TW201835684A - Negative photocurable resin composition, dry film, cured product and printed wiring board - Google Patents

Abstract

The present invention is able to provide: a negative photocurable resin composition which is capable of forming a cured product that has excellent resolution, high heat resistance and high elongation; a dry film which has a resin layer that is obtained from this composition; a cured product of this dry film; and a printed wiring board which comprises this cured product. A negative photocurable resin composition which is characterized by containing (A) an alkali-soluble resin, (B) an organosiloxane compound having a cyclic siloxane skeleton with 6 or more ring members and (C) a photopolymerization initiator, and which is also characterized in that the organosiloxane compound (B) having a cyclic siloxane skeleton with 6 or more ring members has a skeleton represented by general formula (1). (In the formula, n represents an integer of 1 or more).

Description

Negative photocurable resin composition, dry film, cured product and printed wiring board

The present invention relates to a negative-type photocurable resin composition, a dry film, a cured product, and a printed wiring board.

Conventionally, in printed wiring boards, positive or negative photosensitive compositions have been used for the formation of resin layers such as interlayer insulating layers and solder resist layers (for example, Patent Document 1). In general, a positive-type photosensitive composition can form a high-resolution pattern, but the photoacid generator included as one of its components is very expensive and has a cost problem. In addition, diazonaphthoquinone, which is a representative photoacid generator, can generate foam by a denitrification reaction, so there is a problem when forming a coating film of a thick film (mainly 10 μm or more) (for example, Patent Document 2). In order to solve such a problem, conventionally, a negative photosensitive composition excellent in resolution (that is, a negative photocurable resin composition) has been desired.

Also, as described above, the resin layer of the printed wiring board requires high heat resistance and high elongation rate from the viewpoint of reliability, etc. However, the relationship between heat resistance and elongation is trade off, so it cannot be simultaneously Established. Prior art literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 61-243869 Patent Document 2: Japanese Patent Laid-Open No. 2009-204805

"Problems to be solved by invention"

Therefore, an object of the present invention is to provide a negative-type photocurable resin composition capable of forming a cured product having excellent resolution, high heat resistance and high elongation, a dry film having a resin layer obtained from the composition, and the cured product And the printed wiring board with the hardened material. "Means to solve the problem"

In view of the above, the present inventors have carefully reviewed the results and found that by mixing an organic siloxane compound having a cyclic siloxane skeleton of 6 or more rings in the negative photocurable resin composition, the above can be solved Subject, then completed the present invention.

That is, the negative photocurable resin composition of the present invention is characterized by comprising (A) an alkali-soluble resin, (B) an organic siloxane compound having a cyclic siloxane skeleton of 6 or more rings, and ( C) A photopolymerization initiator, (B) an organic siloxane compound having a cyclic siloxane skeleton of 6 or more rings, and a skeleton represented by the following general formula. (In the formula, n represents an integer of 1 or more).

In the negative-type photocurable resin composition of the present invention, the (B) organic siloxane compound having a cyclic siloxane skeleton of 6 or more rings preferably has a thermosetting reactive group.

In the negative-type photocurable resin composition of the present invention, the thermosetting reactive group is preferably an epoxy group.

In the negative-type photocurable resin composition of the present invention, the (B) organic siloxane compound having a cyclic siloxane skeleton of 6 or more rings is preferably a photosensitive group.

In the negative photocurable resin composition of the present invention, the photosensitive group is preferably an ethylenically unsaturated group.

The negative photocurable resin composition of the present invention preferably contains a compound having an ethylenically unsaturated group.

In the negative photocurable resin composition of the present invention, the compound having an ethylenically unsaturated group is preferably a (meth) acrylate compound having at least two functions.

In the negative photocurable resin composition of the present invention, the compound having an ethylenically unsaturated group is preferably a (meth) acrylate compound having an acrylic group equivalent of 100 or more.

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

A cured product of the present invention is characterized by curing the negative photocurable resin composition or the resin layer of the dry film.

A printed wiring board of the present invention is characterized by having the aforementioned cured product. Invention effect

According to the present invention, a negative-type photocurable resin composition capable of forming a cured product having excellent resolution, high heat resistance and high elongation, a dry film having a resin layer obtained from the composition, a cured product thereof, and A printed wiring board having this cured product. Forms for carrying out the invention

The negative photocurable resin composition of the present invention is characterized by containing (A) an alkali-soluble resin, (B) an organic siloxane compound having a cyclic siloxane skeleton of 6 or more rings, and (C) light A polymerization initiator, wherein the aforementioned (B) organic siloxane compound having a cyclic siloxane skeleton of 6 or more rings has a skeleton represented by the following general formula (1), (In the formula, n represents an integer of 1 or more). Although the detailed mechanism is unknown, by formulating (B) an organic siloxane compound having a cyclic siloxane skeleton of 6 or more rings, unexpectedly, the heat resistance and elongation of the trade-off relationship can be established at the same time. In addition, since halation is suppressed, the resolution is also good.

Hereinafter, each component of the negative photocurable resin composition of the present invention will be described.

[(A) Alkali-soluble resin] (A) Alkali-soluble resin is a resin containing one or more functional groups among phenolic hydroxyl group, mercapto group, sulfo group and carboxyl group, and is soluble in an alkaline solution, preferably, it has A compound having two or more phenolic hydroxyl groups, a carboxyl group-containing resin, a compound having a phenolic hydroxyl group and a carboxyl group, a compound having two or more thiol groups, and a compound having a sulfo group. (A) Alkali soluble resin, more preferably resin containing carboxyl group. The aforementioned carboxyl group-containing resin is preferably a carboxyl group-containing resin that does not have an ethylenic unsaturated group in addition to the carboxyl group, in addition to the carboxyl group, from the viewpoint of photocurability or development resistance. The ethylenically unsaturated group is preferably derived from (meth) acrylic acid or their derivatives. Here, (meth) acrylic acid is collectively referred to as acrylic acid, methacrylic acid, and mixtures thereof, and other similar descriptions are also the same. (A) The alkali-soluble resin can be used alone or in combination of two or more.

Specific examples of the carboxyl group-containing resin include the compounds listed below (which may be any of oligomers and polymers).

(1) Obtained by copolymerization of unsaturated carboxylic acids such as (meth) acrylic acid and unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth) acrylates, and isobutylene The resin containing carboxyl group. When the carboxyl group-containing resin has an aromatic ring, at least one of the unsaturated carboxylic acid and the unsaturated group-containing compound may have an aromatic ring.

(2) By using diisocyanate such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, etc. and carboxyl group-containing dimethylol propionic acid, dimethylol butyric acid, etc. Alcohol compounds and polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, bisphenol A-based alkylene oxide adduct diols, Carbamate-containing urethane resin obtained by polyaddition reaction of diol compounds such as compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups. When the carboxyl group-containing urethane resin has an aromatic ring, at least one of the diisocyanate, the carboxyl group-containing diol compound, and the diol compound may have an aromatic ring.

(3) Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate and polycarbonate-based polyol, polyether-based polyol, polyester-based polyol, poly Carbamates obtained by the polyaddition reaction of diol compounds such as olefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups A urethane resin containing terminal carboxyl groups is formed by reacting the end of the resin with an acid anhydride. When the carboxyl group-containing urethane resin has an aromatic ring, at least one of the diisocyanate compound, diol compound, and acid anhydride may have an aromatic ring.

(4) With diisocyanate, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bis-xylenol epoxy resin , (Meth) acrylic acid esters of bifunctional epoxy resins such as biphenol-type epoxy resins or their partial anhydride modified products, carboxyl group-containing diol compounds, and diol compounds. Carboxyl urethane resin. When this photosensitive carboxyl group-containing urethane resin has an aromatic ring, diisocyanate, (meth) acrylate of a bifunctional epoxy resin or partial anhydride modification, carboxyl group-containing diol compound and diol compound At least one type may have an aromatic ring.

(5) In the resin synthesis of the above (2) or (4), a compound having one hydroxyl group and one or more (meth) acryloyl group in the molecule such as hydroxyalkyl (meth) acrylate is added, Carboxyl-containing urethane resin with terminal (meth) acrylation. When the photosensitive carboxyl group-containing urethane resin has an aromatic ring, a compound having one hydroxyl group and one or more (meth) acryloyl groups in the molecule may also have an aromatic ring.

