TWI398458B - A photohardenable thermosetting resin composition, a dry film and a hardened product thereof, and a printed wiring board - Google Patents

Description

Photocurable thermosetting resin composition, dry film and cured product thereof, and printed wiring board using the same

The present invention relates to a photocurable thermosetting resin composition which can be imaged by a dilute aqueous alkali solution, and more particularly to a composition for a solder resist which is photohardened by ultraviolet exposure or laser exposure, and a dry film thereof. And a cured product and a printed wiring board having the hardened film formed using the above.

Conventionally, an alkali-developing photosensitive resin composition has been widely used as a solder resist for printed wiring boards. The solder resist is intended to protect the surface circuit of the printed wiring board, and is required to have high solder heat resistance and electrical insulation. Further, recently, the density of the printed wiring board has become remarkable, and the circuit has a minimum line width of 10 μm and a line pitch of 10 μm, and has higher insulation reliability than conventionally required.

The conventional alkali-developing type solder resist is composed of an acid-modified epoxy acrylate, a photopolymerization initiator, a reactive diluent, an epoxy resin, and a filler. Among these components, in particular, epoxy resins play an important role in improving heat resistance, electrical properties, and adhesion. In particular, in the epoxy resin, a crystalline epoxy resin is an important component from the viewpoint of specific heat resistance and light characteristics (refer to Patent Document 1).

However, in recent years, due to the high density of printed substrates, insoluble substances (inorganic fillers, crystalline epoxy resins, etc.) exist among fine pattern circuits because of the presence of particles, which causes a short circuit between circuits. Further, in the step of producing a printed circuit board by laminating a photocurable thermosetting resin composition on a carrier film and drying the dried film on a substrate on which various circuit patterns have been formed, particles of insoluble matter This may be a cause of poor lamination, and in particular, it may be a cause of a decrease in the yield of a fine pattern substrate which requires high film thickness control. Therefore, in the preparation of the solder resist, various kinds of dispersion treatment are performed, and coarse particles of insoluble components are removed for filtration. However, almost all of the crystalline epoxy resins have affinity with an organic solvent or other resin. The temperature of the dispersion step is partially dissolved, and then recrystallized into coarse particles. Further, since the temperature has to be lowered during filtration, it is difficult to obtain a composition having a high viscosity.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-1-41904 (Scope of Patent Request)

The present invention has been made in view of the above-described conventional techniques, and an object thereof is to provide a dry coating film which is excellent in heat resistance, electroless gold plating resistance, electrical insulation properties, and the like, and particularly prevents coarse particles due to insoluble components. A photocurable thermosetting resin composition for forming a hardened film such as a solder resist which is broken by a fine pitch circuit.

Furthermore, it is an object of the present invention to provide a dry film and a cured product which are excellent in the above-mentioned various properties and smoothness obtained by using such a photocurable thermosetting resin composition, and by the dry film or cured product. A printed wiring board formed by forming a hardened film such as a solder resist.

In order to achieve the above object, according to the present invention, there is provided an alkali-developable photocurable thermosetting resin composition comprising (A) an epoxy resin, (B) a carboxyl group-containing resin, and (C) light. A composition of a polymerization initiator, characterized in that the epoxy resin (A) is a bifunctional biphenyl epoxy resin (A-1) having a structure represented by the general formula (I) At least one ring selected from the group consisting of a phenol A type epoxy resin, a bisphenol A novolac type epoxy resin, and a bisphenol novolac type epoxy resin having a softening point of 40 to 100 ° C and an epoxy equivalent of 180 to 300 A mixture of oxyresin (A-2), and the ratio of (A-1) to (A-2) of the above epoxy resin is (A-1) < (A-2).

【化1】

(wherein R represents H or CH ₃ .)

In a preferred embodiment, the carboxyl group-containing resin (B) has an acid value of 40 to 120 mgKOH/g, and the mixture of (A-1) and (A-2) is 20 to 100 parts by mass. The photocurable thermosetting resin composition containing 60 parts by mass of the photosensitive monomer (E) having two or more ethylenically unsaturated groups in one molecule can be suitably used as a solder resist.

Moreover, according to the present invention, a dry film obtained by applying the photocurable thermosetting resin composition onto a carrier film and drying it, or a photocurable thermosetting resin composition or The photocurable thermosetting resin composition is applied to a cured film obtained by drying and drying a dry film obtained by drying a carrier film, in particular, a cured product obtained by photohardening on copper, or Hardened by light hardening into a pattern.

Furthermore, according to the present invention, there is also provided a printed wiring board having a cured film obtained by thermally curing the cured product, particularly a photocurable thermosetting resin composition or a dry film, into a pattern.

The photocurable thermosetting resin composition of the present invention contains (A) an epoxy resin, (B) a carboxyl group-containing resin, and (C) a photopolymerization initiator, wherein the epoxy resin (A) a bifunctional biphenyl epoxy resin (A-1) having the structure shown in the above general formula (I), and an epoxy resin derived from a bisphenol A type, a bisphenol A novolac type epoxy resin, and a bisphenol novolac a mixture of at least one epoxy resin (A-2) having a softening point of 40 to 100 ° C and an epoxy equivalent of 180 to 300 selected from the group consisting of varnish-type epoxy resins, and the above epoxy resin (A-1) The ratio of (A-2) to (A-2) is (A-1) < (A-2), so that crystallization of the epoxy resin mixture can be excellent in stability over time, and solder heat resistance and electroless gold plating resistance It is excellent in electrical insulation and the like, and is particularly a hardened film having high insulation reliability between fine patterns.

Therefore, the photocurable thermosetting resin composition of the present invention can be effectively applied to the formation of a hardened film such as a solder resist of a printed wiring board or a flexible printed wiring board.

[Formation of the Invention]

As described above, the photocurable thermosetting resin composition of the present invention is characterized by comprising (A) an epoxy resin, (B) a carboxyl group-containing resin, and (C) a photopolymerization initiator. The oxy-resin (A) is a bifunctional biphenyl epoxy resin (A-1) having the structure shown in the above general formula (I), and an epoxy resin derived from bisphenol A type epoxy resin and bisphenol A novolak type epoxy resin. And a mixture of at least one epoxy resin (A-2) having a softening point of 40 to 100 ° C and an epoxy equivalent of 180 to 300 selected from the group consisting of bisphenol novolac type epoxy resins, and the epoxy resin The ratio of (A-1) to (A-2) is (A-1) < (A-2).

According to the study of the present inventors, among the components (A), the bifunctional biphenyl epoxy resin (A-1) having the structure shown in the above general formula (I) has heat resistance in terms of epoxy resin. Excellent in electroless gold plating resistance, electrical insulation, etc., and particularly excellent in insulation reliability between fine patterns, and is an important component. Conversely, due to high crystallinity in resin components or organic solvents, temperature is high. Recrystallization occurs easily due to factors such as changes, and the particles coarsen in the mixture, which causes a short circuit between circuits. In addition, a dry film obtained by applying a photocurable thermosetting resin composition containing a bifunctional biphenyl epoxy resin (A-1) to a carrier film and drying it is laminated on various circuit patterns. In the step of producing a printed circuit board on the substrate, the coarse particles generated may cause lamination failure, and in particular, the yield of the fine pattern substrate which requires high film thickness control may be lowered.

Therefore, the present inventors have found out that the epoxy resin (A) has a bifunctional biphenyl epoxy resin (A-1) having the structure shown in the above general formula (I), and a bisphenol At least one epoxy having a softening point of 40 to 100 ° C and an epoxy equivalent of 180 to 300 selected from the group consisting of A type epoxy resin, bisphenol A novolak type epoxy resin and bisphenol novolac type epoxy resin a mixture of the resin (A-2), and the ratio of the mixture is (A-1) < (A-2), and the bifunctional biphenyl epoxy resin (A-1) is stirred, kneaded, heated, or the like. When the particles are miniaturized or dissolved, the heat resistance and electroless gold plating resistance are excellent, and generation of coarse particles due to the bifunctional biphenyl epoxy resin (A-1) can be prevented, and the circuit can be avoided. Further, since the short circuit is excellent in electrical insulation, it is possible to further prevent lamination failure when laminating a dry film obtained by applying a photocurable thermosetting resin composition onto a carrier film and drying it.遂Complete the invention.

