JP2020148815A - Curable resin composition, dry film and cured product of the same, electronic component having the same, and method for producing cured product of curable resin composition - Google Patents

Abstract

To provide a curable resin composition capable of forming a cured film which has excellent shielding property and concealing property and is excellent in resolution, a dry film and a cured product of the same, an electronic component having the same, and a method for producing a cured product of a curable resin composition.SOLUTION: A curable resin composition contains (A) an alkali-soluble resin, (B) a copolymer resin, (C) a photopolymerization initiator generating a radical and a base, (D) an epoxy resin and (E) a black coloring agent, in which (A) the alkali-soluble resin contains (A1) a carboxyl group-containing imide resin, and a content of (E) the black coloring agent is 1.0 mass% or more with respect to the total mass of the solid content of the curable resin composition.SELECTED DRAWING: None

Description

The present invention relates to a curable resin composition, a dry film and a cured product using the same, an electronic component having the curable resin composition, and a method for producing a cured product of the curable resin composition.

In recent years, remarkable progress has been made in the field of semiconductor technology, and along with this, integrated circuits have changed from LSIs to superLSIs, and electronic devices are rapidly becoming smaller, thinner, and lighter, so-called short, small, and thin. It is progressing. In response to this, printed wiring boards are also becoming denser and finer, and moreover, high precision and high performance are required.

In response to this requirement, the solder resist layer formed as a permanent mask on the outermost layer of the printed wiring board is also required to have high performance in terms of various performances such as resolution and electrical characteristics, and new requirements are increasing. ing. For example, in order to make the conductor pattern of a printed wiring board difficult to see, there is an increasing demand for a dark black color tone of a solder resist.

Further, in the solder resist of the printed wiring board used in the optical sensor or the like, the electromagnetic light emitted from the light emitting element is made to function as a light-shielding material so as not to reach the detector directly, and the detection accuracy by the optical sensor is achieved. There is also a demand to increase. The use of black solder resist is also being considered for such light-shielding purposes.

Conventionally, in order to obtain a black photosolder resist having sufficient blackness and excellent resolution, a black solder resist composition containing a black colorant and one or more colorants other than the black colorant has been used. It has been proposed (Patent Document 1).

JP-A-2008-257045

However, the resin composition of Patent Document 1 does not guarantee the resolution enough to cope with the recent tendency of miniaturization of each product or member.
Further, if the content of the black colorant in the resin composition is increased in order to improve the light-shielding property of the cured film, the transmission of ultraviolet rays is hindered, curing failure occurs in the deep part of the cured film, and the insulation reliability is lowered. .. Therefore, in addition to the photocuring component, there is also a method of performing multiple-step curing using a thermosetting component such as an epoxy resin, but so-called "heat fog" occurs and curing is accelerated even in the resin portion to be developed and removed. However, poor resolution may occur such as unstable pattern and opening shape obtained by development. That is, it is not easy to obtain a resin composition having excellent light-shielding property and insulation reliability, suppressing development residue, and excellent resolution even by the method of using the photocurable component and the thermosetting component in combination. ..
In view of the above circumstances, an object of the present invention is a curable resin composition having excellent shielding property or hiding property and insulation reliability, and capable of forming a cured film having excellent resolution by suppressing development residue. It is an object of the present invention to provide a method for producing a product, a dry film and a cured product thereof, an electronic component having the product, and a cured product of the curable resin composition.

As a result of diligent research, the present inventors
(A) Alkali-soluble resin (B) Copolymer resin,
(C) Photopolymerization initiator that generates radicals and bases,
(D) Epoxy resin, and (E) Black colorant,
A curable resin composition containing
The (A) alkali-soluble resin contains (A1) a carboxyl group-containing imide resin.
It has been found that the content of the black colorant (E) is achieved by a curable resin composition characterized by having a content of 1.0% by mass or more based on the total solid content of the curable resin composition. ..

The curable composition of the present invention preferably further contains (F) a polymerization inhibitor.

Further, the above object of the present invention is achieved by a dry film having a curable resin layer obtained from the curable resin composition and a cured product of the curable resin composition.

The above object of the present invention is also achieved by an electronic component including a cured product of a curable resin composition.

Further, the cured product of the curable resin composition of the present invention is
A curable resin layer forming step (a) of applying the above curable resin composition onto a base material,
By irradiating the curable resin layer applied on the substrate with light in a pattern, the photopolymerization initiator that generates (C) radicals and bases contained in the curable resin layer is activated and irradiated with light. Light irradiation step (b) for curing the portion,
Includes a heating step (c) in which the curable resin layer after light irradiation is further cured by heating, and a development step (d) in which the uncured portion of the curable resin layer is removed by development after the heating step (c). It is produced by a method for producing a cured product of a curable resin composition, which is characterized by the above.

The curable resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a copolymer resin, (C) a photopolymerization initiator that generates radicals and bases, (D) an epoxy resin, and (E) black color. A curable resin composition containing a colorant, wherein (A) the alkali-soluble resin contains (A1) a carboxyl group-containing imide resin, and (E) the content of the black colorant is the solid of the curable resin composition. Since it is 1.0% by mass or more with respect to the total mass, it shields electromagnetic waves, especially visible light, so that the circuit of the printed wiring board can be well concealed, and the development residue has insulation reliability. It is possible to suppress and form a cured film having excellent resolution. Further, the dry film obtained from this curable resin composition and the cured product satisfy the requirements for concealment, high density and high fine line. Therefore, the electronic component having the cured product of the present invention can exhibit excellent performance.

Hereinafter, embodiments of the present invention will be described in detail.

As described above, the curable resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a copolymer resin, (C) a photopolymerization initiator that generates radicals and bases, (D) an epoxy resin, and (E) Contains a black colorant.
The curable resin composition of the present invention is applied onto a substrate, dried, and then cured by selectively irradiating a portion to be cured with active energy rays such as ultraviolet rays, and only the uncured portion is developed. It is used in a photolithography method that removes and forms a negative pattern.

Hereinafter, the components of the curable resin composition of the present invention will be described.

[(A) Alkali-soluble resin]
The curable resin composition of the present invention contains (A) an alkali-soluble resin.
In the present invention, the (A) alkali-soluble resin contains one or more types of (A1) carboxyl group-containing imide resin, and the (A1) carboxyl group-containing imide resin used contains an ethylenically unsaturated group. It may or may not be contained, but from the viewpoint of resolution, it is preferable that at least one type does not contain an ethylenically unsaturated group.
As the (A1) carboxyl group-containing imide resin, any alkali-soluble imide resin can be used, and examples thereof include the following.
(1) Carboxyl group-containing branched polyimide obtained by reacting an isocyanurate ring-containing polyisocyanate compound with an acid anhydride of a polycarboxylic acid having three or more carboxyl groups (2) One of the above compounds (1) Carboxylic group-containing branched polymerizable polyimide, which is a compound obtained by reacting a compound having one or more ethylenically unsaturated groups with one epoxy group, or (3) an isocyanate group in the process of synthesizing the compound of (1) above. A carboxyl group-containing branched polymerizable polyimide obtained by reacting a compound having one hydroxyl group with one or more ethylenically unsaturated groups can be mentioned.

Examples of the above (1) include a compound represented by the following formula (I) (also referred to as compound (I)).

(In the formula, n indicates 0 ≦ n ≦ 15.)