(6) In the resin synthesis of (2) or (4) above, addition of mole reaction products such as isophorone diisocyanate and pentaerythritol triacrylate, etc., with one isocyanate group and one or more (a Group) Acryloyl compound, carboxyl group-containing urethane resin with terminal (meth) acrylation. When the photosensitive carboxyl group-containing urethane resin has an aromatic ring, a compound having one isocyanate group and one or more (meth) acryloyl groups in the molecule may also have an aromatic ring.

(7) The polyfunctional epoxy resin is reacted with (meth) acrylic acid to add dibasic acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride to the side The photosensitive carboxyl group-containing resin of the hydroxyl group of the chain. When the photosensitive carboxyl group-containing resin has an aromatic ring, at least one of the multifunctional epoxy resin and dibasic acid anhydride may have an aromatic ring.

(8) The hydroxy group of the 2-functional epoxy resin is then epoxidized with epichlorohydrin to react with (meth) acrylic acid, and the resulting hydroxy group is added to the photosensitive carboxyl group containing dibasic anhydride Resin. When the photosensitive carboxyl group-containing resin has an aromatic ring, it is sufficient that at least one of the bifunctional epoxy resin and the dibasic acid anhydride has an aromatic ring.

(9) The polyfunctional oxetane resin is reacted with a dicarboxylic acid to form a carboxyl group-containing polyester resin in which a first-order hydroxyl group is added with a dibasic acid anhydride. When the photosensitive carboxyl group-containing polyester resin has an aromatic ring, at least one of the polyfunctional oxetane resin, dicarboxylic acid, and dibasic acid anhydride may have an aromatic ring.

(10) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with alkylene oxide such as ethylene oxide and propylene oxide, and a reaction product obtained by reacting with a monocarboxylic acid containing an unsaturated group , And then the photosensitive resin containing carboxyl group obtained by reaction with polybasic acid anhydride.

(11) 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 and propylene carbonate, and a reaction product obtained by reacting with a monocarboxylic acid containing an unsaturated group Carboxyl group-containing photosensitive resin obtained by reacting with polybasic acid anhydride.

(12) A compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group and (meth) acrylic acid, etc. in one molecule of an epoxy compound having plural epoxy groups in one molecule and p-hydroxyphenylethanol, etc. The alcoholic hydroxyl group of the reaction product obtained by the reaction of the monocarboxylic acid containing unsaturated group, and the multicomponent of maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc. Photosensitive resin containing carboxyl group obtained by reaction of acid anhydride. When the photosensitive carboxyl group-containing polyester resin has an aromatic ring, at least one epoxy compound, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, at least one unsaturated group-containing monocarboxylic acid and polyacid anhydride One kind only needs to have an aromatic ring.

(13) Addition of epoxypropyl (meth) acrylate, α-methylepoxypropyl (meth) acrylate, etc. to any of the resins of (1) to (12) above has 1 in the molecule A photosensitive carboxyl group-containing resin composed of a compound of one epoxy group and one or more (meth) acryloyl groups. When the photosensitive carboxyl group-containing urethane resin has an aromatic ring, a compound having one epoxy group and one or more (meth) acryloyl groups in the molecule may also have an aromatic ring.

(14) A photosensitive carboxyl group-containing resin obtained by reacting a carboxyl group-containing (meth) acrylic copolymer resin with a compound having an ethylene oxide ring and an ethylenically unsaturated group in one molecule.

(15) A copolymer of a compound having an epoxy group and an unsaturated double bond in each molecule and a compound having an unsaturated double bond, reacting with an unsaturated monocarboxylic acid to make the resulting secondary hydroxyl group saturated or Photosensitive carboxyl group-containing resin obtained by the reaction of unsaturated polybasic acid anhydride.

(16) After the hydroxyl-containing polymer is reacted with saturated or unsaturated polybasic acid anhydride, the photosensitive hydroxy-containing and hydroxy-containing compounds obtained by reacting the resulting carboxylic acid with a compound having one epoxy group and unsaturated double bond in each molecule Carboxyl resin.

As mentioned above, the carboxyl group-containing resin has a large number of carboxyl groups in the main chain and the side chain of the polymer, so it can be developed by an aqueous alkali solution.

In addition, as the alkali-soluble resin, an alkali-soluble resin having at least one of the amide and amide imide structures represented by the following formula (2) or (3) may be suitably used. Since it contains a cyclohexane ring or a resin having an amide imide bond directly bonded to a benzene ring, it is possible to obtain a hardened product having superior toughness and excellent heat resistance. In particular, the amide imide resin having the structure shown in (2) below is excellent in light transmittance, so the resolution of the resin composition can be further improved. It is preferable that the alkali-soluble resin having the amide-imide structure of at least one represented by the following formula (2) or (3) has transparency. For example, the transmittance of light with a wavelength of 365 nm in the dry coating film 25 μm More than 70% is better.

The content of the structures of formulas (2) and (3) in the alkali-soluble resin having the above-mentioned amide-imide-imide structure is preferably 10 to 70% by mass. By using this resin, a hardened product excellent in solvent solubility and excellent in physical properties such as heat resistance, tensile strength, elongation, and dimensional stability can be obtained. It is preferably 10 to 60% by mass, and more preferably 20 to 50% by mass.

The alkali-soluble resin having the structure of the amide imide amide imine represented by the formula (2), particularly has the following formula (4A) or (4B) (In formulas (4A) and (4B), each R is a monovalent organic group, preferably H, CF ₃ or CH ₃ , X is a direct bond or a divalent organic group, by direct bond, CH ₂ or A C (CH ₃ ) ₂ or other alkylene group is preferred). A resin having a structure represented by this is preferred because of its excellent physical properties and dimensional stability such as tensile strength and elongation. From the viewpoint of solubility or mechanical properties, the amide imide resin having the structure of formula (2) can be suitably used with resins having the structures of formulas (4A) and (4B) of 10 to 100% by mass. It is more preferably 20 to 80% by mass.

In addition, the amide imide resin having the structure of formula (2), from the viewpoint of solubility or mechanical properties, it is preferable to use amides containing structures of formulas (4A) and (4B) containing 5 to 100 mol% Amide resin. It is more preferably 5 to 98 mol%, even more preferably 10 to 98 mol%, and particularly preferably 20 to 80 mol%.

In addition, the alkali-soluble resin having the amide imide structure represented by the formula (3), particularly having the formula (5A) or (5B) (In formulas (5A) and (5B), each R is a monovalent organic group, preferably H, CF ₃ or CH ₃ , X is a direct bond or a divalent organic group, with direct bond, CH ₂ or C (CH ₃ ) ₂ and other alkylene groups are preferred) The resin having a structure represented by this is preferable because it can obtain a hardened product having excellent mechanical properties such as tensile strength and elongation. From the viewpoint of solubility or mechanical properties, the amide imide resin having the structure of formula (3) is preferably a resin containing structures of formulae (5A) and (5B) containing 10 to 100% by mass. It is more preferably 20 to 80% by mass.

The amide imide resin having the structure of formula (3) exhibits good mechanical properties, and it is preferable to use the amide imide resin containing the structures of formulas (5A) and (5B) containing 2 to 95 mole%. Amine resin. It is more preferably 10 to 80 mol%.

Alkali-soluble resins with an amide imide structure can be prepared by conventional methods. The amide imide resin having the structure of formula (2) can be obtained by using, for example, a diisocyanate compound having a biphenyl skeleton and cyclohexane polycarboxylic acid anhydride.

Examples of diisocyanate compounds having a biphenyl skeleton include 4,4'-diisocyanate-3,3'-dimethyl-1,1'-biphenyl and 4,4'-diisocyanate-3,3'-di Ethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-di Ethyl-1,1'-biphenyl, 4,4'-diisocyanate-3,3'-bis (trifluoromethyl) -1,1'-biphenyl, 4,4'-diisocyanate-2, 2'-bis (trifluoromethyl) -1,1'-biphenyl, etc. In addition, aromatic polyisocyanate compounds such as diphenylmethane diisocyanate can also be used.

