TW201542674A - Curable resin composition, curable resin composition for forming permanent coating film, dry film and printed wiring board - Google Patents

Abstract

To provide: a curable resin composition which has excellent characteristics such as electrical insulation properties, adhesiveness, heat resistance, crack resistance and gold plating resistance, and which is also excellent in terms of electrical insulation properties and adhesiveness in a harsh environment such as a high-temperature high-humidity environment; a curable resin composition for forming a permanent coating film; a dry film; and a printed wiring board. A curable resin composition which contains (A) a carboxyl group-containing resin, (B) an inorganic filler, (C) a thermosetting component and (D) a compound having a urethane bond, and which is characterized in that the carboxyl group-containing resin (A) contains a carboxyl group-containing resin having a novolac skeleton and the thermosetting component (C) contains a maleimide compound.

Description

Curable resin composition, curable resin composition for forming a permanent film, dry film, and printed wiring board

The present invention relates to a curable resin composition, particularly a curable resin composition for forming a permanent film used for a printed wiring board, a dry film using the same, and a printed wiring board.

In the past, the printed wiring board and the flexible printed wiring board (hereinafter referred to as FPC) are required to be electrically insulated and adhered to various electronic devices such as mobile phones, PHS, notebook personal computers, and camera-integrated VTRs. Various properties such as heat resistance and crack resistance. Therefore, one of these permanent coatings also requires the same characteristics. Among them, the FPC is usually a polyimide substrate, and is different from the printed wiring board of the glass epoxy substrate, and is a film. However, since the formed permanent film, the printed wiring board, and the FPC have the same film thickness, the above-described characteristic load on the permanent film is relatively large in the FPC of the film.

For example, JP-A-2007-41107 (Patent Document 1) proposes a reaction between a biphenyl novolac type epoxy resin and an unsaturated monocarboxylic acid. An alkali aqueous solution-soluble resin obtained by adding a polybasic acid anhydride, an alkali aqueous solution-soluble photosensitive resin composition containing a biphenyl novolac type epoxy resin as a curing agent, and a photopolymerization initiator.

In addition to the above-described characteristics, it is proposed to have low warpage and excellent bendability, and it is preferable to use it as a printed wiring board, in particular, TAB (tape-type automatic bonding), COF (film), and JP-A-2011-123420 (Patent Document 2). A photoreceptor resin composition for an alkali-developable printed wiring board of a solder resist for a FPC represented by a flip chip package. The photosensitive resin composition contains at least one of a carboxyl group-containing urethane resin having a biphenyl novolac structure, a photopolymerization initiator, and aluminum hydroxide and a phosphorus-containing compound.

Since the printed wiring board or the FPC is used in various electronic devices as described above, it is required to have resistance even in a severe environment such as high temperature and high humidity. Therefore, resistance to high temperature and high humidity is also required for the permanent film.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] JP-A-2007-41107 (Patent Application Scope)

[Patent Document 2] Japanese Laid-Open Patent Publication No. 2011-123420 (Application No.)

The permanent film obtained from the resin compositions described in Patent Documents 1 and 2 has room for improvement in electrical insulation properties in a severe environment such as high temperature and high humidity. Such characteristics can be evaluated, for example, by the PCBT (Pressure Cooker Bias Test) promotion test (PCBT resistance).

Therefore, the present invention has an object of providing a curable resin composition of a cured film which is excellent in properties such as insulation resistance, heat resistance, crack resistance, and gold plating resistance, and which is excellent in PCBT resistance.

Furthermore, the present invention has an object of providing a curable resin composition for forming a permanent film containing the curable resin composition, a dry film using the curable resin composition, and a printed wiring board.

The above object can be achieved by a curable resin composition containing (A) a carboxyl group-containing resin, (B) an inorganic filler, (C) a thermosetting component, and (D) a compound having a urethane bond, and the foregoing ( A) The carboxyl group-containing resin contains a carboxyl group-containing resin having a novolac skeleton, and the (C) thermosetting component contains a curable resin composition characterized by a maleic imine compound. The maleic imine compound of the present invention is a compound having a maleimine group, that is, a maleimide derivative. The curable resin composition of the present invention generally has at least one of photocurability and thermosetting property.

A preferred embodiment of the curable resin composition of the present invention is as under.

(1) The carboxyl group-containing resin (A) has at least one of a phenol novolak skeleton and a cresol novolak skeleton.

(2) It is preferred that the maleineimine compound is a polyfunctional maleimide compound, a bismaleimide compound, or a bismaleimide compound having an aromatic ring.

(3) The maleidide compound is contained in an amount of 15% by mass or less based on 100 parts by mass of the (A) carboxyl group-containing resin.

(4) (C) The thermosetting component contains an epoxy resin.

(5) further containing a reactive diluent and a photopolymerization initiator.

(6) The compound (D) having a urethane bond contains at least one selected from the group consisting of a carboxyl group, an epoxy group, and a (meth)acryloyl group.

Moreover, the present invention is also a curable resin composition for forming a permanent film which is characterized by containing the curable resin composition of the present invention.

The preferred embodiment of the curable resin composition of the present invention can be applied to the curable resin composition for forming a permanent film of the present invention.

Further, the present invention is also a dry film characterized by a curable resin layer formed of the above curable resin composition on a carrier film.

The residual amount of the solvent of the curable resin layer formed as described above is preferably 5% by weight or less. Thereby, the curable resin layer of the dry film can be favorably transferred onto the substrate.

The preferred aspect of the above-described curable resin composition of the present invention can be applied to the above dry film of the present invention.

Furthermore, the present invention is also a printed wiring characterized by having a cured film obtained by curing the curable resin composition of the present invention, the curable resin composition for forming a permanent film, or the curable resin layer of the dry film. board.

The preferred embodiment of the curable resin composition of the present invention can be applied to the above-described printed wiring board of the present invention.

The curable resin composition of the present invention is characterized in that a carboxyl group-containing resin having a novolac skeleton is used as the (A) carboxyl group-containing resin, and a maleic imine compound is used as the (C) thermosetting component, and (D) is further used. A compound having a urethane bond. In this way, the cured film obtained from the curable resin composition of the present invention is excellent in properties such as insulation resistance, heat resistance, crack resistance, and gold plating resistance, and further excellent in PCBT resistance. This is considered to be electrical insulation under the harsh environment of high temperature, high humidity, etc. by a combination of a carboxyl group-containing resin having a novolak skeleton, a compound having a urethane bond, and a maleimide compound. Adhesion does not increase other characteristics and enhances.

Therefore, the composition for forming a permanent film, the dry film, and the printed wiring board using the composition of the present invention have excellent characteristics as described above.

[Best Practice for Carrying Out the Invention] <Curable resin composition>

The curable resin composition of the present invention has (A) a carboxyl group-containing resin, (B) an inorganic filler, (C) a thermosetting component, and (D) a compound having a urethane bond as a basic component. Further, as the (A) carboxyl group-containing resin, a carboxyl group-containing resin having a novolak skeleton is used, and as the (C) thermosetting component, a maleic imine compound is used.

[(A) Carboxyl group-containing resin]

In the present invention, as the (A) carboxyl group-containing resin, a carboxyl group-containing resin having a novolak skeleton is mainly used. Here, the (A) carboxyl group-containing resin preferably has at least one of a phenol novolak skeleton and a cresol novolak skeleton. (A) When the carboxyl group-containing resin is a phenol novolak skeleton having a nucleus or more, it is excellent in solder heat resistance. Further, the number of nuclei is, for example, 3 or more and 20 or less. By using a resin containing at least one of a carboxyl group-containing resin having a novolak skeleton, particularly a phenol novolak skeleton and a cresol novolak skeleton, electrical insulation, adhesion, heat resistance, crack resistance, and gold plating can be maintained. The properties such as resistance are good, and electrical insulation and adhesion can be improved even in a severe environment such as high temperature and high humidity.

(A) The carboxyl group-containing resin may be a mixed type of a carboxyl group-containing resin having a phenol novolak skeleton and a carboxyl group-containing resin having a cresol novolak skeleton, or a carboxyl group having a phenol novolak skeleton and a cresol novolak skeleton in one molecule. Resin. Carboxyl group-containing resin having a phenol novolak skeleton The adhesion to the substrate forming material is preferably higher than that of the carboxyl group-containing resin having a cresol novolak skeleton.

Further, when the (A) carboxyl group-containing resin is a mixture of a carboxyl group-containing resin having a phenol novolak skeleton and a carboxyl group-containing resin having a cresol novolak skeleton, the solder heat resistance is improved. The carboxyl group-containing resin having a novolak skeleton may be selected from those conventionally known as various carboxyl group-containing resins having a carboxyl group in the molecule, and a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule may be used. It is better to look at the hardenability or resolution. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof.

The carboxyl group-containing resin having a novolak skeleton may, for example, be the following resin.

(1) An epoxy resin having a novolak skeleton is reacted with (meth)acrylic acid, and a polybasic anhydride such as anhydrous phthalic acid, tetrahydroanhydrophthalic acid or hexahydro anhydrous phthalic acid is added to the hydroxyl group present in the side chain. A carboxyl group-containing photosensitive resin.

(2) The epoxy resin according to (1), wherein the polyfunctional epoxy resin epoxylated with epichlorohydrin is reacted with (meth)acrylic acid to form a carboxyl group-containing photosensitive resin of a polybasic acid anhydride in the resulting hydroxyl group.

(3) The epoxy resin described in (1) is reacted with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and an unsaturated group-containing monocarboxylic acid such as (meth)acrylic acid. The alcoholic hydroxyl group of the obtained reaction product is reacted with a polybasic anhydride such as anhydrous maleic acid, tetrahydro anhydrous phthalic acid, anhydrous trimellitic acid, anhydrous pyromellitic acid or adipic acid. The obtained carboxyl group-containing photosensitive resin.

(4) a reaction product obtained by reacting a novolak resin having a plurality of phenolic hydroxyl groups in one molecule with an epoxide such as ethylene oxide or propylene oxide, and an unsaturated group such as (meth)acrylic acid A carboxyl group-containing photosensitive resin obtained by reacting a monocarboxylic acid and reacting the obtained reaction product with a polybasic acid anhydride.