Further, as an example of the above (2), in the above formula (I), a structure (I) in which GMA (glycidyl methacrylate) is added to an arbitrary part of the carboxyl group and / or the terminal carboxyl group of the repeating unit (I-1). Examples thereof include a compound having -2).

Here, R represents a residue of compound (I).

Further, as an example of the above (3), in the above formula (I), any part and / or the terminal imide group of the repeating unit (I-1) is an isocyanate residue, and these are hydroxyl groups of pentaerythritol triacrylate. Examples thereof include a compound having a structure (I-3) added with.

Here, R'represents a residue of compound (I).

(A1) Commercially available carboxyl group-containing imide resins include DIC, solvent-soluble amideimide resin, Luxidia EQG-1170 and DIC, alicyclic ultraviolet curable amideimide resin Luxidia EMG-1015, and DIC. Unidic V-8000 manufactured by the manufacturer can be mentioned.

The content of the (A1) carboxyl group-containing imide resin is, for example, 5 parts by mass or more and 100 parts by mass or less, preferably 10 parts by mass or more and 75 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin excluding the component (A1). It is said to be 20 parts by mass or less, particularly 20 parts by mass or more and 50 parts by weight. By using the (A1) carboxyl group-containing imide resin at this ratio, development can be performed well and the insulation reliability of the cured film can be ensured.
The alkali-soluble resin (A) may contain a known alkali-soluble resin (A2) in addition to the (A1) carboxyl group-containing imide resin.

Examples of the alkali-soluble resin (A2) other than the component (A1) include a resin having no imide structure, for example, a compound having two or more phenolic hydroxyl groups, a carboxyl group-containing resin, a phenolic hydroxyl group, and a carboxyl group. Examples thereof include compounds having two or more thiol groups. Of these, it is preferable that the alkali-soluble resin (A2) is a carboxyl group-containing resin or a phenol resin because the adhesion to the substrate is improved. In particular, the alkali-soluble resin (A2) is more preferably a carboxyl group-containing resin because of its excellent developability. The carboxyl group-containing resin may be a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group or a carboxyl group-containing resin having no ethylenically unsaturated group.

Specific examples of the carboxyl group-containing resin include compounds (either oligomers and polymers) listed below.

(1) A carboxyl group-containing resin obtained by copolymerizing 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.

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

(3) Aliphatic compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, and polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, and bisphenol A-based A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride at the end of a urethane resin by a double addition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(4) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Meta) A carboxyl group-containing urethane resin obtained by a double addition reaction of an acrylate or a modified partial acid anhydride thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

(5) During the synthesis of the resin of (2) or (4) above, a compound having one hydroxyl group and one or more (meth) acryloyl groups is added to the molecule such as hydroxyalkyl (meth) acrylate, and the terminal (5) Meta) Acryloylated carboxyl group-containing urethane resin.

(6) During the synthesis of the resin according to (2) or (4) above, one isocyanate group and one or more (meth) acryloyl groups are added to the molecule, such as an isophorone diisocyanate and pentaerythritol triacrylate equimolar reaction product. A carboxyl group-containing urethane resin that is terminal (meth) acrylicized by adding the compound to be possessed.

(7) A carboxyl group obtained by reacting a polyfunctional epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to a hydroxyl group existing in a side chain. Containing resin.

(8) A carboxyl group-containing resin obtained by reacting a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl groups of a bifunctional epoxy resin with epichlorohydrin with (meth) acrylic acid and adding a dibasic acid anhydride to the generated hydroxyl groups. ..

(9) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the generated primary hydroxyl group.

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

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

(12) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth). Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, anhydrous with respect to the alcoholic hydroxyl group of the obtained reaction product. A carboxyl group-containing resin obtained by reacting a polybasic anhydride such as adipic acid.

(13) In addition to the carboxyl group-containing resins described in (1) to (12) above, one epoxy group and one or more (1) epoxy groups in a molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate. Meta) A carboxyl group-containing resin obtained by adding a compound having an acryloyl group.

Among the above-mentioned carboxyl group-containing resins, it is preferable to contain at least one of the above-mentioned carboxyl group-containing resins (7), (8), (10), (11), and (13). From the viewpoint of further improving the insulation reliability, it is preferable to contain the carboxyl group-containing resin described in (10) and (11) above.

Examples of the compound having a phenolic hydroxyl group include a compound having a biphenyl skeleton, a phenylene skeleton, or both skeletons, and phenol, orthocresol, paracresol, metacresol, 2,3-xylenol, 2,4-xylenol, 2 , 5-Xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, fluoroglucinol, etc. Examples thereof include phenolic resins having various skeletons synthesized in the above.

Examples of the compound having a phenolic hydroxyl group include phenol novolac resin, alkylphenol volac resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene-modified phenol resin, polyvinylphenols, and bisphenol F. , Bisphenol S-type phenolic resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes, and other known and commonly used phenolic resins.

Examples of commercially available phenolic resins include HF1H60 (manufactured by Meiwa Kasei Co., Ltd.), Phenolite TD-2090, Phenolite TD-2131 (manufactured by Dai Nippon Printing Co., Ltd.), Vesmol CZ-256-A (manufactured by DIC Corporation), and Cyonor. Examples thereof include BRG-555, Cyonol BRG-556 (manufactured by Aica Kogyo Co., Ltd.), CGR-951 (manufactured by Maruzen Petroleum Co., Ltd.), and polyvinylphenols CST70, CST90, S-1P, and S-2P (manufactured by Maruzen Petroleum Co., Ltd.).

The acid value of the alkali-soluble resin (A) is preferably in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the alkali-soluble resin is 40 mgKOH / g or more, alkaline development becomes easy, while drawing a normal cured product pattern of 200 mgKOH / g or less becomes easy, which is preferable.

The weight average molecular weight of the alkali-soluble resin (A) varies depending on the resin skeleton, but is preferably in the range of 1,500 to 150,000, more preferably 1,500 to 100,000. When the weight average molecular weight is 1,500 or more, the tack-free performance is good, the moisture resistance of the coating film after exposure is good, the film loss during development can be suppressed, and the decrease in resolution can be suppressed. it can. On the other hand, when the weight average molecular weight is 150,000 or less, the developability is good and the storage stability is also excellent.

As the alkali-soluble resin (A), one type can be used alone or two or more types can be used in combination.
In the present invention, it is preferable to use a resin having an ethylenically unsaturated group as the alkali-soluble resin (A) so that a compound having an ethylenically unsaturated group such as a photosensitive monomer is not separately used.

[(B) Copolymer resin]
The curable resin composition contains (B) a copolymer resin.
The (B) copolymer resin is a resin composed of the polymerization of two or more kinds of monomers, and includes alternating copolymers, block copolymers, random copolymers, and graft copolymers. However, the copolymer resin (B) of the present invention is preferably a block copolymer. The copolymer resin (B) is preferably a solid in the range of 20 ° C. to 30 ° C. It may be a solid within this range, and may be a solid at a temperature outside this range. Since it is a solid in the above temperature range, it has excellent tackiness when it is formed into a dry film or when it is applied to a substrate and temporarily dried.
As the copolymer resin (B), those having a weight average molecular weight in the range of 5,000 to 200,000 are particularly preferably used.

