave this test piece in an environment of 25 ° C. and 65% RH for 1 hour,
The condition of tack when the coating film was touched with a finger was evaluated according to the following criteria. Evaluation Criteria A: No tack is observed. ◯: Slight tackiness is observed. Δ: Remarkably tack is observed. X: Resin adheres to the finger.

(6) Evaluation of UV-curing property A resist ink was dried on a glass substrate using an applicator so as to have a thickness of 30 μm, and dried at 80 ° C. for 30 minutes to obtain a test piece. On top of this test piece, Kodak Step Tablet No.
No. 2 was placed, and 500 mJ / cm ² and 1000 mJ / cm ² and 150 were applied from above using a metal halide lamp [HTE106-M07 manufactured by Hitec Co., Ltd., output 7 kW].
Ultraviolet irradiation with an irradiation dose of 0 mJ / cm ² was applied to different test pieces, and the ultraviolet curability was evaluated according to the following criteria. Evaluation Criteria ⊚: There are 5 or more remaining areas at an irradiation dose of 500 mJ / cm ² . ⊚: There are 5 or more remaining areas at an irradiation dose of 1000 mJ / cm ² . Δ: There are 5 or more remaining areas at an irradiation dose of 1500 mJ / cm ² . X: The residual area is less than 5 steps at an irradiation dose of 1500 mJ / cm ² .

(7) Evaluation of Developability A resist ink was dried on a glass substrate using an applicator so as to have a thickness of 30 μm, and dried at 80 ° C. for 30 minutes to obtain a test piece. Negative resist pattern film (PC
W UGRA82; made by UGRA Co.) is placed, and a metal halide lamp is used to emit ultraviolet rays of 1000 mJ.
/ Cm ² irradiation. Then, this test piece is
C. 1% sodium carbonate aqueous solution and 1% sodium hydroxide aqueous solution as developing solutions, immersed in each developing solution for 4 minutes, shaken for shaking, washed with tap water, and then visually developed with a magnifying glass. It was evaluated by. Evaluation criteria ⊚: A concentric pattern of 10 μm or less could be developed. ◯: A concentric pattern of 20 μm or less could be developed. Δ: Development is possible with a concentric pattern of 20 μm or more, but undeveloped areas are observed. X: A pattern cannot be obtained by development.

(8) Measurement of glass transition temperature and coefficient of linear expansion A resist ink was applied onto a glass substrate using an applicator and dried to a film thickness of 30 μm, and dried at 80 ° C. for 30 minutes to give a test piece. After obtaining, obtain 1 ultraviolet ray using a metal halide lamp on this test piece.
After irradiation with 000 mj / cm ^2, separate test pieces were left to cure in a dryer at 150 ° C. and 170 ° C. for 60 minutes, the cured coating film was peeled off, and then DMA (Dy
natural mechanical analysis
s) method is used to measure the glass transition temperature of the cured coating film.
MA (Thermal mechanical ana
The glass transition temperature (Tg) and the linear expansion coefficient (α1) of the cured coating film were measured by the lysis method. Glass transition temperature (T
The value of g) indicates that the higher the temperature, the more excellent the heat resistance. The coefficient of linear expansion (α1) is the glass transition temperature (T
g) Dimensional stability at the previous temperature is shown, and the smaller the value, the better the thermal dimensional stability.

In the DMA method, Rheoviron RSA-11 manufactured by Rheometric Co. was used, and the distance between jig chucks was 20 mm, the temperature range was 25 to 300 ° C., and the temperature rising rate was 3 ° C. /
Min, the dynamic viscoelasticity was measured under the condition of a measurement frequency of 1 Hz, and the temperature showing the maximum value of Tan δ in the obtained spectrum was determined as the glass transition temperature (Tg).

In the TMA method, using a thermal analysis system TMA-SS6000 manufactured by Seiko Denshi KK, sample length 10 mm, temperature rising rate 10 ° C./min, load 49 mN (5 g).
The glass transition temperature (Tg) and the linear expansion coefficient (α1) were measured under the conditions of JIS K-0129.

