JP2009258367A - New photosensitive resin composition, usage of the same, and method of manufacturing insulating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin which can be microprocessed since the resin has photosensitivity, which is developable with a diluted alkali aqueous solution, curable at a low temperature (200°C or lower), high in flexibility, and excellent in electric insulation reliability, solder heat resistance and organic solvent resistance, and which has small warpage of a substrate after being cured, and has excellent adhesion with a sealing agent. <P>SOLUTION: The photosensitive resin composition contains, at least: (A) an imide oligomer having a hydroxyl group at the molecular end; (B) a diol compound; (C) (Ca) a compound having at least one block isocyanate group and at least one photosensitive group in the molecule and/or (Cb) a compound having at least one photosensitive group and at least one hydroxyl group in the molecule; (D) a block isocyanate compound; (E) a photosensitive compound; (F) a photopolymerization initiator; and (G) a thermosetting compound. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  Since this invention has photosensitivity, it can be finely processed, can be developed with a dilute alkaline aqueous solution, can be cured at a low temperature (200 ° C. or less), has high flexibility, electrical insulation reliability, and solder heat resistance. , A photosensitive resin composition having excellent resistance to organic solvents, low warpage of a substrate after curing, and excellent adhesion to a sealant, a cured film obtained therefrom, an insulating film, and a printed wiring board with an insulating film It is.

  Polyimide resins are widely used in electrical and electronic applications because of their excellent heat resistance, electrical insulation reliability, chemical resistance, and mechanical properties. For example, it is used to form insulating films and protective coatings on semiconductor devices, base materials such as flexible circuit boards and integrated circuits, surface protective materials, and further, interlayer insulating films and protective films for fine circuits. .

  In particular, when used as a surface protection material for a flexible circuit board, a coverlay film obtained by applying an adhesive to a molded body such as a polyimide film has been used. When bonding this coverlay film on a flexible circuit board, there is a method in which an opening is provided in advance by a method such as punching in a terminal portion of a circuit or a joint portion with a component, and after aligning, a method of thermocompression bonding by a hot press or the like is used. It is common.

  However, it is difficult to provide a high-accuracy opening in a thin coverlay film, and since the alignment at the time of lamination is often performed manually, the positional accuracy is poor and the workability of the lamination is also poor. The cost was high.

  On the other hand, a liquid cover coat ink or the like may be used as a surface protection material for a circuit board. In particular, a liquid cover coat ink having a photosensitive function is preferably used when fine processing is required. Yes. As the liquid cover coat ink, a photosensitive ink mainly composed of epoxy resin or the like (generally also referred to as a solder resist) is used. This ink is excellent in electrical insulation reliability as an insulating material, but is bent. Therefore, when it is laminated on a thin and flexible circuit board such as a flexible circuit board, the warpage of the board becomes large and it is difficult to use it for a flexible circuit board.

  In recent years, various proposals have been made as liquid cover coat inks that can exhibit flexibility and high electrical insulation reliability.

  For example, a photosensitive resin composition (for example, see Patent Document 1) containing a polyimide resin using siloxane diamine and a photosensitive resin composition made of a polyamic acid solution that is a polyimide precursor has been proposed (for example, (See Patent Documents 2-3).

  A photosensitive resin composition comprising a urethane compound obtained by reacting a diisocyanate compound and a monovinyl monohydroxy compound having an alicyclic skeleton with a polycarbonate diol, which is excellent in flexibility, photocurability and insulating properties and capable of alkali development. Has been proposed (see, for example, Patent Documents 4 to 5).

In addition, it has excellent heat resistance, electrical properties, and photocurability, can be patterned by development with dilute aqueous alkali, is soluble in solvents, has a urethane bond in the main chain, and has a (meth) acryloyl group and a carboxyl group. There has been proposed an active energy ray-curable resin composition made of a polyimide resin having the following. (For example, refer to Patent Document 6).
Japanese Patent Laid-Open No. 9-100350 Japanese Patent Laid-Open No. 2-50161 JP 2005-148611 A JP 2000-95837 A JP 2000-241969 A JP 2000-344890 A

  However, in the above-mentioned Patent Document 1, when a polyimide-type photosensitive resin composition is used as a cover coat ink, since it is a high molecular weight polyimide solution, the solubility in a solvent is low and the concentration of the solute is increased. For example, when forming a coating film, it is necessary to volatilize a large amount of solvent, and there is a problem that productivity is poor. Moreover, in said patent documents 2-3, in addition to said problem, it has a photosensitive group in the side chain of polyamic acid, The high temperature (for the purpose of removing the photosensitive group and accelerating imidation reaction ( 300 ° C. or higher) is required, and there is a problem that it cannot be used as a protective insulating layer of a general printed wiring board.

  Moreover, in said patent documents 1-3, the solubility to the dilute alkaline aqueous solution generally used as a developing solution of the photosensitive ink for printed wiring boards is scarce, and the organic solvent type developing solution must be used. For this reason, there existed a problem that work environment and workability | operativity were bad. Furthermore, silicon diamine is used to introduce a flexible skeleton, and it is known that the flexibility and electrical insulation reliability of the cured film are greatly improved by using this, When used for an insulating coating, there is a problem of poor adhesion (adhesiveness) with the sealant resin. Furthermore, oligomers contained in siloxane diamine have problems such as inducing malfunction of semiconductors, and are becoming difficult to use.

  In the above-mentioned Patent Document 4, the electrical insulation reliability and heat resistance under high temperature and high humidity are poor as compared with the case where a polyimide type or polyamic acid type photosensitive resin composition is used as the cover coat ink. In Patent Document 5, a phosphoric ester-based additive type flame retardant is added for the purpose of imparting flame retardancy, and hydrolysis of this flame retardant causes a significant decrease in electrical insulation reliability, and in addition, curing. There were problems such as bleeding out of the flame retardant from the film and elution into the organic solvent and gold plating bath.

  In the above-mentioned Patent Document 6, a polyimide resin having a urethane bond in the main chain and having a (meth) acryloyl group and a carboxyl group has a low number average molecular weight, includes a rigid skeleton, and includes a soft segment having flexibility. In addition, since it has a carboxyl group randomly at the end and side chain of the main chain, it has poor flexibility and large curing shrinkage, so it can be used as a protective insulating layer for thin and flexible circuit boards such as flexible circuit boards There was a problem that could not be done.

  In view of the above situation, the problem of the present invention is that it has photosensitivity, can be finely processed, can be developed with a dilute alkaline aqueous solution, can be cured at a low temperature (200 ° C. or less), has high flexibility, An object of the present invention is to provide a photosensitive resin composition that is excellent in insulation reliability, solder heat resistance, and organic solvent resistance, has low warpage of the substrate after curing, and is excellent in adhesion to a sealant.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using the following photosensitive resin composition.

  That is, the present invention comprises (A) a hydroxyl group-terminated imide oligomer, (B) a polyol compound, (C) (Ca) a compound having at least one blocked isocyanate group and at least one photosensitive group in the molecule and / or (Cb ) A compound having at least one bu-sensitive group and at least one hydroxyl group in the molecule, (D) a blocked isocyanate compound, (E) a photosensitive compound, (F) a photopolymerization initiator, and (G) a thermosetting compound. It is a photosensitive resin composition characterized by containing at least.

  The (B) polyol compound is preferably a polyalkyl polyol and / or a polycarbonate polyol, and more preferably a polycarbonate polyol.

  The (A) hydroxyl group-terminated imide oligomer is preferably a (A) hydroxyl group-terminated imide oligomer represented by the following general formula (1).

（式中、Ｘは４価の有機基を示し、Ｙは２価の有機基を示し、複数個のＲ_１はそれぞれ独立に２価の有機基を示す。ｐは０〜２０の整数である。）

(In the formula, X represents a tetravalent organic group, Y represents a divalent organic group, and a plurality of R _{1 s} each independently represent a divalent organic group. P is an integer of 0-20. .)

  The (C) (Ca) molecule has at least one blocked isocyanate group and at least one photosensitive group, and / or (Cb) at least one photosensitive group and at least one in the molecule. It is also preferred that the photosensitive group of the compound having two hydroxyl groups is a (meth) acryloyl group.

  (A) hydroxyl group-terminated imide oligomer contained in the photosensitive resin composition, (B) polyol compound, (Ca) a compound having at least one blocked isocyanate group and at least one photosensitive group in the molecule, (Cb) The number of moles of the compound having at least one hydroxyl group and at least one photosensitive group in the molecule, and (D) the blocked isocyanate compound are respectively (A), (B), (Ca), (Cb), When (D), the mixing molar ratio is [(A) + (B) + (Cb)] mole number of hydroxyl groups / [(Ca) + (D)] mole number of blocked isocyanate groups = 0. It is also preferable that it is .5 to 2.0.

  Moreover, the blend of (A) component, (B) component, (Ca) component, (Cb) component, (D) component, (E) component, (F) component and (G) component in the photosensitive resin composition The amount is 5 to 500 parts by weight of component (E), 0.1 to 20 parts by weight of component (F), and 0 to component (G) with respect to 100 parts by weight of components (A) to (D). It is also preferably 5 to 100 parts by weight.

  Another invention of the present invention is a photosensitive resin composition solution obtained by dissolving the photosensitive resin composition in an organic solvent.

  Another invention of the present invention is a photosensitive film obtained by applying and drying the above photosensitive resin composition on a substrate surface.

  Moreover, another invention of the present invention is an insulating film obtained by curing the photosensitive resin composition.

  Another invention of the present invention is a printed wiring board with an insulating film in which the printed resin board is coated with the photosensitive resin composition.

  Moreover, another invention of the present invention is an insulating film manufacturing method for manufacturing an insulating film by photosensitizing and thermosetting the photosensitive resin composition.

  Since the photosensitive resin composition of the present invention has photosensitivity, it can be finely processed, can be developed with a dilute alkaline aqueous solution, can be cured at a low temperature (200 ° C. or less), is highly flexible, and has electrical insulation. It exhibits excellent reliability, solder heat resistance, and organic solvent resistance, small warpage of the substrate after curing, and excellent adhesion to the sealant.

Hereinafter, each constituent material will be described.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention is (A) a hydroxyl group-terminated imide oligomer, (B) a polyol compound, (C) (Ca) a compound having at least one photosensitive group and at least one blocked isocyanate group in the molecule. And / or (Cb) a compound having at least one photosensitive group and at least one hydroxyl group in the molecule, (D) a blocked isocyanate compound, (E) a photosensitive compound, (F) a photopolymerization initiator, and (G) ( D) A photosensitive resin composition containing at least a thermosetting compound. This invention does not have a complicated polymerization process, and a photosensitive resin composition can be obtained more easily than in the past, and further, an insulating film can be provided by photosensitizing and thermosetting the photosensitive resin composition, and Since development is possible without including a special developable group, the electrical insulation reliability is excellent.

<(A) Hydroxyl-terminated imide oligomer>
The (A) hydroxyl group-terminated imide oligomer of the present invention has at least one hydroxyl group at the end of the main chain and at least one imide ring inside the main chain, and the number average molecular weight is usually 200 or more in terms of polyethylene glycol. It is an oligomer of 30,000 or less.

