JPWO2017138379A1 - Curable resin composition, dry film, cured product and printed wiring board - Google Patents

Abstract

It is providing the curable resin composition etc. which can obtain the hardened | cured material excellent in elongation rate. (A) A curing comprising a carboxyl group-containing resin having at least one of an imide structure and an amide structure, (B) a block copolymer, (C) a thermosetting resin, and (D) a filler. It is an adhesive resin composition.

Description

  The present invention relates to a curable resin composition, a dry film, a cured product thereof, and a printed wiring board having the curable resin composition. Specifically, the curable resin composition, the dry film, The present invention relates to those cured products and a printed wiring board having the same.

  Due to rapid progress in semiconductor components, electronic devices tend to be smaller, lighter, higher performance, and multifunctional. Following this trend, printed wiring boards are also becoming increasingly dense and surface-mounted. In the production of high-density printed wiring boards, photo solder resist compositions are generally employed, and dry film type photo solder resist compositions and liquid photo solder resist compositions have been developed. Among these, in consideration of environmental problems, an alkali development type photosensitive resin composition using a dilute alkaline aqueous solution as a developing solution has become the mainstream, and several composition systems have been conventionally proposed (for example, patents). Reference 1).

  In recent years, it has been required to provide a solder resist with a high elongation rate as the performance of a printed wiring board increases. For example, in a thermal shock test that is one of long-term reliability evaluations of electronic devices, a low elongation rate of a cured coating film is cited as one cause of cracking (for example, Patent Document 2). Moreover, a high elongation rate is also required for a solder resist for a flexible printed wiring board that requires flexibility.

JP 61-243869 (Claims etc.) JP 2002-293882 (paragraph [0006] etc.)

  Then, an object of this invention is to provide the curable resin composition which can obtain the hardened | cured material excellent in elongation rate, a dry film, those hardened | cured materials, and a printed wiring board which has this.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have combined the carboxyl group-containing resin having a specific structure, a block copolymer, a thermosetting resin, and a filler with the above. The present inventors have found that the problem can be solved and have completed the present invention.

  That is, the curable resin composition of the present invention comprises (A) a carboxyl group-containing resin having at least one of an imide structure and an amide structure, (B) a block copolymer, (C) a thermosetting resin, and ( D) A curable resin composition containing a filler.

In the curable resin composition of the present invention, the (B) block copolymer is preferably a block copolymer represented by the following formula (I).
XYX (I)
(In the formula (I), X is a polymer unit having a glass transition point Tg of 0 ° C. or more, and may be the same or different, and Y is a polymer unit having a glass transition point Tg of less than 0 ° C. )

  In the curable resin composition of the present invention, the (A) carboxyl group-containing resin having at least one of an imide structure and an amide structure is preferably a carboxyl group-containing resin having an imide structure and an amide structure.

  It is preferable that the curable resin composition of this invention contains an epoxy resin as said (C) thermosetting resin.

  The curable resin composition of the present invention preferably further contains (E) a photopolymerization initiator.

  The dry film of the present invention is characterized by having a resin layer obtained by applying the curable resin composition to a film and drying it.

  The cured product of the present invention is obtained by curing the curable resin composition or the resin layer of the dry film.

  The printed wiring board of this invention has the said hardened | cured material, It is characterized by the above-mentioned.

  ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition which can obtain the hardened | cured material excellent in the elongation rate, a dry film, those hardened | cured materials, and a printed wiring board which has this can be provided.

  The curable resin composition of the present invention comprises (A) a carboxyl group-containing resin having at least one of an imide structure and an amide structure, (B) a block copolymer, (C) a thermosetting resin, and (D ) A curable resin composition containing a filler. The curable resin composition of the present invention obtains a cured product by subjecting (A) a carboxyl group-containing resin having at least one of an imide structure and an amide structure and (C) a thermosetting resin to an addition reaction by heating. It is a resin composition that makes it possible.

According to the curable resin composition of this invention, as above-mentioned, the hardened | cured material excellent in elongation rate can be obtained. Conventionally, as a method for improving the elongation rate of a cured product, it is known to add a binder polymer to a curable resin composition, but in that case, the Tg (glass transition temperature) of the cured product is lowered, and at a high temperature. There was a problem that the B-HAST resistance was lowered. However, in the curable resin composition of the present invention, it is expected that, by adding the (B) block copolymer, the Tg of the cured product does not decrease or is reduced while improving the elongation rate. It has been found that there are also effects that cannot be achieved.
The reason why the above effects can be obtained is thought to be because (A) carboxyl group-containing resin and (B) block copolymer form a co-continuous structure connected to each other in the cured product. In fact, in the curable resin composition not including the combination of (A) carboxyl group-containing resin and (B) block copolymer, it does not have a co-continuous structure in the cured product, but forms a sea-island structure, and the elongation rate Becomes smaller or Tg decreases.

[(A) Carboxyl group-containing resin having at least one of imide structure and amide structure]
(A) The carboxyl group-containing resin having at least one of an imide structure and an amide structure includes (A1) a carboxyl group-containing resin having an imide structure and an amide structure, and (A2) an amide structure having an amide structure. And carboxyl group-containing resin (A3) having an amide structure and no imide structure. In the present invention, the carboxyl group-containing resin having at least one of (A) an imide structure and an amide structure is preferably (A1) a carboxyl group-containing resin having an imide structure and an amide structure. Further, (A) the carboxyl group-containing resin preferably contains an aliphatic structure, that is, one of an aliphatic chain structure and an alicyclic structure. (A) When the carboxyl group-containing resin contains an aliphatic structure, the resin can have developability with a weak alkaline aqueous solution, deep resolution, and flexibility.

((A1) carboxyl group-containing resin having imide structure and amide structure)
(A1) The carboxyl group-containing resin having an imide structure and an amide structure is preferably a polyamideimide resin, and includes a diamine having an ether bond and a diamine containing a carboxyl group-containing diamine, and at least three carboxyl groups. It is obtained by reacting an acid anhydride (a1) containing an acid anhydride in which two of them are dehydrated to obtain an imidized product, and then reacting the obtained raw material with a reaction raw material containing a diisocyanate compound. be able to. As described later, in addition to the imidized product and the diisocyanate compound, the reaction raw material further includes an acid anhydride (a2) having at least three carboxyl groups, two of which are anhydrous, It is preferable to contain.

(Diamine)
Examples of the diamine having an ether bond include polyoxyethylene diamine, polyoxypropylene diamine, and other polyoxyalkylene diamines containing oxyalkylene groups having different numbers of carbon chains.
The molecular weight of the diamine having an ether bond is preferably 200 to 3,000, and more preferably 400 to 2,000.
Examples of polyoxyalkylenediamines include polyoxyethylene diamines such as Jeffamine ED-600, ED-900, ED-2003, EDR-148, and HK-511 manufactured by Huntsman, Inc., and Jeffamine D-230 and D-400. And polyoxypropylene diamines such as D-2000 and D-4000, and those having polytetramethylene ethylene groups such as Jeffamine XTJ-542, XTJ533, and XTJ536. Further, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane may be used as a diamine having an ether bond.

  Examples of the carboxyl group-containing diamine include 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, diaminobenzoic acids such as 3,4-diaminobenzoic acid, and 3,5-bis (3-aminophenoxy) benzoic acid. Acid, aminophenoxybenzoic acids such as 3,5-bis (4-aminophenoxy) benzoic acid, 3,3′-methylenebis (6-aminobenzoic acid), 3,3′-diamino-4,4′-dicarboxyl Carboxybiphenyl compounds such as biphenyl, 3,3′-diamino-4,4′-dicarboxydiphenylmethane, carboxydiphenylalkanes such as 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 3,3 ′ -Carboxydiphenyl ether compounds such as -diamino-4,4'-dicarboxydiphenyl ether Come, and these may be used alone or in appropriate combination.