(9) Pressure Cooker (PCT) Resistance Test In the same manner as (4) Pressure Cooker (PCT) resistance test, except that the active energy ray-curable imide resin solutions obtained in Examples 5 to 8 were used. (9) A pressure cooker resistance test was conducted to evaluate changes in appearance and adhesion of the coating film.

Example 6 In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 4000 g of diethylene glycol monoethyl ether acetate, 2079 parts of IPDI-N (mol number of isocyanate group: 9 mol) and hexamethylene diisocyanate were derived. Isocyanurate ring-containing polyisocyanate compound (isocyanate group content 2
2.9%, isocyanurate ring-containing triisocyanate compound content 65%) 550 g (mol number of isocyanate groups 3 mol), and dimethylolpropionic acid 134
g (1 mol) was charged, and the temperature was raised to 80 ° C. with stirring. After reacting at this temperature for 5 hours, 1152 g (6 mol) of trimellitic anhydride and 218 g (1 mol) of pyromellitic anhydride were charged and the temperature was raised to 170 ° C.
The reaction proceeded with foaming. The reaction was carried out at this temperature for 4 hours. The inside of the system became a light brown clear liquid. The solution temperature was cooled to 100 ° C, and 288 g (2 mol) of 4-hydroxybutyl acrylate (hydroxyl value 390) was further added.
And 15 g of methylhydroquinone were charged, and the urethane reaction was carried out at this temperature for 5 hours, and IR was 2270 cm.
It was confirmed that the absorption of the isocyanate group of ^-1 had disappeared, and a light brown transparent polymerizable polyimide resin solution was obtained.

This polyimide resin solution was applied to a KBr plate and the IR of a sample in which the solvent was volatilized was measured.
25 cm ^-1 and 1780 cm ^-1 and 1720 cm ^-1 to the absorption of an imide ring, 1690 cm ^-1 and 1460 cm ^-1
Absorption of isocyanurate ring, 1550 cm ^-1
The absorption of urethane bond was confirmed in each case. Further, Mn is 2,900, Mw is 4,800, and an acid value is 10.
8. The concentration of acryloyl group was 0.49 mmol / g. Furthermore, the isocyanurate ring concentration is 1.07 mm
It was ol / g. Hereinafter, this polymerizable polyimide resin solution is abbreviated as resin solution P6.

A resist ink was prepared in the same manner as in Example 5 except that the obtained resin solution P6 was used instead of the resin solution P5, and the evaluation tests (5) to (9) were conducted. The evaluation results are shown in Table 3.

Example 7 In a four-necked flask equipped with a stirrer, a thermometer, and a condenser, 5500 g of propylene glycol monomethyl ether acetate, 2772 g of IPDI-N (12 mol of isocyanate group) and bisphenol A were added.
Ethylene oxide adduct (hydroxyl value 340) 660
g (2 mol) was charged, and the temperature was raised to 80 ° C. while stirring and paying attention to heat generation. The reaction was carried out at this temperature for 3 hours. Then 1536 g (8 mol) of trimellitic anhydride
Was charged and the temperature was raised to 130 ° C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 12 hours. The inside of the system became a light brown clear liquid. Furthermore, 568 g (4 mol) of glycidyl methacrylate, 15 g of triphenylphosphine, and 15 g of methylhydroquinone were charged, and the esterification reaction was carried out at this temperature for 5 hours, and the absorption of isocyanate at 2270 cm ^-1 disappeared. Then, a brown transparent polymerizable polyimide resin solution was obtained.

This polyimide resin solution was applied to a KBr plate and the IR of a sample in which the solvent was volatilized was measured.
Absorption of imide ring at 25 cm ^-1 and 1780 cm ^-1 and 1720 cm ^-1, further 1690 cm ^-1 and 1460c
The absorption of the isocyanurate ring was confirmed at m ⁻¹ . Also, Mn is 2,800, Mw is 6,500, acid value is 75, and methacryloyl group concentration is 0.77 mmol.
/ G. Further, the isocyanurate ring concentration was 0.
It was 79 mmol / g. Hereinafter, this polymerizable polyimide resin solution is abbreviated as resin solution P7.