Examples of the (B) copolymer resin used in the present invention are as follows.
(1) A copolymer having a weight average molecular weight in the range of Mw 5,000 to 30,000, particularly containing an acrylic acid alkyl ester as a constituent unit. The preferred lower limit of the weight average molecular weight Mw is 8,000, more preferably 10,000, and the preferred upper limit is 20,000, more preferably 12,000.
(2) A block copolymer having a weight average molecular weight of Mw of 50,000 to 200,000, which particularly contains an acrylic acid alkyl ester as a constituent unit. The preferred lower limit of the weight average molecular weight Mw is 100,000, and the preferred upper limit is 150,000.
As an example of the block copolymer of (2),
A ternary copolymer represented by the following formula (I) can be mentioned.
XYX or X'-YX (I)
(In the above formula (I), X is a component having C1-C6 alkyl ester of methacrylic acid or a derivative thereof or styrene as a repeating unit, and X'is a C1-C6 alkyl ester of acrylic acid or a derivative thereof or styrene repeatedly. The constituent part as a unit, Y is a constituent part having a C1-C6 alkyl ester of acrylic acid or a derivative thereof as a repeating unit, and X, X', and Y are structural portions different from each other. )
Further, as another example of the block copolymer of (2) above,
A binary copolymer represented by the following formula (II) can be mentioned.
XY (II)
(In formula (II), X and Y have the same meaning as in formula (I).)
In the formula (I), the mass ratio of the block X and the block X'is almost equal, for example, in the range of 45:55 to 55:45, and the mass ratio (X: Y) of the block X and the block Y is 2:98 to 70. It is preferably in the range of ~ 30.

Among the block copolymers containing the structure of the formula (I), X and X'are highly compatible with the above-mentioned (A) alkali-soluble resin, and Y is a block having low compatibility with the (A) alkali-soluble resin. This makes it possible to obtain a cured product having desired toughness.

As X and X'in the formula (I), poly ((C1-C3 alkyl) (meth) acrylate) such as polymethyl (meth) acrylate (PMMA), polystyrene (PS) and the like are preferable, and poly n- is used as Y. Poly ((C1-C6 alkyl) acrylate) such as butyl acrylate (PBA) and poly (C4-C6 diene) such as butadiene (PB) can be mentioned.

Further, the block copolymer of the formula (I) or the formula (II) can be used as a part of the molecular structure such as diethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc. Amid-based monomers, aromatic vinyl-based monomers such as styrene, α-methylstyrene and p-methylstyrene, conjugated diene-based monomers such as butadiene and isoprene; olefin-based monomers such as ethylene and propylene or It may contain a unit derived from these.

The copolymer resin (B) is also preferably used when it is used as a mixture of the copolymers of (1) and (2) above. The curable resin composition of the present invention is a mixture of (B) copolymer resins having different average molecular weights, thereby giving excellent resolution to the cured product obtained from the composition, and the curable resin composition. The substrate can be well protected while ensuring the adhesion and toughness required as an object.
Regarding (B) copolymer resin, "acrylic" means the above (meth) acrylic ester or a derivative thereof in an amount of 80% by mass or more of X (and X') and Y in the case of (I). It means that it is composed of.

Further, as the (B) copolymer resin used in the present invention, a block copolymer whose molecular structure is precisely controlled, which is synthesized by the living polymerization method, is more preferable in order to obtain the effect of the present invention. It is considered that this is because the block copolymer synthesized by the living polymerization method has a narrow molecular weight distribution and the characteristics of each unit are clear. The molecular weight distribution of the block copolymer used is preferably 2.5 or less, more preferably 2.0 or less.

Examples of the method for producing a block copolymer include the methods described in JP-A-2005-515281 and JP-A-2007-516326.

As a commercially available product of the (B) copolymer resin in the range of weight average molecular weight Mw 5,000 to 30,000, DIANL (registered trademark) LR manufactured by Mitsubishi Chemical Corporation can be mentioned.

Further, as a commercially available product of the (B) copolymer resin having a weight average molecular weight of Mw 50,000 to 200,000, an acrylic triblock copolymer produced by using living polymerization manufactured by Arkema can be mentioned. Specific examples include SBM type represented by polystyrene-polybutadiene-polymethyl methacrylate, MAM type represented by polymethyl methacrylate-poly n-butyl acrylate-polymethyl methacrylate, and carboxylic acid modification and hydrophilic groups. Examples thereof include a modified MAMN type and a MAMA type. Examples of the SBM type include E41, E40, E21, E20 and the like, examples of the MAM type include nanostrength (registered trademark) M22, M51, M52, M53, M65 and SM6290XD30, and examples of the MAM type include nanostrength (Nanostrength). Registered trademarks) M22N, M52N (Mw: 50,000-100,000), M65N and the like (Mw: 100,000-200,000), and MAM A type includes SM4032XM10 and the like.

Further, regarding the (B) copolymer resin having a weight average molecular weight of Mw 50,000 to 200,000, as another example of the above MAM type, it is derived from methyl methacrylate such as Kuraray Co., Ltd. and butyl acrylate. It is also possible to use block copolymerization. Examples of commercially available products include Clarity (registered trademark) LA1114, LA2250, LA2140, LA2330 and the like.

Further, the content of the (B) copolymer resin (solid content) is, for example, 0.5 parts by mass to 10 parts by mass, preferably 2 parts by mass with respect to 100 parts by mass of the curable resin composition (solid content). ~ 6 parts by mass.

The curable resin composition of the present invention can obtain appropriate developability and development resistance by using (A1) a carboxyl group-containing imide resin and (B) a copolymer resin in combination. As a result, even if the composition contains (E) a specific amount or more of the black colorant, the desired opening shape can be formed while suppressing the generation of development residue, and a patterned cured film having excellent resolvability can be formed. Can be obtained.

[(C) Photopolymerization initiator that generates radicals and bases]
As the photopolymerization initiator used in the present invention (C) that generates radicals and bases, one type may be used alone, two or more types may be used in combination, and any known one may be used. be able to.
As the photopolymerization initiator used in the present invention (C) for generating radicals and bases, one type may be used alone, two or more types may be used in combination, and any known one may be used. Examples thereof include an oxime ester compound and an α-aminoacetophenone compound. Of these, the oxime ester compound is preferable.
The (C) photopolymerization initiator undergoes an addition reaction between the (A) alkali-soluble resin and the (C) epoxy resin when the molecular structure is changed by irradiation with light such as ultraviolet rays or visible light or the molecules are cleaved. (C) A compound that produces one or more basic substances that can function as a catalyst for the polymerization reaction of an epoxy resin. Examples of the basic substance include secondary amines and tertiary amines. The action of the photopolymerization initiator (C) in the present invention will be described in more detail in the production method described later.

Examples of the oxime ester-based photopolymerization initiator include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butandione and 2- (O-benzoyloxime) -1- [4-]. (Phenylthio) phenyl] -1,2-pentandione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1 -[4- (Phenylthio) phenyl] -1,2-heptandione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyl) Oxime) -1- [4- (methylphenylthio) phenyl] -1,2-butandione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1,2-butandione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butandione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazole-3-yl] etanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone, 1- (O-Acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone, 1- (O-acetyloxime) -1- [9-ethyl-6 -(2-Ethylbenzoyl) -9H-carbazole-3-yl] etanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) -9H-carbazole-3-yl] ] Etanone, 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone, 2- (acetoxyimimino) -4- (4-chlorophenylthio) -1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazole-3-yl] -1-butanone can be used, and as commercial products, TOE-04-A3 manufactured by Nippon Kagaku Kogyo Co., Ltd. and CGI-325 manufactured by BASF Japan Co., Ltd. , Irgacure (registered trademark) OXE01, OXE02, Adecaoptomer N-1919 manufactured by ADEKA, and the like.