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

(6) The resin of (1) to (5) is further added to a carboxyl group-containing photosensitive resin having one epoxy group and one or more (meth) acrylonitrile groups in one molecule.

Among the (A) carboxyl group-containing resins having a novolac skeleton, those of (1), (2), (4) to (6) are preferred, and tetrahydrohydrogen phthalic acid is preferred as the polybasic acid anhydride.

Examples of the novolac resin include a polymer of at least one of a phenol and a phenol derivative and a polymer of formaldehyde, and a polymer of a phenol and/or a phenol derivative and another compound with formaldehyde (for example, a thiol group (alkoxy group). A phenol novolak condensate (for example, a biphenyl novolac) obtained by reacting each isomer of a methyl group with biphenyl or a mixture thereof with a phenol and/or a phenol derivative.

In terms of phenol derivatives, such as alkyl substituted phenols such as cresol The number of bases is preferably 1 or 2, and in the alkyl group, the number of carbon atoms is 1 to 18, preferably 1 to 4, more preferably methyl), and aryl substituted phenol such as phenylphenol (aryl group) The number is preferably 1 or 2, and the aryl group is a phenyl group, an alkyl-substituted phenyl group, a biphenyl group, a naphthol or the like, and a phenyl group (aromatic condensed ring) is substituted with a phenol. Further, in combination with a phenol and/or a phenol derivative, a linear phenol, a methane phenol, a linear phenol, a radial 6-nuclear phenol compound, a polyhydric phenol, or an alkyl substituted polyol may also be used. phenol.

Alkyl substituted phenols such as o-cresol, p-cresol, m-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol , 3,4-xylenol, 3,5-xylenol. Further, examples of the polyhydric phenol include catechol, resorcin, hydroquinone, methyl hydroquinone, 2,6-dimethyl hydroquinone, and trimethyl hydroquinone. Pyrogallol, phloroglucinol.

In terms of at least one of a phenol and a phenol derivative, phenol, cresol or xylenol is preferred, and phenol or cresol is preferred.

Examples of commercially available epoxy resins which can be used for the production of a carboxyl group-containing resin having a novolak skeleton of the present invention include, for example, jER152, jER154, manufactured by Mitsubishi Chemical Corporation, and DEN431, DEN438 manufactured by Dow Chemical Co., Ltd. PIC (share) EPICLONN-730, EPICLONN-770, EPICLONN-865, Dongpo Chemical Co., Ltd. EpoTohtoYDCN-701, YDCN-704, Nippon Chemical Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, PCR1170H, Sumiepoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Industries Co., Ltd., AERECN-235, ECN-299, manufactured by Asahi Kasei Industrial Co., Ltd. Phenolic acid Paint epoxy resin. Moreover, in particular, a commercial example of the carboxyl group-containing resin having a phenol novolak skeleton of the present invention may be, for example, PCR 1170H (manufactured by Nippon Kayaku Co., Ltd.).

In addition to the carboxyl group-containing resin having a novolak skeleton of the present invention, other carboxyl group-containing resins may be used as necessary without impairing the properties. Examples of the other carboxyl group-containing resin include a carboxyl group-containing resin containing an epoxy resin having no novolak skeleton as a starting material, and a carboxyl group-containing resin using an acrylic resin or an oxetane compound as a starting material. Specific examples of the other carboxyl group-containing resin include the following compounds (any of an oligomer and a polymer). In the case of other carboxyl group-containing resins, it is preferred to have no urethane structure.

(7) A carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or more polyfunctional epoxy resin having no novolak skeleton with (meth)acrylic acid to form a dibasic acid anhydride in a hydroxyl group present in a side chain.

(8) The hydroxyl group of the bifunctional epoxy resin having no novolac skeleton is further reacted with (meth)acrylic acid with an epichlorohydrin-epoxylated polyfunctional epoxy resin, and the resulting hydroxyl group is added with a dibasic acid anhydride. A carboxyl group-containing photosensitive resin.

(9) Carboxyl group obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate or isobutylene Resin.

(10) The bifunctional oxetane resin described later is reacted with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid to form an anhydrous phthalic acid or tetrahydrogen-free hydride in the resulting hydroxy group. Phthalic acid, hexahydrogen A carboxyl group-containing resin of a polybasic acid anhydride such as hydrophthalic acid.

(11) A carboxyl group-containing resin obtained by further adding a compound having one epoxy group and one or more (meth)acrylonium groups in one molecule to the resin of the above (7) to (10).

Further, in the present specification, (meth) acrylate is a term generally referred to as acrylate, methacrylate, and the like, and the other similar expressions are also the same.

The above-mentioned carboxyl-containing resin is due to the linear type. The side chain of the polymer (polymer backbone) has a plurality of carboxyl groups which become developable in a dilute aqueous alkali solution.

Further, the acid value of the carboxyl group-containing resin is preferably in the range of 40 to 200 mgKOH/g, and more preferably in the range of 45 to 120 mgKOH/g. In the range of 40 mgKOH/g to 200 mgKOH/g, the adhesion of the cured film can be obtained, the alkali development becomes easy, the dissolution of the exposed portion due to the developer is suppressed, and the line does not become too fine, and the pattern of the normal resist pattern is drawn. It's easy.

Further, although the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, it is usually in the range of 2,000 to 150,000 and further preferably in the range of 5,000 to 100,000. In the range of 2,000 to 150,000, the performance of the tack free is good, the moisture resistance of the cured film is good, and the film is not easily thinned during development. Moreover, in the range of the weight average molecular weight, the resolution is improved, the developability is good, and the storage stability is improved.

The amount of such a carboxyl group-containing resin is preferably in the range of 20 to 80% by mass, preferably 30 to 80% by mass based on the entire composition. At 20 quality When the amount is from 80% by mass to 80% by mass, the strength of the cured film is good, and the viscosity of the composition is lowered, and the coating property is excellent.

The above-mentioned carboxyl group-containing resin is not limited to the above-mentioned ones, and a conventional one can be used. That is, the carboxyl group-containing resin having a novolak skeleton is not limited to the above resin, and a conventional one can be used. In particular, the resin having an aromatic ring in such a carboxyl group-containing resin has a high refractive index and is excellent in resolution. The carboxyl group-containing resin having a novolak skeleton is excellent not only in resolution but also in PCT (saturated vapor pressure test) or crack resistance.

[(B) Inorganic Filler]

The photosensitive resin composition of the present invention contains (B) an inorganic filler in order to enhance the physical strength and the like of the cured film. As the (B) inorganic filler, conventionally used inorganic fillers (also known as inorganic fillers) can be used, and in particular, barium sulfate, spherical cerium oxide and talc are preferably used. Further, in order to obtain a white appearance or flame retardancy, a metal hydroxide such as titanium oxide or a metal oxide may be used as the bulk pigment filler. The inorganic filler preferably has an average particle diameter of 5 μm or less. The amount of the (B) inorganic filler to be used is preferably 300 parts by mass or less, further preferably 0.1 to 200 parts by mass, particularly preferably 1 to 100 parts by mass, per 100 parts by mass of the (A) carboxyl group-containing resin. When the amount of the inorganic filler (B) is 300 parts by mass or less, the viscosity of the composition is not excessively high, and the deterioration of the printability and the embrittlement of the cured film can be suppressed.

[(C) Thermosetting component]

The curable resin composition of the present invention contains a maleic imine compound as (C) a thermosetting component.

The maleated imine compound of the present invention may, for example, be (C-1) monofunctional aliphatic/alicyclic maleimine, (C-2) monofunctional aromatic maleimide, (C) -3) a polyfunctional aliphatic/alicyclic maleimine, (C-4) polyfunctional aromatic maleimide.

Monofunctional aliphatic/alicyclic maleimine (C-1), for example, N-methylmaleimide, N-ethylmaleimide, and JP-A-11-302278 A reaction of maleimine carboxylic acid with tetrahydrofurfuryl alcohol or the like.

The monofunctional aromatic maleimide (C-2) may, for example, be N-phenylmaleimide or N-(2-methylphenyl)maleimide.

Polyfunctional aliphatic/alicyclic maleimide (C-3), such as N, N ' -methylene bismaleimide, N, N ' -ethylene bismaleimide, ginseng (Methoxyethyl)isocyanurate and an aliphatic/alicyclic maleic imine carboxylic acid obtained by dehydration and esterification of an isocyanurate skeleton of a maleic ylide compound, a amide (amino group) An isocyanurate skeleton of an isocyanurate skeleton obtained by ethylation of an acid hexyl)isocyanurate with an aliphatic/alicyclic maleimide Compound isomeric cyanuric acid group polymaleimide, isophorone dimethyl urethane bis (N-ethyl maleimide), triethylene glycol bis (maleimide) Ethyl carbonate), aliphatic/alicyclic maleimide carboxylic acid and various aliphatic/alicyclic polyols for dehydration and esterification, or aliphatic/alicyclic maleimide carboxylates Aliphatic/alicyclic polymaleimide ester compounds obtained by transesterification of various aliphatic/alicyclic polyols, aliphatic/alicyclic maleimide carboxylic acids and various aliphatic/ Alicyclic polyepoxide Aliphatic/alicyclic polymaleimide compounds obtained by ring-opening reaction, aliphatic/alicyclic maleimide and various aliphatic/alicyclic polyisocyanates are subjected to ethyl urethane. An aliphatic/alicyclic polymaleimide ethyl carbamate compound obtained by the reaction. Specifically, for example, an alkyl group having 1 to 6 carbon atoms, more preferably a maleimide alkyl carboxylic acid or a maleimide alkyl carboxylate having a linear alkyl group, and a number average molecular weight of 100 The following is obtained by dehydration esterification or transesterification of polyethylene glycol of ~1000 and/or polypropylene glycol having a number average molecular weight of 100 to 1000 and/or polytetramethylene glycol having a number average molecular weight of 100 to 1000; The aliphatic bismaleimine compound represented by the general formula (1) and the general formula (2).

(wherein m is an integer of 1 to 6, n is a value of 2 to 23, and R ¹ is a hydrogen atom or a methyl group.)