A resist ink was prepared in the same manner as in Example 5, except that the obtained resin solution P7 was used in place of the resin solution P5, and the evaluation tests (5) to (9) were conducted. The evaluation results are shown in Table 3.

Example 8 A 4-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 65 g of diethylene glycol monoethyl ether acetate and 185 g of a tetramethylbiphenol type epoxy resin (epoxy equivalent: 185 g / eq) and heated at 100 ° C. Dissolved. Furthermore, acrylic acid 72g
And 3 g of triphenylphosphine and 5 g of methylhydroquinone were charged and reacted at 120 ° C. for 10 hours to obtain a resin having an acid value of 0.2 and an epoxy equivalent of 24000 g / eq. This is abbreviated as intermediate 1.

Further, in a four-necked flask equipped with a stirrer, a thermometer and a condenser, 4820 g of ethyl diglycol acetate, IP7210 g of IPDI-N (mol of isocyanate group: 12 mol) and 296 parts (2 mol) of dimethylolbutanoic acid were added. After charging and stirring, the temperature was raised to 80 ° C while paying attention to heat generation. After reacting for 3 hours at this temperature, trimellitic anhydride 1152 g (6 mol)
Then, 436 g (2 mol) of pyromellitic dianhydride was charged, and the temperature was raised to 140 ° C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 5 hours. The inside of the system became a light brown transparent liquid. The solution temperature was cooled to 100 ° C., 963 g (1.5 mol) of Intermediate 1 was charged, and the reaction with the acid anhydride group remaining at this temperature was carried out for 5 hours.
Absorption of isocyanate group at 2270 cm ^-1 at R and 1
After confirming that the absorption of the acid anhydride group at 860 cm ⁻¹ had disappeared, a light brown transparent polymerizable polyimide resin solution was obtained.

This polyimide resin solution was coated on a KBr plate, and the IR of the sample in which the solvent was volatilized was measured.
25 cm ^-1 and 1780 cm ^-1 and 1720 cm ^-1 to the absorption of an imide ring, 1690 cm ^-1 and 1460 cm ^-1
Absorption of isocyanurate ring, 1550 cm ^-1
The absorption of urethane bond was confirmed in each case. Also,
Mn is 4,800, Mw is 7,700, acid value is 112,
Concentration of (meth) acryloyl group is 0.67 mmol / g
Met. Furthermore, the isocyanurate ring concentration is 0.78
It was mmol / g. Hereinafter, this polymerizable polyimide resin solution is abbreviated as resin solution P8.

A resist ink was prepared in the same manner as in Example 5 except that the obtained resin solution P8 was used in place of the resin solution P5, and the evaluation tests (5) to (9) were conducted. The evaluation results are shown in Table 3.

Example 9 In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 4300 g of diethylene glycol monoethyl ether acetate, 2079 g of IPDI-N (mol number of isocyanate group: 9 mol) and 222 g of isophorone diisocyanate (mol of isocyanate group). (2 mol)
And 148 g (1 mol) of dimethylolbutanoic acid were charged, and the temperature was raised to 80 ° C. while stirring and paying attention to heat generation. After reacting at this temperature for 3 hours, 1152 g (6 mol) of trimellitic anhydride was charged, and the temperature was raised to 150 ° C. with stirring. The reaction proceeded with foaming and gradually became transparent. React for 4 hours at 150 ° C for 10
Cooled to 0 ° C. Then, methyl hydroquinone 15
g, and 702 g (1.5 mo) of pentaerythritol triacrylate (hydroxyl value 120).
1) was added and reacted at 100 ° C. After reacting at 100 ° C. for 5 hours, it was confirmed by IR that absorption of isocyanate at 2270 cm ⁻¹ had disappeared, and a pale yellow transparent polymerizable polyimide resin solution was obtained.