  Although it will not specifically limit if it is these oligomers, Preferably, it is a compound which has a structure shown by following General formula (1).

（式中、Ｘは少なくとも４価の有機基を示し、Ｙは２価の有機基を示し、複数個のＲ_１はそれぞれ独立に２価の有機基を示す。ｐは０〜２０の整数である。）

(In the formula, X represents at least a tetravalent organic group, Y represents a divalent organic group, and a plurality of R _{1 s} each independently represent a divalent organic group. P is an integer of 0-20. is there.)

  A hydroxyl-terminated imide oligomer having a structure represented by the general formula (1) is obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (2) with an amino alcohol represented by the following general formula (3). Can do.

（式中、Ｘは少なくとも４価の有機基を示す。）

(In the formula, X represents at least a tetravalent organic group.)

（式中Ｒ_１は２価の有機基を示す。）

(In the formula, R ₁ represents a divalent organic group.)

  Examples of the tetracarboxylic dianhydride used as a raw material for the hydroxyl-terminated imide oligomer represented by the general formula (2) of the present invention include 3,3 ′, 4,4′-oxydiphthalic dianhydride, 3,3 ', 4,4'-hydroquinone diphthalic dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (3 4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride or 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide-3,3 ′, 4,4′-tetracarboxylic dianhydride, etc. The tetracarboxylic dianhydride can be used.

  Particularly preferably, it can be obtained by using 3,3 ′, 4,4′-oxydiphthalic dianhydride or 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride. It is preferable at the point which can improve the solubility with the photosensitive compound of the photosensitive resin of the hydroxyl-terminal (ether) imide oligomer to the organic solvent obtained.

  Although it does not specifically limit as amino alcohol used as a raw material of the hydroxyl-terminated imide oligomer shown by General formula (3) of this invention, For example, 2-aminoethanol, 3-amino-1-propanol, 4-amino- 1-butanol, 5-amino-1-pentanol, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2- (4-aminophenyl) ethanol, 2-amino-m-cresol, 2-amino- p-cresol, 3-amino-o-cresol, 4-amino-o-cresol, 4-amino-m-cresol, 5-amino-o-cresol, 6-amino-m-cresol, 2-amino-1, 2-diphenylethanol, 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl Alcohol, 2-aminocyclohexanol, 4-aminocyclohexanol, can be used 2-amino-cyclopentanol or 1-amino-1-cyclopentane methanol.

  Particularly preferably, by using 2-aminoethanol, 3-amino-1-propanol or 4-amino-1-butanol, the solubility of the resulting hydroxyl-terminated imide oligomer in an organic solvent can be improved. preferable.

  Moreover, when synthesizing the hydroxyl group-terminated imide oligomer, a diamino compound represented by the following general formula (4) can be used as a chain extender in addition to tetracarboxylic dianhydride and amino alcohol.

（式中Ｙは２価の有機基を示す。）

(In the formula, Y represents a divalent organic group.)

Although it does not specifically limit as a diamino compound used as a chain extender of the hydroxyl-terminated imide oligomer shown by General formula (4) of this invention, For example, m-phenylenediamine, o-phenylenediamine, p- Phenylenediamine, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,3'- Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, bis [4- (3- Aminophenoxy) phenyl] sulfone, bis [4- 4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 2,2-bis [4- (3-aminophenoxy) ) Phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- [4- (4-aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl)] propane 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) ) Benzene, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, polytetra Methylene oxide-di-p-aminobenzoate, poly (tetramethylene / 3-methyltetramethylene ether) glycol bis (4-aminobenzoate), trimethylene-bis (4-aminobenzoate), p-phenylene-bis (4-amino) Benzoate), m-phenylene-bis (4-aminobenzoate), bisphenol A-bis (4-aminobenzoate), 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 3,3′-diamino-4,4′-dicarboxybiphenyl, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino-2,2′-dicarboxybiphenyl, [bis (4-amino-2-carboxy) phenyl] methane, [bis (4-amino-3-carboxy) phenyl] methane, [bis (3-a Mino-4-carboxy) phenyl] methane, [bis (3-amino-5-carboxy) phenyl] methane, 2,2-bis [3-amino-4-carboxyphenyl] propane, 2,2-bis [4- Amino-3-carboxyphenyl] propane, 3,3′-diamino-4,4′-dicarboxydiphenyl ether, 4,4′-diamino-3,3′-dicarboxydiphenyl ether, 4,4′-diamino-2, 2'-dicarboxydiphenyl ether, 3,3'-diamino-4,4'-dicarboxydiphenyl sulfone, 4,4'-diamino-3,3'-dicarboxydiphenyl sulfone, 4,4'-diamino-2, 2'-dicarboxydiphenyl sulfone, 2,3-diaminophenol, 2,4-diaminophenol, 2,5-diaminophenol, 3,5-diaminophenol Diaminophenols such as 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 4,4′-diamino-2,2′-dihydroxybiphenyl , 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxybiphenyl and the like, 3,3′-diamino-4,4′-dihydroxydiphenylmethane, 4,4′-diamino- Dihydroxydiphenylmethanes such as 3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′-dihydroxydiphenylmethane, 2,2-bis [3-amino-4-hydroxyphenyl] propane, 2,2-bis Bis [hydroxyphenyl] propanes such as [4-amino-3-hydroxyphenyl] propane, 3,3′-diamino-4,4′-dihi Hydroxydiphenyl ethers such as loxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 4,4′-diamino-2,2′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′- Dihydroxydiphenyl sulfones such as dihydroxydiphenyl sulfone, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfone, 4,4′-diamino-2,2′-dihydroxydiphenyl sulfone, 3,3′-diamino-4 , 4′-dihydroxydiphenyl sulfide, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfide, dihydroxydiphenyl sulfides such as 4,4′-diamino-2,2′-dihydroxydiphenyl sulfide, 3,3 ′ -Diamino-4,4'-dihydroxydiph Dihydroxy diphenyl sulfoxides such as phenyl sulfoxide, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfoxide, 4,4′-diamino-2,2′-dihydroxydiphenyl sulfoxide, 2,2-bis [4- ( Bis [(hydroxyphenyl) phenyl] alkane compounds such as 4-amino-3-hydroxyphenoxy) phenyl] propane and bis (hydroxy) such as 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl Phenoxy) biphenyl compounds, bis [(hydroxyphenoxy) phenyl] sulfone compounds such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone, 4,4′-diamino-3,3 '-Dihydroxydiphenylmethane, 4,4'-diamino-2,2'-dihydroxy Bis (hydroxyphenoxy) biphenyl compounds such as phenylmethane, 2,2-bis [3-amino-4-carboxyphenyl] propane, 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,4-cyclohexanebis (methylamine), 4,4′-diaminodicyclohexylmethane, (4-amino-3-methylcyclohexyl) ) Methane, 5-amino-1,3,3-trimethylcyclohexanemethylamine, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.0 ^2,6 ] decane, 2, Alicyclic diamines such as 5 (6) -bis (aminomethyl) bicyclo [2.2.1] heptane and 1,3-diaminoadamantane , Tetramethylenediamine, hexamethylenediamine, 1,12-aliphatic diamines diamino dodecane, polyoxyethylene polyoxyalkylene diamines, such as polyoxyethylene diamine or polyoxypropylene diamines and the like.

  Particularly preferably, m-phenylenediamine, 3,3′-diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- ( 3-aminophenoxy) phenyl] methane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) Heat resistance and electrical insulation reliability of polyimide resin obtained by using aromatic diamine such as benzene), 1,4-bis (4-aminophenoxybenzene) or 1,3-bis (4-aminophenoxybenzene) It is preferable at the point which can improve.

  The raw materials represented by the above general formula (2), general formula (3) and general formula (4) may be used alone or in combination of two or more.

  The method for synthesizing the hydroxyl-terminated imide oligomer represented by the general formula (1) of the present invention comprises a tetracarboxylic dianhydride represented by the general formula (2) and an amino alcohol represented by the general formula (3) in a molar ratio. Preferably, (number of moles of tetracarboxylic dianhydride / number of moles of amino alcohol) = 0.25 to 0.75, more preferably 0.3 to 0.7, and particularly preferably 0.4 to It can be obtained by reacting within the range of 0.6.

  By controlling the addition amount within the above range and reacting, it is preferable because the hydroxyl-terminated imide oligomer can be obtained without generation of unreacted products and by-products. When it is smaller than 0.25, a large amount of unreacted aminoethanol remains in the system, and when used in the photosensitive resin composition, heat resistance and electrical insulation reliability may be lowered. Moreover, when larger than 0.75, the yield of the target hydroxyl-terminated imide oligomer may become low.

  Moreover, when using the diamino compound shown by General formula (4) as a chain extender, it reacts by adding when reacting tetracarboxylic dianhydride and amino alcohol, However, It is not restricted to this . The addition amount of the diamino compound is preferably (molar ratio of tetracarboxylic dianhydride) / (molar number of amino alcohol + molar number of diamino compound) = 0.25 to 1.0, more preferably in molar ratio. Can be obtained by reacting in the range of 0.3 to 0.9, particularly preferably in the range of 0.4 to 0.8.

  By controlling the addition amount within the above range and reacting, it is preferable because the molecular weight of the hydroxyl group-terminated imide oligomer can be controlled within the optimum range. When it is smaller than 0.25, a large amount of unreacted material remains in the system, and thus when used in the photosensitive resin composition, the heat resistance and the electrical insulation reliability may be lowered. Moreover, when larger than 1.0, the molecular weight of a hydroxyl-terminated imide oligomer will become large, and when it uses for the photosensitive resin composition, developability may fall.

  In the hydroxyl group-terminated imide oligomer, each component is dissolved in an organic solvent at 100 ° C. or lower, preferably 80 ° C. or lower, and then heated at 100 ° C. or higher and 300 ° C. or lower, preferably 150 ° C. or higher and 250 ° C. or lower. Can be obtained while the imidization reaction proceeds. Various catalysts may be used in the imidization reaction.

  Examples of the organic solvent used when the hydroxyl group-terminated imide oligomer is reacted include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, Acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or p- Phenolic solvents such as cresol, xylenol, halogenated phenol, catechol, or hexamethylphosphoramide, γ-butyrolactone, methylmonoglyme (1,2-dimethoxyethane), methyldiglyme (bis (2-methoxyether) ether ) Methyltriglyme (1,2-bis (2-methoxyethoxy) ethane), methyltetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), Symmetric glycol diethers such as ethyl diglyme (bis (2-ethoxyethyl) ether) and butyl diglyme (bis (2-butoxyethyl) ether), methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl Acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate (also known as carbitol acetate, 2- (2-butoxyethoxy) ethyl acetate)), diethylene glycol monobutyl Acetates such as ether acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, and dipropylene Glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripylene glycol n-propyl ether, propylene glycol phenyl ether , Dipropylene glycol dimethyl ether, 1,3-dioxy Can run, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, also possible to use diethylene glycol monobutyl ether or solvent ethers such as ethylene glycol monoethyl ether. If necessary, low-boiling hexane, acetone, toluene, xylene and the like can be used in combination. The solvent may be used alone or in combination of two or more. Among them, symmetric glycol diethers are particularly preferable because of high solubility of oligomers.