Hereinafter, each constituent component of the photocurable thermosetting resin composition of the present invention will be described in detail.

In the epoxy resin (A) constituting the alkali-developable photocurable thermosetting resin composition of the present invention, a Japanese epoxy can be used for the bifunctional biphenyl epoxy resin (A-1). A bisphenol type or bisphenol type epoxy resin such as YL-6056, YX4000, YX4000K, YX4000H, YX4000HK, YL6121, YL6121H, YL6640, YL6677 (all trade names) manufactured by Resin Co., Ltd. or a mixture thereof.

Next, among the epoxy resins (A), a bisphenol A type epoxy resin having a softening point of 40 to 100 ° C and an epoxy equivalent of 180 to 300, a bisphenol A novolac type epoxy resin, and/or a bisphenol novolac Examples of the varnish-type epoxy resin (A-2) include jER834 manufactured by Nippon Epoxy Co., Ltd., EPICLON 860 manufactured by Dainippon Ink and Chemicals Co., Ltd., EPOTOHTOYD-134 manufactured by Tosho Kasei Co., Ltd., and DER337 manufactured by Dow Chemical Co., Ltd. Bisphenol A type epoxy resin, etc. (both trade names); bisphenol A novolak type, such as jER157S by Japan Epoxy Resin Co., Ltd., EPICLONN-865 (all trade name) by Dainippon Ink Chemical Industry Co., Ltd. Epoxy resin; bisphenol novolac type epoxy resin such as NC-3000, NC-3000H, NC-3000L, NC-3100 (trade name) manufactured by Nippon Kayaku Co., Ltd., etc., but is not limited thereto. These epoxy resins may be used singly or in combination of two or more.

The ratio of the above epoxy resin (A-1) to (A-2) is (A-1) < (A-2). When the mixing ratio of (A-1) exceeds the mixing ratio of (A-2), the solubility of (A-1) dissolved in the composition is lowered, and the stability with time of crystallization of the mixture becomes low.

The amount of the epoxy resin (A-1) to (A-2) is, for example, 10 to 100 parts by mass, preferably 20 to 60 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (B). The scope is appropriate. When the amount of the epoxy resin (A-1) and (A-2) is more than the above range, the alkali developability is poor, and disproportionability or development residue is likely to occur. On the other hand, when it is less than 10 parts by mass, the solder heat resistance of the obtained cured coating film may be impaired.

Further, other epoxy resins in which the above epoxy resins (A-1) and (A-2) are combined may be used. As the other epoxy resin, a known and customary epoxy resin can be used without particular limitation. Examples of the epoxy resin include a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound.

Examples of the polyfunctional epoxy compound include jER828, jER1001, and jER1004 manufactured by Nippon Epoxy Co., Ltd., EPICLON 840, EPICLON 850, EPICLON 1050, EPICLON 2055 manufactured by DIC Corporation, and ETOPOHTOYD-011, YD-013, and YD manufactured by Tosho Kasei Co., Ltd. -127, YD-128, DER317, DER331, DER661, DER664 manufactured by Dow Chemical Co., Ltd., ARALDITE 6071, ARALDITE6084, ARALDITEGY250, ARALDITEGY260, manufactured by Ciba Specialty Chemicals Co., Ltd., Sumiepoxy ESA-011, ESA manufactured by Sumitomo Chemical Industries, Ltd. - 014, ELA-115, ELA-128, AER330, AER331, AER661, AER664, etc. (all are trade names) made of Asahi Kasei Kogyo Co., Ltd. JERYL 903, EPICLON 152, EPICLON 165 manufactured by DIC Corporation, EPOTOHTOYDB-400 manufactured by Dongdu Chemical Co., Ltd., YDB-500, DER542 manufactured by Dow Chemical Co., Ltd., ARALDITE 8011 manufactured by Ciba Specialty Chemicals Co., Ltd., and Sumiepoxy ESB-400 manufactured by Sumitomo Chemical Industries Co., Ltd. ESB-700, AER711, AER714, etc. (both trade names) manufactured by Asahi Kasei Kogyo Co., Ltd. jER152, jER154, manufactured by Resin Co., Ltd., DEN431, DEN438 manufactured by Dow Chemical Co., Ltd., EPICLONN-730, EPICLONN-770, EPICLONN-865, manufactured by DIC Corporation, EPOTOHTOYDCN-701, YDCN-704, Ciba Specialty, manufactured by Toho Chemical Co., Ltd. ARALDITEECN1235, ARALDITEECN1273, ARALDITEECN1299, ARALDITEXPY307 manufactured by Chemicals, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, manufactured by Nippon Chemical Co., Ltd., Sumiepoxy ESCN-195X, ESCN, manufactured by Sumitomo Chemical Industries, Ltd. -220, a phenol varnish-type epoxy resin such as AERECN-235 and ECN-299 manufactured by Asahi Kasei Industrial Co., Ltd. (both trade names); EPICLON830 manufactured by DIC Corporation, jER807 manufactured by Japan Epoxy Resin Co., Ltd., and manufactured by Dongdu Chemical Co., Ltd. EPOTOHTOY-DF-170, YDF-175, YDF-2004, ARALDITEXPY306 (all are trade names) bisphenol F-type epoxy resin manufactured by Ciba Specialty Chemicals Co., Ltd.; EPOTOHTOST-2004, ST-2007, ST- manufactured by Dongdu Chemical Co., Ltd. Hydrogenated bisphenol A type epoxy resin such as 3000 (trade name); jER604 manufactured by Japan Epoxy Resin Co., Ltd., EPOTOHTOYH-434 manufactured by Tosho Kasei Co., Ltd., and Ciba Specialty Chemicals Co., Ltd. ARALDITEMY720, Sumitip Chemical EL Co., Ltd., Sumiepoxy ELM-120 (both trade names), epoxy propylamine epoxy resin; Ciba Specialty Chemicals, ARALDITECY-350 (trade name), etc. ) epoxy resin; CELLOXIDE 2021 manufactured by DAICEL Chemical Industry Co., Ltd., ARALDITECY 175, CY179, etc. (all trade name) alicyclic epoxy resin manufactured by Ciba Specialty Chemicals Co., Ltd.; YL-933, Dow manufactured by Japan Epoxy Resin Co., Ltd. TEN, EPPN-501, EPPN-502, etc. (all trade names) manufactured by Chemical Company, trihydroxyphenylmethane type epoxy resin; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30, DIC manufactured by Asahi Kasei Kogyo Co., Ltd. Bisphenol S-type epoxy resin such as EXA-1514 (trade name) manufactured by the company; jER YL-931 manufactured by Nippon Epoxy Co., Ltd., ARALDITE 163 manufactured by Ciba Specialty Chemicals Co., Ltd. (all trade names), tetrahydroxybenzene Ethylene glycol type epoxy resin; ARALDITEPT810 manufactured by Ciba Specialty Chemicals Co., Ltd., TEPIC manufactured by Nissan Chemical Industries Co., Ltd. (all of which are trade names), heterocyclic epoxy resin, phthalic acid company BLEMMERDGT, etc. Oxypropyl acrylate resin; tetramethyl propyl propyl methacrylate ethane resin such as ZX-1063 manufactured by Dongdu Chemical Co., Ltd.; ESN-190, ESN-made by Nippon Steel Chemical Co., Ltd. 360, naphthalene-based epoxy resin such as HP-4032, EXA-4750, EXA-4700 manufactured by DIC Corporation; epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC Corporation; Japan Epoxy propyl methacrylate copolymerized epoxy resin of CP-50S, CP-50M, etc. made by the company of fats and oils; further, cyclohexylmaleimide and epoxypropyl methacrylate are mentioned Copolymerized epoxy resin; epoxy-modified polybutadiene rubber derivative (for example, PB-3600 manufactured by DAICEL Chemical Industry Co., Ltd.), CTBN modified epoxy resin (for example, YR-102 and YR-450 manufactured by Dongdu Chemical Co., Ltd.) Etc. etc., but not limited to this. These epoxy resins may be used singly or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is preferable.