This polyimide resin solution was coated on a KBr plate, and the IR of a sample in which the solvent was volatilized was measured.
25 cm ^-1 and 1780 cm ^-1 and 1720 cm ^-1 to the absorption of an imide ring, 1690 cm ^-1 and 1460 cm ^-1
Absorption of isocyanurate ring, 1550 cm ^-1
The absorption of urethane bond was confirmed in each case. Also,
Mn is 4,700, Mw is 14,000, acid value is 85,
The concentration of acryloyl group was 1.14 mmol / g. Furthermore, the isocyanurate ring concentration is 0.76 mmo.
It was 1 / g. Hereinafter, this polymerizable polyimide resin solution is abbreviated as resin solution P9.

A resist ink was prepared in the same manner as in Example 5 except that the obtained resin solution P9 was used instead of the resin solution P5, and the evaluation tests (5) to (9) were conducted. The evaluation results are shown in Table 3.

[0133]

[Table 5]

[0134]

The active energy ray-curable polyimide resin composition of the present invention is excellent in curability, heat resistance, and moisture resistance under high temperature and high pressure, and when used in a resist composition, patterning with a dilute alkaline aqueous solution. It is also possible to use an ordinary organic solvent as the organic solvent, for example, a polar solvent containing no nitrogen atom and sulfur atom.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 26, 2002 (2002.6.2)
6)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
As the polymerizable polyimide resin (I) used in the present invention,
A polymerizable polyimide resin having an isocyanurate ring, a cycloaliphatic structure, an imide ring and a (meth) acryloyl group, which can be patterned with a dilute aqueous alkali solution,
It is not particularly limited, and for example, the concentration of the isocyanurate ring is 0.4 to 1.2 mmol / g (converted to resin solid content), and the concentration of the (meth) acryloyl group is 0.3 to 4
The acid value is 20 to 250 in mmol / g (resin solid content conversion)
The number average molecular weight is 1,000 to 20, in terms of resin solid content.
000 and a weight average molecular weight of 1,500 to 30,
000 polymerizable polyimide resins.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

As the diisocyanate compound containing the above-mentioned cycloaliphatic diisocyanate compound, a diisocyanate compound other than the cycloaliphatic diisocyanate compound, for example, an acyclic aliphatic diisocyanate compound is used.
Those containing in the range of less than or equal to wt% and those containing the aromatic diisocyanate in the range of less than or equal to 30% by weight, among others, since a polymerizable polyimide resin excellent in solvent solubility with heat resistance is obtained, It is preferable that the content of the cycloaliphatic diisocyanate compound is high, and normally, the content of the cycloaliphatic diisocyanate compound is 10 or less.
0% by weight is used. Examples of the cycloaliphatic diisocyanate compound include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate and the like. Further, examples of the acyclic aliphatic diisocyanate include hexamethylene diisocyanate, lysine diisocyanate, trimethylhexane diisocyanate, and the like. These may be used alone or in combination of two or more.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction content]

The above-mentioned polyol compound (a2) is not particularly limited as long as it is a polyol compound having two or more hydroxyl groups in one molecule, and above all, it has 2 to 6 hydroxyl groups.
A compound having an individual group is preferable, and a diol compound is particularly preferable. The polyol compound (a2) is introduced into the resin via the urethane bond with the polyisocyanate compound (A1).
By introducing 2) into the imide resin skeleton, the solvent solubility of the polyimide resin is improved, and the performance such as development speed and development stability during development is improved.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

Examples of the polyol compound (a22) 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, cyclohexanedimethylol, 1,4-cyclohexanediol, spiroglycol, tricyclodecanedimethylol, hydrogenated bisphenol A, A diol such as ethylene oxide-added bisphenol A, propylene oxide-added bisphenol A, dimethylolpropionic acid, and dimethylolbutanoic acid;

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction content]