（式中、Ｘは、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）を表し、Ｙ、Ｚはそれぞれ、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、炭素数１〜１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５−ピロール−ジイル、４，４’−スチルベン−ジイル、４，２’−スチレン−ジイルを表し、ｎは０又は１の整数である）。 Further, a photopolymerization initiator having two oxime ester groups in the molecule can also be preferably used, and specific examples thereof include an oxime ester compound having a carbazole structure represented by the following general formula (I). ..

(In the formula, X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, and a phenyl group (alkyl group having 1 to 17 carbon atoms, an alkoxy having 1 to 8 carbon atoms). Group, amino group, alkylamino group having 1 to 8 carbon atoms or dialkylamino group substituted), naphthyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, It is substituted with an amino group and an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), and Y and Z are a hydrogen atom, an alkyl group having 1 to 17 carbon atoms and 1 carbon atom, respectively. ~ 8 alkoxy group, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkylamino group having alkyl group having 1 to 8 carbon atoms or Alkyl amino group or dialkylamino having an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, and an alkyl group having 1 to 8 carbon atoms), a naphthyl group (substituted by a dialkylamino group) Represents an anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group), where Ar represents an alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, thienylene, which has 1 to 10 carbon atoms. Represents furylene, 2,5-pyrrole-diyl, 4,4'-stillben-diyl, 4,2'-styrene-diyl, where n is an integer of 0 or 1).

In particular, in the above formula, X and Y are methyl groups or ethyl groups, respectively, Z is methyl or phenyl, n is 0, and Ar is phenylene, naphthylene, thiophene or thienylene, respectively. A photopolymerization initiator is preferred.

Specific examples of the α-aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1. -(4-Molholinophenyl) -butane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, Examples thereof include N, N-dimethylaminoacetophenone. Examples of commercially available products include Omnirad 907, Omnirad 369, and Omnirad 379 manufactured by IGM Resins.

The content of the (C) photopolymerization initiator is preferably, for example, 0.01 to 15 parts by mass, particularly 0.5 to 10 parts by mass, with respect to 100 parts by mass of the (A) alkali-soluble resin. By setting the amount to 0.01 part by mass or more and 15 parts by mass or less, the coating film is stably formed, the coating film characteristics such as chemical resistance are maintained, and a sufficient outgas reduction effect can be obtained. The light absorption on the surface is kept constant, and the deep curability is further improved.
Examples of other (C) photopolymerization initiators include a photopolymerization initiator having an acyloxyimino group, an N-formylated aromatic amino group, a photopolymerization initiator having an N-acylated aromatic amino group, and nitro. Examples thereof include a photopolymerization initiator having a benzyl carbamate group and an alkyloxybenzyl carbamate group.

In the curable resin composition of the present invention, in addition to the (C) photopolymerization initiator, a known photopolymerization initiator, photoinitiator aid or sensitizer may be used in combination, for example. , Alkylphenone-based photopolymerization initiator, acylphosphine oxide-based photopolymerization initiator, titanosen-based photopolymerization initiator, and the like can be used.

[(D) Epoxy resin]
The curable resin composition of the present invention contains an epoxy resin and can be further thermoset in addition to photocuring. As a result, characteristics such as heat resistance and insulation reliability of the cured product can be improved.

As the epoxy resin, a known and commonly used compound having one or more epoxy groups can be used, and among them, a compound having two or more epoxy groups is preferable. For example, monoepoxy resins such as monoepoxy resins such as butyl glycidyl ether, phenylglycidyl ether, and glycidyl (meth) acrylate, bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, Cresol novolac type epoxy resin, trisphenol methane type epoxy resin, alicyclic epoxy resin, trimethylolpropanpolyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4'-diglycidyl ether, 1,6 -In one molecule of hexanediol diglycidyl ether, ethylene glycol or propylene glycol diglycidyl ether, sorbitol polyglycidyl ether, tris (2,3-epoxypropyl) isocyanurate, triglycidyltris (2-hydroxyethyl) isocyanurate, etc. Examples include compounds having two or more epoxy groups. These can be used alone or in combination of two or more, depending on the required characteristics.

Specific examples of the compound having two or more epoxy groups include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical, EPICLON840, EPICLON850, EPICLON1050, EPICLON2055 manufactured by DIC, and Epototo YD manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. -011, YD-013, YD-127, YD-128, DIC manufactured by Dow Chemical Japan. E. R. 317, D.I. E. R. 331, D. E. R. 661, D.I. E. R. 664, Sumitomo Chemical's Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128 and other bisphenol A type epoxy resins; Mitsubishi Chemical's jERYL903, DIC's EPICLON152, EPICLON165, Nippon Steel & Sumikin Epoxy YDB-400, YDB-500 manufactured by Kagaku Co., Ltd., and D.D. E. R. 542, brominated epoxy resins such as Sumitomo Chemical's Sumi-epoxy ESB-400 and ESB-700; Mitsubishi Chemical's jER152, jER154, Dow Chemical Japan's D.D. E. N. 431, D.I. E. N. 438, EPICLONN-730, EPICLONN-740, EPICLONN-770, EPICLONN-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. , EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumitomo Chemical's Sumi-Epoxy ESCN-195X, ESCN-220, Nippon Steel & Sumikin Chemical's YDCN-700-2, YDCN-700-3 , YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704 YDCN-704A, EPICLONN-680, N-690, N-695 (all trade names) manufactured by DIC, etc. Epoxy resin type; EPICLON 830 manufactured by DIC, jER807 manufactured by Mitsubishi Chemical Co., Ltd., Epototo YDF-170, YDF-175, YDF-2004 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. -2004, ST-2007, ST-3000 and other hydrogenated bisphenol A type epoxy resins; jER604 manufactured by Mitsubishi Chemical Co., Ltd., Epototo YH-434 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd., etc. Glycidylamine type epoxy resin; Hydant-in type epoxy resin; Alicyclic epoxy resin such as Celoxide 2021 manufactured by Daicel Co., Ltd .; YL-933 manufactured by Mitsubishi Chemical Co., Ltd. E. N. , EPPN-501, EPPN-502 and the like trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Co., Ltd. YL-6056, YX-4000, YL-6121 and the like bixilenol type or biphenol type epoxy resin or mixtures thereof; Bisphenol S type epoxy resin such as EBPS-200 manufactured by Kayakusha, EPX-30 manufactured by ADEKA, EXA-1514 manufactured by DIC; Bisphenol A novolac type epoxy resin such as jER157S manufactured by Mitsubishi Chemical Co., Ltd .; Tetraphenylol ethane type epoxy resin such as jERYL-931; heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Co., Ltd .; diglycidyl phthalate resin such as Blemmer DGT manufactured by Nikko Co., Ltd .; ZX-1063 manufactured by Nippon Steel & Sumitomo Metal Corporation, etc. Tetraglycidyl xylenoyl ethane resin; Naphthalene group-containing epoxy resin such as ESN-190, ESN-360 manufactured by Nippon Steel & Sumitomo Metal Corporation, HP-4032, EXA-4750, EXA-4700 manufactured by DIC; HP-7200 manufactured by DIC, Epoxy resin having a dicyclopentadiene skeleton such as HP-7200H; glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by Nichiyu Co., Ltd .; further, a copolymer epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; CTBN Modified epoxy resins (for example, YR-102, YR-450, etc. manufactured by Nippon Steel & Sumitomo Metal Corporation); trisphenol methane type epoxy resins and the like, but are not limited thereto.