(where m is an integer from 1 to 6, and p is a value from 2 to 14.)

Polyfunctional aromatic maleimide (C-4), such as N,N ' -(4,4 ' -diphenylmethane) bismaleimide, bis-(3-ethyl-5- Methyl-4-maleimine phenyl)methane, 2,2'-bis-(4-(4-maleimidophenoxy)propane, N,N ' -(4,4 ' - Diphenyloxy) bismaleimide, N,N ' -p-phenylene bismaleimide, N,N ' -m-phenylene bismaleimide, N,N ' -2,4-methylphenylene bismaleimide, N,N ' -2,6-methylphenylene bismaleimide, maleic imine carboxylic acid and various aromatic polyols An aromatic polymaleimide compound, a maleimide carboxylic acid, and various aromatics obtained by transesterification or a transesterification reaction of a maleidino carboxylic acid ester with various aromatic polyols Aromatic poly-maleimide compound obtained by ether ring-opening reaction of polyepoxide, aromatic polycondensation obtained by subjecting maleimine alcohol and various aromatic polyisocyanates to ethyl carbamate reaction Maleic acid imide ethyl ester compounds and the like.

The polyfunctional aliphatic/alicyclic maleimide (C-3) is excellent in the physical properties of the cured film after high-hardness and active energy ray irradiation. In particular, it is preferable that the balance between the curability of the obtained composition and the physical properties of the cured film is excellent.

In the present invention, among the above-mentioned maleimide compounds, the polyfunctional aromatic maleimide (C-4) is more preferable from the viewpoint of heat resistance. Among them, aromatic bismaleimide is preferred. Especially N,N ' -(4,4 ' -diphenylmethane) bismaleimide, bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane, 2,2'-bis-(4-(4-maleimidophenoxy)propane, N,N ' -(4,4 ' -diphenyloxy) bismaleimide, N, N ' -p-phenylene bismaleimide, N,N ' -m-phenylene bismaleimide, N,N ' -2,4-methylphenylene double malayan Amine, N,N ' -2,6-methylphenylene bismaleimide is preferred, wherein N,N ' -(4,4 ' -diphenylmethane) bismaleimide BMI (manufactured by KI Chemical Industry Co., Ltd.), commercially available, bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane (with BMI-70 ( KI Chemical Industry Co., Ltd. (manufactured by KI Chemical Industry Co., Ltd.), 2,2'-bis-(4-(4-maleimidophenoxy)propane (by BMI-80 (KI Chemical Industry) Co., Ltd. (manufactured by Co., Ltd.) is commercially available. It is considered that by a combination with a carboxyl group-containing resin having a novolak skeleton, it is easy to form a strong crosslinked structure with a carboxyl group-containing resin having a novolak skeleton. It is good in properties such as insulation resistance, adhesion, heat resistance, and gold plating resistance. More preferably, it is a polyfunctional aromatic. The family of male quinone imine, and then the aromatic bismaleimide.

The blending amount of the maleic imine compound of the present invention is preferably 15 parts by mass or less, more preferably 1 to 10 parts by mass, particularly preferably 1 to 8 parts by mass, per 100 parts by mass of the (A) carboxyl group-containing resin. The adhesion to the substrate forming material is improved by 15 parts by mass or less.

The curable resin composition of the present invention may contain a thermosetting component other than the above-described maleimide compound as the (C) thermosetting component. By adding other thermosetting components, heat resistance can be expected Rise. As the other thermosetting component used in the present invention, an amine resin such as a melamine resin, a benzoguanamine resin, a melamine derivative or a benzoguanamine derivative, a blocked isocyanate compound, a cyclic carbonate compound, or a polyfunctional compound can be used. A conventional thermosetting resin such as an epoxy compound, a polyfunctional oxetane compound, an episulfide resin, or a carbodiimide resin. In particular, a thermosetting resin having at least one of a plurality of cyclic ether groups and a cyclic thioether group (hereinafter, abbreviated as a cyclic (thio)ether group) in the molecule is preferred.

The thermosetting component having a plurality of cyclic (thio)ether groups in the above molecule is any one of a cyclic (thio)ether group having a plurality of 3, 4 or 5 membered rings in the molecule or a compound of two types, for example, A polyfunctional epoxy compound having a complex epoxy group in a molecule, a polyfunctional oxetane compound having a compound having a plurality of oxetanyl groups in the molecule, and a compound having a complex thioether group in the molecule, that is, an epoxy group. Resin and the like. Among them, an epoxy resin of a polyfunctional epoxy compound is preferred. Thereby, in particular, solder heat resistance and the like are improved.

Examples of the polyfunctional epoxy compound include epoxidized vegetable oils such as AdekaCizer O-130P, AdekaCizer O-180A, AdekaCizer D-32, and AdekaCizer D-55 manufactured by ADEKA; and Mitsubishi Chemical Co., Ltd. JE828, jER834, jER1001, jER1004, EHPE3150 made by Daicel Chemical Industry Co., Ltd., EPICLON840, EPICLON850, EPICLON1050, EPICLON2055 made by DIC, EpoTohtoYD-011, YD-013, YD-127 made by Dongdu Chemical Co., Ltd. , YD-128, DER317, DER331, DER661, DER664, live by Dow Chemical SumiepoxyESA-011, ESA-014, ELA-115, ELA-128, AER330, AER331, AER661, AER664, etc. (all are trade names) manufactured by Asahi Chemical Industry Co., Ltd. Bisphenol A type epoxy resin; YDC-1312, hydroquinone epoxy resin, YSLV-80XY bisphenol epoxy resin, YSLV-120TE thioether epoxy resin (all manufactured by Dongdu Chemical Co., Ltd.) ); JERYL 903 from Mitsubishi Chemical Co., Ltd., EPICLON 152, EPICLON 165 from DIC, EpoTohto YDB-400 from Dongdu Chemical Co., YDB-500, DER542 from Dow Chemical, Sumitomo Chemical Co., Ltd. SumiepoxyESB-400, ESB-700, AER711, AER714, etc. (all are trade names) brominated epoxy resin manufactured by Asahi Kasei Industrial Co., Ltd.; jER152, jER154, Dow Chemical by Mitsubishi Chemical Corporation EPICONN-730, EPICLONN-770, EPICLONN-865, EpoTohtoYDCN-701, YDCN-704, manufactured by DEN431, DEN438, DIC, and EPPN manufactured by Nippon Chemical Co., Ltd. -201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, SumiepoxyESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Industries Co., Ltd., A. ERECN-235, ECN-299, etc. (all are trade names) of novolak-type epoxy resin; Nippon Chemical Co., Ltd. NC-3000, NC-3100 and other bisphenol novolak-type epoxy resin; DIC (shares) EPICLON830, JER807 made by Mitsubishi Chemical Co., Ltd., EpoTohtoYDF-170, YDF-175, YDF-2004 bisphenol F type epoxy resin manufactured by Dongdu Chemical Co., Ltd.; EpoTohtoST-made by Dongdu Chemical Co., Ltd. 2004, ST-2007, ST-3000 (trade name) and other hydrogenated bisphenol A epoxy resin; Mitsubishi Chemical Co., Ltd. jER604, Dongdu Chemical Co., Ltd. EpoTohtoYH-434, Sumitomo Chemical Industry Co., Ltd. SumiepoxyELM-120 (all are trade names) glycidylamine type epoxy resin; ethyl ureia type epoxy resin; Daicel Chemical Industry Co., Ltd. Celloxide 2021, CY179, etc. (all are trade names) An alicyclic epoxy resin; YL-933 manufactured by Mitsubishi Chemical Corporation; TEN, EPPN-501, EPPN-502 manufactured by Dow Chemical Co., Ltd. (all trade names), and a trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Co., Ltd. YL-6056, YX-4000, YL-6121 (both trade names) and other bisphenol type or bisphenol type epoxy resin or a mixture thereof; EBPS made by Nippon Chemical Co., Ltd. -200, bisphenol S type epoxy resin such as EPX-30 manufactured by ADEKA Co., Ltd., EXA-1514 (trade name) manufactured by DIC Co., Ltd.; bisphenol A such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation A novolac type epoxy resin; a tetraphenyl phenyl type epoxy resin such as jERYL-931 manufactured by Mitsubishi Chemical Co., Ltd. (all of which are trade names); a TEPIC manufactured by Nissan Chemical Industries Co., Ltd. ( All are trade names) Ring epoxy resin; bis-glycidyl phthalate resin such as BLEMMER DGT made by Japan Oils Co., Ltd.; tetraglycidyl xylene decyl ethane resin such as ZX-1063 made by Dongdu Chemical Co., Ltd.; Iron-based (stock) ESN-190, ESN-360, DIC (share) HP-4032, EXA-4750, EXA-4700 and other naphthyl-containing epoxy resins; DIC (stock) HP-7200, HP-7200H An epoxy resin having a dicyclopentadiene skeleton; a glycidyl methacrylate copolymerized epoxy resin such as CP-50S or CP-50M manufactured by Nippon Oil Co., Ltd. a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; an epoxy-modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Daicel Chemical Industry Co., Ltd.), CTBN modified epoxy resin (for example, YR-102, YR-450, etc. manufactured by Tosho Kasei Co., Ltd.), etc., but is not limited thereto. These epoxy resins may be used alone or in combination of two or more. Among these, phenolic varnish type epoxy resin, bisphenol type epoxy resin, bisphenol type epoxy resin, bisphenol novolac type epoxy resin, naphthalene type ring, especially bisphenol A type or bisphenol F type Oxygen resins or mixtures thereof are preferred.

Examples of polyfunctional oxetane compounds, except bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy) Methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxocyclo) Butylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl-3-oxetanyl)methacrylate, (3- Methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate or polyfunctional oxalates such as oligomers or copolymers thereof Examples of the cyclobutanes include oxetane and novolak resins, poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, cup-resorcinol aromatic hydrocarbons, or hydrazine. An etherified product of a resin having a hydroxyl group such as a sesquioxanes or the like. Other examples thereof include a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

The compound having a plurality of cyclic thioether groups in the molecule is, for example, a bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Also, the same synthetic method can be used to form a novolak type. An epoxy sulfide resin in which an epoxy group of an epoxy resin is substituted with a sulfur atom or the like.