The amount of the other epoxy resin to be used is preferably 75 mol% or less when the total amount of the epoxy resin used is 100 mol%. When more than 75 mol% is used, the characteristics derived from the bifunctional biphenyl epoxy resin (A-1) may not be sufficiently obtained. A better use of other epoxy resins is 50 mol% or less.

In the case of the carboxyl group-containing resin (B), a conventional carboxyl group-containing resin having a carboxyl group in a molecule can be used for the purpose of imparting alkali developability. In particular, from the viewpoint of photocurability or development resistance, a carboxyl group-containing photosensitive resin (B') having an ethylenically unsaturated double bond in its molecule is more preferable. Moreover, it is preferred that the unsaturated double bond be derived from acrylic acid or methacrylic acid or such derivatives. In addition, when only a carboxyl group-containing resin having no ethylenic unsaturated double bond is used, in order to make the composition photocurable, it is necessary to use a photosensitive monomer having one or more ethylenically unsaturated groups in the molecule to be described later ( E).

The specific examples of the carboxyl group-containing resin (B) are preferably those exemplified below (any of an oligomer and a polymer).

(1) a carboxyl group-containing copolymer 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 Resin.

(2) A divalent isocyanate such as an aliphatic diisocyanate, a divalent aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a carboxyl group such as dimethylol propionate or dimethylol butyrate. Alcohol compound, polycarbonate-based polyol, polyether-based polyol, polyester-based polyol, polyolefin-based polyol, acrylic polyol, bisphenol A-based alkylene oxide adduct diol, and phenolic hydroxyl group A carboxyl group-containing urethane resin obtained by subjecting a diol compound such as an alcoholic hydroxyl group to a sequential addition reaction.

(3) making diisocyanate and bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol type epoxy resin, double Photosensitive carboxyl group-containing (meth) acrylate of a bifunctional epoxy resin such as a phenol epoxy resin or a partial acid anhydride modified product thereof, a carboxyl group-containing diol compound, and a diol compound by sequential addition reaction A urethane resin.

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

(5) In the synthesis of the resin of the above (2) or (3), one or more isocyanate groups and one or more molecules are added to the molecule such as a molar reaction product such as isophorone diisocyanate and pentaerythritol triacrylate. The acrylic group-based compound is subjected to a terminal (meth) acrylated photosensitive carboxyl group-containing urethane resin.

(6) Photosensitive property obtained by reacting (meth)acrylic acid on a polyfunctional (solid) epoxy resin having a bifunctional or higher functional group as described later, and adding a 2-base acid anhydride to a hydroxyl group present in a side chain A resin containing a carboxyl group.

(7) reacting (meth)acrylic acid on a polyfunctional epoxy resin in which a hydroxyl group of a bifunctional (solid) epoxy resin described later is further epoxidized with epichlorohydrin, and on the generated hydroxyl group A photosensitive base group-containing resin obtained by adding a 2-base acid anhydride.

(8) A dicarboxylic acid is reacted on a bifunctional oxetane resin to be described later, and a 2-base acid anhydride is added to the resulting hydroxyl group to form a carboxyl group-containing polyester resin.

(9) A photosensitive carboxyl group-containing resin obtained by further adding a compound having one epoxy group and one or more (meth)acrylic groups in one molecule to the resin of the above (1) to (8).

In addition, in this specification, the term "(meth)acrylate type acrylate, methacrylate, and the mixture of these are similar, and other similar performance is the same.

The above-mentioned carboxyl group-containing resin (B) can be imaged by a dilute aqueous alkali solution because it has a large number of free carboxyl groups in the side chain of the backbone ‧ polymer.

Further, the acid value of the carboxyl group-containing resin (B) is in the range of 40 to 200 mgKOH/g, more preferably 45 to 120 mgKOH/g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, alkali development is difficult. On the other hand, if it exceeds 200 mgKOH/g, the dissolution of the exposed portion progresses due to the developing solution, so the line width must be more than necessary. It is thin and, as the case may be, the exposure portion and the unexposed portion are dissolved and peeled off by the developing solution without any difference, which makes it difficult to draw a normal photoresist pattern.

Further, the weight average molecular weight of the carboxyl group-containing resin (B) varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is less than 2,000, the tack-removing property is poor, and the moisture resistance of the coating film after exposure is not good, and film reduction occurs during development, and the resolution is greatly weakened. On the other hand, when the weight average molecular weight exceeds 150,000, the developability is remarkably deteriorated, and the storage stability is also poor.

The amount of the carboxyl group-containing resin (B) is from 20 to 80% by mass in the total composition, preferably from 30 to 60% by mass. If the amount of the carboxyl group-containing resin (B) is less than the above range, the film strength may be lowered. On the other hand, when it is more than the above range, the viscosity of the composition becomes high, and the coatability and the like are lowered.

The carboxyl group-containing resin (B) which can be used is not limited to the above-mentioned ones, and one type may be used, or a plurality of types may be used in combination.

In the case of the photopolymerization initiator (C), an oxime ester photopolymerization initiator (C1) having a group represented by the following general formula (II) is preferably used, and has the following general formula (III). An α-aminoacetophenone photopolymerization initiator (C2) or a fluorenylphosphine oxide photopolymerization initiator (C3) having a group represented by the following formula (IV) It is preferred that one or more photopolymerization initiators selected from the group are formed.

[Chemical 2]

In the formula, R ¹ represents a hydrogen atom, a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (may be substituted by one or more hydroxyl groups, or Having one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzhydryl group (an alkyl group having 1 to 6 carbon atoms) Or a phenyl group), R ² represents a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (may be substituted by one or more hydroxyl groups, It may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzhydryl group (alkane having 1 to 6 carbon atoms) And R ³ and R ⁴ each independently represent an alkyl group or an arylalkyl group having 1 to 12 carbon atoms, and R ⁵ and R ⁶ each independently represent a hydrogen atom and have a carbon number of 1 to 6 The alkyl group or the two cyclic alkyl ether groups, R ⁷ and R ⁸ each independently represent a linear or divalent alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, and a cyclopentyl group. An aryl group or an aryl group which may be substituted by a halogen atom, an alkyl group or an alkoxy group, However, one of R ⁷ and R ⁸ may represent an R'-C(=O)- group (wherein R' is a hydrocarbon group having 1 to 20 carbon atoms).

The oxime ester-based photopolymerization initiator having a group represented by the above formula (II) is preferably 2-(ethylideneoxyiminomethyl) represented by the following formula (V). Thioxan-9-one, a compound represented by the following general formula (VI), and a compound represented by the following general formula (VII).

[化3]

【化4】

In the formula, R ⁹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzamidine group, an alkyl 2 group having 2 to 12 carbon atoms, The alkoxycarbonyl group having 2 to 12 carbon atoms (when the carbon number of the alkyl group constituting the alkoxy group is 2 or more, the alkyl group may be substituted with one or more hydroxyl groups, or may have one or more oxygen groups in the middle of the alkyl chain. The atom or the phenoxycarbonyl group, R ¹⁰ and R ¹² each independently represent a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom) or an alkyl group having 1 to 20 carbon atoms ( It may be substituted with one or more hydroxyl groups, or may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzhydryl group ( It may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group), R ¹¹ represents a hydrogen atom, a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), and a carbon number of 1 to 20 An alkyl group (may be substituted with one or more hydroxyl groups, or one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkyl alkene group having 2 to 20 carbon atoms, or benzene Mercapto (can be an alkyl group having 1 to 6 carbon atoms or Yl group).

【化5】

In the formula, R ¹³ , R ¹⁴ and R ¹⁹ each independently represent an alkyl group having 1 to 12 carbon atoms, and R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a carbon number of 1 to 6. The alkyl group and M represent O, S or NH, and m and p each independently represent an integer of 0 to 5.