  In the present invention, a diamine having an ether bond and a carboxyl group-containing diamine are preferably used as the diamine, but other diamines may be used in combination. As other diamines that can be used in combination, general-purpose aliphatic diamines and aromatic diamines can be used alone or in appropriate combination. Specifically, as other diamines, for example, p-phenylenediamine (PPD), 1,3-diaminobenzene, 2,4-toluenediamine, one benzene nucleus diamine, 4,4′-diaminodiphenyl ether, 3 , 3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and other diaminodiphenyl ethers, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl- 4,4′-diaminobiphenyl, 1,3-bis (3-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,3-bis [2- (4-aminophenyl) isopropyl] Benzene, 1,4-bis [2- (3-aminophenyl) isopropyl] benzene, 3,3′-bi (3-aminophenoxy) biphenyl, 3,3′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, Bis [3- (3-aminophenoxy) phenyl] ether, bis [3- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, 3,3′-diamino-4 , 4'-dihydroxydiphenyl sulfone, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1, Examples thereof include aliphatic diamines such as 7-diaminoheptane and 1,8-diaminooctane.

  Examples of the amino-modified silicone include BY16-205, FZ-3760, BY16-871, BY16-853U manufactured by Toray Dow Corning. From the viewpoint of improving the balance between the alkali solubility of the polyamideimide resin and the mechanical properties of the resulting cured product, the amine equivalent of the polyoxyalkylenediamine is preferably 100 to 1,500 g / eq, 200 More preferably, it is ˜1,000 g / eq.

(Acid anhydride (a1) and acid anhydride (a2))
The acid anhydride (a1) and the acid anhydride (a2) each include an acid anhydride having at least three carboxyl groups, two of which are anhydrous. Examples of the acid anhydride include those having at least one of an aromatic ring and an aliphatic ring, and trimellitic anhydride (trimellitic anhydride) (benzene-) having an aromatic ring. Hydrogenated trimellitic anhydride (cyclohexane-1,2,4) having an aliphatic ring such as 1,2,4-tricarboxylic acid 1,2-anhydride, TMA), 4,4′-oxydiphthalic anhydride 4-tricarboxylic acid-1,2-anhydride, H-TMA) and the like can be preferably mentioned. These acid anhydrides may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the present invention, the acid anhydride is preferably used, but a carboxylic dianhydride may be used in combination. Examples of the carboxylic dianhydride include tetracarboxylic anhydrides such as pyromellitic dianhydride and 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride. Moreover, both terminal type carboxylic anhydride modified silicone etc. are mentioned.

(Diisocyanate compound)
As the diisocyanate compound, diisocyanates such as aromatic diisocyanates and isomers and multimers thereof, aliphatic diisocyanates, alicyclic diisocyanates and isomers thereof, and other general-purpose diisocyanates can be used. Is not to be done. These diisocyanate compounds may be used alone or in combination.

  Examples of the diisocyanate compound include aromatic diisocyanates such as 4,4′-diphenylmethane diisocyanate (MDI), tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, biphenyl diisocyanate, diphenyl sulfone diisocyanate, diphenyl ether diisocyanate, and isomers and multimers thereof. , Aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate, trimethylhexamethylene diisocyanate (TMDI), or alicyclic diisocyanates and isomers hydrogenated with the above aromatic diisocyanates, or others General-purpose diisocyanates can be mentioned.

  As described above, in addition to the imidized product and the diisocyanate compound, the reaction raw material for obtaining the polyamideimide resin further contains the same acid anhydride (a2) as used when obtaining the imidized product. May be. In this case, the content of the acid anhydride (a2) in the reaction raw material is not particularly limited. From the viewpoint of improving the balance between the alkali solubility of the polyamideimide resin and the mechanical properties of the resulting cured product, the acid in the reaction raw material relative to the amount of diamine used to obtain the imidized product in the reaction raw material. The molar ratio of the amount of the anhydride (a2) is preferably 0.25 to 4, more preferably 0.5 to 2, and particularly preferably 0.6 to 1.5.

  The content of the diisocyanate compound in the reaction raw material is not particularly limited. From the viewpoint of improving the balance between the alkali solubility of the polyamideimide resin and the mechanical properties of the resulting cured product, the amount of the diisocyanate compound in the reaction raw material was used to obtain an imidized product in the reaction raw material. The molar ratio with respect to the sum of the amount of diamine and, if necessary, the amount of acid anhydride (a2) contained in the reaction raw material is preferably 0.3 to 1.0, preferably 0.4 to 0.95. Is more preferable, and 0.50 to 0.90 is particularly preferable.

  In the present invention, in particular, in a polyamideimide resin obtained by using a diamine having an ether bond and a tricarboxylic acid having an alicyclic structure, for example, H-TMA which is an alicyclic trimellitic acid, alkali dissolution This is preferable because the properties are improved and the developability is improved. For the same reason, it is also preferable to use an aliphatic diisocyanate compound in the second-stage reaction. Polyimide resins and polyamide-imide resins are characterized by low solubility in solvents and aqueous alkali solutions while having excellent heat resistance and mechanical properties due to the regular arrangement of imide rings and aromatic rings and a planar structure. By effectively incorporating a fatty chain or alicyclic structure into the structure as in the invention, it has become possible to increase alkali solubility without greatly degrading the properties.

  In the present invention, the (A1) carboxyl group-containing resin having an imide structure and an amide structure preferably has an aliphatic structure and an ether bond. Examples of the aliphatic structure in this case include linear hexane or cyclic cyclohexane. Moreover, it is preferable that the said ether bond is a polyether structure whose molecular weight is 200 or more. Many of the imide resins have strong alkali / solvent developability, but by introducing an aliphatic structure or an ether bond, particularly a polyether structure, the carboxyl group-containing resin having the above (A1) imide structure and amide structure can be obtained. It can have developability with a weak alkaline aqueous solution, deep resolution, and flexibility. The aliphatic structure can be introduced, for example, by using an acid anhydride having an aliphatic ring or an isocyanate having an aliphatic structure, and the ether bond is, for example, a diamine having an ether bond. It can be introduced.

  In addition, the amide bond of the carboxyl group-containing resin having the (A1) imide structure and the amide structure may be obtained by reacting isocyanate and carboxylic acid, or may be obtained by other reaction. Good. The carboxyl group-containing resin having the above (A1) imide structure and amide structure may further have other bonds formed by addition and condensation.

  In the present invention, as the blending ratio of each component in obtaining the carboxyl group-containing resin having the (A1) imide structure and amide structure, the acid anhydride is preferably 2. It is 0-2.4 mol, More preferably, it is 2.0-2.2 mol. Although the reaction temperature at the time of making diamine and an acid anhydride react and imidating by dehydration ring closure is not specifically limited, It is preferable to exist in the range of 140-200 degreeC. The reaction temperature between the imidized product obtained by reacting the diamine with the acid anhydride and the diisocyanate compound is not particularly limited, but is preferably in the range of 130 to 200 ° C.

  The (A1) carboxyl group-containing resin having an imide structure and an amide structure preferably has an acid value of 50 mgKOH / g or more, more preferably 50 to 200 mgKOH / g, in order to correspond to the alkali development step. Preferably, it is 70-130 mgKOH / g. When the acid value is 50 mgKOH / g or more, the solubility in alkali is increased, the developability is improved, and further, the degree of crosslinking with the thermosetting component after light irradiation is increased, so that sufficient development contrast is obtained. be able to. On the other hand, when the acid value is 200 mgKOH / g or less, drawing of an accurate pattern becomes easy.

  The molecular weight of the carboxyl group-containing resin having (A1) an imide structure and an amide structure is preferably a mass average molecular weight Mw of 10,000 or less, considering developability and cured coating film properties, 8,000 is more preferable, and 2,000 to 6,000 is more preferable. When the molecular weight is 10,000 or less, the alkali solubility in the unexposed area is increased and the developability is improved. On the other hand, when the molecular weight is 1,000 or more, sufficient development resistance and cured product properties can be obtained in the exposed area.