The polyisocyanate compound (A3) is preferably a diisocyanate compound, for example, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate. , 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
Aromatic diisocyanates such as 3,3′-dimethyldiphenyl-4,4′-diisocyanate, 3,3′-diethyldiphenyl-4,4′-diisocyanate and naphthalene diisocyanate; isophorone diisocyanate,
Aliphatic diisocyanates such as hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbonylene diisocyanate, lysine diisocyanate and the like can be mentioned. Of these, aliphatic diisocyanates are particularly preferable.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

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 acid dianhydride, naphthalene-2,3,6
7-tetracarboxylic dianhydride, naphthalene-1,2,
4,5-tetracarboxylic dianhydride, naphthalene-1,
8,4,5-Tetracarboxylic acid dianhydride, Decahydronaphthalene-1,8,4,5-tetracarboxylic acid dianhydride, 4,8-Dimethyl-1,2,3,5,6,7- Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride;

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

2,6-dichloronaphthalene-1,8,
4,5-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,8,4,5-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,
8,4,5-Tetracarboxylic acid dianhydride, Phenanthrene-1,2,9,10-tetracarboxylic acid dianhydride, Berylene-3,4,9,10-tetracarboxylic acid 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-
Aroma in the molecule of bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride An anhydride of a tetracarboxylic acid having a group organic group may be mentioned. Further, as the tetracarboxylic acid anhydride, there are monoanhydrides other than these dianhydrides, which can be used alone or in combination with the dianhydride. Examples of the monoanhydride include those obtained by ring-opening one of the anhydrous groups of the dianhydride with alcohol or the like.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

When a compound (C1) having a (meth) acryloyl group and a hydroxyl group or a compound (C2) having a (meth) acryloyl group and an epoxy group is added during the reaction, for example, an isocyanate group and / or an acid group is used. The compound (C1) is added into the reaction system in which an anhydrous group remains, and the hydroxyl group in the compound (C1) is reacted with an isocyanate group and / or an acid anhydride group to form a urethane bond and / or When a polyimide resin in which an ester bond is formed and a reactive double bond is introduced, or when the compound (C2) is added to the system in the middle of the reaction where the carboxyl group remains, the compound (C2) is added. The epoxy group and the carboxyl group in the inside are reacted to form an epoxy ester bond,
Examples thereof include the case of using a polyimide resin having a reactive double bond introduced therein, and the above case is particularly preferable.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Name of item to be corrected] 0057

[Correction method] Change

[Correction content]

Furthermore, the carboxyl group or acid anhydride group remaining at the terminal of the polyimide resin (X) can be reacted with an epoxy resin having two or more epoxy groups in the molecule to adjust the molecular weight. As the epoxy resin, the epoxy compound (c21) described above can be used.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0087

[Correction method] Change

[Correction content]

<Evaluation Test Method> (1) Resolubility Test A resist ink was applied onto a tin plate using an applicator of 0.076 mil so as to have a film thickness of 30 μm after drying, and a test piece was obtained. In an oven at 80 ° C for 3
After leaving for 0 minutes, a test piece having a resist ink coating film in which the solvent was volatilized was prepared, its weight and coating area were measured, and then the test piece was placed in a 1% aqueous sodium carbonate solution and a 1% aqueous sodium hydroxide solution at 50 ° C. Then, the coating film is re-dissolved by immersion shaking for 30 seconds, dried and weighed. The weight before re-dissolution, the weight after re-dissolution, the coating area, and the specific gravity of the coating film (however, The specific gravity is 1.2), and the thickness of the coating film redissolved in 60 seconds was calculated, and then the film reduction speed was determined. The larger the value of the film-reducing speed, the better the resolubility.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0090

[Correction method] Change

[Correction content]