Examples of cyclohexane polycarboxylic anhydrides include cyclohexane tricarboxylic anhydride and cyclohexane tetracarboxylic anhydride.

The amide imide resin having the structure of formula (3) can be obtained, for example, by using the diisocyanate compound having a biphenyl skeleton and a polycarboxylic anhydride having two acid anhydride groups.

Polycarboxylic anhydrides having two acid anhydride groups include pyromellitic dianhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, diphenyl ether-3,3', 4 , 4'-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, biphenyl- 2,2 ', 3,3'-tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1- Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (2,3-dicarboxyphenyl ) Propane dianhydride, 2,3-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) benzene dianhydride, bis (3,4-dicarboxyphenyl) Ether diacid anhydride, ethylene glycol bistrimellitic anhydride, etc. alkylene glycol bistrimellitic anhydride, etc.

In addition, specific examples of the alkali-soluble resin having the aforementioned amide-imide-imide structure include UNIDIC V-8000 series manufactured by DIC Corporation and SOXR-U manufactured by Nippon High Paper Industry Corporation.

(A) The acid value of the alkali-soluble resin is preferably in the range of 20 to 120 mgKOH / g, more preferably in the range of 30 to 100 mgKOH / g. By setting (A) the acid value of the alkali-soluble resin to be in the above range, alkali development can be performed well, and a pattern of a normal hardened product can be formed. The weight average molecular weight of the (A) alkali-soluble resin of the resin composition of the present invention varies depending on the resin skeleton, but it is generally preferably 2,000 to 150,000. When the weight average molecular weight is 2,000 or more, the non-stick chirality of the dried coating film and the moisture resistance of the coating film after exposure are good, and the resolution is also better. On the other hand, when the weight average molecular weight is 150,000 or less, the developability and storage stability are good. More preferably, it is 5,000 ~ 100,000.

[(B) Organic siloxane compound having a cyclic siloxane skeleton of 6 or more rings] (B) Organic siloxane compound having a cyclic siloxane skeleton of 6 or more rings (hereinafter also referred to as " (B) Organosiloxane compound "), a well-known and commonly used compound having a cyclic siloxane skeleton of 6 or more rings represented by the following general formula (1) may be used. (In the formula, n represents an integer of 1 or more) In addition, the cyclic siloxane skeleton is preferably 6 to 12 member rings (that is, n in the general formula (1) is an integer of 1 to 4), preferably 6 to 8 members The ring (that is, n in the general formula (1) is 1 or 2) is more preferable.

(B) The organosiloxane compound preferably has a thermosetting reactive group. When it has a thermosetting reactive group, it improves adhesion and is therefore preferable. Thermosetting reactive groups include hydroxyl, carboxyl, isocyanate, amine, imine, epoxy, oxetanyl, mercapto, methoxymethyl, methoxyethyl, ethoxy Methyl, ethoxyethyl, Oxazoline Group, etc. Among them, epoxy groups are preferred. From the viewpoint of preservation stability (life), it is more preferable to have an epoxy group as a cyclohexene oxide group. In addition, when the (B) organosiloxane compound has a thermosetting reactive group, the number of functional groups of the thermosetting reactive group is preferably 1 to 6, more preferably 1 to 4.

(B) The organosilicon compound may have a photosensitive group. When it has a photosensitive base, it can prevent bleed, so it is preferable. Examples of the photosensitive group include ethylenic unsaturated groups such as vinyl, styryl, methacryloyl, and acryloyl. Among them, vinyl, styryl, methacryloyl, and acryloyl are preferred. (B) When the organosilicon compound has a photosensitive group, the number of functional groups of the photosensitive group is preferably from 1 to 6, more preferably from 1 to 4.

(B) The organosilicon compound may have both a thermosetting reactive group and a photosensitive group. When there are both, it can be well balanced to improve heat resistance, adhesion and prevent bleeding.

The thermosetting reactive group and the photosensitive group are preferably bonded directly or via an organic group to Si atoms of a cyclic siloxane skeleton of 6-membered ring or more represented by the general formula (1). The aforementioned organic group may be a branch or a substituent having a hydroxyl group or the like, or may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, or the like. The number of carbon atoms of the aforementioned organic group is preferably 1-10, more preferably 2-8.

(B) Commercial products of organosiloxane compounds include X-40-2670, X-40-2678 manufactured by Shin-Etsu Silicone, CX-783 manufactured by DMI, and 1,3,5-three manufactured by Wako Pure Chemical Industries, Ltd. Vinyl-1,3,5-trimethylcyclotrisiloxane, etc.

(B) Specific examples of the organosiloxane compound include the following compounds, but are not limited thereto.

(B) The organosiloxane compound may be used alone or in combination of two or more. (B) The compounding amount of the organosiloxane compound is 1 to 200 parts by mass, more preferably 5 to 100 parts by mass relative to (A) 100 parts by mass of the alkali-soluble resin.

[(C) Photopolymerization initiator] Any (C) photopolymerization initiator can be used as long as it is a photopolymerization initiator known as a photopolymerization initiator or photoradical generator.

(C) Photopolymerization initiator, for example, bis- (2,6-dichlorobenzyl) phenylphosphine oxide, bis- (2,6-dichlorobenzyl) -2,5 -Dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzyl)- 1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzyl) -2,4 , 4-Trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6 -Trimethylbenzyl) -phenylphosphine oxides (BASF JAPAN, IRGACURE819) and other bis-acetylphosphine oxides; 2,6-dimethoxybenzyldiphenylphosphine oxide Substances, 2,6-dichlorobenzyl diphenylphosphine oxide, methyl 2,4,6-trimethylbenzylphenylphosphonate, 2-methylbenzyl diphenylphosphonate Phosphine oxide, isopropyl trimethylacetoxyphenylphosphonate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (made by BASF JAPAN, DAROCUR TPO), etc. Phosphine oxides; 1-hydroxy-cyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2- -1-propane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane Hydroxyacetophenones such as 1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one; benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzene Benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, etc .; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, rice Benzophenones such as Hillerone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylbenzene Ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinyl-1-acetone, 2-benzyl-2-dimethylamino-1- (4 -Morpholinylphenyl) -butanone-1 (made by BASF JAPAN, IRGACURE369), 2- (dimethylamino) -2-[(4-methylphenyl) methyl) -1- [4 -(4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone and other acetophenones; thioxanthone, 2-ethylthioxanthone, 2- Isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4 -Dithioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and other thioxanthones; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethyl Anthraquinones such as anthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-pentylanthraquinone, 2-aminoanthraquinone, etc; acetophenone dimethyl acetal, benzyl di Acetals such as methyl acetal; ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate, ethyl p-dimethylbenzoate Parabens; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyl oxime)], ethyl ketone, 1- [9-ethyl -6- (2-methylbenzyl) -9H-carbazol-3-yl]-, 1- (O-acetoxy oxime) (manufactured by BASF JAPAN, IRGACURE OXE-02) and other oximes Esters; bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, bis (cyclopentane Dienyl) -bis [2,6-difluoro-3- (2- (1-pyrrol-1-yl) ethyl) phenyl] titanium, such as titanium; phenyl disulfide 2-nitrate Radix, Butyroin, Anisoin ether, Azobisisobutyronitrile, Tetramethylthiuram disulfide, etc. (C) One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

(C) The compounding amount of the photopolymerization initiator is calculated based on solid content, and is preferably 0.01 to 50 parts by mass, and more preferably 0.1 to 30 parts by mass relative to (A) 100 parts by mass of the alkali-soluble resin.

(Compound having an ethylenically unsaturated group) The negative photocurable resin composition of the present invention may contain a compound having an ethylenically unsaturated group. In addition, in the present specification, when the components (A) to (C) have an ethylenically unsaturated group, the compound is removed from the "compound having an ethylenically unsaturated group".

As the compound having an ethylenic unsaturated group, a well-known and commonly used photopolymerizable oligomer, photopolymerizable vinyl monomer, and the like can be used. Among them, the photopolymerizable oligomers include unsaturated polyester oligomers, (meth) acrylate oligomers, and the like. (Meth) acrylate-based oligomers include phenol novolak epoxy (meth) acrylate, cresol novolak epoxy (meth) acrylate, and bisphenol epoxy (meth) acrylate. Epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) Base) acrylate, polybutadiene modified (meth) acrylate, etc.