In particular, the phenol novolac type epoxy resin and the dicyclopentadiene type epoxy resin are particularly preferably used from the viewpoint of BHAST (Biased Highly Accelerated Stress Test).
One of these epoxy resins may be used alone, or two or more of these epoxy resins may be used in combination.
The content of the epoxy resin (D) is, for example, 10 parts by mass to 80 parts by mass, preferably 20 to 70 parts by mass (solid content) with respect to 100 parts by mass (solid content) of the total of the alkali-soluble resin (A). Is the ratio of.

The present invention may contain an inorganic filler. The inorganic filler is not particularly limited, and known and commonly used inorganic fillers such as silica, crystalline silica, Neuburg silica soil, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, and water. Inorganic fillers such as aluminum oxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, and zinc flower can be used. Of these, silica is preferable because it has a small specific gravity, can be highly filled in the cured product, and can be easily increased in strength.

The inorganic filler is preferably a surface-treated inorganic filler (also referred to as "surface-treated inorganic filler"), and more preferably the surface of the inorganic filler is subjected to a surface treatment capable of introducing a curable reactive group. .. Here, the curable reactive group is not particularly limited as long as it is a group that cures with an alkali-soluble resin or an epoxy resin, and may be a photocurable reactive group or a thermosetting reactive group. Examples of the photocurable reactive group include a methacryl group, an acrylic group, a vinyl group, a styryl group and the like, and examples of the thermosetting reactive group include an epoxy group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, an imino group and an oxetanyl. Examples thereof include a group, a mercapto group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, an oxazoline group and the like. The method for introducing the curable reactive group onto the surface of the inorganic filler is not particularly limited, and it may be introduced by using a known and commonly used method, and a surface treatment agent having a curable reactive group, for example, a curable reactive group is introduced as an organic group. The surface of the inorganic filler may be treated with a coupling agent or the like. As the coupling agent, a silane coupling agent (methacrylic type, diphenyldiamino type, etc.), a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, or the like can be used. Examples of the surface-treated inorganic filler having no curable reactive group include silica-alumina surface treatment, titanate-based coupling agent treatment, aluminate-based coupling agent treatment, and organically treated inorganic filler. Can be mentioned.

The inorganic filler may be used alone or in combination of two or more. The content of the inorganic filler is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, per solid content of the photosensitive resin composition.

The resin composition of the present invention may further contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenyl. Imidazole derivatives such as imidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, Examples thereof include amine compounds such as N-dimethylbenzylamine, 4-methyl-N, and N-dimethylbenzylamine, hydrazine compounds such as dihydrazide adipate and dihydrazide sebacic acid; and phosphorus compounds such as triphenylphosphine. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine-isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanulic acid adduct can also be used, preferably as these adhesion-imparting agents. A compound that also functions is used in combination with (F) a thermosetting catalyst.

The content of the thermosetting catalyst is, for example, 0.1 to 20 parts by mass, particularly preferably 1 to 10 with respect to 100 parts by mass of the alkali-soluble resin (A).

[(E) Black colorant]
The curable resin composition of the present invention contains (E) a black colorant.
(E) As an example of the black colorant, as the black colorant, C.I. I. Pigment Black, carbon black pigments such as 6, 7, 9 and 18
C. I. Graphite-based pigments shown in Pigment Black 8, 10, etc.
C. I. Pigment Black 11, 12 and 27, iron oxide pigments such as Pigment Brown 35, etc.
C. I. Pigment Black 20 etc. Anthraquinone pigment,
C. I. Pigment Black Cobalt oxide-based pigments such as 13, 25 and 29, C.I. I. Copper oxide pigments, such as Pigment Black 15 and 28,
C. I. Pigment Black, manganese-based pigments such as 14 and 26,
C. I. Pigment Black 23 and other antimony oxide pigments,
C. I. Nickel oxide pigments such as Pigment Black 30
C. I. Pigment Black 31, 32, etc., a perylene-based pigment,
C. I. Aniline-based pigments represented by Pigment Black 1 and the like, titanium black-based pigments, molybdenum sulfide and bismuth sulfide can also be exemplified as suitable black colorants.
These black colorants are used alone or in combination as appropriate.
Specific examples of commercially available products include carbon blacks such as M-40, M-45, M-50, MA-8 and MA-100 manufactured by Mitsubishi Chemical Corporation, and titanium blacks such as 13M manufactured by Mitsubishi Chemical Corporation. Iron oxide such as KN-370 manufactured by Toda Kogyo Co., Ltd. can be mentioned.

The above black colorants, especially carbon black, exhibit good hiding power (make the circuit invisible).

The blending amount of the black colorant (E) is in the range of 1.0% by mass or more and 3.0% by mass or less with respect to the total mass (solid content) of the curable resin composition, and is particularly preferably 1.5. It is in the range of mass% or more and 2.5 mass% or less.

(Combined use of colored colorants)
It is also possible to adjust the color tone of the (E) black colorant by adding a known colorant such as red, blue, green, yellow, and white as long as the action of the present invention is not impaired.

[(F) Polymerization inhibitor]
The curable resin composition of the present invention preferably contains (F) a polymerization inhibitor.
As the polymerization inhibitor, naphthalene derivatives and / or naphthoquinone and its derivatives can be used in particular. By using such a polymerization inhibitor, it is possible to suppress the occurrence of halation due to light irradiation, suppress the rate of surface hardening of the curable resin composition, and obtain a cured film uniform in the thickness direction. In addition, when the PEB step is carried out when producing a patterned cured film, the inclusion of the (F) polymerization inhibitor not only suppresses the occurrence of halation, but also obtains sufficient deep curability. You can also. Therefore, it is possible to easily form an opening shape or a line pattern close to the design value.

Among the naphthalene derivatives and / or naphthoquinone and its derivatives used in the present invention, as the naphthalene derivatives, ammonium 1,4-dihydroxy-2-naphthalenesulfonate, 4-methoxy-1-naphthol and the like can be used. As naphthoquinone and its derivative, 1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, anthrone and the like can be used.

Examples of commercially available products of naphthalene derivatives include Kinopower (registered trademark) WSI and 4-methoxy-1-naphthol (Kinopower QS-30, manufactured by Kawasaki Kasei Chemicals Co., Ltd.).

Commercially available products of naphthoquinone and its derivatives include, for example, Kinopower (registered trademark) NQI, Kinopower LSN, Kinopower ATR (all manufactured by Kawasaki Kasei Chemicals, Inc.), 1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone. , Antron (both manufactured by Tokyo Chemical Industry Co., Ltd.), etc.

[Other ingredients]
In addition, the curable resin composition of the present invention may further include antifoaming agents, thickeners, silane coupling agents, photoreactive monomers, silicone-based, fluorine-based, polymer-based catalysts, etc., as required. Fluidity modifiers, surface tension modifiers, adhesion imparting agents, surfactants, antioxidants, UV absorbers, and leveling agents, matting agents, polyester resins for adjusting film properties, vinyl resins, At least one of a rubber resin and waxes can be further blended. These components are used in an appropriately adjusted amount within a range in which the desired effect can be obtained by addition without impairing the performance to be obtained in the curable resin composition of the present invention.