The oxime ester photopolymerization initiator is represented by the above formula (V) of 2-(ethylideneoxyiminomethyl)thioxanthene-9-one and the formula (VI). The compound is better. For the commercial product, CGI-325, IRUGACUREOXE01, IRUGACUREOXE02, N-1919 manufactured by ADEKA Co., Ltd., manufactured by Ciba Specialty Chemicals Co., Ltd., and the like are mentioned. These oxime ester-based photopolymerization initiators may be used singly or in combination of two or more.

The α-aminoacetophenone photopolymerization initiator having the group represented by the above general formula (III) is exemplified by 2-methyl-1-[4-(methylthio)phenyl]- 2-morpholinoacetone-1, 2-benzyl-2- dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino) )-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone Wait. As a commercial item, IRUGACURE907, IRUGACURE369, IRUGACURE379, etc. by Ciba Specialty Chemicals company are mentioned.

The mercaptophosphine oxide-based photopolymerization initiator having the group represented by the above general formula (IV) may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or bis( 2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine Oxide, etc. Commercially available products include Lucirin TPO manufactured by BASF Corporation and IRUGACURE 819 manufactured by Ciba Specialty Chemicals.

The amount of the photopolymerization initiator (C) is preferably from 0.01 to 30 parts by mass, preferably from 0.5 to 15 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (B). When the amount of the photopolymerization initiator (C) is less than 0.01 parts by mass, the photocurability on the copper is insufficient, and the coating film is peeled off, and the coating properties such as chemical resistance are lowered, which is not preferable. On the other hand, when it exceeds 30 parts by mass, the light absorption of the surface of the solder resist coating film of the photopolymerization initiator (C) becomes intense, and the deep hardenability tends to be lowered, which is not preferable.

Further, when it is an oxime ester photopolymerization initiator having a group represented by the above formula (II), the amount thereof is preferably 0.01 to 100 parts by mass of the carboxyl group-containing resin (B). 20 parts by mass, more preferably in the range of 0.01 to 5 parts by mass.

Other photopolymerization initiators, photoinitiating aids, and sensitizers which can be used in the photocurable thermosetting resin composition of the present invention of the present invention include benzoin compounds and acetophenone compounds. An anthracene compound, a thioxanthone compound, a ketal compound, a diphenyl ketone compound, an oxone compound, a tertiary amine compound, and the like.

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

Specific examples of the acetophenone compound include, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1 , 1-dichloroacetophenone.

Specific examples of the hydrazine compound include 2-methyl hydrazine, 2-ethyl hydrazine, 2-t-butyl hydrazine, and 1-chloro hydrazine.

Specific examples of the thioxanthone compound include, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthene. ketone.

Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.

Specific examples of the diphenyl ketone compound include diphenyl ketone, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfide, and 4-benzene. Mercapto-4'-ethyldiphenyl sulfide, 4-benzylidene-4'-propyldiphenyl sulfide.

Specific examples of the tertiary amine compound include, for example, an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4'-dimethylaminodiphenyl ketone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.). Dialkylaminodiphenyl ketone, 7-(diethylamino)-4-methyl-2H, etc., 4,4'-diethylaminodiphenyl ketone (EAB, manufactured by Hodogaya Chemical Co., Ltd.) a dialkylamino group-containing coumarin compound, 4-dimethylamine, such as 1-benzopyran-2-one (7-(diethylamino)-4-methylcoumarin) Kean acid ethyl ester (KAYACURE EPA, manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylamino benzoic acid ethyl (Quantacure DMB manufactured by International Biosynthetics Co., Ltd.), 4-dimethylamino benzoic acid (n-butoxy group) Ethyl (Quantacure BEA, manufactured by International Biosynthetics Co., Ltd.), p-dimethylamino benzoic acid isoamylethyl ester (KAYACURE DMBI, manufactured by Nippon Kayaku Co., Ltd.), 4-dimethylamino benzoic acid 2-ethyl Hexyl (Esolol 507, manufactured by Van Dyk Co., Ltd.), 4,4'-diethylaminodiphenyl ketone (EAB, manufactured by Hodogaya Chemical Co., Ltd.).

Among the above compounds, a thioxanthone compound and a tertiary amine compound are preferred. In the composition of the present invention, it is preferable to use a thioxanthone compound from the viewpoint of deep hardenability, and more preferably 2,4-dimethylthioxanthone or 2,4-diethylthioxanthone. A thioxanthone compound such as 2-chlorothioxanthone or 2,4-diisopropylthioxanthone is preferred.

The amount of the thioxanthone compound to be used is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the carboxyl group-containing resin (B). If the amount of the thioxanthone compound is too large, the cost of the product is lowered due to a decrease in the thick film hardenability, which is not preferable.

In the case of the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferred, wherein a dialkylaminodiphenyl ketone compound and a dialkylamine group having a maximum absorption wavelength of 350 to 410 nm are preferred. The coumarin compound is particularly preferred. In the case of the dialkylaminodiphenyl ketone compound, 4,4'-diethylaminodiphenyl ketone is preferred as low toxicity. The coumarin compound containing a dialkylamine group having a maximum absorption wavelength of 350 to 410 nm has a small color absorption due to the maximum absorption wavelength in the ultraviolet region, and the colorless and transparent photosensitive composition can provide a coloring pigment more than the original one. A color resist film that reflects the color of the coloring pigment itself. In particular, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

The amount of the above-mentioned tertiary amine compound is preferably from 0.1 to 20 parts by mass, more preferably from 0.1 to 10 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (B). When the amount of the tertiary amine compound is less than 0.1 part by mass, a sufficient sensitizing effect may not be obtained. On the other hand, when it exceeds 20 parts by mass, the light absorption on the surface of the dry solder resist coating film is severe due to the tertiary amine compound, and the deep hardenability tends to be lowered.

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

The total amount of the photopolymerization initiator, the photoinitiator, and the sensitizer is preferably 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin (B). When it exceeds 35 mass parts, the deep hardenability tends to fall by this light absorption.

In the photocurable thermosetting resin composition of the present invention, a thermosetting resin may be further added to the epoxy resin in order to impart heat resistance. Particularly preferred is a thermosetting component (D) having two or more cyclic ether groups and/or cyclic thioether groups (hereinafter referred to as cyclic (thio)ether groups) in the molecule.

The thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is a cyclic ether group or a cyclic thioether group having two or more 3, 4 or 5 membered rings in the molecule. Examples of the compound having one or two kinds of compounds include a compound having at least two or more oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound (D-1), and two molecules in the molecule. The above thioether group compound means an episulfide resin (D-2) or the like.

In addition to the above polyfunctional oxetane compound (D-1), in addition to bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxo) Heterocyclic butyl methoxy) methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3) -oxetanylmethoxy)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 such oligomers or In addition to polyfunctional oxetane such as copolymers, oxetane and novolak resins, poly(p-hydroxystyrene), Cardo bisphenols, calixarene (calixarene) are also mentioned. An etherified product derived from a resin having a hydroxyl group such as a resorcinol calixarene or a silsesquioxane. Further, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate may be mentioned.

The compound (D-2) having two or more cyclic thioether groups in the above-mentioned molecule may, for example, be a bisphenol A type episulfide resin YL7000 manufactured by Nippon Epoxy Co., Ltd., or the like. Further, an epoxy sulfide resin obtained by substituting an oxygen atom of an epoxy group of a novolac type epoxy resin with a sulfur atom may be used in the same synthesis method.

The amount of the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is preferably from 0.6 to 2.5 equivalents per 1 equivalent of the carboxyl group. It is suitable in the range of 0.8 to 2.0 equivalents. When the amount of the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is less than 0.6, the carboxyl group remains on the solder resist film, and heat resistance, alkali resistance, electrical insulation, and the like may occur. Lower, so it is not good. On the other hand, when it exceeds 2.5 equivalents, a low molecular weight cyclic (thio)ether group remains on the dried coating film, and thus the strength and the like of the coating film are lowered, which is not preferable.