Examples of the photopolymerizable vinyl monomer include well-known ones, such as styrene derivatives of styrene, chlorostyrene, α-methylstyrene, etc .; vinyl acetate, vinyl butyrate, vinyl benzoate, etc. Vinyl esters; vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-pentyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, Vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether, and other vinyl ethers; propylene amide, methacryl amide, N-hydroxymethacryl amide, N -(Meth) acrylamide such as hydroxymethylmethacrylamide, N-methoxymethacrylamide, N-ethoxymethacrylamide, N-butoxymethacrylamide, etc. Amines; allyl ester compounds such as triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, etc .; 2-ethylhexyl (meth) acrylate, Lauryl (meth) acrylate, Furfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (methyl) ) Acrylate etc. (Meth) acrylic acid esters; hydroxyalkyl (meth) acrylic acid esters, hydroxypropyl (meth) acrylic acid esters, pentaerythritol tri (meth) acrylic acid esters and other hydroxyalkyl (meth) acrylic acid esters; Alkoxyalkylene glycol mono (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, etc .; ethylene glycol di (meth) acrylate , Butanediol di (meth) acrylates, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (methyl) Alkyl polyol poly (meth) acrylates such as acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; diethylene glycol di (meth) acrylate, triethyl Polyoxyalkylene glycols such as glycol di (meth) acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri (meth) acrylate, etc. ) Acrylates; poly (meth) acrylates such as neopentyl glycol hydroxypivalate di (meth) acrylate; tri [(meth) acryloyloxyethyl] isocyanuric acid Ester etc. Isocyanurate (isocyanurate) poly (meth) acrylates.

The compound having an ethylenically unsaturated group is preferably a compound having a (meth) acryloyl group, that is, a (meth) acrylate compound. In addition, the (meth) acrylate compound has better heat resistance, so it is preferably bifunctional or more. In addition, when the (meth) acrylate compound has an acrylic equivalent of 100 or more, the elongation is better, halation is suppressed, and warpage of the hardened product is less likely to occur, which is preferable.

In addition, as the compound having an ethylenically unsaturated group, a (meth) acrylate compound represented by the following general formula (6) can also be used. In the formula, R ¹ is a hydrogen atom, an organic group having 1 to 20 carbon atoms, which may be the same or different, and R ² is selected from an alkyl group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, and At least one type of functional group in the phenyl group, R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵ represents a hydrogen atom or Methyl, p represents an integer of 1 to 5, q represents an integer of 3 or more, m represents an integer of 1 to 4, and n represents an integer of 1 to 10. A preferred aspect is that the (meth) acrylate compound is produced by reacting (a) a compound having three or more phenolic hydroxyl groups in one molecule with (b) a cyclic ether compound or a cyclic carbonate compound The acrylate compound obtained by reacting the hydroxyl group of (c) with a compound having an ethylenically unsaturated group. In this case, it is preferable that the compound (a) having three or more phenolic hydroxyl groups in one molecule is a compound having a phenolic hydroxyl group having a softening point of at least room temperature, and the compound having an ethylenically unsaturated group (c) is preferably methacrylic acid.

The compound having an ethylenically unsaturated group may be used alone or in combination of two or more. The compounding amount of the compound having an ethylenic unsaturated group is 1 to 80 parts by mass, more preferably 2 to 70 parts by mass relative to (A) 100 parts by mass of the alkali-soluble resin.

(Thermosetting component) The negative photocurable resin composition of the present invention may contain a thermosetting component. By thermally curing the light-cured composition, the characteristics of the cured product such as heat resistance and insulation reliability can be improved. As the thermosetting component, amine-based resin, melamine resin, maleimide compound, benzoxazine resin, carbodiimide resin, cyclic carbonate compound, epoxy compound, polyfunctional oxetane compound, Well-known and commonly used thermosetting resins such as episulfide resins. In the present invention, epoxy compounds, oxetane compounds, and maleimide compounds can be suitably used, and these can also be used in combination.

As the epoxy compound, a well-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 preferred. Examples include monoepoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, glycidyl (meth) acrylate, bisphenol A type epoxy resin, bisphenol S type epoxy resin, Bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, trimethylolpropane polypropylene oxide ether, phenyl-1,3- Diglycidyl ether, biphenyl-4,4'-diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol or propylene glycol diglycidyl ether, sorbitan Glycidyl ether, tri (2,3-epoxypropyl) isocyanurate, triglycidoxytri (2-hydroxyethyl) isocyanurate, etc. have 2 in 1 molecule More than one epoxy compound.

Compounds having two or more epoxy groups, specifically, jER828, jER834, jER1001, jER1004, EPICLON840, EPICLON850, EPICLON1050, EPICLON2055, and Nippon Steel & Chemical Corporation manufactured by Mitsubishi Chemical Corporation EPOTOHTOYD-011, YD-013, YD-127, YD-128, DER317, DER331, DER661, DER664 manufactured by Dow Chemical Japan, Sumi-epoxyESA-011, ESA-014, ELA manufactured by Sumitomo Chemical -115, ELA-128, AER330, AER331, AER661, AER664 and other bisphenol A type epoxy resins manufactured by Asahi Kasei Corporation; jeryL903 manufactured by Mitsubishi Chemical Corporation, EPICLON152, EPICLON165 manufactured by DIC Corporation, and Nisshin EPOTOHTO YDB-400, YDB-500 manufactured by Tetsumi Chemical Co., Ltd., DER542 manufactured by Dow Chemical Japan, Sumi-epoxyESB-400 manufactured by Sumitomo Chemical Co., ESB-700, AER711, AER714 manufactured by Asahi Kasei Corporation, etc. Of brominated epoxy resin; jER152, jER154 manufactured by Mitsubishi Chemical Corporation, DEN431, DEN438 manufactured by Dow Chemical Japan Corporation, EPICLONN-730, EPICLONN-770, EPICLONN-865 manufactured by DIC Corporation, new EPOTOHTOYDCN-701, YDCN-704 manufactured by Tetsumi Chemical Co., Ltd., EPPN-201 manufactured by Nippon Kayaku Co., Ltd., EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumi manufactured by Sumitomo Chemical -epoxyESCN-195X, ESCN-220, AERECN-235, ECN-299 manufactured by Asahi Kasei Industries, YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. -700-7, YDCN-700-10, YDCN-704 YDCN-704A, novolac epoxy resins such as EPICLONN-680, N-690, N-695 made by DIC; EPICLON830, Mitsubishi Chemical made by DIC Bisphenol F type epoxy resins such as jER807 manufactured by the company and EPOTOHTO YDF-170, YDF-175, YDF-2004 manufactured by Nippon Steel & Sumitomo Chemical Corporation; EPOTOHTO ST-2004 and ST-2007 manufactured by Nippon Steel & Sumitomo Chemical Corporation , ST-3000, etc. hydrogenated bisphenol A type epoxy resin; jER604 made by Mitsubishi Chemical Corporation, EPOTOHTO YH-434 made by Nippon Steel & Sumitomo Chemical Co., Ltd .; propylene oxide, such as Sumi-epoxyELM-120 made by Sumitomo Chemical Co., Ltd. Base amine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin such as CELLOXID 2021 manufactured by DAICEL Corporation; manufactured by Mitsubishi Chemical Corporation YL-933, trihydroxyphenylmethane type epoxy resin of TEN, EPPN-501, EPPN-502, etc. made by Dow Chemical Japan; double of YL-6056, YX-4000, YL-6121, etc. made by Mitsubishi Chemical Corporation Xylenol-type or biphenol-type epoxy resins or their mixtures; bisphenol S-type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Corporation, EPX-30 manufactured by ADEKA Corporation, and EXA-1514 manufactured by DIC Corporation Resin; bisphenol A novolak epoxy resin such as jER157S manufactured by Mitsubishi Chemical Corporation; tetrahydroxyphenylethane epoxy resin such as jERYL-931 manufactured by Mitsubishi Chemical Corporation; TEPIC manufactured by Nissan Chemical Industry Corporation Heterocyclic epoxy resins; diglycidyl phthalate resins such as Blenmer DGT manufactured by NOF Corporation; tetraglycidyl dimethyl ethanes such as ZX-1063 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. Resin; epoxy resins containing naphthyl groups such as ESN-190, ESN-360, HP-4032, EXA-4750, EXA-4700 manufactured by Nippon Steel & Sumitomo Chemical Corporation; HP-7200, HP- manufactured by DIC Corporation Epoxy resin with dicyclopentadiene skeleton such as 7200H; Epoxypropyl methacrylate such as CP-50S and CP-50M manufactured by NOF Corporation Polymerized epoxy resin; in addition, copolymerized epoxy resin of cyclohexyl maleimide and epoxypropyl methacrylate; CTBN modified epoxy resin (such as YR-102 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) , YR-450, etc.), but not limited to this.