Further, in the curable resin composition of the present invention, an organic solvent can be used for synthesizing the alkali-soluble resin (A) and adjusting the composition, or for adjusting the viscosity for coating on a substrate. ..

The curable resin composition of the present invention can be suitably used as a material for forming various resists or insulating layers which are patterned cured films on a printed wiring board, and among them, a solder resist or a material for an interlayer insulating layer. It is useful as.

The curable resin composition of the present invention can form a patterned cured film by a known and commonly used method, but is preferably resolved by performing the following steps in the order of (a) to (d). A cured product having a pattern excellent in properties and the like can be obtained.
That is, by performing the curable resin layer forming step (a) in which the above-mentioned curable resin composition is applied onto the base material and the curable resin layer on the base material being irradiated with light in a pattern. A light irradiation step (b) of activating the (C) photopolymerization initiator contained in the curable resin layer to cure the light-irradiated portion.
Further, a heating step (c) (PEB step) in which the curable resin layer after light irradiation is further cured by heating,
A cured product of the resin composition can be obtained by undergoing the developing step (d) of removing the uncured portion (other than the portion cured in the negative pattern) of the curable resin layer by development.

Each step will be described in more detail.
[Step (a): Curable resin layer forming step]
The step (a) is a step of forming a curable resin layer made of a curable resin composition on a base material. The method for forming the curable resin layer is a method of applying and drying a liquid curable resin composition on a substrate, or a method of laminating a dry film of a curable resin composition on a substrate. be able to.

The curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method with, for example, an organic solvent, and is subjected to a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, and a curtain on a substrate. It can be applied by a method such as a coating method.
The applied curable resin composition can form a dry coating film by volatilizing and drying (temporarily drying) the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. In the case of a dry film having a curable resin layer after the above composition is applied onto a carrier film and dried, the curable resin layer is laminated on the base material by a laminator or the like so as to come into contact with the base material. After that, the curable resin layer can be laminated on the base material by peeling off the carrier film.

As the base material, in addition to the pre-circuit-formed printed wiring base material and flexible printed wiring base material, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy Copper-clad laminates of all grades (FR-4, etc.) using composite materials such as resin, glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, fluororesin / polyethylene / polyphenylene ether, polyphenylene oxide / cyanate ester , Polyimide film, PET film, glass base material, ceramic base material, wafer base material and the like can be used.

The volatile drying performed after applying the curable resin composition of the present invention uses a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, or the like equipped with an air heating type heat source using steam, and hot air in the dryer. Can be carried out by using a method of making a countercurrent contact and a method of spraying the support from a nozzle.

[Step (b): Photocuring (patterning) step]
In the step (b), patterning is performed by irradiating the curable resin layer with light in a pattern (irradiation with active energy rays, particularly ultraviolet rays or the like) after the step (a). In one embodiment, the ethylenically unsaturated groups react with each other due to the radicals generated from the (C) photopolymerization initiator in the curable resin layer, and the generated bases cause the (A) alkali-soluble resin and the (D) epoxy resin. Reacts to cure the exposed part (the part irradiated with active energy rays, especially ultraviolet rays, etc.). In the case of such an embodiment, it is possible to form a negative pattern with respect to the alkaline developer.

Further, in the light irradiation step (b), the contact type (or non-contact type) is used to selectively expose the pattern with active energy rays or directly expose the pattern with a direct drawing device through the photomask on which the pattern is formed. In the following, a portion covered with a photomask or a portion not directly exposed to a pattern by a direct drawing device (non-irradiated portion) is also referred to as a non-cured portion.

Light irradiators used for light irradiation include direct drawing devices (for example, laser direct imaging devices that draw images directly with a laser using CAD data from a computer), light irradiators equipped with metal halide lamps, and (ultra) high-pressure mercury lamps. An on-board light irradiator, a light irradiator equipped with a mercury short arc lamp, an ultraviolet lamp such as an (ultra) high-pressure mercury lamp, or a direct drawing device using an LED can be used.

As the active energy ray, it is preferable to use laser light or scattered light having a maximum wavelength in the range of 350 to 410 nm. By setting the maximum wavelength in this range, the photoreactivity of the curable resin composition can be efficiently improved. As long as this range is used, in the case of laser light, either a gas laser or a solid-state laser may be used. The amount of light irradiation varies depending on the film thickness and the like, but can generally be in the range of 100 to 1500 mJ / cm ² , preferably 300 to 1500 mJ / cm ² .

[Step (c): Heating (PEB) step]
In the PEB step (c), the curable resin layer cured by the above light irradiation can be further cured by heating.
Further, when the curable resin composition of the present invention is irradiated with light in the light irradiation step (b), the photopolymerization initiator (C) contained in the curable resin layer is destabilized and a base is generated. Multiply. The base thus generated and propagated can further cure the above-mentioned light-irradiated portion by further heating in the heating step (c) (PEB: Post Exposure Bake). For example, the base generated in the light irradiation step (b) undergoes an addition reaction with the epoxy resin (D), so that the curable resin composition can be cured to a deep part of the coating film.

In the conventional curable resin composition, when a small-diameter opening of 250 μm level is provided in patterning, it is considered that the resolution is improved because the development residue is reduced when the PEB treatment is not performed. .. However, according to the curable resin composition of the present invention, even if the PEB treatment is performed, an opening having a small diameter can be formed and the cured film is excellent in deep curability. Therefore, in the production method of the present invention, it is preferable to carry out the PEB step. That is, it can be said that the curable resin composition of the present invention is suitable for production method applications in which the PEB process is performed.

The heating temperature after the step (c), that is, the light irradiation step (b) and before the developing step (d) is a temperature at which the light-irradiated portion of the curable resin composition is thermosetting, but the non-curing portion is not thermosetting. Is preferable. For example, it is preferable to heat the non-irradiated curable resin composition at a temperature lower than the heat generation start temperature or heat generation peak temperature and higher than the heat generation start temperature or heat generation peak temperature of the light-irradiated curable resin composition. .. By heating in this way, only the light-irradiated portion can be selectively cured.

As a specific example, the heating temperature in step (c) is, for example, 40 to 140 ° C, preferably 60 to 120 ° C. By setting the heating temperature to 40 ° C. or higher, the light-irradiated portion can be sufficiently cured. On the other hand, by setting the heating temperature to 140 ° C. or lower, only the light-irradiated portion can be selectively cured. The heating time is, for example, 1 to 120 minutes, preferably 10 to 80 minutes. The heating method is the same as the above drying method.

Further, when the (F) polymerization inhibitor is added to the resin composition, the resolution is excellent due to the effect of suppressing the photocrosslinking reaction in the step (a) and the thermal crosslinking reaction in the PEB step (c). A patterned cured film can be formed.

In the unirradiated portion, since no base is generated from the photopolymerization initiator, thermosetting is suppressed.

[Step (d): Development step]
The step (d) is a step of forming a negative-shaped patterned cured film by removing the uncured portion by development. The developing method can be a known method such as a dipping method, a shower method, a spray method, or a brush method, and the developing solution is potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, silicic acid. Amines such as sodium, ammonia and ethanolamine, an alkaline aqueous solution such as tetramethylammonium hydroxide aqueous solution (TMAH), or a mixture thereof can be used.

From the viewpoint of the environment, it is preferable that the resin composition of the present invention can be developed with a developing solution having a pH of less than 12.