The amount of the thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is preferably in the range of from 1 to 2 equivalents based on the carboxyl group of the (A) carboxyl group-containing resin and from 0.6 to 2.5 equivalents in the cyclic (thio)ether group. . When the amount of the compound is 0.6 or more, the heat resistance, alkali resistance, and electrical insulation of the cured film are improved. On the other hand, when the amount is 2.5 equivalent or less, the strength of the cured film or the like is improved. More preferably, it is 0.8 to 2.0 equivalents.

Further, examples of the amine resin such as a melamine derivative or a benzoguanamine derivative which are exemplified as other thermosetting resins are a methylol melamine compound, a methylol benzoguanamine compound, and a methylol glycoluril compound. And hydroxymethyl urea compounds and the like. Further, an alkoxymethylated melamine compound, an alkoxymethylated benzoguanamine compound, an alkoxymethylated glycoluril compound, and an alkoxymethylated urea compound can be obtained by using a respective methylol group The melamine compound, the methylol benzoguanamine compound, the methylol glycoluril compound, and the methylol group of the methylol urea compound are converted into an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group.

Such commercial products, such as Cymel 300, the same 301, the same 303, the same 370, the same 325, the same 327, the same 701, the same 266, the same 267, the same 238, the same 1141, the same 272, the same 202, the same 1156, Same as 1158, the same 1123, the same 1170, the same 1174, the same UFR65, the same 300 (all manufactured by Mitsui Cyanamid Co., Ltd.), NIKALAC Mx- 750, the same Mx-032, the same Mx-270, the same Mx-280, the same Mx-290, the same Mx-706, the same Mx-708, the same Mx-40, the same Mx-31, the same Ms-11, the same Mw- 30, the same as Mw-30HM, the same Mw-390, the same Mw-100LM, the same Mw-750LM, (all three and Mitsui Cyanamid Co., chemical (stock) system). Such a thermosetting component may be used alone or in combination of two or more.

The amount of the thermosetting component such as the amine-based resin is preferably 30 parts by mass or less, more preferably 0.1 to 20 parts by mass, even more preferably 1 to 15 parts by mass, per 100 parts by mass of the carboxyl group-containing resin.

[(D) Compound having a urethane bond]

As the compound having a urethane bond, a conventional compound having a urethane bond can be used. For example, an isocyanate compound (for example, a monoisocyanate, a diisocyanate, a polyisocyanate) and a compound having an OH group (for example, a polyol such as a monohydric alcohol, a polyester polyol, a polyether polyol, or a (meth) acrylate of an epoxy resin) The reaction product, and the like, and the like.

In the present invention, those having a urethane bond are preferably those having a carboxyl group, having an epoxy group, and having a (meth) acrylonitrile group, and examples thereof include the following carboxyl group-containing resin (1). Epoxy resin (2), (3), and (meth) acrylonitrile-based resin (1), (4), (5). Further, in the following exemplification, at least two of a carboxyl group, an epoxy group, and a methacryl group may be contained in one resin.

(1) by diisocyanate and bisphenol A type epoxy resin, Hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol phenol epoxy resin, bisphenol epoxy resin, etc. a carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of a partial acid anhydride modified product of an acrylate, a carboxyl group-containing diol compound, and a diol compound.

(2) A metal urethane bond having an isocyanate group obtained by reacting a polyhydroxy compound with a polyisocyanate compound and a hydroxyl group-containing epoxy compound is reacted to have a urethane bond and 2 More than one epoxy-based urethane-modified epoxy resin.

(3) A diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, a polycarbonate polyol, a polyether polyol, or a polyester polyol, a polyolefin-based polyol, an acrylic polyol, an epoxy resin having a hydroxyl group (by which an epoxy group-containing urethane resin can be obtained), a bisphenol A-based epoxide addition diol, and a phenol A urethane resin obtained by a polyaddition reaction of a diol compound such as a compound having a hydroxyl group and an alcoholic hydroxyl group.

(4) In the above reaction (3), a part or all of the diisocyanate is substituted with a molar reactant such as isophorone diisocyanate and pentaerythritol triacrylate, and has one isocyanate group and one molecule in the molecule. The above-mentioned (meth) acrylonitrile-based compound is a photosensitive urethane resin obtained by a polyaddition reaction of an isocyanate with the above diol compound.

(5) In the synthesis of the resin of any one of the above (3) and (4), a compound having one hydroxyl group and one or more (meth)acryl fluorenyl groups in a molecule such as a hydroxyalkyl (meth) acrylate is added. A terminal (meth)acrylated photosensitive urethane resin.

Among the above-mentioned resins having a urethane bond, (1) in the carboxyl group-containing resin, (2) in the epoxy group-containing resin, and (5) in the (meth)acryl oxime group-containing resin are preferred.

As the diisocyanate, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Examples of aromatic polyisocyanates are, for example, 4,4'-diphenylmethane diisocyanate, 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate, naphthalene-1,5-di Isocyanate, o-fluorene diisocyanate, m-fluorene diisocyanate, 2,4-methylphenyl dimer, and the like. Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethyl hexamethylene diisocyanate, and 4,4-methylene bis ( Cyclohexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include, for example, bicycloheptane triisocyanate. Among these, aliphatic isocyanates are particularly preferred.

A commercial example of a carboxyl group-containing resin having a urethane bond, for example, UXE-3000 (manufactured by Nippon Kayaku Co., Ltd.), and a commercially available product of a resin having a urethane bond can be used. For example, Ebecryl 210 (aromatic urethane acrylate; manufactured by Daicel Chemical Industry Co., Ltd.), EPU-7N (ethyl urethane modified epoxy resin; manufactured by ADEKA).

(D) When the compound having a urethane bond is a carboxyl group-containing resin having a urethane bond, the acid value of the carboxyl group-containing resin is preferably in the range of 40 to 200 mgKOH/g, and further preferably 45 to 120 mgKOH/ The range of g is better. In the range of 40 mgKOH/g to 200 mgKOH/g, the adhesion of the cured film can be obtained, the alkali development becomes easy, the dissolution of the exposed portion due to the developer is suppressed, and the line does not become too fine, and the pattern of the normal resist pattern is drawn. It's easy.

(D) When the compound having a urethane bond is a carboxyl group-containing resin having a urethane bond, the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally 2,000 to 150,000, and further The range of 5,000 to 100,000 is preferred. In the range of 2,000 to 150,000, the performance without peeling off is good, the moisture resistance of the cured film is good, and the film is not easily thinned during development. Moreover, in the range of the weight average molecular weight, the resolution is improved, the developability is good, and the storage stability is improved.

In the present invention, in order to obtain excellent characteristics, a carboxyl group-containing resin having a phenol novolak skeleton and a compound having a urethane bond are used in combination. In order to highly combine these characteristics, the mass ratio of the carboxyl group-containing resin having the phenol novolak skeleton to the compound having a urethane bond (the carboxyl group-containing resin having a phenol novolak skeleton: having an amino formate B) The compound of the ester bond is preferably 1:9 to 9:1, and further 4:6 to 8:2, especially 5:5 to 8:2. By increasing the ratio of the carboxyl group-containing resin having a phenol novolak skeleton in the carboxyl group-containing resin, heat resistance is improved. Conversely, by increasing the proportion of the compound having a urethane bond, the crack resistance or PCBT resistance is improved.

Further, the compound having a urethane bond is used in combination with the above-mentioned bismaleimide (C) and the above-mentioned carboxyl group-containing resin (A) having a novolak skeleton, in addition to insulation resistance, adhesion, and heat resistance. In addition to properties such as properties and gold plating resistance, crack resistance or PCBT resistance is improved.

[Photopolymerization initiator]

The curable resin composition of the present invention, particularly in the case of photocuring, preferably contains a photopolymerization initiator. As the photopolymerization initiator, an oxime ester photopolymerization initiator having an oxime ester group, an alkyl acetophenone photopolymerization initiator, an α-aminoacetophenone photopolymerization initiator, and ruthenium are preferably used. One or more kinds of photopolymerization initiators selected from the group consisting of a phosphine oxide-based photopolymerization initiator and a titanocene-based photopolymerization initiator.

In particular, the above-mentioned oxime ester-based initiator can be added in a small amount, and the exhaust gas can be suppressed, so that it is effective for PCT resistance or crack resistance.

For the oxime ester-based photopolymerization initiator, for example, CGI-325, IRGACURE OXE01, IRGACURE OXE02 manufactured by BASF Japan Co., Ltd., N-1919 manufactured by ADEKA Co., Ltd., NCI-831, and the like can be mentioned. Further, a photopolymerization initiator having two oxime ester groups in the molecule may also be preferably used. Further, an oxime ester photopolymerization initiator having a carbazole structure is preferred. The amount of the oxime-based photopolymerization initiator is preferably from 0.01 to 5% by mass, more preferably from 0.25 to 3% by mass, based on the total amount of the composition.

A commercially available product of an alkyl acetophenone-based photopolymerization initiator may, for example, be IRGACURE 184, DAROCUR 1173, IRGACURE 2959, IRGACURE 127, etc., manufactured by BASF Japan Co., Ltd. Alpha-hydroxyalkyl acetophenone type. The α-aminoacetophenone photopolymerization initiator may specifically be, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1, 2 -benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylbenzene) Methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone and the like. For the commercial product, for example, IRGACURE 907, IRGACURE 369, IRGACURE 379, etc., manufactured by BASF Japan Co., Ltd., may be mentioned.

The fluorenylphosphine oxide-based photopolymerization initiator may specifically be, for example, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or bis(2,4,6-trimethylbenzene). Mercapto)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, and the like. For the commercial product, for example, Lucirin TPO manufactured by BASF Japan Co., Ltd., IRGACURE 819 manufactured by BASF Japan Co., Ltd., and the like can be mentioned.

The amount of the α-aminoacetophenone-based photopolymerization initiator and the fluorenylphosphine oxide-based photopolymerization initiator is preferably from 0.1 to 25% by mass, preferably from 1 to 20% by mass, based on the total amount of the composition. .