  The amount of the organic solvent used in the reaction is preferably such that the solute weight concentration in the reaction solution is 5 wt% or more and 80 wt% or less, more preferably 10 wt% or more and 60 wt% or less. Is 15 to 50% by weight, a uniform and transparent hydroxyl-terminated imide oligomer solution can be obtained. When the solution concentration is 5% by weight or less, the contact efficiency of each component is deteriorated, the reaction is difficult to occur, and the reaction rate may be reduced. When the solution concentration is 80% by weight or more, each component is not completely dissolved in the organic solvent, a uniform reaction does not occur, and a desired structural substance may not be obtained.

  The hydroxyl group-terminated imide oligomer produced as described above is preferable because it can be handled as a hydroxyl group-terminated imide oligomer solution as it is in the reaction solution, so that handling in the next step is facilitated and the reaction can proceed uniformly.

<(B) polyol compound>
The polyol compound of the present invention is not the above-mentioned (A) hydroxyl group-terminated imide oligomer but a compound having at least two hydroxyl groups in the molecule. That is, it is a polydiol compound containing no imide ring in the molecule. If it is these structures, it will not specifically limit.

  Examples of the polyol compound of the present invention include polyalkylene polyol, poly (oxyalkylene) glycol such as poly (oxypropylene) glycol and poly (oxytetramethylene) glycol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, diene polyol, Examples include olefinic polyols, which can be used alone or in combination of two or more. Among these, a polyalkylene polyol and / or a polycarbonate polyol is preferable, and is preferable in that the flexibility of the photosensitive resin composition can be improved. More preferably, it is a polycarbonate polyol, and is preferable in terms of further improving chemical resistance in addition to the flexibility of the photosensitive resin composition. The polycarbonate polyol is a polyol compound containing at least one carbonate group, and is a polyol compound having a repeating unit having a carbonate skeleton represented by the general formula (5).

（式中Ｒ_２は２価の有機基を示す。ｑは自然数である。）

(In the formula, R ₂ represents a divalent organic group. Q is a natural number.)

  For example, alkylene such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,12-dodecanediol, etc. It can be obtained by reacting a diol alone or in combination of two or more with a carbonate compound such as dialkyl carbonate, alkylene carbonate or diphenyl carbonate.

  The number average molecular weight of the polycarbonate polyol is preferably in the range of 500 to 5000, more preferably 750 to 2500 in terms of polystyrene, thereby improving the chemical resistance and flexibility of the resulting photosensitive resin composition. It is preferable in that it can be performed. When the number average molecular weight is less than 500, the flexibility of the obtained polyimide resin is lowered, and when it is 5000 or more, the developability may be lowered.

  Examples of the polycarbonate polyol include trade names PCDL T-4671, T-4672, T-4611, T-4692, T-5650J, T-5651, T-5651, T-6601, T manufactured by Asahi Kasei Chemicals Corporation. -6002, trade name Plaxel CD CD205, CD205PL, CD205HL, CD210, CD210PL, CD210HL, CD220, CD220PL, CD220HL, trade names Kuraray Polyol C-1015N, C-1050, C, manufactured by Daicel Chemical Industries, Ltd. -1065N, C-1090, C-2015N, C-2065N, C-2090, and those sold by Nippon Polyurethane Industry Co., Ltd. under the trade names NIPPOLAN 981, 980R, 982R. It can be used in or in combination of two or more.

<(C) (Ca) Compound having at least one blocked isocyanate group and at least one photosensitive group in the molecule and / or (Cb) Compound having at least one hydroxyl group and at least one hydroxyl group in the molecule>
The compound having at least one blocked isocyanate group and at least one photosensitive group in the (Ca) molecule of the present invention is not particularly limited as long as it is a compound having at least one blocked isocyanate group and at least one photosensitive group. . The blocked isocyanate of the present invention is a compound that is inactive at room temperature and regenerates the isocyanate group by dissociating the blocking agent such as oximes, diketones, phenols, caprolactams, etc. when heated. The photosensitive group of the present invention is a functional group that can react in the presence of radicals generated from light or the like. A compound having at least one blocked isocyanate group and at least one (meth) acryloyl group in the molecule is preferable, and a compound having a structure represented by the following general formula (6) is more preferable.

（式中、Ｒ_３は２価の有機基を示し、Ｒ_４は水素もしくは、アルキル基を示す。ｍは１〜３の整数である。）

(In the formula, R ₃ represents a divalent organic group, R ₄ represents hydrogen or an alkyl group, and m is an integer of 1 to _3. )

  Examples of the compound having at least one blocked isocyanate group and at least one (meth) acryloyl group in the (Ca) molecule of the present invention include 2- (meth) acryloyloxyethyl isocyanate and 1,1- (bisacryloyloxy). Methyl) ethyl isocyanate, 2- (2-methacryloyloxyethyloxy) ethyl isocyanate and the like can be mentioned, and these can be used alone or in combination of two or more. Examples of the compound having a blocked isocyanate group and at least one (meth) acryloyl group in the molecule include those commercially available under the trade names Karenz AOI, MOI, BEI, and EG manufactured by Showa Denko K.K. . By using a compound having a blocked isocyanate group and at least one (meth) acryloyl group in these molecules, the photosensitivity and chemical resistance of the photosensitive resin composition are improved.

  The compound having at least one hydroxyl group and at least one photosensitive group in the molecule (Cb) of the present invention is not particularly limited as long as it is a compound having at least one hydroxyl group and at least one photosensitive group in the molecule. The photosensitive group described here is a functional group capable of reacting in the presence of radicals generated from light or the like. Preferably, there is a compound having at least one hydroxyl group and at least one (meth) acryloyl group in the molecule. More preferred is a compound having a structure represented by the following general formula (7).

（式中、Ｒ_５は２価の有機基を示し、Ｒ_６は水素もしくは、アルキル基を示す。ｍは１〜３の整数である。）

(In the formula, R ₅ represents a divalent organic group, R ₆ represents hydrogen or an alkyl group, and m is an integer of 1 to 3.)

  Examples of the compound having at least one hydroxyl group and at least one (meth) acryloyl group in the (Cb) molecule of the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-1-acryloxy-3-methacryloxypropane, o-phenylphenol glycidyl ether (meth) acrylate, polyethylene glycol mono (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 4-hydro Ciphenyl (meth) acrylate, 2- (4-hydroxyphenyl) ethyl (meth) acrylate, N-methylol acrylamide, 3,5-dimethyl-4-hydroxybenzyl acrylamide, etc. may be mentioned, and these may be used alone or in combination of two or more. Can be used in combination. By using a compound having a hydroxyl group and at least one (meth) acryloyl group in these molecules, the photosensitivity and chemical resistance of the photosensitive resin composition are improved.

<(D) Block isocyanate compound>
The (D) blocked isocyanate compound of the present invention is a compound having at least one blocked isocyanate group and at least one photosensitive group in the molecule, or a compound having at least one hydroxyl group and at least one photosensitive group in the molecule. Rather, it is inactive at room temperature, and when heated, it is a compound that dissociates blocking agents such as oximes, diketones, phenols, caprolactams and regenerates isocyanate groups, for example, hexamethylene diisocyanate series As block isocyanate, trade names Duranate 17B-60PX, Duranate TPA-B80E, Duranate MF-B60X, Duranate MF-K60X, Duranate E402-B80T, Mitsui Chemicals Polyurethane Co., Ltd. manufactured by Asahi Kasei Chemicals Corporation Brand names Takenate B-830, Takenate B-815N, Takenate B-846N, Takenate B-882N, Nippon Polyurethane Industry Co., Ltd. trade names Coronate AP-M, Coronate 2503, Coronate 2507, Coronate 2513, Coronate 2515 Millionate MS-50 and the like.

<(E) Photosensitive compound>
The photosensitive compound (E) in the present invention is a compound having at least one blocked isocyanate group and at least one photosensitive group in the molecule, or a compound having at least one hydroxyl group and at least one photosensitive group in the molecule. Instead, it is a compound that has at least one (meth) acryloyl group in the molecule, and a (meth) acryloyl group reacts with a photopolymerization initiator to form a chemical bond.

  For example, ethoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol F di (meth) acrylate, polyethylene glycol di (meth) acrylate (n = 2-30), polypropylene glycol di (meth) acrylate (n = 2-30) ), 1,4-cyclohexanedimethanol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxylated tomethylolpropane tri (meth) acrylate, propoxylated totimethy Propanetri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, ethoxylated pentathritol tetra (meth) acrylate, propoxylated pentathritol tetra (meth) acrylate, caprolactone-modified ditrimethylolpropane tetra (meth) acrylate, ethoxy Dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like, but are not limited thereto. In particular, the number of repeating units of EO (ethylene oxide) contained in one molecule of ethoxylated di (meth) acrylate is preferably in the range of 2-50, more preferably in the range of 2-40. By using the EO repeating unit in the range of 2 to 50, the solubility in an aqueous developer typified by an alkaline aqueous solution is improved, and the development time is shortened. In addition, stress hardly remains in the cured film obtained by curing the photosensitive resin composition. For example, among printed wiring boards, when laminated on a flexible printed wiring board based on a polyimide resin, the printed wiring board warps. Features such as being able to be suppressed.

  In particular, it is preferable to use the EO-modified di (meth) acrylate in combination with a photosensitive compound having 3 or more (meth) acrylic groups in order to improve photosensitivity and developability.

  Further, 2-hydroxy-3-phenoxypropyl (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate, ω-carboxy-polycaprolactone mono (meth) acrylate, (meth) acrylic acid dimer, pentaesitol tris and Those having a hydroxyl group or a carbonyl group in the molecular structure skeleton such as tetra (meth) acrylate are also preferably used.

  In addition, any photosensitive compound such as an epoxy (meth) acrylate resin, a polybasic acid anhydride-modified epoxy (meth) acrylate resin, a urethane (meth) acrylate resin, or a polyester (meth) acrylate resin may be used.

<(F) Photopolymerization initiator>
Examples of the photopolymerization initiator (F) in the present invention include benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and 1-hydroxycyclohexyl phenyl ketone, and ketal compounds such as benzyl dimethyl ketal and benzyl diethyl ketal; , 2′-diethoxyacetophenone, 2,2′-dibutoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) ) Phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methyl Acetophenone compounds such as propane, benzophenone, o Methyl benzoylbenzoate, 3,3′-dimethyl-4-methoxybenzophenone, [4- (methylphenylthio) phenyl] phenylmethane, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) ) Benzophenone compounds such as benzophenone and 4-methoxy-4′-dimethylaminobenzophenone, thioxanthone compounds such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and 2,4-diethylthioxanthone, ethyl-4-dimethylaminobenzoate Aminobenzoate compounds such as 2-ethylhexyl-4-dimethylaminobenzoate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1- Α-aminoalkyl such as 4-morpholinophenyl) butanone-1,2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one Phenone compounds, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4- Phosphine oxide compounds such as trimethylpentylphosphine oxide, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6 -(2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) Muesuteru compounds, etc. These can be used alone or in combinations of two or more.