(4) Pressure Cooker (PCT) Resistance Test 0.076 on a glass epoxy printed circuit board having a circuit pattern formed by pre-etching a resist ink.
Test using a mill applicator so as to have a film thickness of 30 μm after drying, and leave the resulting test piece in a dryer at 80 ° C. for 30 minutes to evaporate the solvent and have a resist ink coating film As a piece, after irradiating the coating film with ultraviolet rays of 500 mJ / cm ² using an ultra-high pressure mercury lamp, separate test pieces were left for 60 minutes in a dryer at 150 ° C. and 170 ° C. to form a cured coating film. The test piece thus obtained is used as a test piece
After treating with a T tester (PC-304RIII, Hirayama Seisakusho Co., Ltd.) under a saturated vapor pressure of 121 ° C. and 100% RH for 50 hours, the temperature was returned to room temperature and the change in appearance was visually evaluated. In addition, according to the JISD-0202 cellophane tape peeling test, a grid-like cross cut is put in the obtained coating film at 1 mm intervals, and a peeling test is performed with cellophane tape to count the number of peeled coating films. The adhesion of the coating film was evaluated according to the following criteria. Appearance evaluation criteria A: No change or abnormality is observed before and after the PCT test. Good: After the PCT test, coating film abnormalities such as blister, whitening, and dissolution can be confirmed within a range of less than 10% of the coating film area. Δ: After the PCT test, abnormality of the coating film such as blister, whitening and dissolution can be confirmed in the range of 10% or more and less than 50% by weight of the coating film area. X: After the PCT test, coating film abnormalities such as blister, whitening, and dissolution can be confirmed in a range of 50% or more of the coating film area. Adhesion evaluation ◎: No cross-cutting. ◯: The number of cross-cuts separated from 100 cross-cuts is less than 20. Δ: The number of cross-cuts separated from 100 cross-cuts is 20 or more and less than 70. X: The number of cross-cuts was 70 or more with respect to 100 cross-cuts.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0098

[Correction method] Change

[Correction content]

This polyimide resin solution was coated on a KBr plate and the IR of a sample in which the solvent was volatilized was measured.
Absorption of imide ring at 780 cm ⁻¹ and 735 cm ⁻¹ , 1
Absorption of amide group at 660 cm ⁻¹ , absorption of acid anhydride group at 1850 cm ⁻¹ and 1780 cm ⁻¹ and 720 cm ⁻¹ ,
Absorption of carboxyl group at 3390 cm ^-1 , further 16
Absorption of acryloyl group at 38cm ^-1 and 810 cm ^-1 was confirmed, respectively. Also, Mn is 2,110, M
The w was 4,400, the acid value was 77.6, and the concentration of the acryloyl group was 1.28 mmol / g. Furthermore, the isocyanurate ring concentration was 0.93 mmol / g. Hereinafter, this polymerizable polyimide resin solution is abbreviated as resin solution P4.

[Procedure Amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0114

[Correction method] Change

[Correction content]

(6) Evaluation of UV-curing property A resist ink was dried on a glass substrate using an applicator so as to have a thickness of 30 μm, and dried at 80 ° C. for 30 minutes to obtain a test piece. On top of this test piece, Kodak Step Tablet No.
No. 2 was placed, and 500 mJ / cm ² and 1000 mJ / cm ² and 150 were applied from above using a metal halide lamp [HTE106-M07 manufactured by Hitec Co., Ltd., output 7 kW].
Ultraviolet irradiation with an irradiation dose of 0 mJ / cm ² was applied to different test pieces, and the ultraviolet curability was evaluated according to the following criteria. Evaluation Criteria ⊚: There are 5 or more remaining areas at an irradiation dose of 500 mJ / cm ² . ◯: There are 5 or more remaining areas at an irradiation dose of 1000 mJ / cm ² . Δ: There are 5 or more remaining areas at an irradiation dose of 1500 mJ / cm ² . X: The residual area is less than 5 steps at an irradiation dose of 1500 mJ / cm ² .