Further, as a photopolymerization initiator, IRGACURE 389 manufactured by BASF Japan Co., Ltd. may also be preferably used. The suitable amount of IRGACURE 389 is preferably 0.1 to 20% by mass, and further preferably 1 to 15% by mass of the entire composition.

Next, a titanocene-based photopolymerization initiator such as IRGACURE 784 can also be preferably used. The suitable amount of the titanocene-based photopolymerization initiator is 0.01 to 5% by mass, and more preferably 0.01 to 3% by mass based on the entire composition.

By making these photopolymerization initiators suitable for matching, A cured film which is excellent in photocurability and resolution, and has improved adhesion and PCT resistance, and is excellent in chemical resistance such as electroless gold plating resistance.

In such a curable resin composition, a photoinitiator or a sensitizer can be used in addition to the photopolymerization initiator. Examples of the photopolymerization initiator, photoinitiator, and sensitizer which are suitably used in the curable resin composition include a benzoin compound, an acetophenone compound, an anthraquinone compound, and a thioxanthone compound. A ketal compound, a benzoacetophenone compound, a tertiary amine compound, and a xanthone compound.

As the benzoin compound, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and the like.

In terms of acetophenone compounds, such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-di Chloroacetophenone and the like.

As the hydrazine compound, for example, 2-methyl hydrazine, 2-ethyl hydrazine, 2-t-butyl hydrazine, 1-chloroindole or the like can be mentioned.

In terms of thioxanthone compounds, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorosulfanthone, 2,4-di Propylthioxanthone and the like.

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

Examples of benzoacetophenone compounds, such as benzoacetophenone, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfide, 4-benzylformamidine Base-4'-ethyldiphenyl sulfide, 4-benzylidene-4'- Propyl diphenyl sulfide or the like.

As the tertiary amine compound, for example, an ethanolamine compound or a compound having a dialkylaminobenzene structure, for example, a commercially available product, for example, 4,4'-dimethylaminobenzoacetophenone (Japan Soda) ) Nisso Cure MABP), 4,4'-diethylaminobenzoacetophenone (EAB from HODOGAYA CHEMICAL CO., LTD.), dialkylaminobenzobenzophenone, 7-(two) Dialkylamino group containing ethylamino)-4-methyl-2H-1-benzopyran-2-one (7-(diethylamino)-4-methylcoumarin) Coumarin compound, ethyl 4-dimethylamino benzoate (KAYACURE EPA, manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylamino benzoate (Quantacure DMB, manufactured by International Bio-Synthetics) , 4-dimethylamino benzoic acid (n-butoxy) ethyl ester (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylamino benzoic acid isoamyl ethyl ester (Japanese chemical ( KAYACUREDMBI), 2-ethylhexyl benzoic acid 2-ethylhexyl ester (Esolol 507 manufactured by Van Dyk Co., Ltd.), 4,4'-diethylaminobenzophenone (HODOGAYA CHEMICAL CO.) , LTD. system EAB) and so on.

Among these, a thioxanthone compound and a tertiary amine compound are preferred. In particular, the sulfur-containing xanthone compound is preferably from the viewpoint of deep hardenability. Among them, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorosulfanthone, 2,4-diisopropylthioindole A sulfur-based xanthone compound such as a ketone or the like is preferred.

With respect to the amount of such a sulfur-based xanthone compound, 20% by mass or less of the entire composition is preferable. When the amount of the sulfur-based xanthone compound is 20% by mass or less, the thick film hardenability is improved. More preferably, it is 10% by mass or less.

Further, in the case of the tertiary amine compound, a compound having a dialkylaminobenzene structure, wherein a dialkylaminobenzophenone compound and a maximum absorption wavelength in the range of 350 to 450 nm are preferable. Alkylamino coumarin compounds and coumarin ketones are particularly preferred.

In the case of dialkylaminobenzobenzophenone compounds, the toxicity of 4,4'-diethylaminobenzoacetophenone is also low. The dialkylamine-based coumarin compound has a maximum absorption wavelength of 350 to 410 nm and an ultraviolet ray, and a coloring agent can be used for the hardening film which is less colored and colorless and transparent, and provides a colored hardening film reflecting the color of the coloring agent itself. In particular, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm, which is preferable.

The amount of such a tertiary amine compound is preferably from 0.01 to 20% by mass based on the total amount of the composition. When the amount of the tertiary amine compound is less than 0.01% by mass, there is a tendency that a sufficient sensitizing effect cannot be obtained. On the other hand, in the case of 20% by mass or less, there is a tendency to improve the deep curing property. More preferably, it is 0.5 to 10% by mass.

These photopolymerization initiators, photoinitiating aids, and sensitizers may be used singly or in combination of two or more kinds.

The total amount of the photopolymerization initiator, the photoinitiating aid, and the sensitizer is preferably 30% by mass or less based on the entire composition.

[Reactive diluent]

In the case where the curable resin composition of the present invention is photocured, it is preferred to contain a reactive diluent. As the reactive diluent, a compound having an ethylenically unsaturated group in the molecule is preferred. The compound having an ethylenically unsaturated group in the molecule is photocured by irradiation with an active energy ray, and the photosensitive resin composition of the present invention can be insoluble in an aqueous alkali solution or insolubilized. As such a compound, conventional polyester (meth) acrylate, polyether (meth) acrylate, ethyl urethane (meth) acrylate, carbonate (meth) acrylate, epoxy group can be used. (meth) acrylate, ethyl urethane (meth) acrylate, specifically hydroxyalkyl acrylate such as 2-hydroxyethyl acrylate or 2-hydroxy propyl acrylate; ethylene glycol, a diacrylate of a diol such as methoxytetraethylene glycol, polyethylene glycol or propylene glycol; N,N-dimethyl decylamine, N-methylol acrylamide, N,N-dimethyl Acrylamides such as propylaminopropyl acrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate a polyol such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, cis-hydroxyethyl isocyanurate or the like, or such an ethylene oxide adduct, a propylene oxide adduct, or a polyvalent acrylate such as an ε-caprolactone adduct; a phenoxy acrylate, a bisphenol A diacrylate, and an ethylene oxide adduct of such phenols or Polyvalent acrylates such as oxypropylene adducts; shrinkage of glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc. a polyvalent acrylate of a glyceryl ether; not limited to the above, for example, a polyether polyol, a polyhydric alcohol such as a polycarbonate diol, a hydroxyl terminated polybutadiene or a polyester polyol, or an acrylate and melamine acrylate which is acrylated with a diisocyanate; At least one of each of the methacrylates of the above acrylate is used.

Further, for example, an epoxy acrylate resin in which a polyfunctional epoxy resin such as a cresol novolac type epoxy resin and acrylic acid are reacted, or a hydroxyl group of the epoxy acrylate resin and a hydroxy acrylate such as pentaerythritol triacrylate may be used. An epoxy group-ethyl urethane acrylate compound or the like which is reacted with an ethyl melamine compound of a diisocyanate such as isophorone diisocyanate. Such an epoxy acrylate-based resin does not lower the dryness of the touch and can improve the photocurability.

The compound having an ethylenically unsaturated group in the above-mentioned molecule may be used singly or in combination of two or more kinds. In particular, a compound having four to six ethylenically unsaturated groups in one molecule is preferred from the viewpoint of photoreactivity and resolution, and further, if a compound having two ethylenically unsaturated groups in one molecule is used, Therefore, the coefficient of thermal expansion of the cured product is lowered, and the peeling at the time of PCT is lowered, which is preferable.

The compounding amount of the compound having an ethylenically unsaturated group in the above-mentioned molecule is preferably from 2 to 50% by mass based on the entire composition. When the amount of matching is 2% by mass or more, pattern formation becomes easy. On the other hand, in the case of 50% by mass or less, the strength of the cured film is increased. More preferably, it is 3 to 40% by mass.

[Isocyanate compound]

In the curable resin composition of the present invention, a compound having a complex isocyanate group in one molecule and a compound having a plurality of blocked isocyanate groups in one molecule can be added. Examples of the compound having a complex isocyanate group or a blocked isocyanate group in one molecule include a polyisocyanate compound or a blocked isocyanate compound. Further, the blocked isocyanate group refers to a group in which an isocyanate group is protected by a reaction with a block agent, and a group which is temporarily inactivated is heated to a specific temperature, and the block agent is dissociated to form an isocyanate group. By adding the above polyisocyanate compound or the blocked isocyanate compound, the hardenability and the toughness of the obtained cured product are improved.

As such a polyisocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate can be used.

Specific examples of the aromatic polyisocyanate are, for example, 4,4'-diphenylmethane diisocyanate, 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate, naphthalene-1,5- Diisocyanate, o-fluorene diisocyanate, m-fluorene diisocyanate, 2,4-methylphenyl dimer, and the like.

Specific examples of the aliphatic polyisocyanate include, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, and 4,4-methylene double. (cyclohexyl isocyanate) and isophorone diisocyanate.

Specific examples of the alicyclic polyisocyanate include, for example, bicycloheptane triisocyanate. And an adduct of an isocyanate compound, a biuret body, an isocyanurate body, etc. which were mentioned previously.

For blocked isocyanate compounds, isocyanates can be used. An addition reaction product of a compound and an isocyanate block agent. The isocyanate compound which can be reacted with a block agent, for example, the above polyisocyanate compound or the like.

In the case of isocyanate block agents, for example, phenolic blockers such as phenol, cresol, xylenol, chlorophenol and ethylphenol; ε-caprolactam, δ-valeroguanamine, γ-butyrolactone and Hydrazine blocker such as β-propionalamine; active methylene blocker such as ethyl acetate and acetonitrile; methanol, ethanol, propanol, butanol, amyl alcohol, Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, glycolic acid methyl ester, two Alcohol blocker such as butyl acrylate, diacetone alcohol, methyl lactate and ethyl lactate; formaldehyde oxime, acetald oxime, acetone oxime, methyl ethyl ketone oxime, diethyl hydrazino monohydrazine, a thiol blocker such as cyclohexane hydrazine; a thiol blocker such as butyl thiol, hexyl thiol, t-butyl thiol, thio phenol, methyl thiophenol or ethyl thiophenol; An amide-based blocker such as decylamine or benzamidine; a quinone imide blocker such as succinimide succinate or succinimide; guanamine, aniline, butylamine, dibutyl Amine-based amine blocker; imidazole, 2-ethylimidazole, etc. An azole blocker; an imine blocker such as a methyleneimine or a propyleneimine.