Next, the oxetane compound will be described. Contains the following general formula (7) (In the formula, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) Specific examples of the oxetane compound represented by the oxetane ring include 3-ethyl-3-hydroxymethyl Oxetane (OXT-101 manufactured by East Asia Synthesis), 3-ethyl-3- (phenoxymethyl) oxetane (OXT-211 manufactured by East Asia Synthesis), 3-ethyl-3 -(2-ethylhexyloxymethyl) oxetane (OXT-212 manufactured by East Asia Synthetic Co., Ltd.), 1,4-bis {[(3-ethyl-3-oxetanyl ( oxetanyl ) Methoxy] methyl} benzene (OXT-121 manufactured by East Asia Synthetic Corporation), bis (3-ethyl-3-oxetanylmethyl) ether (OXT-221 manufactured by East Asia Synthetic Corporation), etc. In addition Also, a phenol novolak type oxetane compound, etc. may be mentioned. The oxetane compound may be used in combination with the above-mentioned epoxy compound, or may be used alone.

Examples of the maleimide compound include polyfunctional aliphatic / alicyclic maleimide and polyfunctional aromatic maleimide. A maleimide compound having more than two functions (multifunctional maleimide compound) is preferred. Multifunctional aliphatic / alicyclic maleimide, for example, N, N´-methylenebismaleimide, N, N´-ethylidenebismaleimide, ginseng (hydroxyl) Ethyl) isocyanurate) maleic imide ester compound of isocyanurate skeleton obtained by dehydration esterification of aliphatic / alicyclic maleimide carboxylic acid; ginseng (carbamic acid Carbamate (hexyl) isocyanurate and aliphatic / alicyclic maleimide alcohol, maleimide aminocarboxylic acid of isocyanurate skeleton obtained by carbamate esterification Isocyanuric skeleton polymaleimides such as ester compounds; isophorone diaminocarbamate bis (N-ethylmaleimide), triethylene glycol bis ( (Maleimide ethyl carbonate), aliphatic / alicyclic maleimide carboxylic acid and various aliphatic / alicyclic polyols, dehydration esterification, or aliphatic / alicyclic maleimide Aliphatic / alicyclic polymaleimide compounds obtained by transesterification of imine carboxylic acid esters with various aliphatic / alicyclic polyols; aliphatic / alicyclic maleimide carboxylates Acid and various aliphatic / cycloaliphatic poly Oxides, aliphatic / alicyclic polymaleimide compounds obtained by ether ring-opening reaction; aliphatic / alicyclic maleimide alcohols and various aliphatic / alicyclic polyisocyanates Aliphatic / alicyclic polymaleimide aminocarbamate compounds obtained by urethane reaction.

The polyfunctional aromatic maleimide includes maleimide carboxylic acid and various aromatic polyols for dehydration esterification, or maleimide carboxylic acid ester and various aromatic polyols for transesterification Aromatic polymaleimide compounds obtained by the reaction; Aromatic polymaleimide compounds obtained by performing ether ring-opening reaction between maleimide carboxylic acid and various aromatic polyepoxides; Aromatic polyfunctional maleimide compounds such as aromatic polymaleimide aminocarbamate compounds obtained by the urethane reaction between maleimide alcohol and various aromatic polyisocyanates Wait. The above-mentioned multifunctional maleimide, especially the elongation is better, so the liquid multifunctional maleimide is preferred. In the present invention, the liquid multifunctional maleimide refers to a multifunctional maleimide having a viscosity of 50,000 cp or less measured at 60 ° C. and 5 rpm with a conical plate-type viscometer (TVH-33H manufactured by Toki Industries Co., Ltd.). Imine.

The thermosetting component may be used alone or in combination of two or more. The blending amount of the thermosetting component is calculated based on the solid content, relative to 100 parts by mass of (A) alkali-soluble resin, preferably 0.1 to 100 parts by mass, more preferably 0.5 to 100 parts by mass, and still more preferably 1 to 60 parts by mass Copies. When blending the maleimide compound as the thermosetting component, the blending amount of the maleimide compound is converted into solid content, and is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the (A) alkali-soluble resin. It is more preferably 0.2 to 20 parts by mass. When the blending amount of the maleimide compound is in the range of 0.1 to 50 parts by mass, the balance between high elongation and heat resistance is excellent.

(Thermosetting catalyst) The negative photocurable resin composition of the present invention may contain a thermosetting catalyst. As the thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl Imidazole derivatives such as -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethyl Amino group) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc. Hydrazine compounds such as amine compounds, adipic acid dihydrazide, sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine.

In addition, commercially available products include, for example, 2MZ-AP, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are trade names of imidazole compounds) manufactured by Shikoku Chemical Industry Co., Ltd., manufactured by San-apro Corporation. U-CAT3503N, U-CAT3502T (all trade names of dimethylamine block isocyanate compounds), DBU, DBN, U-CATSA102, U-CAT5002 (all bicyclic amidine compounds and their salts), etc. In particular, it is not limited to this, as long as it is a thermosetting catalyst of an epoxy compound or an oxetane compound, or a reaction of other thermosetting promoting components, one type may be used alone or two or more types may be used in combination.

In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-triazine, 2-vinyl-2, 4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine ･ isocyanuric acid adduct, 2,4-diamino-6-methyl S-triazine derivatives such as acryloxyethyl-S-triazine / isocyanuric acid adducts, etc. It is preferable to use a compound that functions as an adhesion-imparting agent and a thermosetting catalyst for this purpose .

The blending amount of the thermosetting catalyst is calculated based on solid content, and is preferably 0.1 to 20 parts by mass, and more preferably 0.2 to 20 parts by mass relative to (A) 100 parts by mass of the alkali-soluble resin. When the amount of the thermosetting catalyst is in the range of 0.1 to 20 parts by mass, the balance between storage stability and hardening property is excellent.

(Polymerization inhibitor) The negative photocurable resin composition of the present invention preferably contains a polymerization inhibitor, and is more capable of suppressing halation.

The polymerization inhibitor is not particularly limited, and a photopolymerization inhibitor or a thermal polymerization inhibitor can be used. Examples of the photopolymerization inhibitor include p-benzoquinone, naphthoquinone, di-t-butyl p-cresol, hydroquinone monomethyl ether, α-naphthol, acetamidine acetate, hydrazine hydrochloride , Benzyltrimethylammonium chloride, dinitrobenzene, picric acid, quinone dioxime (quinone dioxime), pyrogallol, tannic acid (tannic acid), resorcinol, copper iron reagent (Cupferron ), Phenothiazine, etc. Thermal polymerization inhibitors include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methyl Oxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, tetrachlorobenzoquinone, naphthylamine, β-naphthol, 2,6-di-t-butyl-4 -Cresol, 2,2'-methylidene bis (4-methyl-6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper With organic chelating agent reactant, methyl salicylate, phenothiazine, nitroso compound, nitroso compound and Al chelate, etc. The polymerization inhibitor is preferably a photopolymerization inhibitor. Among them, quinone-based photopolymerization inhibitors such as p-benzoquinone, naphthoquinone, hydroquinone monomethyl ether, and benzoquinone dioxime are preferred. The polymerization inhibitor may be used alone or in combination of two or more.