((A2) carboxyl group-containing resin having an imide structure and no amide structure)
In the present invention, (A2) the carboxyl group-containing resin having an imide structure and not having an amide structure is not particularly limited as long as it is a resin having a carboxyl group and an imide ring. (A2) For the synthesis of a carboxyl group-containing resin having an imide structure and not having an amide structure, a publicly known and commonly used method for introducing an imide ring into the carboxyl group-containing resin can be used. Examples thereof include a resin obtained by reacting a carboxylic anhydride component with an amine component and / or an isocyanate component. The imidization may be performed by thermal imidization or chemical imidization, and these can be used in combination.

  Here, examples of the carboxylic acid anhydride component include tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides, but are not limited to these acid anhydrides, and acid anhydrides that react with amino groups or isocyanate groups. Any compound having a physical group and a carboxyl group can be used, including derivatives thereof. These carboxylic anhydride components may be used alone or in combination.

  Examples of the amine component include diamines such as aliphatic diamines and aromatic diamines, polyvalent amines such as aliphatic polyether amines, diamines having carboxylic acids, and diamines having phenolic hydroxyl groups. It is not limited to. These amine components may be used alone or in combination.

  Diisocyanates such as aromatic diisocyanates and their isomers and multimers, aliphatic diisocyanates, alicyclic diisocyanates and their isomers, and other general-purpose diisocyanates can be used as the isocyanate component. It is not limited. These isocyanate components may be used alone or in combination.

  (A2) The carboxyl group-containing resin having an imide structure and no amide structure preferably has an acid value of 20 to 200 mg KOH / g, more preferably 60 to It is preferable that it is 150 mgKOH / g. When the acid value is 20 mgKOH / g or more, the solubility in alkali increases, the developability becomes good, and further, the degree of crosslinking with the thermosetting component after light irradiation becomes high, so that sufficient development contrast is obtained. be able to. Further, when the acid value is 200 mgKOH / g or less, in particular, so-called heat fogging in a PEB (POST EXPOSURE BAKE) step after light irradiation described later can be suppressed, and the process margin is increased.

  The molecular weight of the carboxyl group-containing resin (A2) having an imide structure and not having an amide structure is preferably a mass average molecular weight of 1,000 to 100,000 in consideration of developability and cured coating film characteristics. 50,000 to 50,000 are more preferable. When the molecular weight is 1,000 or more, sufficient development resistance and cured properties can be obtained after exposure and PEB. On the other hand, when the molecular weight is 100,000 or less, alkali solubility increases and developability improves.

((A3) carboxyl group-containing resin having an amide structure and no imide structure)
In the present invention, (A3) the carboxyl group-containing resin having an amide structure and not having an imide structure is not particularly limited as long as it is a resin having a carboxyl group and an amide bond.

  In addition, the carboxyl group-containing resin having at least one of (A) an imide structure and an amide structure may further have a phenolic hydroxyl group.

[(B) Block copolymer]
The block copolymer generally means a copolymer having a molecular structure in which two or more kinds of polymer units having different properties are connected by a covalent bond to form a long chain.

The block copolymer used in the present invention is preferably an XY type or XYX type block copolymer, and more preferably an XYX type block copolymer. X in the XY-X type block copolymer may be the same or different from each other.
In the XY type or XYX type block copolymer, X is preferably a polymer unit having a glass transition point Tg of 0 ° C. or higher. More preferably, it is a polymer unit having a glass transition point Tg of 50 ° C. or higher. Y is preferably a polymer unit having a glass transition point Tg of less than 0 ° C. More preferably, it is a polymer unit having a glass transition point Tg of −20 ° C. or lower. The glass transition point Tg is measured by differential scanning calorimetry (DSC).

  The block copolymer is preferably solid at 20 to 30 ° C. (the solid may be solid within this range, and may be solid even at a temperature outside this range). By being solid in the above temperature range, it is excellent in tackiness when formed into a dry film or applied to a substrate and temporarily dried.

  Of the XY-X type block copolymers, X is preferably one having high compatibility with (C) thermosetting resin, and Y is one having low compatibility with (C) thermosetting resin. Is preferred. Thus, it is considered that a specific structure in the matrix can be easily shown by using a block copolymer in which the blocks at both ends are compatible with the matrix and the central block is incompatible with the matrix.

  The polymer unit X is preferably polymethyl methacrylate (PMMA), polystyrene (PS) or the like, and the polymer unit Y is preferably poly n-butyl (meth) acrylate (PBA) or polybutadiene (PB). In addition, a part of the polymer unit X is excellent in compatibility with the above-described (A) carboxyl group-containing resin represented by styrene unit, hydroxyl group-containing unit, carboxyl group-containing unit, epoxy-containing unit, N-substituted acrylamide unit and the like. If the hydrophilic unit is introduced, the compatibility can be further improved. It is particularly preferable to introduce an epoxy-containing unit into a part of the polymer unit X. Among the above, the polymer unit X is preferably polystyrene, polyglycidyl methacrylate, N-substituted polyacrylamide, polymethyl (meth) acrylate, a carboxylic acid-modified product or a hydrophilic group-modified product thereof. Y is preferably poly n-butyl (meth) acrylate or polybutadiene. X and Y may each be composed of one type of polymer unit, or may be composed of polymer units of two or more components.

  Examples of the method for producing the block copolymer include the methods described in Japanese Patent Application Nos. 2005-515281 and 2007-516326.

  As a commercial item of an XYX type block copolymer, the acryl-type triblock copolymer manufactured using the living polymerization made from Arkema is mentioned. Specific examples include MAM types represented by polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate (for example, M51, M52, M53, M22, etc.), MAM A type modified with carboxylic acid (for example, SM4032XM10, etc.) And MAM N type (for example, 52N, 22N, M65N, etc.) subjected to hydrophilic group modification treatment, KULARITY LA2140e, LA2330, LA2250, LA4285, etc. manufactured by Kuraray.

  Moreover, the mass average molecular weight (Mw) of a block copolymer is 20,000-400,000, and what is in the range of 30,000-300,000 is preferable. The molecular weight distribution (Mw / Mn) is preferably 3 or less.

  When the mass average molecular weight is 20,000 or more, the effects of toughness and flexibility are good, and the tackiness is also good. On the other hand, when the mass average molecular weight is 400,000 or less, the viscosity of the curable resin composition does not become too high, and the printability and developability are not easily lowered.

  A block copolymer may be used individually by 1 type, and may be used in combination of 2 or more type. The blending amount of the block copolymer is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, and particularly preferably 3 to 15 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. The elongation rate and intensity | strength of a coating film improve that it is 1 mass part or more. If it is 30 parts by mass or less, the developability is improved.

[(C) Thermosetting resin]
The curable resin composition of the present invention includes a thermosetting resin. By thermosetting the resin composition of the present invention, properties such as heat resistance and insulation reliability of the cured product can be improved.

  Thermosetting resins include known and commonly used thermosetting resins such as isocyanate compounds, blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, epoxy compounds, polyfunctional oxetane compounds, and episulfide resins. Can be used.

  In the curable resin composition of the present invention, an epoxy resin is particularly preferably used. As the epoxy resin, a known and commonly used polyfunctional epoxy resin having at least two epoxy groups in one molecule can be used. The epoxy resin may be liquid, and may be solid or semi-solid.