Block isocyanate compounds are commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desumosamu 2170, Desumosamu 2265 (all are made by Sumitomo Basel Ethyl Ester Co., Ltd.), CORONATE 2512, CORONATE 2513, CORONATE 2520 (all are Japanese polyamines) Acid Ethyl Industrial Co., Ltd.), B-830, B-815, B-846, B-870, B-874, B-882 (all are Mitsui Cyanamid Co., manufactured by Mitsui Takeda) TPA-B80E, 17B-60PX, and E402-B80T (all of which are manufactured by Mitsui Cyanamid Co., Chemical Co., Ltd.). Further, Sumidur BL-3175 and BL-4265 were obtained by using methyl ethyl hydrazine as a block agent. The compound having a complex isocyanate group or a blocked isocyanate group in one molecule may be used singly or in combination of two or more kinds.

The compounding amount of the compound having a complex isocyanate group or a blocked isocyanate group in one molecule is preferably from 0.1 to 50% by mass based on the total amount of the composition. When the amount of the compound is 0.1% by mass or more, the toughness of the sufficiently cured film can be obtained. On the other hand, in the case of 50% by mass or less, the storage stability is improved. More preferably, it is 1 to 30% by mass.

[Organic solvents]

In the curable resin composition of the present invention, an organic solvent can be used for the preparation of the above-mentioned carboxyl group-containing resin or the preparation of the composition or the viscosity adjustment applied to the substrate or the carrier film.

Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, for example, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, and Solvesso 150; cellosolve, methyl cellosolve, butyl cellosolve, and card Glycol ethers such as alcohol, methyl carbitol, butyl carbitol, propylene glycol monomethyl 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, propylene glycol butyl ether acetate, diethylene glycol single Esters such as ethyl ether acetate (carbitol acetate), diethylene glycol monobutyl ether acetate, alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; octane and decane Such as aliphatic hydrocarbons; petroleum ethers such as petroleum ether, naphtha, hydrogenated naphtha, and solvent oil. Such an organic solvent may be used alone or in combination of two or more.

[hardening accelerator]

In the present invention, a hardening accelerator (hardening catalyst) of a thermosetting component, a hardening accelerator (hardening catalyst) for reacting a thermosetting component with a carboxyl group-containing resin, or an imidazole may also be used. Isocyanate adduct.

The hardening accelerator may, for example, be dicyandiamide, a derivative of dicyandiamide, melamine, imidazole, benzimidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methyl Imidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc. Imidazole derivative; benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4 - an amine compound such as methyl-N,N-dimethylbenzylamine; a heterocyclic compound such as benzoxazole or benzothiazole benzotriazole, such as triphenylphosphine or tri-p-tolylphosphine; Grade III phosphine such as tri-o-tolylphosphine, tri-m-tolylphosphine, Torinadono 2,4dimethylphenylphosphine, tetradecyltetraphenylborate, tetraphenylphosphonium tetra-p-methylphenylborate, four a quaternary phosphonium salt such as phenylsulfonium thiocyanate or tetrabutyl decanoate. Among them, 4 grades of strontium salt It is better. Further, among them, tetraphenylphosphonium tetra-p-methylphenylborate is particularly preferable from the viewpoint of storage stability.

These hardening accelerators may be used alone or in combination of two or more. The amount of the hardening accelerator is generally from 0.01% by mass to 15% by mass, more preferably from 0.1% by mass to 10% by mass based on the total mass of the composition.

In general, when a large amount of a polymer material starts to oxidize, it is oxidatively degraded in a chain, and the polymer material function is lowered. Therefore, in the curable resin composition of the present invention, in order to prevent oxidation, a radical which invalidates the generated radical can be added. The scavenger or/and an antioxidant such as a peroxide decomposing agent that decomposes the produced peroxide into a harmless substance without generating a new radical.

As the antioxidant used as the radical scavenger, specific examples of the compound include hydroquinone, 4-t-butylcatechol, 2-t-butyl hydroquinone, and hydroquinone. Methyl ether, 2,6-di-t-butyl-p-cresol, 2,2-methylene-bis(4-methyl-6-t-butylphenol), 1,1,3- Ginseng (2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-paran (3,5-di-t-butyl 4--4-hydroxybenzyl)benzene, 1,3,5-gin (3',5'-di-t-butyl-4-hydroxybenzyl)-S-triazine-2,4,6-( 1H, 3H, 5H) ketones such as ketones, ruthenium, phenylhydrazine, etc., bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate, thio An amine compound such as diphenylamine or the like.

The radical scavenger may be a commercially available one, such as 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, Solitaire (manufacturing system, trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111 FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, Ciba Specialty Chemicals Inc., trade name).

Specific examples of the antioxidant used as the peroxide decomposer include a phosphorus compound such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, and dilauryl thiodipropionate. A sulfur-based compound such as distearylsulfonyl 3,3'-thiodipropionate.

The peroxide decomposing agent may be a commercially available one, and examples thereof include, for example, ADK STAB TPP (manufactured by Asahi Kasei Co., Ltd., trade name), Mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd., trade name), and Sumilizer. TPS (Sumitomo Chemical Co., Ltd., trade name), etc.

These antioxidants may be used alone or in combination of two or more.

Generally, due to the absorption of light by polymer materials, it is decomposed. In the curable resin composition of the present invention, in order to prevent the ultraviolet rays from being stabilized, an ultraviolet absorber may be used in addition to the above antioxidant.

Examples of the ultraviolet absorber include a benzoacetophenone derivative, a benzoate derivative, a benzotriazole derivative, a triazine derivative, a benzothiazole derivative, a cinnamate derivative, and an ortho-aminobenzene. a formate derivative, a benzhydrylmethane derivative or the like. Specific examples of the benzoacetophenone derivative include 2-hydroxy-4-methoxybenzoacetophenone, 2-hydroxy-4-n-octyloxybenzoacetophenone, and 2,2. '-Dihydroxy-4-methoxybenzoacetophenone and 2,4-dihydroxybenzoacetophenone. Specific examples of benzoate derivatives The surface may, for example, be 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate or 2,4-di-t-butylphenyl-3,5- Di-t-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivative include, for example, 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole and 2-(2'-hydroxy-5'-methyl group. Phenyl)benzotriazole, 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 and 2-(2'- Hydroxy-3',5'-di-t-pentylphenyl)benzotriazole and the like. Specific examples of the triazine derivative include hydroxyphenyltriazine and bisethylhexyloxyphenol methoxyphenyltriazine.

As the ultraviolet absorber, it can 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) , BASF Japan (share) system, product name), etc.

The ultraviolet ray absorbing agent can be used singly or in combination of two or more kinds, and the molded article obtained from the photosensitive resin composition of the present invention can be stabilized by being used in combination with the above-mentioned antioxidant.

Further, the curable resin composition of the present invention may be blended with a cyanate resin, an organic solvent, an elastomer, a mercapto compound, a colorant, an antioxidant, an ultraviolet absorber, an adhesion promoter, a polymerization inhibitor, or an optional component. At least any of antifoaming agents such as fine powder of cerium oxide, organic bentonite, and montmorillonite, antifoaming agents such as fluorenone, fluorine, and polymer. One type of flammable agent such as a decane coupling agent such as an imidazole system, a thiazole system or a triazole system, a rust inhibitor, a phosphonate, a phosphate derivative or a phosphazene compound, and a conventional additive such as a block copolymer. .

The curable resin composition of the present invention is preferably used for forming a printed wiring board, particularly a cured film for FPC, more preferably for forming a permanent film, and for forming a cover film or a solder resist. Further, the curable resin composition of the present invention can also be used for the formation of an interlayer insulating material, a tin bank or the like.

<dry film>

The dry film of the present invention has a curable resin layer formed by coating and drying the curable resin composition of the present invention. The dry film of the present invention is used by laminating a curable resin layer so as to be in contact with a substrate. The residual amount of the solvent of the curable resin layer formed as described above is preferably 5% by weight or less. Thereby, the curable resin layer can be favorably transferred to the substrate.

In the dry film of the present invention, the curable resin composition can be uniformly applied by a suitable method such as a knife coater, a lip coater, a notch coater, or a film coater by a film such as a carrier film. Drying to form the above-mentioned curable resin layer is preferably produced by laminating a cover film thereon. The cover film and the carrier film may be the same film material or a dissimilar film may be used.

The carrier film of the dry film of the present invention and the film material of the cover film can be used as a dry film by a person skilled in the art.

For the carrier film, for example, a thickness of 2 to 150 μm can be used. A thermoplastic film such as a polyester film such as polyethylene terephthalate.

In the case of the cover film, a polyethylene film, a polypropylene film, or the like can be used, but the adhesion to the curable resin layer is preferably smaller than that of the carrier film.

The film thickness of the curable resin layer on the carrier film of the present invention is preferably 100 μm or less, more preferably 5 to 50 μm.

<Printed wiring board>

The printed wiring board of the present invention is produced using the curable resin composition of the present invention or the curable resin layer of the present invention which constitutes a dry film. The printed wiring board of the present invention is preferably produced by laminating a dry film on a substrate. The printed wiring board of the present invention may be formed by directly applying a curable resin composition to a substrate by a suitable method such as a knife coater, a lip coater, a notch coater, or a film coater. Harden the film.

When the cured film is formed by laminating a dry film or directly coating a curable resin composition, the curable resin layer formed on the substrate is selectively contacted or non-contacted to form a pattern-type mask. Exposure with active energy lines or direct pattern exposure with a laser direct exposure machine. The curable resin layer is cured by the exposed portion, that is, the portion irradiated with the active energy ray.