[Step (e): Photocuring step]
The method for producing a cured product further includes a photocuring step (e) after the step (d). By further performing light irradiation such as ultraviolet irradiation after the step (d), it is possible to react the components remaining without reacting during the exposure in the light irradiation step (b). The wavelength of the irradiation light and the light irradiation amount (exposure amount) in the light curing step (e) may be the same as or different from those in the light irradiation step (b). A suitable light irradiation amount (exposure amount) is 150 to 2000 mJ / cm ² .

[Step (f): Thermosetting (post-cure) step]
The method for producing a cured product may further include a thermosetting (post-cure) step (f) after the photocuring step (e). When both the step (e) and the step (f) are performed after the step (d), the step (f) is preferably performed after the step (d).

In the post-cure step (f), the resin layer is sufficiently thermoset by the base generated from the photopolymerization initiator in the light irradiation step (b) or the light irradiation step (b) and the photocuring step (e). Can be made to. Since the unirradiated portion has already been removed at the time of the post-cure step (f), this step (f) can be performed at a temperature equal to or higher than the curing reaction start temperature of the unirradiated curable resin composition. As a result, the patterned cured film can be sufficiently thermoset. The heating temperature can be, for example, 150 ° C. or higher, and it is generally preferable to cure by heating at 120 ° C. to 170 ° C. for 5 to 60 minutes.

Further, when the curable resin composition of the present invention is used for electronic parts and the like, it is beneficial because a cured film having the above-mentioned excellent physical properties can be obtained in the production and use thereof.

In the present invention, the electronic component means a component used in an electronic circuit, and includes active components such as printed wiring boards, transistors, light emitting diodes, and laser diodes, as well as passive components such as resistors, capacitors, inductors, and connectors. included. The cured product of the present invention exerts the effect of the present invention as these insulating cured films.

The curable resin composition of the present invention, a dry film thereof, or a cured film obtained from the curable resin composition has excellent properties such as blackness, circuit concealment, and resolution, as well as HAST resistance, which is essential for electronic components. It can be applied to various uses, and there is no particular limitation on the application target. For example, it is preferably used for solder resists for printed wiring boards, markings, etc., and when the printed wiring board thus obtained is applied to an optical sensor such as a photoresistor, it receives necessary light in just proportion. However, high functionality such as accurate output can be obtained.
In view of the above circumstances, an object of the present invention is a curable resin that has excellent shielding properties and insulation reliability due to its black color, and can suppress development residues to form a cured film having excellent resolution. An object of the present invention is to provide a composition, a dry film using the curable resin composition, a cured product thereof, and an electronic component having the composition.

Hereinafter, the present invention will be described in detail with reference to Examples. The present invention is not limited to the following examples, and the "parts" and "%" described below are all based on mass unless otherwise specified.

[Examples 1 to 16, Comparative Examples 1 to 4]
I. Preparation of resin composition and preparation of dry film After mixing and stirring each component at the ratio (unit: parts by mass) shown in Table 1 and dispersing in a 3-roll mill, 3 to 15% by mass with respect to the total mass. The resin compositions of the present invention (Examples 1 to 16) and comparative resin compositions (Comparative Examples 1 to 4) (both in a paste state) were obtained by adding the methyl ethyl ketones of the above.
The amounts of the components used in Table 1 are all based on the solid content.

Each of the above resin compositions was applied onto a PET film having a thickness of 25 μm with an applicator gap of 60 μm using an applicator. This was dried at 80 ° C. for 20 minutes using a hot air circulation type dryer to prepare a dry film having a dry film thickness of 20 μm.

II. Preparation of evaluation substrate II-A. Preparation of Bubble Evaluation Substrate A A solid copper substrate (electrolytic copper substrate) manufactured by CMK Products Co., Ltd. was washed with an organic acid (CZ-8101) as a pretreatment.
Next, the above dry film made of the resin compositions of each Example and Comparative Example was first subjected to the following conditions using a laminator CVP-300 (fully automatic 2-stage laminator) manufactured by Nikko Materials Co., Ltd. An evaluation substrate A having a resin layer on the solid copper substrate was produced by a laminating step and a second laminating step following the laminating step.

In the first laminating step, the resin composition is first held at 80 ° C. for 30 seconds under vacuum conditions and stretched into a film, and the obtained film-like composition is placed on the above-mentioned solid copper substrate at a pressure of 0. It was bonded by slap-down at 4 Mpa and 5 seconds. The obtained laminate was further pressed by the second lamination step at 80 ° C. and a pressure of 8 Kgf / cm ² for 60 seconds. As a result, the evaluation substrate A was obtained.
II-B. Development resistance (surface whitening by development) Preparation of evaluation substrate B A cover film (PET) was attached to each of the obtained substrates in the same manner as the evaluation substrate A. An exposure machine EXP-2960 (manufactured by Oak Mfg. Co., Ltd.) was used to expose the cover film with ultraviolet rays at an integrated light intensity of 1000 mJ / cm ² so as to leave a negative pattern having a diameter of 250 μm. After 30 minutes had passed after the completion of the exposure, the cover film was peeled off and heat-treated at 60 ° C. for 70 minutes with a hot air circulation type dryer (PEB step).

Then, at 30 ° C. and 0.2 MPa, a 1% aqueous sodium carbonate solution was used as a developing solution, and these were developed with a developing machine for printed wiring boards manufactured by Fuji Kiko Co., Ltd. for 50 seconds, dried, and subjected to evaluation substrate B. did.

II-C. Preparation of Resolution Evaluation Substrate C Each substrate obtained in the same manner as the evaluation substrate B was exposed to an integrated light amount of 1000 mJ / cm ² using an ultraviolet exposure machine equipped with a high-pressure mercury lamp (precure), and further 150 ° C. Was heat-treated (post-cure) at 60 ° C. This was designated as the evaluation substrate C.

II-D. Preparation of Transparency Evaluation Substrate D A substrate D for transparency evaluation was prepared by the same method as that for evaluation substrate C, except that the substrate and PEB processing time were changed and the development step was omitted.
That is, in the production of the substrate D, a glass substrate (F1 glass, 1.0 mm thickness) was used without using a solid copper substrate, and the PEB treatment time was 40 minutes at 60 ° C. using a hot air circulation dryer.

II-E. Preparation of HAST Confirmation Substrate E The HAST confirmation substrate E was prepared by the same method as that of the evaluation substrate C except that the substrate, its pretreatment, and the PEB treatment time were changed.
That is, in the production of the substrate E, SR-TEG-04 (L / S = 12/13) manufactured by Kyocera Corporation was used without using a solid copper substrate, whereas MEC Etching Bond CZ-8101 manufactured by MEC Co., Ltd. was used. Was applied so that the etching amount was 1 μm. Further, in the production of the substrate E, the PEB treatment time was set to 60 ° C. and 40 minutes by a hot air circulation type dryer.

III. Evaluation III-A. Bubble evaluation The presence or absence of bubbles on the evaluation substrate A was visually confirmed. No bubbles were generated on any of the substrates.
III-B. Evaluation of surface whitening by development The surface of the evaluation substrate B was visually confirmed. No surface whitening was observed in Examples 1 to 16, but surface whitening was observed on any of the substrates in Comparative Examples 1 to 4.
III-C. Resolution evaluation The diameter of the opening of the evaluation substrate B was measured with an optical microscope (ECLIPSE-VV100 manufactured by Nikon Corporation). The closer it is to the design value of 250 μm, the better the resolution.
In Comparative Examples 1 and 2, the opening diameter could not be measured because a residue was generated at the opening edge of the cured product and a wavy opening shape was obtained. Further, in Comparative Examples 3 and 4, all the coating films were developed and removed, and measurement was impossible.