The compounding amount of the polymerization inhibitor is 0.005 to 20 parts by mass, more preferably 0.01 to 10 parts by mass relative to (A) 100 parts by mass of the alkali-soluble resin.

(Flat agent) The negative photocurable resin composition of the present invention may contain a flat agent. The flattening agent is not particularly limited, and examples thereof include polyacrylate-based polymers, polyether-modified dimethyl polysiloxane copolymers, polyester-modified dimethyl polysiloxane copolymers, and polyether modified Methyl alkyl polysiloxane copolymer, aralkyl modified methyl alkyl polysiloxane copolymer and polyether modified methyl alkyl polysiloxane copolymer, etc. Commercial products of the flattening agent include, for example, BYK-350, -352, -354, -356, -361N, -392 manufactured by BYK-Chemie Japan Co., Ltd., and polyflow series manufactured by Kyoeisha Chemical Company. The flattening agent may be used alone or in combination of two or more.

The blending amount of the flattening agent is preferably 0.005 to 20 parts by mass, and more preferably 0.01 to 10 parts by mass relative to (A) 100 parts by mass of the alkali-soluble resin.

(Colorant) The negative photocurable resin composition of the present invention may contain a colorant. The coloring agent is not particularly limited, and conventionally known coloring agents such as red, blue, green, yellow, white, and black can be used, and any of pigments, dyes, and pigments can be used. Specifically, those with a color index (C.I .; issued by The Society of Dyers and Colourist) can be cited. However, from the viewpoint of reducing the environmental load and the impact on the human body, it is better to use a halogen-free coloring agent.

Red colorants include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, quinacridine Ketones, etc. Blue colorants include metal-substituted or unsubstituted phthalocyanine-based and anthraquinone-based, and pigment-based compounds include compounds classified as pigments. Green colorants also include metal-substituted or unsubstituted phthalocyanine-based, anthraquinone-based, and perylene-based. Examples of the yellow colorant include monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, and anthraquinone-based. Examples of the white colorant include titanium oxide such as rutile type and anatase type. Examples of black colorants include titanium black, carbon black, graphite, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, and aniline pigments. , Molybdenum sulfide, bismuth sulfide, etc. In addition, for the purpose of adjusting the hue, colorants such as purple, orange, and brown can also be added.

The colorant can be used alone or in combination of two or more. The formulation amount of the colorant is not particularly limited, and it is preferably 10 parts by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin. It is more preferably 0.1 to 5 parts by mass.

(Organic solvent) The negative photocurable resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition or adjusting the viscosity when applied to a substrate or a carrier film. Organic solvents, such as ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethyl benzene; cellosolve, methyl cellosolve, butyl cellosolve, card Bis alcohol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether, etc. Alcohol ethers; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether Acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate and other esters; aliphatic hydrocarbons such as octane and decane; petroleum-based solvents such as petroleum ether, petroleum naphtha, solvent petroleum naphtha, etc. Organic solvent. These organic solvents may be used alone or in combination of two or more.

In addition, other additives known and commonly used in the field of electronic materials may be added to the negative photocurable resin composition of the present invention. Other additives include antioxidants, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial and anti-mold agents, defoamers, organic fillers, inorganic fillers, and tackifiers. Agents, adhesion-imparting agents, thixotropy-imparting agents, photoinitiators, sensitizers, hardening accelerators, mold release agents, surface treatment agents, dispersants, wetting and dispersing agents, dispersing aids, surface modifiers , Stabilizers, phosphors, etc.

The negative photocurable resin composition of the present invention can be used after being dried into a thin film, or can be used in a liquid form. When used as a liquid, it may be one-liquid or two-liquid. (B) When the organosilicon compound has a thermosetting reactive group, from the viewpoint of stability during storage, it is preferably separated from the thermosetting catalyst, and is preferably 2 or more. In addition, when the (B) organosilicon compound has a photosensitive group, it is preferably separated from the photopolymerization initiator, and is preferably 2 or more.

Next, the dry film of the present invention has a resin layer obtained by applying the negative photocurable resin composition of the present invention on a carrier film and then drying. When forming a dry film, first, the negative photocurable resin composition of the present invention is diluted with the above-mentioned organic solvent and adjusted to an appropriate viscosity by means of a corner wheel coater, blade coater, lip die coater , Rod coater, extrusion coater, reverse roll coater, transfer roll coater, gravure coater, spray coater, etc., to apply a uniform thickness on the carrier film. Then, by drying the coated composition, usually at a temperature of 50 to 130 ° C. for 1 to 30 minutes, a resin layer can be formed. The thickness of the coating film is not particularly limited. Generally, the thickness of the film after drying is appropriately selected within the range of 10 to 150 μm, preferably 20 to 60 μm.

The carrier film can be a plastic film, such as polyester film such as polyethylene terephthalate (PET), polyimide film, polyimide film, polypropylene film, polystyrene film, etc. . There is no particular restriction on the thickness of the carrier film, and it can be appropriately selected in the range of 10 to 150 μm.

After the resin layer made of the negative photocurable resin composition of the present invention is formed on the carrier film, a cover film that can be peeled off on the surface area of the film is preferable for the purpose of preventing dust and the like from adhering to the surface of the film . As the peelable cover film, for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc. can be used. As long as the cover film is a peeling cover film, it may be less than the adhesive force between the resin layer and the carrier film.

In addition, in the present invention, it is also possible to apply a negative-type photocurable resin composition of the present invention to the cover film and dry to form a resin layer, and the surface area of the carrier film. That is, in the present invention, when producing a dry film, either the carrier film or the cover film may be used as the film to which the curable resin composition of the present invention is applied.

When the negative photocurable resin composition of the present invention is used as a photocurable thermosetting resin composition, the resin layer obtained by applying the composition and evaporating and drying the solvent is exposed (light irradiation), The exposed part (the part irradiated with light) is hardened. Specifically, by contact or non-contact methods, through patterned photomasks, selective pattern exposure by active energy ray exposure, or direct pattern exposure by a laser direct exposure machine, the unexposed portion is exposed to alkali An aqueous solution (for example, 0.3 to 3% by mass sodium carbonate aqueous solution) is developed to form a resist pattern. In addition, by heating to a temperature of about 100 to 180 ° C, thermal curing (post-curing) can form a cured film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics ( Hardened).

When the negative-type photocurable resin composition of the present invention is used as a photocurable resin composition, the composition is applied and the solvent is volatilized and dried. After exposure (light irradiation), the exposed portion (after light irradiation) The part of) hardens and can form a hardened film (hardened material).

The negative-type photocurable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using, for example, the above-mentioned organic solvent, and is applied on a substrate by a dip coating method, a shower coating method, a roll coating method, and a coating bar After coating by methods such as screen printing, screen printing, and curtain coating, the organic solvent contained in the composition is evaporated to dryness (temporary drying) at a temperature of about 60 to 100 ° C to form a non-stick Hand resin layer. In addition, when the above composition is applied to a carrier film or a cover film and dried as a dry film wound as a film, the composition layer of the present invention is brought into contact with the substrate by a laminator or the like, and bonded to the substrate After the application, the resin layer can be formed by peeling off the carrier film.

The above-mentioned substrates include, in addition to printed wiring boards or flexible printed wiring boards in which circuits are first formed of copper, etc., phenol paper, epoxy paper, epoxy glass cloth, glass polyimide, glass Cloth / epoxy non-woven fabric, glass cloth / epoxy paper, epoxy resin synthetic fiber, fluororesin, polyethylene, polyphenylene ether, polyphenylene ether, cyanate, etc. Material, all grades (FR-4, etc.) of copper-clad laminates, other metal substrates, polyimide film, PET film, polyethylene naphthalate (PEN) film, glass substrate, ceramic substrate, wafer Board etc.

For the above volatile drying or thermal hardening, a hot air circulation type drying furnace, an IR furnace, a heating plate, a convection oven, etc. can be used (using a heat source with an air heating method by steam, the method of contacting the hot air in the dryer by convection and using The nozzle is blown toward the support).