The photocurable thermosetting resin composition of the present invention preferably contains a thermosetting catalyst. Examples of such a thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 1 - an imidazole derivative such as cyanoethyl-2-phenylimidazole or 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodiamide, benzyldimethyl Amine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N, An amine compound such as N-dimethylbenzylamine, a hydrazine compound such as diammonium adipate or bismuth sebacate; a phosphorus compound such as triphenylphosphine or the like. In addition, as for the commercially available product, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole-based compounds) manufactured by Shikoku Chemicals Co., Ltd., and U-CAT manufactured by SAN-APRO Co., Ltd. (registered trademark) 3503N, U-CAT3502T (all trade names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic guanidine compounds and their salts), etc. . In particular, these are not particularly limited, and may be a thermosetting catalyst of an epoxy resin or an oxetane compound or a reaction of an epoxy group and/or an oxetanyl group with a carboxyl group. It can be used alone or in combination of two or more. Further, guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-triazine, 2-vinyl-2,4 can be used. -diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine ‧ iso-cyanuric acid adduct, 2,4-diamino-6-methyl propylene An S-triazine derivative such as a methoxyethyl-S-triazine ‧ isocyanurate addition product, wherein a compound which acts as a adhesion imparting agent for this purpose is used in combination with the above-mentioned thermosetting catalyst It is better.

The amount of such a thermosetting catalyst is sufficient in a general amount, for example, a carboxyl group-containing resin (B) or a thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule. It is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass, per 100 parts by mass.

The photosensitive monomer (E) having two or more ethylenically unsaturated groups in the molecule used in the photocurable thermosetting resin composition of the present invention is photocured by irradiation with an active energy ray, and the above-mentioned ethylene is contained. The unsaturated group-containing carboxyl group-containing resin (B) is insoluble in an aqueous alkali solution or contributes to insolubilization. Examples of such a compound include diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexane diol, trimethylolpropane, pentaerythritol, and a polyvalent acrylate such as pentaerythritol, a hydroxyethyl isocyanurate or the like, or an oxyethylene adduct such as an oxyethylene adduct or a propylene oxide adduct; phenoxy acrylate, bisphenol A diacrylate, an ethylene oxide adduct of such a phenol, or a polyvalent acrylate such as a propylene oxide adduct; glycerol diepoxypropyl ether, glycerol triepoxypropyl a polyvalent acrylate of a glycopropyl ether such as an ether, trimethylolpropane triepoxypropyl ether or tricoxypropyl isocyanurate; and melamine acrylate, and/or corresponding Each of the methacrylates of the above acrylates.

Further, an epoxy acrylate resin obtained by reacting acrylic acid on a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, or a pentaerythritol three on the hydroxyl group of the epoxy acrylate resin may be mentioned. An epoxy urethane acrylate compound obtained by reacting a hydroxy acrylate such as acrylate with a halfurethane compound of a diisocyanate such as isophorone diisocyanate. Such an epoxy acrylate-based resin can improve photocurability without lowering the dryness of the touch.

The amount of the photosensitive monomer (E) having two or more ethylenically unsaturated groups in the above-mentioned molecule is 100 parts by mass or less, more preferably 100 parts by mass or less, based on 100 parts by mass of the carboxyl group-containing resin (B). The ratio of 5 to 70 parts by mass. When the amount of the collocation is less than 5 parts by mass, the photocurability is lowered, and it is difficult to form a pattern by alkali imaging after irradiation with an active energy ray. On the other hand, when it exceeds 100 parts by mass, the solubility in the aqueous alkali solution is lowered to make the coating film brittle, which is not preferable.

The photocurable thermosetting resin composition of the present invention can be blended with a coloring agent (F). As the coloring agent, conventionally known coloring agents such as red (F-1), blue (F-2), green (F-3), and yellow (F-4) can be used, and pigments, dyes, and pigments can be used. Either. However, from the viewpoint of reducing the environmental load and the influence on the human body, it is preferred that halogen is not contained.

Red colorant (F-1):

Examples of the red coloring agent include monoazo, diazo, monoazo, benzimidazolone, anthracene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quin The quinacridone system and the like, specifically, the following are listed.

Monoazo systems: Pigment Red 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114,146,147,151,170,184,187,188,193,210,245,253,258,266,267,268,269.

Diazo system: Pigment Red 37, 38, 41.

Monoazo lake system: Pigment Red 48:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,52:2,53:1,53 :2,57:1,58:4,63:1,63:2,64:1,68.

Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.

The system is: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.

Diketopyrrolopyrrole: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

Condensed azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242.

蒽醌: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.

Quinacridone is: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant (F-2):

In the case of the blue coloring agent, there are anthracycline-based and anthraquinone-based, and the pigment system is classified into a pigment (Pigment), and specifically, a color index (CI; The Society of Issued by Dyers and Colourists) Number: Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16, Pigment Blue 60.

For dye systems, Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67 are available. , Solvent Blue 70, etc. In addition to the above, a metal-substituted or unsubstituted anthraquinone compound can also be used.

Green colorant (F-3):

For the green colorant, there are similarly anthracycline, anthraquinone, and anthraquinone. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. can be used. . In addition to the above, a metal-substituted or unsubstituted anthraquinone compound can also be used.

Yellow colorant (F-4):

The yellow coloring agent is a monoazo type, a diazo type, a condensed azo type, a benzimidazolone type, an isoindolinone type, an anthraquinone type, etc., and specifically, the following are mentioned.

Lanthanum: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.

Isoindolone: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.

Condensed azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.

Monoazo system: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183.

Diazo system: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

In addition, for the purpose of adjusting the color tone, a coloring agent such as purple, orange, brown, or black may be added.

Specifically, it can be exemplified as Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI color orange 1, CI color orange 5, CI color orange 13 , CI color orange 14, CI color orange 16, CI color orange 17, CI color orange 24, CI color orange 34, CI color orange 36, CI color orange 38, CI color orange 40, CI color orange 43, CI color orange 46, CI color orange 49, CI color orange 51, CI color orange 61, CI color orange 63, CI Color orange 64, CI color orange 71, CI color orange 73, CI color brown 23, CI color brown 25, CI color black 1, CI color black 7 and so on.

The ratio of the above-mentioned coloring agent (F) is not particularly limited, and is preferably from 0 to 10 parts by mass, particularly preferably from 0.1 to 5 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (B). To be full.

In order to enhance the physical strength and the like of the coating film, the photocurable thermosetting resin composition of the present invention may be blended with a filler as needed. As such a filler, a conventionally known inorganic or organic filler 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, a metal acidate or aluminum hydroxide may be used as the extender pigment filler. The blending amount of the filler is preferably 75 mass% or less, more preferably 0.1 to 60 mass%, based on the total amount of the composition. When the amount of the filler is more than 75% by mass based on the total amount of the composition, the viscosity of the insulating composition is increased, and the coating and the formability are deteriorated, and the cured product becomes brittle, which is not preferable.

Further, the photocurable thermosetting resin composition of the present invention may be prepared for the synthesis of the carboxyl group-containing resin (B) or the composition for coating, or the viscosity for coating on a substrate or a carrier film. Use an organic solvent.

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, there are ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; ethoxyethanol, methyl ethoxyethanol, and butyl b. Oxyethanol, diethylene glycol ethyl ether, methyl diglycol ether, butyl diglycol ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl a glycol ether such as 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, etc. Esters; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum light oil, hydrogenated petroleum light oil, solvent light oil, etc. . Such an organic solvent may be used singly or in combination of two or more.

The photocurable thermosetting resin composition of the present invention may be blended with conventionally known additives such as hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, and benzene, depending on the needs thereof. A well-known conventional thermal polymerization inhibitor such as phenol or phenothiazine, a conventionally known tackifier such as fine powder of cerium oxide, organic clay or montmorillonite, an antifoaming agent such as an anthrone, an fluorene or a polymer. And/or a leveling agent, a decane coupling agent such as an imidazole type, a thiazole type or a triazole type, an antioxidant, a rust preventive agent, and the like.