  Examples of epoxy resins include jER828, jER834, jER1001, and jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, Epoto YD-011, YD-013 manufactured by Tohto Kasei Co., Ltd. YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Sumitomo Epoxy ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Mitsubishi Chemical, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., manufactured by Dow Chemical Of D. E. R. 542, Sumitomo Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd., EPPN-201, EOCN-1025, EOCN manufactured by Nippon Kayaku Co., Ltd. -1020, EOCN-104S, RE-306, NC-3000, Sumitomo Epoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Co., Ltd., A.C. E. R. ECN-235, ECN-299, YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704, YDCN manufactured by Nippon Steel Chemical Co., Ltd. -704A, novolak type epoxy resin such as Epicron N-680, N-690, N-695 (all trade names) manufactured by DIC; Epicron 830 manufactured by DIC, jER807 manufactured by Mitsubishi Chemical Corporation, manufactured by Tohto Kasei Co., Ltd. Epototo YDF-170, YDF-175, YDF-2004 and the like (all trade names) bisphenol F type epoxy resin; Toto Kasei Co., Ltd. Epototo ST-2004, ST-2007, ST-3000 (trade names) and other water Bisphenol A type epoxy resin; jER604 manufactured by Mitsubishi Chemical Corporation, Epototo YH-434 manufactured by Toto Kasei Co., Ltd. Glycidylamine type epoxy resin such as Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (all trade names); Hydantoin type epoxy resin; Celoxide 2021 manufactured by Daicel Chemical Industries Ltd. Epoxy resin: YL-933 manufactured by Mitsubishi Chemical Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all trade names) Type or biphenol type epoxy resin or a mixture thereof; Nippon Kayaku EBPS-200, ADEKA EPX-30, DIC EXA-1514 (trade name), etc .; bisphenol S type epoxy resin; Bisphenol A novolac type epoxy resin such as jER157S (trade name); tetraphenylolethane type epoxy resin such as jERYL-931 (all trade name) made by Mitsubishi Chemical; TEPIC made by Nissan Chemical Industries (all) Product name) heterocyclic epoxy resin; diglycy such as NOF's Bremer DGT Ruphthalate resin; Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Tohto Kasei Co., Ltd .; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by DIC Naphthalene group-containing epoxy resin; epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by NOF; Examples include, but are not limited to, copolymerized epoxy resins of cyclohexylmaleimide and glycidyl methacrylate; CTBN-modified epoxy resins (for example, YR-102 and YR-450 manufactured by Tohto Kasei Co., Ltd.) and the like.

  A thermosetting resin may be used individually by 1 type, and may be used in combination of 2 or more type. The compounding amount of the thermosetting resin is preferably 10 to 50 parts by mass, more preferably 10 to 45 parts by mass, and particularly preferably 10 to 40 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. The intensity | strength of a coating film improves that it is 10-50 mass parts. When it is 50 parts by mass or less, the developability is good.

[(D) Filler]
The curable resin composition of the present invention contains at least one filler selected from the group consisting of inorganic fillers and organic fillers for the purpose of improving properties such as adhesion, hardness, and heat resistance. Examples of the inorganic filler include barium sulfate, calcium carbonate, barium titanate, silicon oxide, amorphous silica, talc, clay, hydrotalcite, Neuburg siliceous particles, mica powder, and the like, and the organic filler includes silicon powder, Examples thereof include nylon powder and fluorine powder. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers. Among the fillers, silica is particularly excellent in low hygroscopicity and low volume expansion. Silica may be a mixture of these materials regardless of melting or crystallinity, but in particular, silica surface-treated with a coupling agent or the like is preferable because it can improve electrical insulation. In addition, examples of the filler include fiber reinforcements such as organic bentonite, montmorillonite, glass fiber, carbon fiber, and boron nitride fiber.

  The average particle size (D50) of the filler is preferably 25 μm or less, more preferably 10 μm or less, and even more preferably 3 μm or less. Here, D50 is a particle size at a volume accumulation of 50% obtained by using a laser diffraction scattering type particle size distribution measuring method based on Mie scattering theory. More specifically, it can be measured by creating a particle size distribution of fine particles on a volume basis with a laser diffraction / scattering particle size distribution measuring device and setting the median diameter as an average particle size. As the measurement sample, a sample in which fine particles are dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction particle size distribution measuring apparatus, LA-500 manufactured by Horiba, Ltd. can be used.

  A filler may be used individually by 1 type and may be used in combination of 2 or more type. The blending amount of the filler is suitably 300 parts by mass or less, preferably 5 to 150 parts by mass, per 100 parts by mass of the (A) carboxyl group-containing resin. When the blending amount of the filler is 300 parts by mass or less, the folding resistance of the cured film is unlikely to decrease.

[(E) Photopolymerization initiator]
The photopolymerization initiator includes at least one light selected from the group consisting of an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. A polymerization initiator can be preferably used.

（式中、Ｘは、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）を表し、Ｙ、Ｚはそれぞれ、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、結合か、炭素数１〜１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５−ピロール−ジイル、４，４’−スチルベン−ジイル、４，２’−スチレン−ジイルで表し、ｎは０か１の整数である。）Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, NCI-831 manufactured by Adeka, and the like as commercially available products. Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.

(In the formula, X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms). A group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms), And Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon number 1). Alkyl group having 1 to 8 alkoxy group, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkyl group having 1 to 8 carbon atoms) Group or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms, or Represents an anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, and Ar is a bond or alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene , Anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, and n is an integer of 0 or 1.)

  In particular, in the above general formula, X and Y are each a methyl group or an ethyl group, Z is a methyl group or a phenyl group, n is 0, Ar is a bond, phenylene, naphthylene, thiophene, or thienylene. It is preferable that

  It is preferable that the compounding quantity of such an oxime ester system photoinitiator shall be 0.01-5 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin. When it is 0.01 parts by mass or more, the photocurability on copper becomes good, the coating film is hardly peeled off, and the coating properties such as chemical resistance are improved. On the other hand, when it is 5 parts by mass or less, light absorption on the surface of the coating film is suppressed, and the deep curability tends to be improved. More preferably, it is 0.5-3 mass parts.

  As the α-aminoacetophenone photopolymerization initiator, specifically, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N , N-dimethylaminoacetophenone and the like. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by BASF Japan.

  Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO and Irgacure 819 manufactured by BASF Japan.

  The blending amount of these α-aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of (A) carboxyl group-containing resin. . When it is 0.01 parts by mass or more, the photocurability on copper becomes good, the coating film is hardly peeled off, and the coating properties such as chemical resistance are improved. On the other hand, when the amount is 15 parts by mass or less, an effect of reducing outgas is obtained, light absorption on the surface of the coating film is further suppressed, and deep curability tends to be improved. More preferably, it is 0.5-10 mass parts.

  Here, as the photopolymerization initiator to be used, the oxime ester initiator is added in a small amount, and outgassing is suppressed, which is effective in terms of PCT resistance and crack resistance. Further, it is particularly preferable to use an acylphosphine oxide photopolymerization initiator in addition to the oxime ester initiator because a shape with good resolution can be obtained.

These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.
The total amount of such a photopolymerization initiator, photoinitiator assistant, and sensitizer is 35 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin having at least one of the imide structure and the amide structure. The following is preferable. When the amount is 35 parts by mass or less, these light absorptions are suppressed, and the deep curability tends to be improved.

  Photopolymerization initiators, photoinitiator assistants, and sensitizers that can be suitably used in the curable resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenone compounds. , Xanthone compounds, and tertiary amine compounds.

  Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

  Examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.

  Examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, and the like.

  Examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.

  Examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.

  Examples of the benzophenone compound include benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4′-methyl diphenyl sulfide, 4-benzoyl-4′-ethyl diphenyl sulfide, 4-benzoyl-4′-propyl diphenyl sulfide, and the like. It is done.

  As the tertiary amine compound, an ethanolamine compound, a compound having a dialkylaminobenzene structure, for example, 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylaminobenzophenone (Hodogaya Chemical Co., Ltd.) Dialkylaminobenzophenones such as EAB); dialkylamino group-containing coumarin compounds such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin); Ethyl dimethylaminobenzoate (Kayacure (registered trademark) EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-dimethylaminobenzoic acid (n-buto Ii) Ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoic acid (Esolol 507 manufactured by Van Dyk) ) And the like. In particular, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are preferable. As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. A dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has a maximum absorption wavelength in the ultraviolet region, so that it is less colored and uses not only a colorless and transparent curable resin composition, but also a color pigment, and the color pigment itself It becomes possible to provide a colored cured film reflecting the color of the color. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

  Of these compounds, thioxanthone compounds and tertiary amine compounds are preferred. The composition of the present invention preferably contains a thioxanthone compound from the viewpoint of deep curable properties. Among them, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone A thioxanthone compound such as

  As a compounding quantity of a thioxanthone compound, 20 mass parts or less are preferable with respect to 100 mass parts of carboxyl group-containing resin. When the blending amount of the thioxanthone compound is 20 parts by mass or less, the thick film curability is good, and the cost of the product is suppressed. More preferably, it is 10 parts by mass or less.