For the substrate, paper phenol, paper epoxy resin, glass cloth epoxy resin, glass polyimide, glass cloth/non-woven epoxy resin, etc., may be used in addition to a circuit printed wiring board or a flexible printed wiring board. Glass cloth / paper epoxy resin, synthetic fiber epoxy resin, using fluororesin. Polyethylene . Polyethylene. Polyphenylene ether. A copper-clad laminate, a polyimide film, a PET film, a glass substrate, a ceramic substrate, a wafer plate, or the like of all grades (FR-4, etc.) of a composite material such as a cyanate ester resin.

For the exposure machine used for the active energy ray irradiation, a direct drawing device (for example, a laser direct imaging device that directly draws an image by using CAD data from a computer), an exposure machine equipped with a metal halide lamp, and a mount (super) can be used. An exposure machine for a high-pressure mercury lamp, an exposure device equipped with an LED, and an exposure device equipped with a mercury short-arc lamp.

In terms of the active energy ray, it is preferred to use light having a maximum wavelength in the range of 350 to 410 nm. By setting the maximum wavelength within this range, radicals can be efficiently generated from the photopolymerization initiator. Further, although the exposure amount varies depending on the film thickness or the like, it is usually in the range of 5 to 500 mJ/cm ² , preferably 10 to 300 mJ/cm ² .

For the direct drawing device, for example, an Orbotech (stock) system, a PENTAX (stock) system, an ORC (stock) system, a large Japanese SCREEN system, or the like can be used, for example, an active energy ray that emits a maximum wavelength of 350 to 410 nm. The device can be used.

Then, the exposed portion is cured by exposing the curable resin layer in this manner, and then the unexposed portion is developed with a dilute alkali aqueous solution (for example, 0.3 to 3 wt% aqueous sodium carbonate solution) to form a pattern on the curable resin layer.

The development method may be a dipping method, a shower method, a spray method, a brush method, or the like. Further, as the developer, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia or an amine can be used.

Further, by curing the curable resin layer at a temperature of, for example, about 140 to 180 ° C, it is possible to form excellent properties such as adhesion to the substrate forming material, heat resistance, chemical resistance, and electrical insulating properties. The pattern of the hardened film. Further, the pattern of the cured film can also be formed by irradiating a semiconductor laser such as a CO ₂ laser or a UV-YAG laser.

The total thickness of the cured film in the printed wiring board of the present invention is preferably 100 μm or less, more preferably 1 to 50 μm.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples. In addition, the following "parts" and "%" are all based on quality unless otherwise specified.

(modulation of carboxyl group-containing resin) (Synthesis Example 1) (A1: Modulation of a carboxyl group-containing resin having a phenol novolak type skeleton)

190 parts (1 equivalent) of phenol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., P-201, epoxy equivalent 190 g/eq), 140.1 parts of carbitol acetate, and 60.3 parts of solvent oil were added to the flask. Medium, heating at 90 ° C. Stir and dissolve. Once the obtained solution was cooled to 60 ° C, 72 parts (1 mol) of acrylic acid, 0.5 part of methyl hydroquinone, and 2 parts of triphenylphosphine were added, and the mixture was heated to 100 ° C for about 12 hours to obtain an acid value. 0.2 mg KOH / g of reactant. 80.6 parts of tetrahydroanhydrophthalic acid (0.53 mol) was added thereto, and the mixture was heated to 90 ° C for about 6 hours to obtain a resin solution having a solid acid value of 60 mgKOH/g and a solid content of 64.9%. Hereinafter referred to as painting A1.

(Synthesis Example 2) (A2: Modulation of a carboxyl group-containing resin having a cresol novolak type skeleton)

220 parts (1 equivalent) of cresol novolak type epoxy resin (EOCN-104S, epoxy equivalent 220 g/eq), 140.1 parts of carbitol acetate, and 60.3 parts of solvent oil were added. In a flask, heat at 90 ° C. Stir and dissolve. Once the obtained solution was cooled to 60 ° C, 72 parts (1 mol) of acrylic acid, 0.5 part of methyl hydroquinone, and 2 parts of triphenylphosphine were added, and the mixture was heated to 100 ° C for about 12 hours to obtain an acid value. 0.2 mg KOH / g of reactant. 80.6 parts (0.53 mol) of tetrahydro anhydrous phthalic acid was added thereto, and the mixture was heated to 90 ° C for about 6 hours to obtain a resin solution having a solid acid value of 85 mgKOH/g and a solid content concentration of 64.9%. Hereinafter referred to as painting A2.

(Synthesis Example 3) (A3: Modulation of carboxyl group-containing resin (comparative synthesis example))

In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, diethylene glycol monoethyl ether acetate as a solvent and azobisisobutyronitrile as a catalyst were added, and heated to 80 in a nitrogen atmosphere. °C, a monomer in which methacrylic acid and methyl methacrylate are mixed at a molar ratio of 0.40:0.60 It takes about 2 hours to drip.

After further stirring for 1 hour, the temperature was raised to 115 ° C to deactivate the resin solution.

After cooling the resin solution, tetrabutylammonium bromide was used as a catalyst, and butyl glycidyl ether was subjected to a molar ratio of 0.40 to a carboxyl group of the obtained resin at 95 to 105 ° C for 30 hours. The addition reaction was carried out in equal amounts and cooled.

Further, the OH group of the obtained resin was subjected to an addition reaction of anhydrous tetrahydrophthalic acid at a molar ratio of 0.26 at 95 to 105 ° C for 8 hours.

After cooling, it was taken out, and a solution containing a 43% by mass (nonvolatile) solid content of an acid value of 78.1 mgKOH/g and a weight average molecular weight of 35,000 without a aromatic ring was obtained. Hereinafter referred to as painting A3.

(Preparation of carboxyl group containing urethane resin) (A4: Modulation of carboxyl group-containing urethane resin) (Synthesis Example 4)

RE-310S (2-functional bisphenol-A type epoxy resin, ring) manufactured by Nippon Kayaku Co., Ltd., which is an epoxy compound having two or more epoxy groups in the molecule, is added to a 3 L flask equipped with a stirring device and a reflux tube. Oxygen equivalent: 184.0 g/eq., 368.0 g, as a monocarboxylic acid compound having an ethylenically unsaturated group in the molecule, methacrylic acid (molecular weight: 86.09), 168.7 g, 5.49 g of 3,5-di-t-butyl-4-hydroxytoluene which is a thermal polymerization inhibiting agent, after homogenization at 60 ° C, 1.610 g of triphenylphosphine as a reaction catalyst was added, and the reaction was carried out at a temperature of 98 ° C. The acid value of the reaction solution becomes 0.5 mg. An epoxy group-containing carboxylic acid ester compound (theoretical molecular weight: 540.2) was obtained from KOH/g or less.

Then, 854.1 g of carbitol acetate as a solvent for the reaction, and 2,2-bis(dimethylol)-propionic acid as a carboxylic acid compound having two hydroxyl groups in the molecule were added to the reaction liquid (molecular weight: 134.16) 444.6g and warmed to 45 °C. In the solution, 604.8 g of trimethylhexamethylene diisocyanate (molecular weight: 210.3) as a diisocyanate compound was gradually dropped at a reaction temperature of not more than 65 °C. After the completion of the dropwise addition, the temperature was raised to 80 ° C, and the absorption in the vicinity of 2250 cm ^{-1 of the} photosensitive resin was not carried out until the reaction was carried out for 4 hours by the infrared absorption spectrum measurement method, and further, the reaction was carried out at 98 ° C for 2 hours. To the reaction liquid, 29.4 g of carbitol acetate as a solvent for the reaction, and 54.6 g of glycidyl methacrylate (molecular weight: 142.15) which is an epoxy compound having an ethylenically unsaturated group in the molecule were added. After uniformizing at 60 ° C, 7.573 g of triphenylphosphine as a reaction catalyst was added, and the reaction was carried out at 98 ° C until the acid value of the reaction liquid became a set acid value (100.0 mg.KOH/g) to obtain an aqueous alkali solution containing the present invention. Soluble polyurethane urethane compound 65.8 wt% resin solution. The acid value was measured and found to be 64.8 mg. KOH/g (solids acid value: 99.7 mg.KOH/g). Hereinafter referred to as painting A4.

[Examples 1 to 12 and Comparative Examples 1 to 4] (modulation of curable resin composition)

The components shown in the following Table 1 and the ratios (mass parts) shown in Table 1 were blended, mixed with a stirrer, and kneaded in a 3-roll mixer to prepare a curable resin composition.

The meanings of the abbreviations and the reference numerals in Table 1 above are as follows.

※1 painting A1

※2 painting A2

※3 painting A3

※4 barium sulfate

*5 Maleic imine compound BMI-70 (manufactured by KI Chemical Industry Co., Ltd.)

*6 Maleic imine compound BMI-80 (manufactured by KI Chemical Industry Co., Ltd.)

*7 bisphenol A novolac type epoxy resin N-870 (epoxy equivalent 210~220) (made by DIC)

*8 bisphenol type epoxy resin NC-3000H (epoxy equivalent 260~270) (manufactured by JER Co., Ltd.)

※9 painted A4

*10 Aromatic urethane acrylate Ebecryl 210 (manufactured by Daicel-Allnex)

*11 Ethyl urethane modified epoxy resin EPU-7N (epoxy equivalent 200~210) (made by ADEKA)

*12 DPHA (manufactured by Kyoeisha Chemical Co., Ltd.)

*13 Irg907 2-methyl 1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one (BASF JAPAN)

*14 DETX-S 2,4-Diethylthioxanthene-9-one (BASF JAPAN)

※15 2-Phenyl-4,5-dihydroxymethylimidazole

※16 melamine

※17 Pigment Blue 15:4

※18 diethylene glycol monoethyl ether acetate

*19 Aromatic hydrocarbon-based organic solvent Solvesso 150 (manufactured by Exxon Mobil Co., Ltd.)

[Characteristics of Examples 1 to 12 and Comparative Examples 1 to 4]

The following characteristics were carried out using the following evaluation substrate.