<(G) Thermosetting compound>
The (G) thermosetting compound in the present invention is a compound having at least one blocked isocyanate group and at least one photosensitive group in the molecule, and a compound having at least one hydroxyl group and at least one photosensitive group in the molecule. Alternatively, it is not a blocked isocyanate but a compound that forms a crosslinked structure by heating and functions as a thermosetting agent. Examples include, but are not limited to, epoxy resins, isocyanate compounds, oxetane compounds, and the like. The said thermosetting compound can be used individually or in combination of 2 or more types. Among these, it is preferable to use an epoxy resin. By containing a thermosetting compound, heat resistance can be imparted to a cured film obtained by curing the photosensitive resin composition, and adhesion to a conductor such as a metal foil or a circuit board can be imparted.

  The epoxy resin is a compound containing at least two epoxy groups in the molecule. For example, as a bisphenol A type epoxy resin, product names jER828, jER1001, jER1002, and ADEKA manufactured by Japan Epoxy Resin Co., Ltd. Trade names of Adeka Resin EP-4100E, Adeka Resin EP-4300E, trade names RE-310S and RE-410S manufactured by Nippon Kayaku Co., Ltd., trade names Epicron 840S, Epicron 850S, Epicron 1050 and Epicron 7050 manufactured by Dainippon Ink, Inc. The product names Epototo YD-115, Epototo YD-127, Epototo YD-128, and bisphenol F type epoxy resins manufactured by Toto Kasei Co., Ltd. are trade names jER806 and jER8 manufactured by Japan Epoxy Resin Co., Ltd. 7. Trade names Adeka Resin EP-4901E, Adeka Resin EP-4930, Adeka Resin EP-4950, manufactured by Adeka Co., Ltd., trade names RE-303S, RE-304S, RE-403S, RE-404S, manufactured by Nippon Kayaku Co., Ltd. Product names Epicron 830 and Epicron 835 manufactured by Nippon Ink Co., Ltd. Product names Epototo YDF-170, Epototo YDF-175S, Epototo YDF-2001, and Bisphenol S type epoxy resin manufactured by Toto Kasei Co., Ltd. Trade name Epiklon EXA-1514 manufactured by Japan, Hydrogenated bisphenol A type epoxy resin includes Japan Epoxy Resin Co., Ltd. trade names jERYX8000, jERYX8034, jERYL7170, ADEKA Co., Ltd. trade names Adeka Resin P-4080E, Dainippon Ink Co., Ltd. trade name Epicron EXA-7015, Toto Kasei Co., Ltd. trade name Epototo YD-3000, Epototo YD-4000D, biphenyl type epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd. Trade names jERYX4000, jERYL6121H, jERYL6640, jERYL6677, trade names NC-3000 and NC-3000H manufactured by Nippon Kayaku Co., Ltd., and phenoxy type epoxy resins include trade names jER1256, jER4250, jER4275, and naphthalene manufactured by Japan Epoxy Resins Co., Ltd. As the type epoxy resin, trade names “Epicron HP-4032”, “Epicron HP-4700”, “Epicron HP-4200” manufactured by Dainippon Ink Co., Ltd., “NC-” manufactured by Nippon Kayaku Co., Ltd. As 7000L, phenol novolac type epoxy resin, trade names jER152 and jER154 manufactured by Japan Epoxy Resin Co., Ltd., trade name EPPN-201-L manufactured by Nippon Kayaku Co., Ltd., trade name Epicron N- manufactured by Dainippon Ink Co., Ltd. 740, Epicron N-770, Toto Kasei Co., Ltd. trade name Epototo YDPN-638, Cresol novolac type epoxy resin, Nippon Kayaku Co., Ltd. trade names EOCN-1020, EOCN-102S, EOCN-103S, EOCN -104S, trade names manufactured by Dainippon Ink Co., Ltd. Epicron N-660, Epicron N-670, Epicron N-680, Epicron N-695, and Trisphenolmethane type epoxy resin are trade names of Nippon Kayaku Co., Ltd. EPPN-501H, EPP -501HY, EPPN-502H, dicyclopentadiene type epoxy resin, Nippon Kayaku Co., Ltd. trade name XD-1000, Dainippon Ink Co., Ltd. trade name Epicron HP-7200, amine type epoxy resin, Product names of Toto Kasei Co., Ltd. Epototo YH-434, Epototo YH-434L, and flexible epoxy resins include trade names jER871, jER872, jERYL7175, jERYL7217, manufactured by Dainippon Ink, Inc. As the name Epicron EXA-4850, urethane-modified epoxy resin, trade names of Adeka Resin EPU-6, Adeka Resin EPU-73, Adeka Resin EPU-78-11 manufactured by ADEKA Corporation, and ADE Co., Ltd. as ADE Co., Ltd. Product names Adeka Resin EPR-4023, Adeka Resin EPR-4026, Adeka Resin EPR-1309, and chelate-modified epoxy resins manufactured by A include Adeka Resin EP-49-10, Adeka Resin EP-49-20, etc., manufactured by ADEKA Corporation. It is done.

  The isocyanate compound is a compound having two isocyanate groups in the molecule. For example, aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, tetramethylxylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, etc. Aliphatic diisocyanates such as alicyclic diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate, and the like can be used alone or in combination of two or more. Among these diisocyanate compounds, preferably, tolylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate is used to improve the heat resistance and electrical insulation reliability of the resulting polyimide resin.

  Although it does not specifically limit as a hardening | curing agent of the said thermosetting compound in the photosensitive resin composition of this invention, For example, phenol resins, such as a phenol novolak resin, a cresol novolak resin, a naphthalene type phenol resin, an amino resin, and a urea resin , Melamine, dicyandiamide and the like, and these can be used alone or in combination of two or more.

  Further, the curing accelerator is not particularly limited, but for example, phosphine compounds such as triphenylphosphine; amine compounds such as tertiary amine, trimethanolamine, triethanolamine and tetraethanolamine; 1,8- Borate compounds such as diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate, imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-un Imidazoles such as decylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole; 2-methylimidazoline, 2- Ethyl imidazoline, 2 Imidazolines such as isopropylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline; 2,4-diamino-6- [2′-methylimidazolyl- ( 1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2 ′ Examples include azine-based imidazoles such as -ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, and these can be used alone or in combination of two or more.

<The ratio of the structural component of the photosensitive resin composition>
The photosensitive resin composition of the present invention comprises at least (A) a hydroxyl group-terminated imide oligomer, (B) a polycarbonate polyol, and (C) ((Ca) a compound having an isocyanate group and at least one (meth) acryloyl group in the molecule. And / or ((Cb) a compound having a hydroxyl group and at least one (meth) acryloyl group in the molecule), (D) a blocked isocyanate compound, (E) a photosensitive compound, (F) a photopolymerization initiator, and (G ) Obtained by reacting a thermosetting compound. The number of moles of the component (A), the component (B), the component (Ca), the component (Cb), and the component (D) in the photosensitive resin composition is respectively determined as (A), (B), (Ca ), (Cb), (D), the mixing molar ratio is preferably [(A) + (B) + (Cb)] moles of hydroxyl group / [(Ca) + (D)]. The number of moles of the blocked isocyanate group is 0.5 to 2.0, more preferably 0.75 to 1.75, and particularly preferably 0.9 to 1.5.

  By controlling the addition amount within the above range and reacting, the molecular weight of the photosensitive resin composition can be controlled within the optimum range, which is preferable. When it is smaller than 0.5 or larger than 2.0, a large amount of unreacted substances remain in the system, so that when used in the photosensitive resin composition, heat resistance and electrical insulation reliability may be lowered. is there.

  The blending amount of the component (A) and the component (B) in the photosensitive resin composition of the present invention is preferably (A) component parts by weight / (B) component parts by weight = 0.10 to 9.00. More preferably, it is 0.40-2.30, Most preferably, it is 0.65-1.50.

  By controlling the addition amount within the above range and reacting, it is preferable because the flexibility and various characteristics of the photosensitive resin composition can be adjusted to the optimum range. If it is less than 0.1, the coating film after exposure of the photosensitive resin composition becomes brittle and cracks may occur. If it is greater than 9.0, when the photosensitive resin composition is dried, the stickiness, heat resistance, and electrical insulation reliability of the coated film after drying may decrease. Therefore, by setting the addition amount within the above range, it becomes possible to adjust various characteristics of the photosensitive resin composition to an optimal range.

  The blending amounts of the component (A), the component (B), the component (Ca), the component (Cb), the component (D), the component (E) and the component (G) in the photosensitive resin composition of the present invention are preferably (E) component is 5 to 500 parts by weight, (F) component is 0.1 to 20 parts by weight, and (G) component is 0.5 to 100 parts per 100 parts by weight of the total of components (A) to (D). Parts by weight.

  By mix | blending in the said range, the photosensitivity of the photosensitive resin composition, the heat resistance of a cured film, chemical resistance, a softness | flexibility, and electrical insulation reliability improve.

  When the amount of component (E) is less than the above range, it may be difficult to obtain contrast when the photosensitive resin composition is exposed and developed. Moreover, in the case of the compounding quantity more than the said range, the coating film after exposure of the photosensitive resin composition will become weak, and a crack may generate | occur | produce. Therefore, by making the addition amount within the above range, it becomes possible to adjust the resolution and the suitability of the production process of the photosensitive resin composition to an optimum range.

  When the amount of component (F) is less than or equal to the above range, the curing reaction of the photosensitive compound during light irradiation hardly occurs and curing may be insufficient. Moreover, in the case of the compounding quantity more than the said range, the hardening reaction of the photosensitive compound at the time of light irradiation may progress too much and may be in an overexposed state. Therefore, it becomes possible to advance the photocuring reaction of the photosensitive resin composition efficiently by making the addition amount within the above range.

  When the amount of component (G) is less than the above range, the heat resistance, flexibility, chemical resistance, and electrical insulation reliability of the cured film of the photosensitive resin composition may decrease. In addition, when the blending amount is in the above range or more, when the photosensitive resin composition is applied onto a substrate such as a printed wiring board and dried, the thermosetting reaction is accelerated during drying, and is typically represented by an alkaline aqueous solution. In some cases, the solubility in an aqueous developer is reduced. Therefore, by making the addition amount within the above range, the thermosetting reaction of the photosensitive resin composition is controlled and the heat resistance, chemical resistance and electrical insulation reliability of the cured film of the photosensitive resin composition are improved. Is possible.

  In the photosensitive resin composition of the present invention, an inorganic filler can be used for the purpose of improving the adhesion and the hardness of the cured film. The inorganic filler is not particularly limited, and examples thereof include barium sulfate, barium titanate, talc, ultrafine anhydrous silica, synthetic silica, natural silica, calcium carbonate, magnesium carbonate, aluminum oxide, aluminum hydroxide and the like. These can be used alone or in combination of two or more.