  As a compounding quantity of a tertiary amine compound, 0.1-20 mass parts is preferable with respect to 100 mass parts of (A) carboxyl group-containing resin. When the amount of the tertiary amine compound is 0.1 parts by mass or more, a sufficient sensitizing effect tends to be obtained. On the other hand, if it is 20 parts by mass or less, light absorption on the surface of the dried coating film by the tertiary amine compound is suppressed, and the deep curability tends to be improved. More preferably, it is 0.1-10 mass parts. These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.

  The total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of (A) carboxyl group-containing resin. When the amount is 35 parts by mass or less, these light absorptions are suppressed, and the deep curability tends to be improved.

  (E) The photopolymerization initiator may be a photobase generator that generates a base by light irradiation. The photobase generator functions as a reaction catalyst between (A) a carboxyl group-containing resin and (C) a thermosetting resin by changing the molecular structure upon irradiation with ultraviolet light or visible light, or by cleaving the molecule. It is a compound that produces one or more types of basic substances. Examples of basic substances include secondary amines and tertiary amines.

  (E) When the photopolymerization initiator generates a base by light irradiation, the curable resin composition of the present invention does not need to contain the following photopolymerizable monomer, and a cured product having a high tensile elongation can be obtained. .

  Examples of the photopolymerization initiator that generates a base by light irradiation include an oxime ester photopolymerization initiator and an α-aminoacetophenone photopolymerization initiator. One photopolymerization initiator that generates a base by light irradiation may be used alone, or two or more photoinitiators may be used in combination. The amount of the photopolymerization initiator that generates a base by light irradiation is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the thermosetting resin.

(Other carboxyl group-containing resins)
The curable resin composition of the present invention may include (A) a resin other than the carboxyl group-containing resin, that is, a carboxyl group-containing resin having neither a known or commonly used imide structure or amide structure. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is more preferable in terms of photocurability and development resistance. And the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof. In the case of using only a carboxyl group-containing resin having no ethylenically unsaturated double bond, in order to make the composition photocurable, a compound having a plurality of ethylenically unsaturated groups in the molecule described below, That is, it is necessary to use a photopolymerizable monomer in combination.
As specific examples of the carboxyl group-containing resin having neither an imide structure nor an amide structure, compounds listed below (any of oligomers and polymers) can be suitably used.

  (1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.

  (2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (3) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

  (4) During the synthesis of the resin of the above (2) or (3), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic carboxyl group-containing photosensitive urethane resin.

  (5) During the synthesis of the resin of (2) or (3), one isocyanate group and one or more (meth) acryloyl groups are added in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. A carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal (meth) acrylate.

  (6) A carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or higher polyfunctional epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride to a hydroxyl group present in the side chain. Here, the epoxy resin is preferably solid.

  (7) Carboxyl group-containing photosensitivity in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin, and a dibasic acid anhydride is added to the resulting hydroxyl group. Resin. Here, the epoxy resin is preferably solid.

  (8) Two bases such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are reacted with a dicarboxylic acid such as adipic acid, phthalic acid, and hexahydrophthalic acid by reacting the bifunctional oxetane resin. A carboxyl group-containing polyester resin to which an acid anhydride is added.

  (9) Reaction product obtained by reacting a compound obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.

  (10) Obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a reaction product obtained by reacting a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.

(11) A carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule to the resins (1) to (10).
In addition, in this specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

Since the carboxyl group-containing resin as described above has a large number of carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.
The acid value of the carboxyl group-containing resin is suitably in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is 40 mgKOH / g or more, alkali development is facilitated. On the other hand, when the acid value is 200 mgKOH / g or less, the dissolution of the exposed portion by the developer is difficult to proceed, and the line may be thinner than necessary Depending on the case, it is possible to suppress the dissolution and peeling with the developer without distinguishing between the exposed portion and the unexposed portion, and to satisfactorily draw the resist pattern.

  Moreover, although the weight average molecular weight of the said carboxyl group containing resin changes with resin frame | skeletons, what is generally in the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. When the weight average molecular weight is 2,000 or more, the tack-free performance is good, the moisture resistance of the coated film after exposure is good, the film loss is suppressed during development, and the resolution can be prevented from being lowered. On the other hand, when the weight average molecular weight is 150,000 or less, the developability is good and the storage stability is excellent.

  The amount of such a carboxyl group-containing resin is 20 to 60% by mass, preferably 30 to 50% by mass in the entire composition. When the blending amount of the carboxyl group-containing resin is 20% by mass or more, the film strength is good. On the other hand, when the amount is 60% by mass or less, the viscosity of the composition does not become too high, and the coating property and the like become good.

  These carboxyl group-containing resins can be used without being limited to those listed above, and can be used singly or in combination. In particular, among the carboxyl group-containing resins, resins having an aromatic ring are preferable because they have a high refractive index and excellent resolution, and those having a novolak structure not only have resolution but also PCT and It is preferable because of excellent crack resistance.

(Photopolymerizable monomer)
The curable resin composition of the present invention may contain a known and commonly used photopolymerizable monomer. The photopolymerizable monomer is a compound having one or more ethylenically unsaturated groups in the molecule. The ethylenically unsaturated group is preferably derived from acrylic acid, methacrylic acid or derivatives thereof. The photopolymerizable monomer assists photocuring of the carboxyl group-containing resin having an ethylenically unsaturated group by irradiation with active energy rays.

  Examples of the compound used as the photopolymerizable monomer include conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, and epoxy (meth) acrylate. It is done. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethylacrylamide Acrylamides such as N-methylol acrylamide and N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like Polyvalent acrylates such as a tylene oxide adduct, a propylene oxide adduct, or an ε-caprolactone adduct; a polyvalent acrylate such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adduct or propylene oxide adduct of these phenols Acrylates; glyceryl diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyglycerides of glycidyl ether such as triglycidyl isocyanurate; not limited to the above, polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, A polyol such as polyester polyol is directly acrylated or urethane acrylate is added via diisocyanate. Examples include acrylates and melamine acrylates, and at least any one of methacrylates corresponding to the acrylates.

  Among these, the use of a photopolymerizable monomer having an aromatic ring is preferable in terms of reduction in warpage.

  Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, or a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. An epoxy urethane acrylate compound obtained by reacting a half urethane compound may be used as a photoreactive monomer. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

  The compounding quantity of a photopolymerizable monomer is 5-100 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin, Preferably, it is a ratio of 5-70 mass parts. In the case of 5 parts by mass or more, photocurability is improved, and pattern formation is facilitated by alkali development after irradiation with active energy rays. On the other hand, when the amount is 100 parts by mass or less, the solubility in an alkaline aqueous solution is improved and the coating film strength is improved.

(Coloring agent)
A coloring agent can be mix | blended with the curable resin composition of this invention.

  As the colorant, conventionally known colorants such as red, blue, green, yellow, white, and black can be used, and any of pigments, dyes, and pigments may be used. However, it is preferable that the colorant does not contain a halogen from the viewpoint of reducing environmental burden and affecting the human body.

  Although there is no restriction | limiting in particular in the mixture ratio of a coloring agent, Preferably it is 0-10 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin, More preferably, it is used in the ratio of 0.1-5 mass parts. . When the colorant is white, the blending amount of the white colorant is preferably 300 parts by mass or less, more preferably 250 parts by mass or less with respect to 100 parts by mass of the (A) carboxyl group-containing resin.

(Binder polymer)
For the resin composition of the present invention, conventionally known binder polymers can be used for the purpose of improving the flexibility and dryness of the touch of the resulting cured product.

  As the binder polymer, a cellulose-based, polyester-based, or phenoxy resin-based polymer is preferably used.

  As the cellulose polymer, Eastman's cellulose acetate butyrate (CAB), cellulose acetate propionate (CAP) series, as the polyester polymer, Toyobo's Byron series, as the phenoxy resin polymer as bisphenol A, Bisphenol F and phenoxy resins of their hydrogenated compounds are preferred.