The exposure machine used for the above active energy ray irradiation may be a device that irradiates ultraviolet rays in the range of 350 to 450 nm with a high-pressure mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, short-arc mercury lamp, etc., or a direct drawing device (For example, a laser direct imaging apparatus that directly draws an image by laser using CAD data from a computer. The light source of the light of a direct plotter or the laser light source is in the range of the maximum wavelength of 350 ~ 410nm The exposure amount for image formation varies depending on the film thickness, etc., but it can be generally 20 to 1000 mJ / cm ² , preferably 20 to 800 mJ / cm ² .

The above-mentioned developing method can be by dipping method, spraying method, spraying method, brushing method, etc. The developing solution can use potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines Etc. alkaline aqueous solution.

The negative photocurable resin composition of the present invention can be used to form a patterned layer as a permanent coating of a printed wiring board such as a solder resist, a coating layer, an interlayer insulating layer, and particularly can be used to form an interlayer insulating layer. In addition, the negative photocurable resin composition of the present invention is excellent in resolution and can be applied to the pattern layer of IC packages required for the formation of fine patterns, especially FOWLP (Fan-Out Wafer Level Package) or PLP (Panel Level Package) Rewiring layer formation. The negative-type photocurable resin composition of the present invention is excellent in resolution, heat resistance, and elongation even when cured at a low temperature of 200 ° C or lower, so that, for example, in the manufacture of IC packages, difficulty in high-temperature processing can be suppressed Adverse effects of the material.

Examples

The following examples and comparative examples specifically illustrate the present invention, but the present invention is not limited to those in the following examples and comparative examples. In addition, below, "parts" and "%", unless otherwise stated, are the quality standards.

[Synthesis of alkali-soluble resin] (Synthesis Example 1: Alkali-soluble resin A-1 (photosensitive novolak type carboxyl group-containing resin)) In 600 g of diethylene glycol monoethyl ether acetate, o-cresol novolak ( ortho - cresol novolac) type epoxy resin (DIC Corporation, EPICLON N-695, softening point 95 ° C, epoxy equivalent 214, average number of functional groups 7.6) 1070g (epoxypropyl number (total number of aromatic rings): 5.0 moles) , 360g of acrylic acid (5.0 mol), and 1.5g of hydroquinone, heated to 100 ℃ to stir and evenly dissolve. Next, 4.3 g of triphenylphosphine was added, heated to 110 ° C, and after 2 hours of reaction, the temperature was raised to 120 ° C, and the reaction was further performed for 12 hours. 415 g of aromatic hydrocarbon (o-cresol novolac 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added to the prepared reaction liquid, and the reaction was carried out at 110 ° C. for 4 hours. After cooling, it had ethylenic properties A solution of unsaturated group carboxyl group-containing resin A-1. The solid content of the carboxyl group-containing resin solution A-1 thus obtained was 65%, and the acid value of the solid content was 89 mgKOH / g.

[Synthesis of Alkali Soluble Resin] (Synthesis Example 2: Alkali Soluble Resin A-2 (Alkali Soluble Amidimide Resin)) In a four-necked flask equipped with a stirring device, a thermometer, and a condenser, put diethylene glycol monomer 103.5 parts by weight of diethyl ether acetate, 222.0 parts by weight of isophorone diisocyanate, and 192.0 parts by weight of trimellitic anhydride were heated to 120 ° C while stirring. Vigorous foaming started around 60 ° C, and the contents of the flask gradually became transparent. The reaction was carried out at 120 ° C for 5 hours, and when the NCO% in the system became 9.0% by weight, it was cooled to 40 ° C. Then, 166.4 parts by weight of diethylene glycol monoethyl ether acetate and 1.0 part by weight of methylhydroquinone were added, and 58.4 parts by weight of butanol was added, and the temperature was raised to 80 ° C while paying attention to heat generation. After reacting at 80 ° C for 9 hours, it was confirmed by infrared absorption spectrum that the absorption of isocyanate at 2270 cm ^-1 disappeared, and a pale yellow transparent liquid was obtained. According to the molecular weight distribution measurement of GPC, the number average molecular weight is 934 in terms of polystyrene, and the weight average molecular weight is 1420 in terms of polystyrene. Moreover, the acid value was 63.2KOH-mg / g (solid content conversion).

[Synthesis of Alkali Soluble Resin] (Synthesis Example 3: Alkali Soluble Resin A-3 (Alkali Soluble Acrylate Addition Amidimide Resin)) In a four-necked flask with a stirring device, thermometer, and condenser, put two 103.5 parts by weight of ethylene glycol monoethyl ether acetate, 222.0 parts by weight of isophorone diisocyanate, and 192.0 parts by weight of trimellitic anhydride were heated to 120 ° C while stirring. Vigorous foaming started around 60 ° C, and the contents of the flask gradually became transparent. The reaction was carried out at 120 ° C for 5 hours, and when the NCO% in the system became 9.0% by weight, it was cooled to 40 ° C. Then add 166.4 parts by weight of diethylene glycol monoethyl ether acetate and 1.0 part by weight of methylhydroquinone, and add 234.7 parts by weight of Aronix M-305 (manufactured by East Asia Synthesizer, hydroxyl value 120KOH-mg / g). While heating up to 80 ℃. After reacting at 80 ° C for 9 hours, it was confirmed by infrared absorption spectrum that the absorption of isocyanate at 2270 cm ^-1 disappeared, and a pale yellow transparent liquid was obtained. By measuring the molecular weight distribution of GPC, the number average molecular weight is 1084 in terms of polystyrene, and the weight average molecular weight is 1524 in terms of polystyrene. Moreover, the acid value was 68.3KOH-mg / g (solid content conversion).

[Synthesis of Alkali Soluble Resin] (Synthesis Example 4: Alkali Soluble Resin A-4 (Phenol-Starting Alkali Soluble Resin)) In a pressure cooker equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device and a stirring device, put phenolic resin Varnish-type soluble phenolic resin (manufactured by Showa Polymer Co., Ltd., trade name "Shonol CRG 951", OH equivalent: 119.4) 119.4g, potassium hydroxide 1.19g, and toluene 119.4g, stirring to replace nitrogen in the system, Heating up. Next, 63.8g of propylene oxide was slowly dropped and reacted at 125 to 132 ° C and 0 to 4.8kg / cm ² for 16 hours. Then, it was cooled to room temperature, 1.56 g of 89% phosphoric acid was added to this reaction solution, and potassium hydroxide was mixed and neutralized to obtain a novolak-type soluble phenolic resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / eq. Propylene oxide reaction solution. This is an alkylene oxide with 1 equivalent of phenolic hydroxyl group and an average addition of 1.08 mole. Next, the obtained novolak-type soluble phenolic resin alkylene oxide reaction solution 293.0g, acrylic acid 43.2g, methanesulfonic acid 11.53g, methyl hydroquinone 0.18g and toluene 252.9g were put into a mixer, thermometer and air blow tube In the reactor, air was blown in at a rate of 10 ml / min, and the reaction was carried out at 110 ° C for 12 hours with stirring. The water produced by the reaction was distilled into an azeotropic mixture with toluene, and 12.6 g of water was distilled off. Then, it was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution, followed by washing with water. Then, using an evaporator, 118.1 g of diethylene glycol monoethyl ether acetate was substituted while distilling off toluene to obtain a novolac-type acrylate resin solution. Next, 332.5g of the obtained novolac-type acrylate resin solution and 1.22g of triphenylphosphine were put into a reactor equipped with a stirrer, thermometer, and air blowing tube, and air was blown in at a rate of 10ml / min while stirring 60.8g of tetrahydrophthalic anhydride was added, and it was made to react at 95-101 degreeC for 6 hours. A resin solution A-4 of a photosensitive resin containing a carboxyl group having an acid value of 88 mgKOH / g of solid matter and a nonvolatile content of 65% was obtained.