  In the photosensitive resin composition of the present invention, additives such as an antifoaming agent, a leveling agent, a flame retardant, a colorant, an adhesion imparting agent, and a polymerization inhibitor can be used as necessary. These additives are not particularly limited. For example, as an antifoaming agent, a silicon compound, an acrylic compound, as a leveling agent, a silicon compound, an acrylic compound, and as a flame retardant, a phosphate ester Compounds, phosphazene compounds, colorants include phthalocyanine compounds, azo compounds, carbon black, titanium oxide, and adhesion promoters include silane coupling agents, triazole compounds, tetrazole compounds, triazine compounds, polymerization Examples of the inhibitor include hydroquinone and hydroquinone monomethyl ether, and these can be used alone or in combination of two or more.

  The photosensitive resin composition of the present invention includes, for example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N, N-dimethylacetamide, Acetamide solvents such as N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or p-cresol, xylenol, halogenated phenol , Phenol solvents such as catechol, or hexamethylphosphoramide, γ-butyrolactone, methylmonoglyme (1,2-dimethoxyethane), methyldiglyme (bis (2-methoxyether) ether), methyltriglyme (1 , 2-Bis (2-methoxy Toxi) ethane), methyltetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyldiglyme (bis (2-ethoxyethyl) ether) , Symmetric glycol diethers such as butyl diglyme (bis (2-butoxyethyl) ether), γ-butyrolactone, N-methyl-2-pyrrolidone, methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate , Propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate (also known as carbitol acetate, 2- (2-butoxyethoxy) ethyl acetate)), diethylene glycol monobutyl Acetates such as ruether acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, and dipropylene Glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripylene glycol n-propyl ether, propylene glycol phenyl ether , Dipropylene glycol dimethyl ether, 1,3-di Kisoran, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, various organic solvents such as ethers such as ethylene glycol monoethyl ether can be used. If necessary, low-boiling hexane, acetone, toluene, xylene and the like can be used in combination.

  Among these, symmetric glycol diethers are particularly preferable because the solubility of the photosensitive resin composition is high.

  The amount of the organic solvent used in the photosensitive resin composition solution of the present invention is preferably (A) component, (B) component, (C) component, (D) component, (E) component, (F) component, The organic solvent is 10 parts by weight or more and 100 parts by weight or less with respect to 100 parts by weight of the total solid content of the component (G).

  By adjusting the solid content of the photosensitive resin composition solution within the above range, the viscosity of the photosensitive resin composition can be controlled within the optimum range when coating, and the film thickness after coating and drying is reduced. The rate is reduced.

  The photosensitive resin composition of the present invention is obtained by uniformly mixing the components (A) to (G). As a method of uniformly mixing, for example, a general kneading apparatus such as a three roll or bead mill apparatus may be used for mixing. Moreover, when the viscosity of a solution is low, you may mix using a general stirring apparatus.

<Photosensitive resin composition>
After preparing the photosensitive resin composition solution by dissolving the photosensitive resin composition of the present invention directly or in the above organic solvent, the pattern can be formed as follows. First, the photosensitive resin composition is applied onto a substrate and dried to remove the organic solvent. The substrate can be applied by screen printing, roller coating, curtain coating, spray coating, spin coating using a spinner, or the like. The coating film (preferably having a thickness of 5 to 100 μm) is dried at 120 ° C. or lower, preferably 40 to 100 ° C. Next, exposure is performed. After drying, a negative photomask is placed on the dried coating film and irradiated with actinic rays such as ultraviolet rays, visible rays, and electron beams. Next, the pattern can be obtained by washing the unexposed portion with a developing solution using various methods such as shower, paddle, dipping or ultrasonic waves. Since the time until the pattern is exposed varies depending on the spray pressure and flow velocity of the developing device and the temperature of the developer, it is preferable to find the optimum device conditions as appropriate.

  As the developer, an aqueous alkali solution is preferably used. The developer is water-soluble such as methanol, ethanol, n-propanol, isopropanol, N-methyl-2-pyrrolidone and the like. An organic solvent may be contained. Examples of the alkaline compound that gives the alkaline aqueous solution include hydroxides, carbonates, hydrogen carbonates, amine compounds, and the like of alkali metals, alkaline earth metals, or ammonium ions, specifically sodium hydroxide. , Potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium Hydroxide, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylethanolamine, triethanolamine, triisopropanolamine, trii Propylamine and the like, aqueous solution compound other than this as long as it exhibits basicity can also be used. The concentration of the alkaline compound that can be suitably used in the development step of the photosensitive resin composition of the present invention is preferably 0.01 to 10% by weight, particularly preferably 0.05 to 5% by weight. Further, the temperature of the developer depends on the composition of the photosensitive resin composition and the composition of the developer, and is generally 0 ° C. or higher and 80 ° C. or lower, more generally 20 ° C. or higher and 50 ° C. or lower. It is preferable to use it.

  The pattern formed by the development step is rinsed to remove unnecessary developer residue. Examples of the rinsing liquid include water and acidic aqueous solutions.

  Next, thermosetting is performed. That is, a heat-cured cured film can be obtained. Although a cured film is determined in consideration of wiring thickness etc., it is preferable that thickness is about 2-50 micrometers. The final curing temperature at this time is desired to be cured by heating at a low temperature for the purpose of preventing oxidation of the wiring and the like and not reducing the adhesion between the wiring and the substrate. The heat curing temperature at this time is preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower, and particularly preferably 130 ° C. or higher and 190 ° C. or lower. When the final heating temperature becomes high, the wiring may be oxidized and deteriorated. In this way, an insulating film can be obtained by photosensitive and thermosetting the photosensitive resin composition.

A pattern comprising an insulating film (cured film) formed from the photosensitive resin composition of the present invention is excellent in heat resistance, electrical and mechanical properties, and particularly excellent in flexibility. For example, the insulating film of the present invention preferably has a thickness of about 2 to 50 μm and a resolution of at least 10 μm after photocuring, and particularly a resolution of about 10 to 1000 μm. For this reason, the insulating film of the present invention is particularly suitable as an insulating material for a high-density flexible substrate. Furthermore, it is used for various photo-curing type wiring coating protective agents, photosensitive heat-resistant adhesives, electric wire / cable insulation coatings and the like.
In addition, even if the photosensitive film obtained by apply | coating the said photosensitive resin composition solution to the base-material surface and drying is used for this invention, the same insulating material can be provided.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

(Synthesis Example 1)
In a light-shielded reaction vessel, 52.07 g (0.10 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 6.11 g (0.20 mol) of 2-aminoethanol Was added to 38.79 g of 1,2-bis (2-methoxyethoxy) ethane, heated to 130 ° C. under a nitrogen stream, and stirred uniformly for 1 hour. Next, the temperature was raised to 180 ° C. and heated under reflux for 2 hours to carry out an imidization reaction. This solution was cooled to room temperature to obtain a hydroxyl-terminated imide oligomer. The solid content concentration of this solution is 60% by weight. The number average molecular weight of this imide oligomer by GPC measurement was 546. In the obtained compound, the hydroxyl-terminated imide oligomer is abbreviated as A1.

(Synthesis Example 2)
In a reaction vessel, 31.04 g (0.10 mol) of 3,3 ′, 4,4′-oxydiphthalic dianhydride and 6.11 g (0.20 mol) of 2-aminoethanol were added to 1,2-bis (2-methoxyethoxy). ) It was charged into 24.76 g of ethane, heated to 130 ° C. under a nitrogen stream, and stirred uniformly for 1 hour. Next, the temperature was raised to 180 ° C. and heated under reflux for 2 hours to carry out an imidization reaction. This solution was cooled to room temperature to obtain a hydroxyl-terminated imide oligomer. The solid content concentration of this solution is 60% by weight. The number average molecular weight of this imide oligomer by GPC measurement was 336. In the obtained compound, the hydroxyl-terminated imide oligomer is abbreviated as A2.

(Synthesis Example 3)
In a reaction vessel, 104.14 g (0.20 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 29.10 g of 1,3-bis (3-aminophenoxy) benzene (0.10 mol) and 6.11 g (0.20 mol) of 2-aminoethanol were added to 92.90 g of 1,2-bis (2-methoxyethoxy) ethane, and the temperature was raised to 130 ° C. under a nitrogen stream. Stirred uniformly over time. Next, the temperature was raised to 180 ° C. and heated under reflux for 2 hours to carry out an imidization reaction. This solution was cooled to room temperature to obtain a hydroxyl-terminated imide oligomer. The number average molecular weight of this imide oligomer by GPC measurement was 1322. The solid content concentration of this solution is 60% by weight. In the obtained compound, the hydroxyl-terminated imide oligomer is abbreviated as A3.

(Synthesis Example 4)
45.48 g of imide oligomer solution A1 in a reaction vessel, 50.00 g (0.050 mol) of polycarbonate diol (manufactured by Asahi Kasei Chemicals, trade name PCDL T5651, number average molecular weight: 1000), 2-methacryloyloxyethyl isocyanate (Showa Denko) Co., Ltd., trade name Karenz MOI) 6.21 g (0.040 mol), blocked isocyanate (manufactured by Asahi Kasei Chemicals Corporation, trade name Duranate MF-K60X, effective NCO%: 6.6%, solid content 60 wt%, viscosity 250 mPa S / 25 ° C.) 169.74 g, 1,2-bis (2-methoxyethoxy) ethane 86.19 g, dibutyltin dilaurate 0.185 g, hydroquinone monomethyl ether 0.185 g were charged at room temperature under an air stream. Stir for 1 hour. The solid content concentration of this solution is 50% by weight. The obtained composition is abbreviated as polyimide resin composition B1.

(Synthesis Example 5)
27.96 g of the imide oligomer solution A2 in a reaction vessel, 50.00 g (0.050 mol) of polycarbonate diol (manufactured by Asahi Kasei Chemicals Corporation, trade name PCDL T5651, number average molecular weight: 1000), 2-methacryloyloxyethyl isocyanate (Showa Denko) Co., Ltd., trade name Karenz MOI) 6.21 g (0.040 mol), blocked isocyanate (manufactured by Asahi Kasei Chemicals Corporation, trade name Duranate MF-K60X, effective NCO%: 6.6%, solid content 60 wt%, viscosity 250 mPa S / 25 ° C.) 169.74 g, 1,2-bis (2-methoxyethoxy) ethane 79.08 g, dibutyltin dilaurate 0.175 g, hydroquinone monomethyl ether 0.175 g were charged at room temperature under an air stream. Stir for 1 hour. The solid content concentration of this solution is 50% by weight. The obtained composition is abbreviated as polyimide resin composition B2.