  The blending amount of the binder polymer is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, and particularly preferably 5 to 30 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. When the blending amount of the binder polymer is 50 parts by mass or less, the alkali developability of the curable resin composition becomes good, and the usable potable time for development does not become too short.

(Elastomer)
The curable resin composition of the present invention can be blended with an elastomer for the purpose of imparting flexibility to the resulting cured product and improving the brittleness of the cured product.

  Examples of the elastomer include polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyesteramide elastomers, acrylic elastomers, and olefin elastomers.

  In addition, a resin in which a part or all of epoxy groups of epoxy resins having various skeletons are modified with a carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can be used.

  Furthermore, epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers and the like can also be used.

  One type of elastomer may be used alone, or a mixture of two or more types may be used.

(Thermosetting catalyst)
The curable resin composition of the present invention preferably contains a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are trade names of bicyclic amidine compounds and salts thereof) and the like. It is done. In particular, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with a thermosetting catalyst.
In the curable resin composition of the present invention, the tensile strength is improved by combining imidazole or an imidazole derivative and melamine. On the other hand, the tensile elongation rate is improved by combining the phosphorus compound and melamine.

  The blending amount of these thermosetting catalysts is sufficient at a normal quantitative ratio. For example, 0.1 to 20 parts by mass, and more preferably 0.5 to 100 parts by mass of (C) thermosetting resin. -15.0 parts by mass.

(Adhesion promoter)
In the curable resin composition of the present invention, an adhesion promoter can be used in order to improve the adhesion between layers or the adhesion between the photosensitive resin layer and the substrate.

  Examples of the adhesion promoter include benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, List 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent, etc. Can do.

(Antioxidant)
In many polymer materials, once oxidation starts, oxidative degradation occurs one after another in a chain, resulting in a decrease in the function of the polymer material. In the curable resin composition of the present invention, (1) a radical scavenger that invalidates the generated radical and (2) the generated peroxide is decomposed into harmless substances so that no new radical is generated. At least one of antioxidants such as a peroxide decomposer can be added.

  Specific examples of the radical scavenger include hydroquinone, 4-tert-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2-methylene-bis- (4-methyl- 6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3 5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′di-t-butyl-4-hydroxybenzyl) -S-triazine-2,4,6- Phenolic compounds such as (1H, 3H, 5H) trione, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6,6-tetramethyl-4-piperidyl - sebacate, and the like amine compounds such as phenothiazine.

  The radical scavenger may be commercially available, for example, ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (above, manufactured by ADEKA, trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN S Japan 5100, manufactured by TINUVIN S ) And the like.

  Specific examples of the antioxidant that acts as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3 ′. -Sulfur compounds such as thiodipropionate.

  The peroxide decomposing agent may be commercially available, for example, ADK STAB TPP (manufactured by ADEKA, trade name), Mark AO-412S (manufactured by ADEKA, trade name), Sumilizer TPS (manufactured by Sumitomo Chemical Co., Ltd. Name).

  An antioxidant may be used individually by 1 type and may be used in combination of 2 or more type.

(UV absorber)
Since the polymer material absorbs light and thereby decomposes and deteriorates, the curable resin composition of the present invention uses an ultraviolet absorber in addition to the antioxidant in order to take a countermeasure against stabilization against ultraviolet rays. can do.

  Examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like.

Specific examples of benzophenone derivatives include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone and the like can be mentioned.
Specific examples of benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl. Examples include -4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate.
Specific examples of the benzotriazole derivative include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) enzotriazole, 2- (2 ′ -Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, and the like.
Specific examples of the triazine derivative include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.

  Ultraviolet absorbers may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, manufactured by BASF Japan Ltd., trade name).

  An ultraviolet absorber may be used individually by 1 type, and may be used in combination of 2 or more type. By using in combination with an antioxidant, the molded product obtained from the curable resin composition of the present invention can be stabilized.

(Other additives)
In the curable resin composition of the present invention, additives such as a thermal polymerization inhibitor, a thickener, an antifoaming agent, a leveling agent, a silane coupling agent, and a rust inhibitor can be used as necessary.

Examples of the thickener include finely divided silica, organic bentonite, and montmorillonite.
Examples of antifoaming agents and leveling agents include silicones, fluorines, and polymers.
Examples of the silane coupling agent include imidazole, thiazole, and triazole.

  The thermal polymerization inhibitor can be used to prevent unintentional thermal polymerization or temporal polymerization of the resin composition.

  Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

(Organic solvent)
Furthermore, an organic solvent can be used in the present invention. The organic solvent comprises (A) synthesis of a carboxyl group-containing resin, components (A) to (C), optionally a mixture of components (D) and other additives, and the resulting curable resin composition as a substrate or carrier. Used to adjust viscosity when applied to film.

  Examples of the organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like.

  More specifically, ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate, ethanol, propano , Ethylene glycol, alcohols such as propylene glycol, octane, can be exemplified aliphatic hydrocarbons decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, a petroleum-based solvents such as solvent naphtha.

  Such an organic solvent may be used individually by 1 type, and may be used as a 2 or more types of mixture.

  The curable resin composition of this invention can also be made into the form of the dry film provided with the carrier film (support body) and the resin layer which consists of a curable resin composition formed on this carrier film.

  In forming a dry film, the curable resin composition of the present invention is diluted with an organic solvent to adjust to an appropriate viscosity, a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, A film can be obtained by applying a uniform thickness on a carrier film with a gravure coater, spray coater or the like, and usually drying at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Although there is no restriction | limiting in particular about a coating film thickness, Generally, it is a film thickness after drying, 5-150 micrometers, Preferably it selects suitably in the range of 10-60 micrometers.

  As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers.

  After the resin layer is formed on the carrier film using the curable resin composition of the present invention, the cover film can be peeled off from the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer. Are preferably laminated.

  As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. In consideration of peeling of the cover film, the adhesive force between the membrane and the cover film is made smaller than the adhesive force between the membrane and the carrier film.

  The curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using, for example, an organic solvent, and on a substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, a curtain A tack-free dry coating film can be formed by coating by a method such as a coating method and volatile drying (temporary drying) of an organic solvent contained in the composition at a temperature of about 60 to 100 ° C. In the case of a dry film obtained by applying a curable resin composition on a carrier film and drying and winding it as a film, the carrier layer is laminated on the substrate so that the resin layer comes into contact with the substrate by a laminator or the like. A resin layer can be formed on a base material by peeling off the film.

  In addition to printed circuit boards and flexible printed circuit boards that are pre-formed on the circuit board, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy , Copper-clad laminates of all grades (FR-4 etc.) and other polyimide films using materials such as copper-clad laminates for high-frequency circuits using fluorine, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate esters, etc. , PET film, glass substrate, ceramic substrate, wafer plate and the like.

  Volatile drying performed after the application of the curable resin composition of the present invention is performed by using a hot-air circulating drying furnace, an IR furnace, a hot plate, a convection oven, or the like (with a steam-heated air source). Can be carried out by using a counter current contact method and a method of spraying a nozzle on a support.

  In this invention, when curable resin composition contains the photoinitiator (D), light irradiation is performed with respect to the said dry coating film or resin layer. Here, when (D) the photopolymerization initiator generates a base, the base is generated from the light irradiation part. The generated base reacts with (A) the carboxyl group-containing resin and (C) the thermosetting resin, and cures by heating at a low temperature as necessary.

  As the light irradiation method, for example, the curable resin composition or the dried film after drying can be exposed with an active energy ray through a photomask having a pattern formed by a contact method or a non-contact method. In addition, the exposed portion can be photocured by directly pattern-exposing the curable resin composition or the dry film with a laser direct exposure machine.

  In any of the above methods, the unexposed portion can be developed with a dilute alkaline aqueous solution (for example, a 0.3 to 3 wt% sodium carbonate aqueous solution) to form a cured product pattern.

  As an exposure machine used for active energy ray irradiation, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, or the like may be used as long as it irradiates ultraviolet rays in the range of 350 to 450 nm.