The photocurable thermosetting resin composition of the present invention is adjusted to a viscosity suitable for a coating method by, for example, the organic solvent, and is applied to a substrate by a dip coating method, a cast coating method, a roll coating method, or the like. Coating by a bar coating method, a screen printing method, a curtain coating method, or the like, by volatilizing and drying (false drying) the organic solvent contained in the composition at a temperature of about 60 to 100 ° C Forming a tack-free coating film. Further, a resin insulating layer can be formed by laminating the composition onto a carrier film and drying it to be wound into a film. Thereafter, by contact (or non-contact), the light mask that has formed the pattern can be selectively exposed by the active energy line or directly exposed by the laser direct exposure machine, and will not be exposed. The exposed portion is developed with a dilute aqueous alkali solution (for example, 0.3 to 3 wt% aqueous sodium carbonate solution) to form a photoresist pattern. Further, the epoxy resin (A) or even the heat having two or more cyclic ether groups and/or cyclic thioether groups in the molecule is thermally cured by, for example, heating to a temperature of about 140 to 180 °C. The curable component (D) reacts with the carboxyl group of the carboxyl group-containing resin (B) to form a cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. .

In the above substrate, in addition to a printed wiring board or a flexible printed wiring board in which a circuit is formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyfluorene can be used. All grades of composites such as imine, glass cloth/non-woven fabric-epoxy resin, glass cloth/paper-epoxy resin, synthetic fiber-epoxy resin, fluororesin, polyethylene, PPO, cyanate, etc. -4, etc.) copper-clad laminate, polyimide film, PET film, glass substrate, ceramic substrate, wafer board, and the like.

The volatilization drying performed after applying the photocurable thermosetting resin composition of the present invention may be a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, or the like (the use of a method of heating air by using steam) The heat source can be implemented by a method of bringing the hot air in the dryer into contact with the support and blowing the support from the nozzle.

The coating film obtained by applying the photocurable thermosetting resin composition of the present invention and volatilizing and drying is subjected to exposure (irradiation of active energy rays) as described below. The coating film exposure portion (the portion irradiated by the active energy ray) is hardened.

In the above exposure machine for active energy ray irradiation, a direct drawing device (for example, a laser direct imaging device that directly images a laser based on CAD data from a computer), an exposure machine equipped with a metal halide lamp, or the like can be used. An exposure machine equipped with a (super) high-pressure mercury lamp, an exposure machine equipped with a mercury short-arc light lamp, or a direct drawing device using an ultraviolet lamp such as a (super) high-pressure mercury lamp. In the case of the active energy ray, if laser light having a maximum wavelength of 350 to 410 nm is used, it may be either a gas laser or a solid laser. Further, although the exposure amount varies depending on the film thickness or the like, it is usually 5 to 200 mJ/cm ² , preferably 5 to 100 mJ/cm ² , more preferably 5 to 50 mJ/cm ² . In the above-described direct drawing device, for example, a device manufactured by Orbotech Co., Ltd., PENTAX Corporation, or the like can be used, and any device that emits laser light having a maximum wavelength of 350 to 410 nm can be used.

In the above-mentioned developing method, it may be a dipping method, a rinsing method, a spraying method, a painting method, or the like, and in the case of a developing liquid, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, or phosphoric acid may be used. An aqueous solution of an alkali such as sodium, sodium citrate, ammonia or an amine.

The photocurable thermosetting resin composition of the present invention may be coated with a film which is previously coated on a film such as polyethylene terephthalate, in addition to a method of directly applying a liquid to a substrate. The flux is dried and dried to form a dry film of the solder resist layer. The case where the photocurable thermosetting resin composition of the present invention is used as a dry film is as follows.

The dry film has a structure in which a carrier film, a solder resist layer, and a peelable coating film which is used as needed are laminated in this order. The solder resist layer is a layer obtained by applying an alkali-developable photocurable thermosetting resin composition onto a carrier film or a coating film and drying it. After the solder resist layer is formed on the carrier film, the coated film is laminated thereon, or a solder resist layer is formed on the coated film, and the laminate is laminated on the carrier film to obtain a dry film.

For the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm can be used.

The solder resist layer is an alkali-developing photocurable thermosetting resin composition, and is applied by a blade coater, a lip coater, and a chamfer coater (comma). A coater, a film coater, or the like is formed by uniformly applying a thickness of 10 to 150 μm to a carrier film or a coating film, followed by drying.

As the coating film, a polyethylene film, a polypropylene film, or the like can be used, but it is preferable that the adhesion force to the solder resist layer is smaller than that of the carrier film.

In the case of using a dry film to form a protective film (permanent protective film) on a printed wiring board, the coated film is peeled off, and the solder resist layer is superposed on the substrate on which the circuit has been formed, and a laminator or the like is used. The solder resist layer is formed on the substrate on which the circuit has been formed. When the solder resist layer formed is exposed, developed, and cured in the same manner as described above, a cured coating film can be formed. The carrier film may be peeled off before or after exposure.

[Examples]

The present invention will be specifically described below by showing 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 without any special restrictions.

Synthesis Example 1 (Synthesis of a carboxyl group-containing resin)

A cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C) was introduced into a 2 L separation flask equipped with a stirrer, a thermometer, a circulation cooling tube, a dropping funnel, and a nitrogen introduction tube. Epoxy equivalent of 220) 660g, diethylene glycol ethyl ether acetate 421.3g, and solvent light oil 180.6g, heated to 90 ° C, stirred and dissolved. Then, once cooled to 60 ° C, 216 g of acrylic acid, 4.0 g of triphenylphosphine, and 1.3 g of methyl hydroquinone were added, and the mixture was reacted at 100 ° C for 12 hours to obtain an acid value of 0.2 mg KOH / g. Things. 241.7 g of tetrahydrophthalic anhydride was placed in the product, and the mixture was heated to 90 ° C to carry out a reaction for 6 hours. Thereby, a photosensitive carboxyl group-containing resin solution having an acid value of 50 mgKOH/g, a double bond equivalent (g weight of the unsaturated group per 1 mol of the resin) 400, and a solid content concentration of 7,000 and a solid content concentration of 65% was obtained. Hereinafter, the photosensitive carboxyl group-containing resin solution is referred to as a B1 varnish.

Synthesis Example 2 (Synthesis of a carboxyl group-containing resin)

400 parts of bisphenol F-type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 ° C was dissolved in 925 parts of epichlorohydrin and 462.5 parts of dimethyl hydrazine, and then stirred at 70 ° C for 100 minutes with stirring. 81.2 parts of 98.5% NaOH was added. After the addition, the reaction was further carried out at 70 ° C for 3 hours. Then, the excess unreacted epichlorohydrin and dimethyl hydrazine are mostly distilled off under reduced pressure, and the reaction product containing the by-produced salt and dimethyl hydrazine is dissolved in 750 parts of methyl isobutyl ketone. Further, 10 parts of 30% NaOH was further added and allowed to react at 70 ° C for 1 hour. After the completion of the reaction, the mixture was washed twice with 200 parts of water. After the oil-water separation, methyl isobutyl ketone was distilled off from the oil layer to obtain 370 parts of an epoxy resin (A-0) having an epoxy equivalent of 290 and a softening point of 62 °C.

Next, 2900 parts (10 equivalents) of the obtained epoxy resin (A-0), 720 parts (10 equivalents) of acrylic acid, 2.8 parts of methyl hydroquinone, and 1950 parts of diethylene glycol diethyl ether acetate were placed and heated. The reaction mixture was dissolved by stirring at 90 °C. Next, the reaction liquid was cooled to 60 ° C, 16.7 parts of triphenylphosphine was placed, and the mixture was heated to 100 ° C for about 32 hours to obtain a reactant having an acid value of 1.0 mgKOH/g. Next, 786 parts (7.86 mol) of anhydrous succinic acid and 423 parts of diethylene glycol diethyl ether acetate were placed in the reaction mixture, and the mixture was heated to 95 ° C to carry out a reaction for about 6 hours. Thereby, a photosensitive carboxyl group-containing resin solution having a solid content of 100 mg KOH/g and a solid component concentration of 65% was obtained. Hereinafter, this photosensitive carboxyl group-containing resin solution is referred to as B2 varnish.