(Synthesis Example 6)
110.13 g of imide oligomer solution A3, 50.00 g (0.050 mol) of polycarbonate diol (manufactured by Asahi Kasei Chemicals Corporation, trade name PCDL T5651, number average molecular weight: 1000), 2-methacryloyloxyethyl isocyanate (Showa Denko) Co., Ltd., trade name Karenz MOI) 6.21 g (0.040 mol), blocked isocyanate (manufactured by Asahi Kasei Chemicals Corporation, trade name Duranate MF-K60X, effective NCO%: 6.6%, solid content 60 wt%, viscosity 250 mPa S / 25 ° C.) 169.74 g, 1,2-bis (2-methoxyethoxy) ethane 111.95 g, dibutyltin dilaurate 0.224 g, hydroquinone monomethyl ether 0.224 g were charged at room temperature under an air stream. Stir for 1 hour It was. The solid content concentration of this solution is 50% by weight. The obtained composition is abbreviated as polyimide resin composition B3.

(Synthesis Example 7)
45.48 g of imide oligomer solution A1 in a reaction container, polycarbonate diol (Asahi Kasei Chemicals Corporation, trade name PCDL T5652, number average molecular weight: 2000) 100.00 g (0.050 mol), 2-methacryloyloxyethyl isocyanate (Showa Denko) Co., Ltd., trade name Karenz MOI) 6.21 g (0.040 mol), blocked isocyanate (manufactured by Asahi Kasei Chemicals Corporation, trade name Duranate MF-K60X, effective NCO%: 6.6%, solid content 60 wt%, viscosity 250 mPa S / 25 ° C.) 169.74 g, 1,2-bis (2-methoxyethoxy) ethane 86.09 g, dibutyltin dilaurate 0.235 g, hydroquinone monomethyl ether 0.235 g were charged at room temperature under an air stream. Stir for 1 hour. The solid content concentration of this solution is 50% by weight. The obtained composition is abbreviated as polyimide resin composition B4.

(Synthesis Example 8)
45.48 g of imide oligomer solution A1 in a reaction vessel, 50.00 g (0.050 mol) of polycarbonate diol (manufactured by Asahi Kasei Chemicals, trade name PCDL T5651, number average molecular weight: 1000), 2-methacryloyloxyethyl isocyanate (Showa Denko) Co., Ltd., trade name Karenz MOI) 6.21 g (0.040 mol), blocked isocyanate (manufactured by Asahi Kasei Chemicals Corporation, trade name Duranate MF-B60X, effective NCO%: 8.0%, solid content 60 wt%, viscosity 300 mPa S / 25 ° C.) 140.04 g, 1,2-bis (2-methoxyethoxy) ethane 74.21 g, dibutyltin dilaurate 0.168 g, hydroquinone monomethyl ether 0.168 g were charged at room temperature under an air stream. Stir for 1 hour The solid content concentration of this solution is 50% by weight. The obtained composition is abbreviated as polyimide resin composition B5.

(Synthesis Example 9)
45.48 g of imide oligomer solution A1 in a reaction vessel, 50.00 g (0.050 mol) of polycarbonate diol (manufactured by Asahi Kasei Chemicals, trade name PCDL T5651, number average molecular weight: 1000), 2-methacryloyloxyethyl isocyanate (Showa Denko) Co., Ltd., trade name Karenz MOI) 6.21 g (0.040 mol), blocked isocyanate (made by Asahi Kasei Chemicals Corporation, trade name Duranate 17B-60PX, effective NCO%: 9.5%, solid content 60 wt%, viscosity 300 mPa S / 25 ° C.) 117.93 g, 1,2-bis (2-methoxyethoxy) ethane 65.36 g, dibutyltin dilaurate 0.154 g, hydroquinone monomethyl ether 0.154 g were charged at room temperature under an air stream. Stir for 1 hour It was. The solid content concentration of this solution is 50% by weight. The obtained composition is abbreviated as polyimide resin composition B6.

(Synthesis Example 10)
45.48 g of imide oligomer solution A1 in a reaction vessel, 50.00 g (0.050 mol) of polycarbonate diol (manufactured by Asahi Kasei Chemicals, trade name PCDL T5651, number average molecular weight: 1000), 2-methacryloyloxyethyl isocyanate (Showa Denko) Co., Ltd., trade name Karenz MOI) 6.21 g (0.040 mol), blocked isocyanate (made by Asahi Kasei Chemicals Corporation, trade name Duranate E402-B80T, effective NCO%: 6.0%, solid content 80 wt%, viscosity 2500 mPa S / 25 ° C.) 140.04 g, 1,2-bis (2-methoxyethoxy) ethane 46.20 g, dibutyltin dilaurate 0.196 g, hydroquinone monomethyl ether 0.196 g were charged at room temperature under an air stream. Stir for 1 hour went. The solid content concentration of this solution is 50% by weight. The obtained composition is abbreviated as polyimide resin composition B7.

(Synthesis Example 11)
45.48 g of imide oligomer solution A1 in a reaction vessel, 50.00 g (0.050 mol) of polycarbonate diol (manufactured by Asahi Kasei Chemicals, trade name PCDL T5651, number average molecular weight: 1000), 2-methacryloyloxyethyl isocyanate (Showa Denko) Co., Ltd., trade name Karenz MOI) 6.21 g (0.040 mol), blocked isocyanate (manufactured by Asahi Kasei Chemicals Corporation, trade name Duranate TPA-B80E, effective NCO%: 12.5%, solid content 80 wt%, viscosity 1500 mPa S / 25 ° C.) 67.22 g, 1,2-bis (2-methoxyethoxy) ethane 31.64 g, dibutyltin dilaurate 0.137 g, hydroquinone monomethyl ether 0.137 g were charged at room temperature under an air stream. Stir for 1 hour It was. The solid content concentration of this solution is 50% by weight. The obtained composition is abbreviated as polyimide resin composition B8.

(Synthesis Example 12)
45.48 g of imide oligomer solution A1 in a reaction vessel, 50.00 g (0.050 mol) of polycarbonate diol (manufactured by Asahi Kasei Chemicals Corporation, trade name PCDL T5651, number average molecular weight: 1000), 2.60 g of 2-hydroxyethyl methacrylate ( 0.020 mol), blocked isocyanate (trade name DURANATE MF-K60X, manufactured by Asahi Kasei Chemicals Corporation, effective NCO%: 6.6%, solid content 60 wt%, viscosity 250 mPa · s / 25 ° C.) 297.05 g, 1,2 -137.01 g of bis (2-methoxyethoxy) ethane, 0.258 g of dibutyltin dilaurate, and 0.258 g of hydroquinone monomethyl ether were added, and the mixture was stirred at room temperature for 1 hour in an air stream. The solid content concentration of this solution is 50% by weight. The obtained composition is abbreviated as polyimide resin composition C1.

(Synthesis Example 13)
In a reaction vessel, 27.96 g of imide oligomer solution A2, 50.00 g (0.050 mol) of polycarbonate diol (manufactured by Asahi Kasei Chemicals Corporation, trade name PCDL T5651, number average molecular weight: 1000), 2.60 g of 2-hydroxyethyl methacrylate ( 0.020 mol), blocked isocyanate (trade name DURANATE MF-K60X, manufactured by Asahi Kasei Chemicals Corporation, effective NCO%: 6.6%, solid content 60 wt%, viscosity 250 mPa · s / 25 ° C.) 297.05 g, 1,2 -130.00 g of bis (2-methoxyethoxy) ethane, 0.248 g of dibutyltin dilaurate, and 0.248 g of hydroquinone monomethyl ether were added, and the mixture was stirred at room temperature for 1 hour in an air stream. The solid content concentration of this solution is 50% by weight. The obtained composition is abbreviated as polyimide resin composition C2.

(Synthesis Example 14)
110.13 g of imide oligomer solution A3, 50.00 g (0.050 mol) of polycarbonate diol (manufactured by Asahi Kasei Chemicals Corporation, trade name PCDL T5651, number average molecular weight: 1000), 2.60 g of 2-hydroxyethyl methacrylate in a reaction vessel ( 0.020 mol), blocked isocyanate (trade name DURANATE MF-K60X, manufactured by Asahi Kasei Chemicals Corporation, effective NCO%: 6.6%, solid content 60 wt%, viscosity 250 mPa · s / 25 ° C.) 297.05 g, 1,2 162.87 g of bis (2-methoxyethoxy) ethane, 0.297 g of dibutyltin dilaurate and 0.297 g of hydroquinone monomethyl ether were added, and the mixture was stirred at room temperature for 1 hour in an air stream. The solid content concentration of this solution is 50% by weight. The obtained composition is abbreviated as polyimide resin composition C3.

(Synthesis Example 15)
Polycarbonate diol (made by Asahi Kasei Chemicals Corporation, trade name: PCDL T5651, number average molecular weight: 1000) 100.00 g (0.100 mol), 2-methacryloyloxyethyl isocyanate (made by Showa Denko KK, trade name Karenz MOI) 6.21 g (0.040 mol), blocked isocyanate (manufactured by Asahi Kasei Chemicals Corporation, trade name Duranate MF-K60X, effective NCO%: 6.6%, solid content 60 wt%, viscosity 250 mPa · s / 25 ° C.) 169.74 g 1,2-bis (2-methoxyethoxy) ethane (118.82 g), dibutyltin dilaurate (0.281 g), and hydroquinone monomethyl ether (0.281 g) were added, and the mixture was stirred at room temperature for 1 hour in an air stream. The solid content concentration of this solution is 50% by weight. The obtained composition is abbreviated as polyurethane resin composition D1.

(Synthesis Example 16)
90.97 g of imide oligomer solution A1 in a reaction vessel, 6.21 g (0.040 mol) of 2-methacryloyloxyethyl isocyanate (made by Showa Denko KK, trade name Karenz MOI), blocked isocyanate (made by Asahi Kasei Chemicals Corporation, trade name) Duranate MF-K60X, effective NCO%: 6.6%, solid content 60 wt%, viscosity 250 mPa · s / 25 ° C.) 169.74 g, 1,2-bis (2-methoxyethoxy) ethane 104.28 g, dibutyltin dilaurate 0.163 g and hydroquinone monomethyl ether 0.163 g were added, and the mixture was stirred at room temperature for 1 hour under an air stream. The solid content concentration of this solution is 50% by weight. The obtained composition is abbreviated as polyimide resin composition D2.

(Synthesis Example 17)
45.48 g of imide oligomer solution A1 in a reaction vessel, polycarbonate diol (manufactured by Asahi Kasei Chemicals Corporation, trade name PCDL T5651, number average molecular weight: 1000) 50.00 g (0.050 mol), block isocyanate (manufactured by Asahi Kasei Chemicals Corporation) Product name Duranate MF-K60X, effective NCO%: 6.6%, solid content 60 wt%, viscosity 250 mPa · s / 25 ° C.) 212.18 g, 1,2-bis (2-methoxyethoxy) ethane 103.06 g, dibutyl 0.205 g of tin dilaurate and 0.205 g of hydroquinone monomethyl ether were added, and the mixture was stirred for 1 hour at room temperature under an air stream. The solid content concentration of this solution is 50% by weight. The obtained composition is abbreviated as polyimide resin composition D3.