  Furthermore, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) can also be used. As a laser light source of the direct drawing machine, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used.

The amount of exposure for image formation varies depending on the film thickness and the like, but is generally 20 to 800 mJ / cm ² , preferably 20 to 600 mJ / cm ² .

  As the developing method, dipping method, shower method, spray method, brush method, etc. can be used, and as the developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia An alkaline aqueous solution such as amines can be used.

Further, the cured product pattern is irradiated with active energy rays at, for example, 500 to 2000 mJ / cm ² , and heated to a temperature of, for example, about 140 to 180 ° C. to be thermally cured, whereby (A) a carboxyl group-containing resin and (C ) The thermosetting resin can further react to form a cured product pattern excellent in various characteristics such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.

In the case where the curable resin composition of the present invention is a thermosetting resin composition that does not contain a photopolymerizable monomer and a photopolymerization initiator, the curable resin composition of the present invention is applied onto the substrate as described above. And dried to obtain a dried coating film. Or the resin layer of the dry film of this invention is laminated on a base material.
Then, for example, a cured product is obtained by heating to a temperature of about 140 to 180 ° C. and thermosetting. Then, the cured product pattern can be obtained by irradiating the cured product with a semiconductor laser such as a CO ₂ laser or a UV-YAG laser to form an opening.

The cured product obtained from the curable resin composition of the present invention has a co-continuous structure in which (A) a carboxyl group-containing resin and (B) a block copolymer are connected to each other. High.
The curable resin composition of the present invention is suitable for a printed wiring board, particularly suitable as a permanent film, and particularly suitable as a solder resist, a coverlay, and an interlayer insulating material. In addition, the curable resin composition of this invention can also be used as a solder dam.

  The following examples illustrate the invention in more detail. The present invention is not limited to the following examples. In the examples, “parts” and “%” in the blending amounts of each component are based on mass unless otherwise specified.

(Synthesis of a carboxyl group-containing resin having an imide structure and an amide structure)
(Synthesis Example 1: Carboxyl group-containing resin (A-1) having imide structure and amide structure)
3.8 g of 3,5-diaminobenzoic acid, 2,2′-bis [4- (4-aminophenoxy) in a separable three-necked flask equipped with a stirrer, nitrogen inlet tube, fractional ring, and cooling ring 6.98 g of phenyl] propane, 8.21 g of Jeffamine XTJ-542 (manufactured by Huntsman, molecular weight 10225.64) and 86.49 g of γ-butyrolactone were charged at room temperature and dissolved.

  Next, 17.84 g of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and 2.88 g of trimellitic anhydride were charged and held at room temperature for 30 minutes. Next, 30 g of toluene was added, the temperature was raised to 160 ° C., the mixture was stirred for 3 hours while distilling off toluene and water, and then cooled to room temperature to obtain an imidized product solution.

  To the obtained imidized product solution, 9.61 g of trimellitic anhydride and 17.45 g of trimethylhexamethylene diisocyanate were charged and stirred at a temperature of 160 ° C. for 32 hours. Thus, a polyamideimide resin solution (A-1) having a carboxyl group was obtained. The obtained resin solution (A-1) had a solid content of 40.1% by mass and an acid value of the solid content of 88.1 mgKOH.

(Synthesis Example 2: Carboxyl group-containing resin having an imide structure and no amide structure (A-2))
To a separable three-necked flask equipped with a stirrer, a nitrogen introduction tube, a fractionation ring, and a cooling ring, 22.4 g of 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, 2,2′-bis [4 -(4-aminophenoxy) phenyl] propane 8.2 g, NMP 30 g, γ-butyrolactone 30 g, 4,4′-oxydiphthalic anhydride 27.9 g, trimellitic anhydride 3.8 g, The mixture was stirred at room temperature and 100 rpm for 4 hours under a nitrogen atmosphere. Next, 20 g of toluene was added and stirred for 4 hours while distilling off toluene and water at a silicon bath temperature of 180 ° C. and 150 rpm to obtain an alkali-soluble resin solution (A-2) having an imide ring.
The obtained resin solution (A-2) had a solid content of 35.7% by mass, a solid content acid value of 18 mgKOH, Mw of 10,000, and a hydroxyl group equivalent of 390.

(Preparation of block copolymer)
(Preparation Example 1)
50 g of carbitol acetate was added to 50 g of hydrophilically treated XYX type block copolymer (Nanostrength M52N manufactured by Arkema), and the mixture was stirred and heated to 85 ° C. to dissolve. This is named Varnish B-1. X includes a polymethyl methacrylate structure, and Y includes a polybutyl acrylate structure.

(Preparation Example 2)
50 g of carbitol acetate was added to 50 g of a hydrophilically treated XYX type block copolymer (Nanostrength M65N manufactured by Arkema), and the mixture was stirred and heated to 85 ° C. to dissolve. This is named Varnish B-2. X includes a polymethyl methacrylate structure, and Y includes a polybutyl acrylate structure.

(Preparation Example 3)
50 g of carbitol acetate was added to 50 g of XY-X type block copolymer (Kuraray 2250 manufactured by Kuraray Co., Ltd.), stirred and dissolved by heating at 85 ° C. This is named Varnish B-3. X includes a polymethyl methacrylate structure, and Y includes a polybutyl acrylate structure.

(Example of binder polymer varnish adjustment)
(Comparison adjustment example)
50 g of carbitol acetate was added to 50 g of polymethylmethacrylate (Mitsubishi Rayon Dianal BR-83), stirred and dissolved by heating at 85 ° C. This is called PMMA varnish.

(Preparation of carboxyl group-containing resin (R-1) having neither imide structure nor amide structure)
(Synthesis example)
A novolac-type cresol resin (trade name “Shonol CRG951”, manufactured by Showa Polymer Co., Ltd., OH equivalent: 119.4) is added to an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device. 4 parts, 1.19 parts of potassium hydroxide and 119.4 parts of toluene were charged, the system was purged with nitrogen while stirring, and the temperature was raised. Next, 63.8 parts of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
293.0 parts of an alkylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 part of methylhydroquinone and 252.9 parts of toluene were mixed with a stirrer and a temperature. A reactor equipped with a meter and an air blowing tube was charged, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring. 12.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 parts of the obtained novolak acrylate resin solution and 1.22 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was supplied at a rate of 10 ml / min. While blowing and stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added, reacted at 95 to 101 ° C. for 6 hours, cooled and taken out. In this manner, a carboxyl group-containing photosensitive resin solution (hereinafter abbreviated as R-1) having a non-volatile content of 65% and a solid acid value of 87.7 mgKOH / g was obtained.

(Examples 1-18, Comparative Examples 1-4)
In the composition described in Table 1 below, each component was blended, premixed with a stirrer, and then kneaded with a three-roll mill to prepare a curable resin composition.

＊１：ＰＭＭＡ（ポリメチルメタアクリレート）ワニス
＊２：ビスフェノールＡ型エポキシ樹脂（三菱化学社製ｊＥＲ８２８）
＊３：球状シリカ（アドマテックス社製ＳＯ−Ｅ２）
＊４：エタノン，１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−１−（Ｏ−アセチルオキシム） （ＢＡＳＦジャパン社製イルガキュアーＯＸＥ０２）
＊５：ジペンタエリスリトールヘキサアクリレート（日本化薬社製）
＊６：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：３
＊７：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ １４７
＊８：メラミン（日産化学工業社製）
＊９：トリフェニルホスフィン（北興化学工業社製）
＊１０：イミダゾール（四国化成社製２Ｅ４ＭＺ）

* 1: PMMA (polymethyl methacrylate) varnish * 2: Bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation)
* 3: Spherical silica (SO-E2 manufactured by Admatechs)
* 4: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-1- (O-acetyloxime) (Irgacure OXE02 manufactured by BASF Japan)
* 5: Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.)
* 6: C.I. I. Pigment Blue 15: 3
* 7: C.I. I. Pigment Yellow 147
* 8: Melamine (manufactured by Nissan Chemical Industries)
* 9: Triphenylphosphine (Hokuko Chemical Co., Ltd.)
* 10: Imidazole (2E4MZ manufactured by Shikoku Chemicals)

Performance evaluation:
<Crack resistance>
(Examples 1-10 and Comparative Examples 1-4)
A circuit pattern substrate having a copper thickness of 15 μm is polished with buffalo, washed with water and dried, and then the curable resin compositions of Examples and Comparative Examples are applied to the entire surface by a screen printing method, and a hot air circulation drying oven at 80 ° C. For 30 minutes. After drying, the dried coating film was exposed with an optimum exposure amount measured by a method described later using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp). Thereafter, a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. was developed for 120 seconds under a spray pressure of 2 kg / cm ² to obtain a cured product pattern. The cured product pattern was irradiated with ultraviolet rays under the condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 160 ° C. for 60 minutes. A cured product pattern of the curable resin composition was formed in a form having an opening of 80 μm on copper forming a circuit of a printed wiring board. Next, heat history was added to the obtained printed wiring board at -65 ° C. for 30 minutes and 150 ° C. for 30 minutes as one cycle. Evaluation was made according to the following criteria.