Examples 1 to 5 and Comparative Examples 1 to 3

The various components shown in Table 1 were blended in the proportions (mass parts) shown in each of the matching examples, premixed in a blender, placed in a sealed container, and heated in a hot air circulating dryer at 100 ° C for 60 minutes. After confirming that the obtained composition was completely dissolved, it was stirred with a stirrer, left at room temperature for 2 hours, and after confirming returning to room temperature, the mixture was filtered using a 5 μm filter to obtain a liquid A. The obtained liquid A was subjected to particle size measurement by a particle size analyzer manufactured by Eriksen Co., Ltd., and the degree of dispersion was evaluated to be 5 μm or less. After the solution A was placed at 5 ° C for 24 hours, the particle size was measured by a particle size analyzer manufactured by Eriksen Co., Ltd., and the degree of dispersion was evaluated.

The evaluation results of the dispersion are shown in Table 2.

As shown in Table 2, in Examples 1 to 5 using the epoxy resins of (A-1) and (A-2) and Comparative Example 3 in which the A-1 component was not used, according to the present invention, the dispersion was In the case of 5 μm or less, Comparative Examples 1 and 2 in which the epoxy resins of (A-1) and (A-2) were not used in the ratio specified in the present invention, any of them produced coarse particles due to the factor of the A-1 component. The dispersion is greatly reduced.

Example 6

20 parts of KAYARAD TMPTA (trimethylolpropane triacrylate, manufactured by Nippon Kayaku Co., Ltd.) was used instead of the DPHA of the above-mentioned collateral example 1-4 to adjust the liquid A, and the dispersion degree was evaluated in the same manner as in Example 4. The degree of dispersion is 5 μm or less.

Example 7

20 parts of NK ester A-DCP (dimethylol tricyclodecane diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) was used in place of DPHA of the above-mentioned collocation example 1-4 to prepare a liquid A, which was the same as in Example 4. The dispersion degree was evaluated to obtain a degree of dispersion of 5 μm or less.

Example 8

20 parts of ARONIX M-350 (trimethylolpropane EO-modified triacrylate, manufactured by Toagosei Co., Ltd.) was used instead of the DPHA-adjusted liquid A of the above-mentioned collateral example 1-4, and dispersed in the same manner as in Example 4. The degree of dispersion was 5 μm or less.

Example 9

20 parts of TMPTMA (trimethylolpropane trimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) was used instead of the DPHA of the above-mentioned collocation example 1-4 to adjust the liquid A, and the dispersion degree was evaluated in the same manner as in Example 4. The dispersion is 5 μm or less.

Example 10

20 parts of NK ester BPE-500 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) were used in place of DPHA of the above-mentioned collocation example 1-4 to adjust liquid A, and Example 4 In the same manner, the dispersion degree was evaluated to obtain a degree of dispersion of 5 μm or less.

Examples 11 to 13 and Comparative Example 4

Using the carboxyl group-containing resin solution B1 varnish of the above-mentioned synthesis example, in addition to the barium sulfate slurry among the various components shown in the mixing example 2 of Table 3, the ratio (mass part) shown in Table 3 was mixed with the mixer. After premixing, the mixture was kneaded by a 3-roll sander. Next, the barium sulfate slurry was added in the composition in the proportion (parts by mass) shown in Table 3, and stirred in a blender. This composition was filtered using a 5 μm filter to prepare a liquid B. The obtained liquid B was subjected to particle size measurement by a particle size measuring instrument manufactured by Eriksen Co., Ltd., and the degree of dispersion was evaluated to be 5 μm or less. Next, this composition was allowed to stand at 5 ° C for 24 hours, and then the particle size was measured by a particle size analyzer manufactured by Eriksen Co., Ltd., and the degree of dispersion was evaluated to be 5 μm or less.

Next, the components shown in the mixing example 3 of Table 4 were mixed in the ratio (parts by mass) shown in Table 3, premixed in a blender, and then kneaded by a 3-roll sander to prepare a liquid C. The obtained liquid C was measured for particle size by a particle size measuring instrument manufactured by Eriksen Co., Ltd., and the degree of dispersion was evaluated to be 15 μm or less.

<Coarse particles on the dried coating film>

Each of the liquid B of the mixing example 2 and the liquid C of the mixing example 3 were mixed and mixed in a stirrer to obtain a photocurable thermosetting resin composition. Each of the photocurable thermosetting resin compositions was appropriately diluted with methyl ethyl ketone, and sufficiently stirred by a stirrer, and then subjected to particle size measurement by a particle size analyzer manufactured by Eriksen Co., Ltd., and the dispersion was evaluated, although the dispersion of the C liquid was evaluated. The degree is 15 μm or less, and the dispersion is 5 μm or less. This is because the coarse particles of 5 μm or more of the C liquid are dissolved when mixed with the liquid B. Next, this liquid was applied onto a PET film (FB-50: 16 μm manufactured by TORAY Co., Ltd.) by an applicator to dry the film to 50 μm, and dried in a hot air circulating drying oven at 80 ° C for 30 minutes. It was allowed to stand at 15 ° C for 24 hours. The plate was observed under an optical microscope to evaluate the presence or absence of coarse crystal particles. The judgment criteria are as follows.

○: no crystal coarse particles

△: slightly crystallized

×: many crystalline coarse particles are produced

<Layerability of dried coating film>

After rubbing and polishing the copper foil substrate having a pattern, the dry coating film thus observed was subjected to a vacuum laminator (MVLP-500 manufactured by Nihon Seiki Co., Ltd.) to have a pressurization degree of 0.8 MPa, 70. Heating lamination was carried out under the conditions of ° C, 1 minute, and vacuum: 133.3 Pa to obtain a substrate (unexposed substrate) having an unexposed solder resist layer.

The substrate was observed under an optical microscope and evaluated using the following criteria. The evaluation results are shown in Table 5.

○: Smoothing of the surface after lamination

△: Partial unevenness due to poor lamination

×: Overall unevenness due to poor lamination

As shown in Table 5, in the case of Examples 11 to 13 in which the epoxy resins (A-1) and (A-2) were used in the present invention, the photocuring heat obtained by mixing the liquid B and the liquid C was carried out. Each of the curable resin compositions was appropriately diluted with methyl ethyl ketone, and when the mixture was sufficiently stirred by a stirrer, the coarse particles were completely dissolved, and even after drying for 24 hours, no cause was caused on the dried coating film. Large particles of 1 component. Also, even if the coating film is laminated, it is smooth. On the other hand, in the case of Comparative Example 4, it was diluted with methyl ethyl ketone, and after stirring, all the coarse particles were dissolved, but after drying, coarse particles due to the A-1 component were generated, and after lamination, The coating film on the substrate is also not uniform.

Example 14

A dry film was prepared in the same manner as in Example 11 except that 155 parts of B2 varnish was used instead of the B1 varnish of the mixing example 2, and the surface state was evaluated. The results were the same as in Example 11.

Example 15

In place of the B1 varnish of the mixing example 2, 222 parts of CYCLOMER P (ACA) Z250 (a carboxyl group-containing resin manufactured by DAICEL-CYTEC Co., Ltd., solid content: 45 mass%) was used to prepare a liquid B, and dried in the same manner as in Example 11. The film was evaluated and the surface state was evaluated. The results were the same as in Example 11.

Examples 16 to 20 and Comparative Examples 5 to 7

The components shown in the mixing example 4 of Table 6 were mixed in the ratio (parts by mass) shown in the mixing example 4, and premixed in a mixer, and then kneaded by a 3-roll sander to prepare a D liquid. The degree of dispersion of the obtained composition was 15 μm or less as measured by particle size measurement by a particle size analyzer manufactured by Eriksen Co., Ltd.