III-D. Transmittance Evaluation The transmittance at 400-1500 nm was measured for the evaluation substrate C using an ultraviolet-visible spectrophotometer (JASCO Corporation, V-670EX) and an integrating sphere device (JASCO Corporation, ILN-725). , Each of the wavelength range ranges (a) to (c) shown in Table 1 was measured, and the highest transmittance was shown in each case.
In Comparative Examples 1 and 2, the surface of the cured film is wavy, and accurate transmittance cannot be measured. Further, in Comparative Examples 3 and 4, all the coating films were developed and removed as described above, and measurement was impossible.

III-E. HAST test evaluation The HAST test was carried out by placing the evaluation substrate D in a high-temperature and high-humidity tank in an atmosphere of 130 ° C. and 85% humidity, applying a voltage of 5 V and maintaining it for 500 hours, and evaluating it according to the following criteria. did.
〇: No problem was observed even after applying a voltage of 5V for 500 hours.
X: In Comparative Examples 1 and 2 in which a short circuit occurred when a voltage of 5 V was applied for less than 500 hours, the surface of the cured film could not be obtained in a wavy smooth manner, so that the HAST test could not be performed. Further, in Comparative Examples 3 and 4, all the coating films were developed and removed as described above, and the HAST test could not be performed.

The results of each of the above evaluations are shown in Table 1.

-Alkali-soluble resin A: Manufactured by Synthesis Example 1 described later (solid content)
-Luxidia EMG-1015: Solvent-soluble amidimide resin manufactured by DIC (without acryloyl group)
-Luxidia EQG-1170: DIC, alicyclic UV curable amidimide resin (containing acryloyl group)
-Dianar LR-950: manufactured by Mitsubishi Chemical Corporation, Mw = 17,500
Clarity A2140: Kuraray Co., Ltd., Methyl methacrylate-butyl acrylate-methyl methacrylate block copolymer, Mw = 125,000
Clarity A2330: Kuraray Co., Ltd., Methyl methacrylate-butyl acrylate-methyl methacrylate block copolymer, Mw = 75,000
-Nanostrength M52N: manufactured by Arkema Co., Ltd., methyl acrylate-butyl acrylate-methyl methacrylate, Mw = 100,000
-Nanostrength M65N: manufactured by Arkema Co., Ltd., methyl acrylate-butyl acrylate-methyl methacrylate, Mw = 150,000
-TOE-04-A3: Nihon Kagaku Kogyo Co., Ltd., oxime ester-based photopolymerization initiator-Methoxyrad TPO H, IGM Resins, 2,4,6-trimethylbenzoyldiphenylphosphine oxide-EPICLON N-740: DIC Manufactured by Phenolic Novolac Epoxy Resin HP-7200L: DIC, Dicyclopentadiene Epoxy Resin MA-100: Mitsubishi Chemical Co., Ltd., Carbon Black 13M: Mitsubishi Materials Electronics Chemical Co., Ltd., Titanium Black Kinopower QS-30: 1-methoxy-4-naphthol / spherical silica manufactured by Kawasaki Kasei Kogyo Co., Ltd .: Solid content in the spherical silica slurry produced by Synthesis Example 2 described later.

[Synthesis Example 1: Synthesis of Alkali Soluble Resin A]
In an autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device, and a stirring device, 119.4 parts of a novolak type cresol resin (Shonol CRG951 manufactured by Showa Denko Co., Ltd., OH equivalent: 119.4), potassium hydroxide 1. 19 parts and 119.4 parts of toluene were introduced, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 parts of propylene oxide was gradually added dropwise, and the mixture was reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Then, the mixture was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The non-volatile content was 62.1% and the hydroxyl value was 182.2 mgKOH / g (307. A propylene oxide reaction solution of a novolak-type cresol resin at 9 g / eq.) Was obtained. This was an average of 1.08 mol of propylene oxide added per equivalent of phenolic hydroxyl group.

293.0 parts of propylene oxide reaction solution of the obtained novolak type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone and 252.9 parts of toluene were mixed with a stirrer and temperature. It was introduced into a reactor equipped with a meter and an air blowing tube, and air was blown at a rate of 10 ml / min and reacted at 110 ° C. for 12 hours with stirring. As for the water produced by the reaction, 12.6 parts of water was distilled off as an azeotropic mixture with toluene. Then, the mixture was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Then, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak type acrylate resin solution. Next, 332.5 parts of the obtained novolak type acrylate resin solution and 1.22 parts of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was introduced at a rate of 10 ml / min. With stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added, reacted at 95 to 101 ° C. for 6 hours, cooled, and then taken out. In this way, a solution of a carboxyl group-containing photosensitive resin having a solid content of 65% and an acid value of 87.7 mgKOH / g as a solid content was obtained, and this was used as the (A) alkali-soluble resin solution A.

[Synthesis Example 2: Synthesis of Spherical Silica]
70 g of spherical silica (SO-C2 manufactured by Admatex, average particle size d50 = 1.0 μm), 28 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and Shinetsu Silicone Co., Ltd. as a silane coupling agent having a methacryl group. A silica slurry (solid content 72%) was obtained by uniformly dispersing 2.0 g of KBM-503 manufactured by KBM-503 using a bead mill (LMZ-015 manufactured by Ashizawa Finetech Co., Ltd.) filled with zirconia beads having a diameter of 0.3 mm.

The dry film made of the curable resin composition of the present invention has a smooth surface without generation of bubbles even after laminating, and the surface is not whitened by development. Moreover, the cured film of the curable resin composition of the present invention showed excellent effects in all the test items of resolution, transmittance and HAST. In particular, with respect to the cured product obtained in the comparative example, the resolution is extremely good, and excellent blackness or visible light shielding property is also ensured.

The present invention is not limited to the configuration and examples of the above-described embodiment, and various modifications can be made within the scope of the gist of the invention.

Claims (6)

(A) Alkali-soluble resin (B) Copolymer resin,
(C) Photopolymerization initiator that generates radicals and bases,
(D) Epoxy resin, and (E) Black colorant,
A curable resin composition containing
The (A) alkali-soluble resin contains (A1) a carboxyl group-containing imide resin.
A curable resin composition characterized in that the content of the black colorant (E) is 1.0% by mass or more with respect to the total solid content of the curable resin composition. The curable resin composition according to claim 1, further comprising (F) a polymerization inhibitor. A dry film having a resin layer obtained from the curable resin composition according to claim 1 or 2. A cured product of the curable resin composition according to any one of claims 1 to 3. An electronic component comprising the cured product according to claim 4. The curable resin layer forming step (a), in which the curable composition according to claim 1 or 2 is applied onto a substrate.
By irradiating the curable resin layer applied on the substrate with light in a pattern, the photopolymerization initiator that generates the (C) radicals and bases contained in the curable resin layer is activated. Light irradiation step (b), in which the light irradiation portion is cured by polymerizing.
Includes a heating step (c) in which the curable resin layer after light irradiation is further cured by heating, and a development step (d) in which the uncured portion of the curable resin layer cured by heating is removed by development. A method for producing a cured product of a curable resin composition, which comprises the above.