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0120

[Correction method] Change

[Correction content]

Example 6 In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 4000 g of diethylene glycol monoethyl ether acetate, 2079 g of IPDI-N (mol number of isocyanate group: 9 mol) and hexamethylene diisocyanate were derived. Isocyanurate ring-containing polyisocyanate compound (isocyanate group content 2
2.9%, isocyanurate ring-containing triisocyanate compound content 65%) 550 g (mol number of isocyanate groups 3 mol), and dimethylolpropionic acid 134
g (1 mol) was charged, and the temperature was raised to 80 ° C. with stirring. After reacting at this temperature for 5 hours, 1152 g (6 mol) of trimellitic anhydride and 218 g (1 mol) of pyromellitic anhydride were charged and the temperature was raised to 170 ° C.
The reaction proceeded with foaming. The reaction was carried out at this temperature for 4 hours. The inside of the system became a light brown clear liquid. The solution temperature was cooled to 100 ° C, and 288 g (2 mol) of 4-hydroxybutyl acrylate (hydroxyl value 390) was further added.
And 15 g of methylhydroquinone were charged, and the urethane reaction was carried out at this temperature for 5 hours, and IR was 2270 cm.
It was confirmed that the absorption of the isocyanate group of ^-1 had disappeared, and a light brown transparent polymerizable polyimide resin solution was obtained.

[Procedure Amendment 15]

[Document name to be amended] Statement

[Name of item to be corrected] 0127

[Correction method] Change

[Correction content]

Further, a 4-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 4820 g of ethyl diglycol acetate, 2772 g of IPDI-N (mol number of isocyanate group: 12 mol) and 296 g (2 mol) of dimethylolbutanoic acid. The mixture was stirred, and the temperature was raised to 80 ° C while paying attention to heat generation. After reacting for 3 hours at this temperature, trimellitic anhydride 1152 g (6 mol)
Then, 436 g (2 mol) of pyromellitic dianhydride was charged, and the temperature was raised to 140 ° C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 5 hours. The inside of the system became a light brown transparent liquid. The solution temperature was cooled to 100 ° C., 963 g (1.5 mol) of Intermediate 1 was charged, and the reaction with the acid anhydride group remaining at this temperature was carried out for 5 hours.
Absorption of isocyanate group at 2270 cm ^-1 at R and 1
After confirming that the absorption of the acid anhydride group at 860 cm ⁻¹ had disappeared, a light brown transparent polymerizable polyimide resin solution was obtained.

Continuation of front page (51) Int.Cl. ⁷ identification code FI theme code (reference) H01L 21/027 H01L 21/30 502R (31) Priority claim number Japanese Patent Application No. 2001-357519 (P2001-357519) (32) Priority Japan November 22, 2001 (November 22, 2001) (33) Country claiming priority Japan (JP) F-term (reference) 2H025 AA04 AA10 AA11 AA20 AB15 AB16 AC01 AD01 BC14 BC66 BC69 BC74 BC84 CA00 CC03 CC17 FA17 4J027 AD05 AE00 AG01 CB10 CC05 CD10 4J034 BA02 CA03 CA04 CA05 CA23 CA24 CA25 CA26 CB03 CB04 CB05 DK00 FA02 FB01 FB04 HA01 HA06 HA07 HC01 HC02 HC03 HC11 HC15 HC22 HC23 HC26 HC32 HC33 HC71 HC41 HC73 HC21 HC41 HC73 HC71 HC67 HC67 HC67 HC67 HC67 LA23 LA33 QA01 QA02 QA05 SA01 4J043 QB47 QB58 RA04 TA13 TA14 TA21 TA22 TA43 TA44 TA67 UA122 UA132 UA262 UB012 UB122 UB302 WA02 WA17 XB28 ZA12 ZB22 ZB50

Claims (11)