Example 21, Comparative Example 8

The components shown in the mixing example 5 of Table 7 were mixed in the ratio (parts by mass) shown in the mixing example 5, premixed in a mixer, and kneaded by a 3-roll sander to prepare an E liquid. The degree of dispersion of the obtained composition was 15 μm or less as measured by particle size measurement by a particle size analyzer manufactured by Eriksen Co., Ltd.

Then, the liquid A, the liquid E, and the liquid D were mixed in the combination shown in Table 8, and then stirred in a stirrer to obtain a photocurable thermosetting resin composition. Further, the liquids A and E were prepared by placing the solution at 15 ° C for 7 days after preparation.

Performance evaluation: <Coarse particles on the dried coating film>

The photocurable thermosetting resin compositions of the above Examples 16 to 21 and Comparative Examples 5 to 8 were applied to a glass plate by an applicator to have a coating film of 50 μm after drying, and were dried in a hot air circulating drying oven at 80 °C. It was dried for 30 minutes and left to cool at room temperature for 24 hours. The plate was observed under an optical microscope to evaluate the presence or absence of coarse crystal particles. The judgment criteria are as follows.

○: no crystal coarse particles

△: slightly crystallized

×: many crystalline coarse particles are produced

<Optimum exposure amount>

The circuit pattern substrate having a copper thickness of 35 μm was polished by a rubbing roller, and then washed with water and dried to apply the photocurable thermosetting resin composition of the above Examples 16 to 21 and Comparative Examples 5 to 8 by screen printing. It was dried in a hot air circulating drying oven at 80 ° C for 60 minutes. After drying, exposure was carried out through a ladder plate (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and development was performed for 60 seconds (30 ° C, 0.2 MPa, 1 wt% Na ₂ CO _{3 ).} When the pattern of the ladder plate remaining in the aqueous solution is 7 segments, the optimum exposure amount is obtained.

Characteristic test:

The composition of each of Examples 16 to 21 and Comparative Examples 5 to 8 was applied to the copper foil substrate on which the pattern was formed by screen printing, and the film thickness after drying was 20 μm at 80 ° C. Dry for 30 minutes and let stand to cool to room temperature. On the substrate, an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp) was used to expose the solder resist pattern at an optimum exposure amount, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C was applied under a spray pressure of 0.2 MPa. Second impression, get the photoresist pattern. This substrate was subjected to ultraviolet irradiation under the conditions of an integrated exposure amount of 1000 mJ/cm ² in a UV transfer furnace, and then cured by heating at 150 ° C for 60 minutes. The obtained printed substrate (evaluation substrate) was evaluated for the following characteristics.

<Solder heat resistance>

The evaluation substrate on which the rosin-based flux was applied was immersed in a solder bath set at 260 ° C in advance, and the flux was washed with a modified alcohol, and then the swelling and peeling of the photoresist layer were visually evaluated. The judgment criteria are as follows.

◎: Peeling did not occur even if the immersion was repeated 6 times or more for 10 seconds.

○: Peeling did not occur even if the immersion was repeated 3 times or more for 10 seconds.

△: The immersion was repeated three times or more for 10 seconds, that is, a slight peeling occurred.

X: When immersed within 3 times for 10 seconds, swelling and peeling occurred on the photoresist layer.

<electroless gold plating resistance>

Using a commercially available electroless nickel plating bath and an electroless gold plating bath, plating was carried out under the conditions of 0.5 μm of nickel and 0.03 μm of gold, and after peeling off the tape, the peeling of the photoresist layer was observed by visual inspection, or whether the plating was present or not. Infiltration. The judgment criteria are as follows.

◎: No infiltration or peeling was observed.

○: Although it was confirmed that there was a little infiltration after plating, no peeling was observed after the tape was peeled off.

△: Only a little infiltration was observed after plating, and peeling was also observed after the tape was peeled off.

×: Peeling was observed after plating.

<Electrical characteristics>

The gate electrode pattern of line width/line distance=20/20 μm was used instead of the copper foil substrate, and the evaluation substrate was fabricated under the above conditions, and a bias voltage of DC10V was applied to the gate electrode 10 sheet at 130 ° C, 85% RH. Next, the insulation resistance value was measured in the tank. In the measurement, the gate electrode having a resistance value of 10 ⁴ Ω or less was judged to be a short circuit, and the number of gate electrodes in which no short circuit occurred after 100 hours was counted.

Example 22 <Production of dry film>

Each of the photocurable thermosetting lipid compositions of Example 16 was appropriately diluted with methyl ethyl ketone, and then applied to a PET film (FB-50: 16 μm manufactured by TORAY Co., Ltd.) using an applicator to dry. Thereafter, the film thickness was 20 μm, and it was dried at 80 ° C for 30 minutes to obtain a dry film.

<Production of Substrate>

After rubbing and polishing a copper foil substrate having a pattern, a dry film produced by the above method was used, and a laminator (MVLP-500 manufactured by KK) was used. The pressurization degree was 0.8 MPa. The laminate was heated and laminated at 70 ° C, 1 minute, and a vacuum of 133.3 Pa to obtain a substrate (unexposed substrate) having an unexposed solder resist layer.

Each of the obtained test substrates having a hardened film was subjected to each evaluation test by the aforementioned test method and evaluation method.

The results of the above respective evaluation tests are shown in Table 9.

As shown in the above Table 9, in the cases of Examples 16 to 22 of the present invention, compared with Comparative Examples 5 to 8, no coarse particles were formed on the dried coating film, and solder heat resistance and electroless gold plating resistance were obtained. Excellent in electrical characteristics.

On the other hand, in the case of Comparative Example 5 in which the A-2 component was not sufficiently contained, it was confirmed that the coarse particles in the form of crystals were reduced, but the occurrence of recrystallization was not completely prevented. Further, in the cases of Comparative Examples 6 and 8, it was confirmed that the electrical characteristics were lowered due to the generation of many coarse particles. On the other hand, in Comparative Example 7, although coarse particles were not produced, the solder heat resistance and electrical properties were lowered.

Claims (8)

An alkali-developable photocurable thermosetting resin composition comprising (A) an epoxy resin, (B) a carboxyl group-containing resin, and (C) a photopolymerization initiator; The epoxy resin (A) is a bifunctional biphenyl epoxy resin (A-1) having a structure represented by the general formula (I), and a bisphenol A epoxy resin or a bisphenol A novolak type. a mixture of at least one epoxy resin (A-2) having a softening point of 40 to 100 ° C and an epoxy equivalent of 180 to 300 selected from the group consisting of an epoxy resin and a bisphenol novolac type epoxy resin, and the ring The ratio of (A-1) to (A-2) of the oxygen resin is (A-1) <(A-2); [Chemical 1] (wherein R represents H or CH ₃ ). The photocurable thermosetting resin composition according to claim 1, wherein the epoxy resin (A) is in a state of being dissolved during mixing. The photocurable thermosetting resin composition according to claim 1, wherein the carboxyl group-containing resin (B) has an acid value of 40 to 120 mgKOH/g, and the epoxy resin is 100 parts by mass or more. The mixture of (A-1) and (A-2) is 20 to 60 parts by mass. The photocurable thermosetting resin composition according to claim 1, further comprising (E) a liquid photosensitive monomer having two or more ethylenically unsaturated groups in one molecule. The photocurable thermosetting resin composition according to any one of claims 1 to 4, which is used for formation of a solder resist. A dry film obtained by applying the photocurable thermosetting resin composition according to any one of the above claims 1 to 4 to a film and drying the film. A cured product obtained by applying the photocurable thermosetting resin composition according to any one of the above claims 1 to 4 to a substrate, dried or dried, or the photocurable property The heat-curable resin composition is obtained by applying a dry film obtained by drying a dry film formed on a film to a substrate, and performing photohardening and/or heat curing. A printed wiring board comprising the cured product described in claim 7 above.