Evaluation substrate

The curable resin composition of each of the examples and the comparative examples was applied onto a copper foil substrate on which a pattern was formed, and was applied by screen printing so as to have a dry film thickness of 20 μm, and dried at 80 ° C for 30 minutes. Allow to cool to room temperature. An exposure apparatus equipped with a high-pressure mercury lamp was used for the substrate, and the pattern was exposed to an optimum exposure amount, and then sprayed at a pressure of 0.2 MPa in a 1 wt% aqueous sodium carbonate solution at 30 ° C for 90 seconds to obtain a pattern. The substrate was subjected to ultraviolet irradiation under the conditions of a cumulative exposure amount of 1000 mJ/cm ² in a UV conveyor belt furnace, and then heated and cured at 150 ° C for 90 minutes to obtain an evaluation substrate on which a cured film was formed.

Using the obtained evaluation substrate, evaluation was performed as follows.

<PCBT tolerance>

The evaluation substrate fabricated under the above conditions was comb-shaped using IPCB-25 The electrode B piece was subjected to a bias of DC 30 V to the comb electrode, and was treated at 121 ° C and a humidity of 97% using a PCT apparatus (HAST YSTEM TPC-412MD manufactured by ESPEC Corp.), and the resistance value was measured to be reduced to 1.0 × 107 Ω or less. Time.

The criterion is as follows.

◎: More than 300 hours

○: less than 250 hours for 250 hours or more

△: less than 200 hours after 200 hours

×: less than 200 hours

<Electrical insulation (insulation resistance)>

The evaluation substrate produced under the above conditions was evaluated for electrical characteristics using a comb B pattern having a line/pitch of 50/50 μm.

The evaluation method is such that the comb electrode is subjected to a temperature of 25 to 65 ° C and 90% RH under humidification and humidification conditions for 7 days plus a bias voltage of DC 100 V, so that the resistance value (Ω) after humidification and 500 V addition is performed. The measurement was performed at a score of 1.

○: 1 × 10 ¹² or more.

×: Not up to 1 × 10 ¹² .

<Welding heat resistance>

On the polyimine film substrate on which the circuit pattern is formed, as described above A pattern of a hardened film is formed. The rosin-based flux was applied to the evaluation substrate thus prepared, and immersed in a welding bath set at 260 ° C for 5 times for 5 times, and the flux was washed with a modified alcohol, and the expansion and peeling of the cured film were visually evaluated. . The judgment criteria are as follows.

◎: No peeling.

○: There are 1 to 2 spots that are whitened but not peeled off.

△: The edge portion was peeled off at the center, and it was spotted and whitened.

×: There is swelling, peeling, and overall whitening.

<Gold plating tolerance>

The curable resin composition of each of the above Examples and Comparative Examples was applied to a printed wiring board by a screen printing method, and then dried in a hot air circulating drying oven at 80 ° C for 30 minutes. After cooling to room temperature, the film was exposed to an exposure amount of 700 mJ/cm ² , and hardening was carried out at 150 ° C for 60 minutes in a hot air circulating drying oven to obtain an evaluation sample. The obtained evaluation sample was immersed in an acidic degreasing liquid (20 vol% aqueous solution of Nippon MacDermid, METEX L-5B) at 30 ° C for 3 minutes, and then washed with water, followed by 3 minutes at room temperature in an aqueous solution of 14.4 wt% ammonium persulfate. After immersing and washing with water, it was further immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute. Next, the evaluation substrate was immersed in a 30 ° C catalyst liquid (10 vol% aqueous solution of MELPLATE ACTIVATOR 350, manufactured by Meltex Inc.) for 5 minutes, and then washed with water. The nickel plating solution (Meltex Inc., MELPLATENi-made by Meltex Inc.) was washed at 85 °C. The 865 M 20 vol% aqueous solution, pH=4.6) was immersed for 30 minutes, and after nickel plating, it was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute, and washed with water. Next, the sample substrate was immersed in a gold plating solution (manufactured by Meltex Inc., 15 vol% of Aurolctroless UP and a 3 vol% aqueous solution of potassium cyanide, pH=6) at 95 ° C for 30 minutes, and subjected to electroless gold plating, followed by water washing. The mixture was immersed in warm water at 60 ° C for 3 minutes, and washed with running water. The obtained gold plating evaluation sample was pasted with a scotch tape, and the state of the hardened film at the time of peeling was confirmed. The judgment criteria are as follows.

○: No peeling.

△: There are some peeling of the edge portion.

×: There is peeling and whitening.

<crack tolerance>

The photosensitive composition was applied to a substrate having a copper wire pattern of 2 mm, and exposed and developed in the same manner as described above, followed by ultraviolet irradiation and thermal curing to form 17 3 mm square resist patterns on the copper wire. Evaluation of the substrate. The evaluation substrate was placed in a thermal cycler which was subjected to temperature cycling between -65 ° C and 150 ° C to carry out a TCT (Thermal Cycle Test). Next, the appearance at 1000 cycles was observed, and the number of cracks was counted.

Further, the denominator value "68" indicates four corners (four) × 17 of the 3 mm square resist pattern, and is an angle of 68, and the molecular value "30" indicates the number of cracks.

◎: 20/68 or less

○: 21/68 or more and 30/68 or less

△: 31/68 or more and 40/68 or less

×: 41/68 or more

The results of the above characteristic tests are shown in Table 1.

[Production of dry film:]

Using the curable resin compositions of the above Examples 1 to 11 and Comparative Examples 1 to 4, a dry film having a curable resin layer was produced. The dry film was formed on a polyester film having a thickness of 38 μm as a carrier film, and the curable resin composition was applied by an applicator and dried at 80 ° C for 10 minutes. Here, in the curable resin layer, the organic solvent remains 5% or less with respect to the entire composition.

The same physical property test as described above was carried out using the dry film, but the same result could not be obtained.

Further, after the dry film of each of the examples was laminated on a substrate, the carrier film was peeled off, and it was visually judged whether or not a curable resin composition derived from the curable resin layer was adhered to the carrier film. As a result, the dry film of each of the examples was confirmed, and the curable resin composition was not adhered to the carrier film.

<Measurement of Residual Amount (%) of Organic Solvent in Curable Resin Composition>

After the carrier film was peeled off from the dry film of each of the examples, about 1.2 g of the curable resin layer was taken, and the sealed container was placed, and the quality of the cured resin layer was accurately weighed (W). Add 1 drop of ethyl 3-ethoxypropionate as an internal standard substance in the container with a pipette to make the quality (We) Correct weighing. Thereafter, 5 ml of acetone was added as a Vollpipette, and the mixture was sealed, and the container was sufficiently shaken to dissolve the cured resin layer. Then, the solution was filtered through a filter having an opening of 0.5 μm, and the filtrate composition was analyzed by a gas chromatograph (TRACEGCULTRA, manufactured by Thermo Fisher Scientific Inc.). The mass (Ws) of the organic solvent relative to 1 g of the internal standard substance was determined by a separately prepared calibration curve. Thus, the residual amount of the organic solvent is calculated according to the following formula.

Residual amount of organic solvent (% by mass) = (We × Ws / W) × 100

Further, the measurement conditions of the gas chromatograph are as follows. Column: AgilentTechnologies capillary column DB-1MS (30m × 0.25mm), detector: MS (ITQ900), carrier gas: helium, syringe temperature: 300 ° C, detection temperature: 230 ° C, column temperature conditions: The initial temperature was 50 ° C, and after the sample was injected, the temperature was maintained at 50 ° C for 2 minutes, the temperature was raised to 300 ° C at 10 ° C / minute, and the temperature was maintained at 300 ° C for 10 minutes.

As is apparent from Table 1, the use of the present invention contains (A) a carboxyl group-containing resin having a novolak skeleton, (B) an inorganic filler, (C) a maleimide compound, and (D) having a urethane bond. Examples 1 to 12 of the curable resin composition of the compound (ethyl urethane compound) have excellent properties in PCBT resistance, insulation resistance, solder heat resistance, gold plating resistance, and crack resistance. In particular, in the case where the epoxy resin is further contained (Examples 2, 4, 5, 6, 7 to 9, 11), it is generally seen that the above characteristics (especially PCBT resistance) are further improved. However, (A) Example 10 having a small amount of the carboxyl group-containing resin having a novolac skeleton showed slightly poor performance. On the other hand, in Comparative Examples 1 to 4 in which only one of the components (A) to (D) was absent, insufficient performance was exhibited in all or a plurality of items among the above characteristics.

[industrial use]

The curable resin composition of the present invention can be used as various coating materials such as paints, printing inks, surface treatment agents, molding materials, adhesives, adhesives, adhesives, various resist materials, materials for color filter manufacturing, and light. The material for the waveguide or the like can be particularly used for forming a solder resist of a printed wiring board or an interlayer insulating layer of a multilayer printed wiring board, an optical waveguide layer, or the like.

Claims (10)

A curable resin composition comprising (A) a carboxyl group-containing resin, (B) an inorganic filler, (C) a thermosetting component, and (D) a compound having a urethane bond, which is characterized by the above ( A) The carboxyl group-containing resin contains a carboxyl group-containing resin having a novolac skeleton, and the (C) thermosetting component contains a maleic imine compound. The curable resin composition according to claim 1, wherein the (A) carboxyl group-containing resin has at least one of a phenol novolak skeleton and a cresol novolak skeleton. The curable resin composition according to claim 1 or 2, wherein the maleimide compound is a bismaleimide compound. The curable resin composition according to any one of claims 1 to 3, further comprising a reactive diluent and a photopolymerization initiator. The curable resin composition according to any one of claims 1 to 4, wherein the maleidene compound is contained in an amount of 15 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin (A). The curable resin composition according to any one of claims 1 to 4, wherein the (C) thermosetting component contains an epoxy resin. The curable resin composition according to any one of claims 1 to 6, wherein the compound having a urethane bond (D) contains a carboxyl group, an epoxy group, and a (meth) acrylonitrile group. Select at least 1 base. A curable resin composition for forming a permanent film, characterized by The curable resin composition according to any one of claims 1 to 7 is contained. A dry film comprising the curable resin composition according to any one of claims 1 to 7 or the curable resin layer formed of the curable resin composition for forming a permanent film according to claim 6. A printed wiring board having a curable resin composition according to any one of claims 1 to 5, a curable resin composition for forming a permanent film described in claim 6, or a request 7 A cured film obtained by curing the curable resin layer of the dry film described.