(Synthesis Example 18)
45.48 g of imide oligomer solution A1 in a reaction vessel, 2.60 g (0.020 mol) of 2-hydroxyethyl methacrylate, block isocyanate (trade name Duranate MF-K60X, manufactured by Asahi Kasei Chemicals Corporation, effective NCO%: 6.6% 297.05 g, 1,2-bis (2-methoxyethoxy) ethane 155.21 g, 0.235 g dibutyltin dilaurate, 0.235 g hydroquinone monomethyl ether The mixture was stirred for 1 hour at room temperature under an air stream. The solid content concentration of this solution is 50% by weight. The obtained composition is abbreviated as polyimide resin composition D4.

(Examples 1-11, Comparative Examples 1-4)
A photosensitive compound, a photopolymerization initiator, a thermosetting compound, and an organic solvent are added to the polyimide resin compositions obtained in Synthesis Examples 4 to 14 and 16 to 18 and the polyurethane resin composition obtained in Synthesis Example 15. Thus, a photosensitive resin composition was prepared. Tables 1 to 9 show the blending amount of each constituent raw material in the resin solid content and the type of raw material. In addition, 1,2-bis (2-methoxyethoxy) ethane, which is a solvent in the table, is the total amount of solvent including the solvent and the like contained in the photosensitive resin composition solution.

  The photosensitive resin composition was first mixed with a general stirring device equipped with a stirring blade, and the solution was passed twice with a three-roll mill to obtain a uniform solution. When the particle diameter was measured with a grindometer, all were 10 μm or less. The following evaluation was carried out by completely defoaming the foam in the solution with a defoaming device. The evaluation results are shown in Tables 10-12.

(Preparation of coating film on polyimide film)
The above photosensitive resin composition was cast and applied to an area of 100 mm × 100 mm on a 75 μm polyimide film (manufactured by Kaneka Corporation: trade name 75 NPI) using a Baker type applicator so that the final dry thickness was 25 μm. After drying at 80 ° C. for 20 minutes, a negative photomask having a line width / space width of 50 mm × 50 mm = 100 μm / 100 μm was placed and exposed to UV light at 300 mJ / cm 2 under reduced pressure for exposure. This photosensitive film was spray-developed for 90 seconds at a discharge pressure of 1.0 kgf / mm 2 using a solution in which a 1.0 wt% sodium carbonate aqueous solution was kept at 30 ° C. After development, the film was thoroughly washed with pure water, and then dried by heating in an oven at 150 ° C. for 60 minutes to prepare a cured film of the photosensitive resin composition.

(Photosensitive)
The evaluation of the photosensitivity of the photosensitive resin composition was determined by observing the surface of the cured film obtained in the above item (Preparation of coating film on polyimide film).
◯: Clear line width / space width = 100/100 μm photosensitive pattern is drawn on the polyimide film surface, no line shaking occurs due to peeling of the line part, and there is no residual residue in the space part thing.
Δ: A clear photosensitive pattern having a line width / space width = 100/100 μm is drawn, and the line portion is shaken due to peeling, but there is no undissolved residue in the space portion.
×: Clear line width / space width = 100/100 μm photosensitive pattern is not drawn, and dissolution residue is generated in the space portion.

(Coating film adhesion)
The adhesive strength of the cured film of the photosensitive resin composition obtained in the above item (Preparation of coating film on polyimide film) was evaluated by a cross-cut tape method according to JIS K5400.
○: No peeling by cross-cut tape method.
Δ: 95% or more of the cells remain.
X: The remaining amount of the mesh is less than 80%.

(Solvent resistance)
The solvent resistance of the cured film of the photosensitive resin composition obtained in the above item (preparation of coating film on polyimide film) was evaluated. In the evaluation method, the film was dipped in methyl ethyl ketone at 25 ° C. for 15 minutes and then air-dried to observe the state of the film surface.
○: There is no abnormality in the coating film.
X: Abnormality such as swelling or peeling occurs in the coating film.

(Flexibility)
A cured film laminated film of a photosensitive resin composition was prepared on the surface of a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as the above item (Preparation of a coating film on a polyimide film). The cured film laminated film was cut into a 30 mm × 10 mm strip, bent 10 times at 180 ° at 15 mm, and the coating film was visually confirmed to check for cracks.
○: The cured film has no cracks.
Δ: The cured film has some cracks.
X: The cured film has cracks.

(Warpage amount)
Using the Baker type applicator, the photosensitive resin composition was cast and applied to a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) to an area of 100 mm × 100 mm so that the final dry thickness was 25 μm. Dry at 80 ° C. for 20 minutes. The entire surface was exposed to 300 mJ / cm 2 of ultraviolet light under reduced pressure. This photosensitive film was spray-developed at a discharge pressure of 1.0 kgf / mm 2 using a solution obtained by heating a 1.0 wt% sodium carbonate aqueous solution to 30 ° C. However, since the entire surface was exposed, no change in the film area was observed. After development, the film was thoroughly washed with pure water, and then dried by heating in an oven at 150 ° C. for 60 minutes to prepare a cured film of the photosensitive resin composition.

  The cured film was cut into a film having an area of 50 mm × 50 mm and placed on a smooth table so that the coating film was on the upper surface, and the warp height of the film edge was measured. A schematic diagram of the measurement site is shown in FIG. The smaller the amount of warpage on the polyimide film surface, the smaller the stress on the surface of the printed wiring board and the lower the amount of warping of the printed wiring board. The warp amount is preferably 5 mm or less.

(Solder heat resistance)
The photosensitive resin composition was cast and applied to an area of 100 mm × 100 mm on a 75 μm polyimide film (manufactured by Kaneka Corporation: trade name 75 NPI) using a Baker type applicator so that the final dry thickness was 25 μm. After drying at 80 ° C. for 20 minutes, a negative photomask having a line width / space width of 50 mm × 50 mm = 100 μm / 100 μm was placed and exposed to UV light at 300 mJ / cm 2 under reduced pressure for exposure. This photosensitive film was spray-developed at a discharge pressure of 1.0 kgf / mm 2 using a solution obtained by heating a 1.0 wt% sodium carbonate aqueous solution to 30 ° C. After development, the film was thoroughly washed with pure water, and then dried by heating in an oven at 150 ° C. for 60 minutes to prepare a cured film of the photosensitive resin composition.
The coated film was floated so that the surface coated with the cured film of the photosensitive resin composition was in contact with a solder bath completely dissolved at 260 ° C., and then pulled up 10 seconds later. The operation was performed three times, and the adhesive strength of the cured film was evaluated by a cross-cut tape method according to JIS K5400.
○: No peeling by cross-cut tape method.
Δ: 95% or more of the cells remain.
X: The remaining amount of the mesh is less than 80%.

(Insulation reliability)
A comb-shaped pattern of line width / space width = 100 μm / 100 μm on a flexible copper-laminated laminate (copper foil thickness 12 μm, polyimide film is Apical 25 NPI manufactured by Kaneka Corporation, and copper foil is bonded with a polyimide adhesive) After being prepared and immersed in a 10% by volume sulfuric acid aqueous solution for 1 minute, the surface of the copper foil was treated by washing with pure water. Then, the cured film of the photosensitive resin composition was produced on the comb pattern by the method similar to the production method of the cured film on a polyimide film, and the test piece was adjusted. A 100 V direct current was applied to both terminals of the test piece in an environmental test machine at 85 ° C. and 85% RH, and changes in the insulation resistance value and occurrence of migration were observed.
◯: A resistance value of 10 9 or more after 1000 hours from the start of the test and no occurrence of migration, dendrite, copper discoloration, etc.
X: The occurrence of migration, dendrite, discoloration of copper, etc. in 1000 hours or more after the start of the test.

(Wettability)
A cured film laminated film of a photosensitive resin composition was prepared on the surface of a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as the above item (Preparation of a coating film on a polyimide film). Using this cured film, the wettability of the coating film surface was evaluated according to JIS K6768. The better the wettability of the cured coating film surface, the higher the value of the wetting index and the better the adhesion with the sealant resin. The wetting index is preferably 36 or more.

(Comparative Example 5)
In a reaction vessel, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride 25.06 g (0.085 mol), N-methyl-2-pyrrolidone 108 g, hydroquinone 1.20 g, 4-methoxyhydroquinone 1.20 g And cooled with dry ice / methanol (−30 ° C.) while passing dry air, 3,5-diaminobenzoic acid ethyl methacrylate 6.00 g (0.023 mol), diaminopolysiloxane (Shin-Etsu Chemical) 54.0 g (0.062 mol) manufactured by Co., Ltd., trade name KF-8010) was added over 5 minutes, and the apparatus and the instrument were washed with 40 g of N-methyl-2-pyrrolidone. The outside was cooled and stirred uniformly at 25 ° C. for 30 hours to obtain a polyamic acid solution. Next, 472 g of N-methyl-2-pyrrolidone was added to dilute the reaction solution, and 145.2 g of acetic anhydride and 62.2 g of pyridine were added at 25 ° C. over 10 minutes while cooling the outside. Subsequently, the imidization reaction was performed by stirring overnight at 20 ° C. The obtained imide resin solution was deposited in a 3 liter container containing 1.5 liters of methanol over 2 minutes using a disperser. The precipitate was collected using a filter paper (No. 3 Advantech) and washed with a small amount of methanol. After this operation was repeated three times, the filtrated product was vacuum dried (25 ° C., 15 hours) to obtain 85.5 g of a photosensitive polyimidesiloxane resin.

  After dissolving 30 g of the above photosensitive polyimidesiloxane resin in 45 g of N-methyl-2-pyrrolidone, 5.25 g of Aerosil (average particle size: about 0.02 μm), 12 g of talc (average particle size: 1.5 μm), 1 6.92 g of -hydroxy-cyclohexyl phenyl ketone and 6.92 g of 2-benzyl-1,2-dimethylamino-1- (4-morpholinophenyl) butane-1 were added and stirred. This mixture was kneaded with three rolls to obtain a photosensitive resin composition solution. The resulting photosensitive resin composition solution was completely defoamed with a defoaming apparatus and subjected to the same evaluation as in Examples 1-11. The evaluation results are shown in Table 13.

  The obtained cured film was poor in solvent resistance, and the wetting index on the surface of the cured coating film was very low. Furthermore, it was insoluble in the dilute alkaline aqueous solution of the developer during development.