[Claims] 1. A polymerizable polyimide resin (I) having an isocyanurate ring, a cycloaliphatic structure, an imide ring, and a (meth) acryloyl group, which is capable of patterning with a dilute alkaline aqueous solution. An active energy ray-curable polyimide resin composition. 2. The polymerizable polyimide resin (I) has an isocyanurate ring concentration of 0.4 to 1.2 mmol / g,
The concentration of the (meth) acryloyl group is 0.3 to 4 mmol /
g, acid value 20-250, number average molecular weight 1.00
0 to 20,000 and a weight average molecular weight of 1,50
The active energy ray-curable polyimide resin composition according to claim 1, which is a polyimide resin (I) of 0 to 30,000. 3. The active energy ray-curable polyimide resin composition according to claim 1, which further contains an organic solvent (II), an epoxy compound (III) and a photoinitiator (IV). 4. The active energy ray-curable polyimide resin according to claim 1, further comprising an organic solvent (II), an epoxy compound (III), a photoinitiator (IV) and a reactive diluent (V). Composition. 5. The polymerizable polyimide resin (I) is an isocyanurate ring-containing polyisocyanate compound (A1) derived from a cycloaliphatic diisocyanate compound, and / or the polyisocyanate compound (A1) and a polyol compound (A1). a2) a polyisocyanate compound (A) containing a urethane prepolymer (A2) having an isocyanate group at the terminal and an acid anhydride (B) of a polycarboxylic acid having three or more carboxyl groups are organic. A polymerizable imide resin obtained by reacting in a solvent and then reacting a compound (C1) having a (meth) acryloyl group and a hydroxyl group and / or a compound (C2) having a (meth) acryloyl group and an epoxy group. The active energy ray-curable polyimide resin composition according to claim 1 or 3. 6. A polymerizable polyimide resin (I) containing an acid anhydride having a carboxyl group as an acid anhydride (B) of a polycarboxylic acid is reacted with a polyisocyanate compound (A), A compound having a (meth) acryloyl group and a hydroxyl group (C1) and / or a compound having a (meth) acryloyl group and an epoxy group (C
2) or by reacting with a polyisocyanate compound (A) using an acid anhydride having no carboxyl group as the acid anhydride (B) of polycarboxylic acid, and then reacting with a (meth) acryloyl group and a hydroxyl group. The active energy ray-curable polyimide resin composition according to claim 5, which is a resin obtained by reacting a compound (C1) having: 7. The polyisocyanate compound (A1) is
6. A triisocyanate compound containing one isocyanurate ring in an amount of 30% by weight or more.
The active energy ray-curable polyimide resin composition described. 8. A compound (C1) wherein the polymerizable imide resin (I) has a (meth) acryloyl group and a hydroxyl group during the reaction between the polyisocyanate compound (A) and the acid anhydride (B) of a polycarboxylic acid. Ratio (n _c1 ) / of the number of moles of hydroxyl groups (n _c1 ) and the total number of moles of acid anhydride groups and isocyanate groups remaining in the reaction system (n _ab ) /
When the (n _ab ) is 0.9 to 2.0, the compound (C
The active energy ray-curable polyimide resin composition according to claim 5, which is a resin obtained by adding and reacting 1). 9. The urethane prepolymer (A2) comprises a polyisocyanate compound (A1) and a polyol compound containing a carboxyl group-containing polyol (a21), and the isocyanate group in the polyisocyanate compound (A1) is the polyol compound. 6. A urethane prepolymer having an isocyanate group at a terminal, which is obtained after the reaction is carried out at an excess molar ratio with respect to the hydroxyl group therein.
The active energy ray-curable polyimide resin composition described. 10. The polymerizable imide resin (I) uses an anhydride of tricarboxylic acid and / or an anhydride of tetracarboxylic acid as the acid anhydride (B) of polycarboxylic acid, and
A compound having a (meth) acryloyl group and a hydroxyl group (C
1) and / or a resin obtained by using a compound having 2 to 5 (meth) acryloyl groups and one hydroxyl group as the compound (C2) having a (meth) acryloyl group and an epoxy group, Item 5. The active energy ray-curable polyimide resin composition according to item 5. 11. The active energy ray-curable polyimide resin composition according to claim 6, wherein the organic solvent is a polar solvent containing no nitrogen atom and no sulfur atom and dissolves the polymerizable polyimide resin (I). .