(Examples 11-14)
A circuit pattern substrate having a copper thickness of 15 μm was polished with buffalo, washed with water and dried, and then the curable resin compositions of Examples 11 to 14 were applied to the entire surface by a screen printing method, and a hot air circulation drying oven at 80 ° C. For 30 minutes. After drying, the dried coating film was exposed with an optimum exposure amount measured by a method described later using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp). Thereafter, the mixture was heated in a drying furnace at 90 ° C. for 30 minutes, and then developed with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. under a spray pressure of 2 kg / cm ² for 120 seconds to obtain a cured product pattern. The cured product pattern was irradiated with ultraviolet rays under the condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 160 ° C. for 60 minutes. A cured product pattern of the curable resin composition was formed in a form having an opening of 80 μm on copper forming a circuit of a printed wiring board. Next, heat history was added to the obtained printed wiring board at -65 ° C. for 30 minutes and 150 ° C. for 30 minutes as one cycle. After 1000 cycles, the presence or absence of cracks in the cured product pattern was confirmed by observation with an optical microscope. Evaluation was made according to the following criteria.

(Examples 15 to 18)
A circuit pattern substrate having a copper thickness of 15 μm was polished with buffalo, washed with water and dried, and then the curable resin compositions of Examples 15 to 18 were applied to the entire surface by a screen printing method, and a hot air circulation drying oven at 80 ° C. For 30 minutes. Thereafter, it was cured by heating at 160 ° C. for 60 minutes. The cured product pattern of the curable resin composition is formed with a CO ₂ laser manufactured by Hitachi Via Mechanics Co., Ltd. so as to have an 80 μm opening on copper forming the circuit of the printed wiring board, and then desmeared. It was. Next, heat history was added to the obtained printed wiring board at -65 ° C. for 30 minutes and 150 ° C. for 30 minutes as one cycle. After 1000 cycles, the presence or absence of cracks in the cured product pattern was confirmed by observation with an optical microscope. Evaluation was made according to the following criteria.

A: Crack occurrence rate less than 20% B: Crack occurrence rate of 20% or more and less than 30% Δ: Crack occurrence rate of 30% or more and less than 50% ×: Crack occurrence rate of 50% or more

(Optimal exposure)
After the copper-clad laminated substrate was polished with buffalo, washed with water and dried, the curable resin compositions of Examples 1 to 14 and Comparative Examples 1 to 4 were applied by a screen printing method, and heated at 80 ° C. in a hot air circulation drying oven. Dried for minutes. After drying, exposure was performed using a high-pressure mercury lamp exposure apparatus through a photomask (manufactured by Eastman Kodak Company, Step Tablet No. 2). The irradiated piece was used as a test piece, and after developing for 60 seconds with a developer having a spray pressure of 2 kg / cm ² (1 mass% sodium carbonate aqueous solution at 30 ° C.), the number of steps of the remaining coating film was visually determined. The exposure amount at which the number of steps of the remaining coating film was 10 was determined as the optimum exposure amount.

<Glass transition temperature>
Using the curable resin compositions of the examples and comparative examples, a cured coating film having a size of 5 mm × 10 mm was obtained by the same treatment as the curing treatment in the crack resistance test. With respect to this cured coating film, dynamic viscoelasticity measurement was performed in a temperature range of −50 ° C. to 260 ° C. at a constant temperature increase rate with EXTER 6000 (manufactured by Seiko Instruments Inc.), and the glass transition temperature was measured.

<Tensile test>
Using the curable resin compositions of the examples and comparative examples, a cured coating film having a size of 10 mm × 40 mm was obtained by the same treatment as the curing treatment in the crack resistance test. The tensile strength and tensile elongation of the cured coating film were measured with a tensile strength tester (Autograph AG-X manufactured by Shimadzu Corporation).

<B-HAST resistance>
An evaluation board having a cured product pattern is prepared by performing the same treatment as the curing treatment in the crack resistance test on a comb-type electrode pattern of line / space = 15/15 μm, and electrical characteristics (insulation reliability, electrode corrosion) Evaluation).
The evaluation method was that this comb-shaped electrode was 121 ° C., 97% R.D. H. A bias voltage of DC 5 V was applied under the heating and humidifying conditions, and the time until insulation deterioration was measured. Here, when the electric resistance value fell below 1 × 10 ⁻⁶ Ω, it was determined that the insulation was deteriorated. The evaluation criteria are as follows.
○: Time until insulation deterioration is 200 hours or more Δ: Time until insulation deterioration is more than 100 hours and less than 200 hours ×: Time until insulation deterioration is 100 hours or less

(Example 19, comparative example 5)
<Dry film production>
Each of the curable fat compositions of Example 1 and Comparative Example 1 was appropriately diluted with methyl ethyl ketone, and then, using an applicator, a PET film (FB-50: 16 μm manufactured by Toray Industries Inc.) so that the film thickness after drying was 30 μm. And dried at 40-100 ° C. to obtain a dry film. The obtained dry films were referred to as Example 19 and Comparative Example 5, respectively.

<Production of evaluation substrate>
After the circuit-formed substrate is buffed, the dry film produced by the above method is pressurized using a vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.) at a pressure of 0.8 MPa, 70 ° C., 1 minute, vacuum. Degree: 133.3 Pa was laminated by heating to obtain a substrate (unexposed substrate) having an unexposed resin layer. The dry coating film on the obtained substrate was evaluated for crack resistance, glass transition temperature, tensile test, and B-HAST resistance in the same manner as in the above evaluation method. The PET film was peeled off after exposure. The evaluation results are shown in Table 5.

  Considering the results of the above tests, it can be seen that a cured product having excellent elongation can be obtained by using the curable resin composition of the present invention. Moreover, the cured product obtained from the curable resin composition of the present invention shows satisfactory results in crack resistance, glass transition temperature, tensile strength, and B-HAST resistance.

Claims (8)

(A) a carboxyl group-containing resin having at least one of an imide structure and an amide structure;
(B) a block copolymer,
(C) a thermosetting resin, and
(D) A curable resin composition comprising a filler. The curable resin composition according to claim 1, wherein the block copolymer (B) is a block copolymer represented by the following formula (I).
XYX (I)
(In the formula (I), X is a polymer unit having a glass transition point Tg of 0 ° C. or more, and may be the same or different, and Y is a polymer unit having a glass transition point Tg of less than 0 ° C. )   2. The curable resin composition according to claim 1, wherein the carboxyl group-containing resin having at least one of (A) an imide structure and an amide structure is a carboxyl group-containing resin having an imide structure and an amide structure. object.   The curable resin composition of Claim 1 containing an epoxy resin as said (C) thermosetting resin.   The curable resin composition according to claim 1, further comprising (E) a photopolymerization initiator.   A dry film comprising a resin layer obtained by applying and drying the curable resin composition according to claim 1 on a film.   A cured product obtained by curing the curable resin composition according to any one of claims 1 to 5 or the resin layer of the dry film according to claim 6.   A printed wiring board comprising the cured product according to claim 7.