(Comparative Example 6)
After introducing air into the reaction vessel, polycarbonate diol (manufactured by Daicel Chemical Industries, trade name: Plaxel CD205PL, number average molecular weight: 500) 196.8 g (0.394 mol), 2,2-bis (hydroxymethyl) butane Acid 58.3 (0.394 mol) g, diethylene glycol 37.6 g (0.353 mol), 1,4-cyclohexanedimethanol monoacrylate 148.1 (0.748 mol) g, p-methoxyphenol 0.55 g, dibutyltin 0.55 g of dilaurate and 110.2 g of methyl ethyl ketone were charged, and the temperature was raised to 65 ° C. with uniform stirring under an air stream. 305.9 g (1.457 mol) of trimethylhexamethylene diisocyanate was charged into the dropping vessel and dropped into the reaction vessel over 3 hours with uniform stirring at 65 ° C. After the completion of dropping, the dropping container was washed with 76.5 g of methyl ethyl ketone, and the washed solution was put into the reaction container as it was. Further, the mixture was kept warm for 2 hours with uniform stirring, then heated to 75 ° C. and stirred uniformly for 5 hours. Next, 9.3 g of methanol was added to the reaction vessel, and uniform stirring was performed at 60 ° C. for 30 minutes. Thereafter, 56.4 g of methyl ethyl ketone was added to obtain a transparent resin solution. This resin solution had a solid concentration of 75% by weight and a viscosity of 20 poise at 23 ° C.

  To 50 g of the resin solution, 0.25 g of 2,2-dimethoxy-2-phenylacetone was added and stirred. This mixture was kneaded with three rolls to obtain a photosensitive resin composition solution. The resulting photosensitive resin composition solution was completely defoamed with a defoaming apparatus and subjected to the same evaluation as in Examples 1-11. The evaluation results are shown in Table 13.

  The cured film obtained had poor solvent resistance and solder heat resistance, and the copper circuit was discolored black after the insulation reliability test.

(Comparative Example 7)
62.5 g of resin solution obtained in Comparative Example 3 (solid content 50 g), 30 g of 2,2′-bis (4-methacryloxypentaethoxyphenyl) propane, methacrylic acid / methyl methacrylate / butyl acrylate = 22/71 / 16 (weight ratio) copolymer dissolved in methyl cellosolve / toluene = 6/4 (weight ratio) solution to a solid content of 40% by weight (solid content: 65 g), benzophenone 5 g, 0.1 g of N, N′-tetraethyl-4,4′-diaminobenzophenone, blocked isocyanate compound (manufactured by Asahi Kasei Chemicals Corporation, trade name Duranate TPA-B80E, solid content 80% by weight) 18.75 g (solid content 15 g) ), Phosphoric ester-based flame retardant (trade name CR-747, manufactured by Daihachi Chemical Industry Co., Ltd.) 40 g and acetone 85 g were added and stirred. It was. This mixture was kneaded with three rolls to obtain a photosensitive resin composition solution. The resulting photosensitive resin composition solution was completely defoamed with a defoaming apparatus and subjected to the same evaluation as in Examples 1-11. The evaluation results are shown in Table 13.

  The resistance value after the insulation reliability test was 10 9 or less, the surface of the coating film became sticky due to the bleed-out of the flame retardant, migration occurred, and the copper circuit turned black.

(Comparative Example 8)
40.68 g of ethyl diglycol acetate, 22.20 g (0.1 mol) of isophorone diisocyanate, and 8.88 g (0.06 mol) of 2,2-bis (hydroxymethyl) butanoic acid are put into a reaction vessel, and the mixture is stirred under a nitrogen stream. The temperature was raised to 0 ° C. and uniform stirring was performed for 3 hours. Next, 9.60 g (0.05 mol) of trimellitic anhydride was added, the temperature was raised to 160 ° C., and the mixture was heated to reflux for 4 hours to carry out an imidization reaction. Next, 7.10 g (0.05 mol) of glycidyl methacrylate was added, and stirred uniformly at 100 ° C. for 5 hours to obtain an imide-urethane acrylate. Further, 6.84 g (0.045 mol) of tetrahydrophthalic anhydride was charged and stirred uniformly at 100 ° C. for 5 hours. The resulting resin solution had a solid content concentration of 56% by weight and a number average molecular weight of 5,500 in terms of polyethylene glycol.

  133.93 g of the above resin solution (solid content: 75 g), 25 g of cresol novolac type epoxy resin (trade name EOCN-104S, manufactured by Nippon Kayaku Co., Ltd.), 10 g of dipentaerythritol hexaacrylate, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one (5 g) and N, N-dimethylbenzylamine (1 g) were added and stirred. This mixture was kneaded with three rolls to obtain a photosensitive resin composition solution. The resulting photosensitive resin composition solution was completely defoamed with a defoaming apparatus and subjected to the same evaluation as in Examples 1-11. The evaluation results are shown in Table 13.

  The obtained cured film was poor in flexibility, and in the bendability test, a crack was generated by one folding. Furthermore, the amount of warping of the test piece after curing showed a value of 20 mm or more.

(Comparative Example 9)
A reaction vessel was charged with 58.8 g (0.20 mol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 30 g (0.40 mol) of 3-aminopropanol, and 200 g of dimethylacetamide under a nitrogen atmosphere. And stirred uniformly at 100 ° C. for 1 hour. Next, 50 g of toluene was added, the temperature was raised to 180 ° C., and the mixture was heated to reflux for 4 hours to remove water generated by imidization azeotropically with toluene. The reaction solution was poured into 2 liters of water, and the resulting precipitate was collected by filtration, washed with water and dried under reduced pressure to obtain 43.16 g of hydroxyl-terminated imide oligomer powder.

  In a reaction vessel, polycarbonate diol (Kuraray Co., Ltd., trade name Kuraray polyol C-2015 29.94 g (0.015 mol), 2,2-bis (hydroxymethyl) propionic acid 1.01 g (0.0075 mol), 4 , 4'-diphenylmethane diisocyanate (8.53 g, 0.034 mol) and isophorone (13.7 g) were charged and stirred uniformly in a nitrogen atmosphere for 1.5 hours at 80 ° C. Subsequently, the synthesized hydroxyl-terminated imide oligomer (6.13 g) ( 0.015 mol) and 31.9 g of isophorone were added and stirred uniformly for 1.5 hours at 80 ° C. The polyimide resin solution thus obtained (number average molecular weight was 26000 in terms of polyethylene glycol). The solid concentration was 50% by weight, and the solution viscosity was 600 poise at 23 ° C.

  200 g of the above polyimide resin solution (solid content is 100 g), 10 g of epoxy resin (manufactured by Daicel Chemical Industries, Ltd., trade name Epolide PB3600), 20 g of a blocked isocyanate compound (trade name Burnock D-550, manufactured by Dainippon Ink & Chemicals, Inc.) , 0.8 g of an amine compound (Shikoku Kasei Kogyo Co., Ltd., trade name Curezol 2E4MZ), 10 g of Filler 1 (Nihon Aerosil Co., Ltd., trade name Aerosil 130), Filler 2 (Nihon Aerosil Co., Ltd., trade name Aerosil 50) ) 5 g was added and stirred. This mixture was kneaded with three rolls to obtain a polyimide resin composition solution. The obtained polyimide resin composition solution was subjected to the same evaluation as in Examples 1 to 11 by completely defoaming bubbles in the solution with a defoaming apparatus. The evaluation results are shown in Table 13.

  The resulting polyimide resin composition did not exhibit photosensitivity and was insoluble in the dilute alkaline aqueous solution of the developer during development.

* 1: Brand name NK ester BPE-1300N (2,2-bis (4- (methacryloxypolyethoxy) phenyl) propane, manufactured by Shin-Nakamura Chemical Co., Ltd.)
* 2: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 manufactured by Ciba Specialty Chemicals
* 3: Bisphenol A type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd. * 4: Ultrafine anhydrous silica manufactured by Nippon Aerosil Co., Ltd.

Schematic diagram measuring the amount of warping of the film

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Polyimide film which laminated the photosensitive resin composition 2 Warpage amount 3 Smooth stand

Claims (12)

  (A) hydroxyl-terminated imide oligomer, (B) polyol compound, (C) (Ca) a compound having at least one blocked isocyanate group and at least one photosensitive group in the molecule, and / or (Cb) at least one in the molecule. It contains at least a compound having two hydroxyl groups and at least one photosensitive group, (D) a blocked isocyanate compound, (E) a photosensitive compound, (F) a photopolymerization initiator, and (G) a thermosetting compound. A photosensitive resin composition.   The photosensitive resin composition according to claim 1, wherein the (B) polyol compound is a polyalkyl polyol and / or a polycarbonate polyol.   The photosensitive resin composition according to claim 2, wherein the (B) polyol compound is a polycarbonate polyol. The photosensitive resin composition according to any one of claims 1 to 3, wherein the (A) hydroxyl-terminated imide oligomer is (A) a hydroxyl-terminated imide oligomer represented by the following general formula (1). .

(In the formula, X represents at least a tetravalent organic group, Y represents a divalent organic group, and a plurality of R _{1 s} each independently represent a divalent organic group. P is an integer of 0-20. is there.)   (C) The photosensitive group of the compound having at least one blocked isocyanate group and at least one photosensitive group in the (Ca) molecule and / or (Cb) at least one photosensitive group and at least one hydroxyl group in the molecule. The photosensitive resin composition according to any one of claims 1 to 4, wherein the photosensitive group of the compound having a hydrogen atom is a (meth) acryloyl group.   (A) hydroxyl group-terminated imide oligomer, (B) polyol compound, (Ca) compound having at least one blocked isocyanate group and at least one photosensitive group in the molecule, (Cb) contained in the photosensitive resin composition; ) The number of moles of the compound having at least one hydroxyl group and at least one photosensitive group in the molecule, and (D) the blocked isocyanate compound are respectively determined as (A), (B), (Ca), (Cb), (D ), The blending molar ratio is [(A) + (B) + (Cb)] mole number of hydroxyl groups / [(Ca) + (D)] mole number of blocked isocyanate groups = 0.5. It is -2.0, The photosensitive resin composition of any one of Claims 1-5 characterized by the above-mentioned.   Compounding amount of (A) component, (B) component, (Ca) component, (Cb) component, (D) component, (E) component, (F) component, and (G) component in the photosensitive resin composition Are (E) component 5 to 500 parts by weight, (F) component 0.1 to 20 parts by weight, and (G) component 0.5 to 100 parts by weight of components (A) to (D). It is -100 weight part, The photosensitive resin composition of any one of Claims 1-6 characterized by the above-mentioned.   The photosensitive resin composition solution obtained by melt | dissolving the photosensitive resin composition of any one of Claims 1-7 in the organic solvent.   The photosensitive film obtained by apply | coating the photosensitive resin composition of any one of Claims 1-7 to the base-material surface, and drying.   The insulating film obtained by photosensitizing and thermosetting the photosensitive resin composition of any one of Claims 1-7.   The printed wiring board with an insulating film which coat | covered the photosensitive resin composition of any one of Claims 1-7 on the printed wiring board.   In the method for producing an insulating film, (A) a hydroxyl group-terminated imide oligomer, (B) a polyol compound, (C) (Ca) a compound having at least one blocked isocyanate group and at least one photosensitive group in the molecule, and / or ( Cb) a compound having at least one photosensitive group and at least one hydroxyl group in the molecule, (D) a blocked isocyanate compound, (E) a photosensitive compound, (F) a photopolymerization initiator, and (G) a thermosetting compound. A method for producing an insulating film, comprising producing an insulating film by photosensitizing and thermosetting a photosensitive resin composition containing at least the photosensitive resin composition.

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