[Synthesis of Alkali Soluble Resin] (Synthesis Example 5: Alkali Soluble Resin A-5 (Copolymerized Acrylate Addition Alkali Soluble Resin)) Heat 325.0 parts by mass of dipropylene glycol monomethyl ether as a solvent to 110 ° C, and 174.0 parts by mass of acrylic acid, 174.0 parts by mass of ε-caprolactone modified methacrylic acid (average molecular weight 314), 77.0 parts by mass of methyl methacrylate, 222.0 parts by mass of dipropylene glycol monomethyl ether, and t as a polymerization catalyst -A mixture of 12.0 parts by mass of butyl peroxy 2-ethylhexanoate (manufactured by NOF Corporation, PerbutylO) was dropped into a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser in 3 hours, After stirring at 110 ° C for 3 hours, the polymerization catalyst was deactivated to obtain a resin solution. After cooling this resin solution, Cyclomer M100 (289.0 parts by mass) manufactured by DAICEL, 3.0 parts by mass of triphenylphosphine and 1.3 parts by mass of hydroquinone monomethyl ether were added, the temperature was raised to 100 ° C, and the epoxy group was opened by stirring The cycloaddition reaction yielded a carboxyl group-containing resin solution A-5 having a solid acid value of 79.8 mgKOH / g and a solid content of 45.5 mass%.

[Synthesis Example of Compound with Ethylene Unsaturation] (Synthesis Example 6: Phenol-started alkylene oxide-modified acrylate) In a pressure cooker equipped with a thermometer, nitrogen introduction device and alkylene oxide introduction device, and stirring device, 106 parts of novolak type phenol resin (manufactured by Showa Polymer Co., Ltd., hydroxyl equivalent 106), 2.6 parts of 50% sodium hydroxide aqueous solution, 100 parts of toluene / methyl isobutyl ketone (mass ratio = 2/1) were added, and stirred Simultaneously, nitrogen was substituted in the system, followed by heating and temperature increase, and at 150 ° C and 8 kg / cm ² , 60 parts of propylene oxide was slowly introduced to react. The reaction was continued for about 4 hours until it reached a gauge pressure of 0.0 kg / cm ^{2 and} then cooled to room temperature. To this reaction solution, 3.3 parts of 36% hydrochloric acid aqueous solution was added for mixing, and sodium hydroxide was neutralized. The neutralization reaction product was diluted with toluene, washed three times with water, and desolvated using an evaporator to obtain an alkylene oxide adduct of a novolak type phenol resin having a hydroxyl equivalent of 164 g / eq. This is the equivalent of 1 equivalent of hydroxyl groups, plus an average of 1 mole of alkylene oxide. 164 parts of the obtained novolak-type soluble phenol resin alkylene oxide adduct, 72 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.05 parts of hydroquinone monomethyl ether, and 100 parts of toluene were placed in a mixer, thermometer, and air. The reactor was blown into the tube, and the reaction was carried out at 90 ° C for 12 hours while stirring air. The water produced by the reaction, as an azeotropic mixture with toluene, started to be distilled off, and then the reaction was allowed to proceed for 5 hours and cooled to room temperature. The resulting reaction solution was washed with 5% NaCl aqueous solution, toluene was distilled off with an evaporator, and carbitol acetate was added to obtain a phenol-started alkylene oxide modified acrylate resin solution with a solid content of 70%.

(Examples 1 to 15, Comparative Example 1) The ingredients were blended according to the blending ratios shown in Tables 1 and 2 below, and after preliminary mixing using a blender, they were dispersed with a three-roll mill, and the curable resins were separately prepared by kneading. Composition. In addition, the compounding quantity in the table is a mass part.

* 1: Resin solution A-1 of photosensitive novolak type carboxyl group-containing resin synthesized in Synthesis Example 1 above (solid content 65%) * 2: Resin solution of alkali-soluble amide imide resin synthesized in Synthesis Example 2 above A-2 (solid content 45%) * 3: Resin solution of alkali-soluble acrylate addition amide imide resin synthesized in Synthesis Example 3 above A-3 (solid content 42%) * 4: Synthesis in Synthesis Example 4 above Resin solution A-4 of phenol starting type alkali-soluble resin (solid content 65%) * 5: Resin solution A-5 (solid content 46%) of the copolymerized acrylate addition alkali-soluble resin synthesized in Synthesis Example 5 above * 6: IRGACURETPO (phosphorus oxide-based photopolymerization initiator) manufactured by BASF JAPAN * 7: IRGACUREOXE02 (oxime-based photopolymerization initiator) manufactured by BASF JAPAN * 8: methyl ethyl ketone * 9: Shikoku Chemicals 1B2PZ (Imidazole-based hardening catalyst; 1-benzyl-2-phenylimidazole) * 10: Shikoku Chemical Co., Ltd. 2PHZ (imidazole-based hardening catalyst; 2-phenyl-4,5-dihydroxymethylimidazole) ) * 11: QS-30 (quinone-based photopolymerization inhibitor) manufactured by Kawasaki Chemical Industry Co., Ltd. * 12: BYK-361N (polyacrylate-based surface conditioner) manufactured by BYK Corporation * 13: A-DCP manufactured by Shin Nakamura Chemical Industry Corporation (2-functional; tricyclodecane dimethanol diacrylate; molecular weight 304) * 14: Laromer LR 8863 manufactured by BASF JAPAN (3-functional; ethylene oxide addition trimethylolpropane triacrylate; molecular weight about 340) * 15: UN9200A (2-functional; polycarbonate-based urethane acrylate with a non-aromatic polycarbonate skeleton; molecular weight 15000) manufactured by Genshang Industrial Co., Ltd. * 16: dipentaerythritol hexaacrylate (6-functional; Molecular weight 578; propylene acetyl equivalent weight less than 100) * 17: A-TMPT (3-functional; trimethylolpropane triacrylate produced by Shin Nakamura Chemical Industry Company; molecular weight 296; propylene acetyl equivalent weight less than 100) * 18: IBXA (monofunctional; isobornyl acrylate; molecular weight 208; acryloyl equivalent 208) manufactured by Osaka Organic Chemical Industry Co., Ltd. * 19: phenol-started alkylene oxide-modified acrylate resin solution (solid) synthesized in Synthesis Example 6 above Ingredient 70%) * 20: BMI-1500 (Liquid bismaleimide: bismaleimide oligomer, 60 ° C, 5rpm, cone-cone plate type viscometer (East Machinery Industry) manufactured by Designer Molecules TVH-33H manufactured by the company: Viscosity measured: 20,000 ± 10,000cp) * 21: HP-7200L manufactured by DIC (alicyclic epoxy compound; diluted product of carbitol acetate, solid content 85%) * 22 : X-40-2670 manufactured by Shin-Etsu SILICONES (with ring 4-functional alicyclic epoxy compound of organic silicone 8-membered ring skeleton) * 23: X-40-2678 (a 2-functional alicyclic epoxy compound with a cyclic organosiloxane 8-membered ring skeleton manufactured by Shin-Etsu SILICONES) * 24: CS-783 manufactured by DMI (glycidyl acrylate with cyclic organosiloxane 8-membered ring skeleton) * 25: manufactured by Wako Pure Chemical Industries (manufactured with cyclic organosiloxane 6-membered ring skeleton 3-functional vinyl compound) * 26: 850-S (Bis-A skeleton epoxy compound) manufactured by DIC Corporation

The negative photocurable resin composition of each obtained example and comparative example was evaluated according to the following. The results are shown in the table above.

(Preparation of a cured film for evaluation) The negative-type photocurable resin compositions of each of the obtained Examples and Comparative Examples were applied to screen-formed copper foil substrates for evaluation with an arbitrary film thickness by screen printing , Dry at 80 ℃ for 20 minutes, let cool to room temperature. Then, the obtained substrate was exposed to a resist pattern with an exposure amount of 500 mJ / cm ² using an exposure device equipped with a high-pressure mercury lamp. Then, the obtained substrate was irradiated with ultraviolet rays using a UV conveyor furnace under the condition of a cumulative exposure of 1000 mJ / cm ² , and then cured by heating at 180 ° C. for 60 minutes. From the cured coating film obtained above, the copper foil was peeled off to obtain a single cured film. With respect to the obtained cured film, the characteristics were evaluated as follows.

(Heat resistance (glass transition temperature Tg)) Tg is measured by the DMA method in accordance with IPC TM-650 at a temperature increase rate of 5 ° C / min and in a tensile mode. Those with a Tg of 190 ° C or higher were evaluated as ⊚, those who did not reach 190 ° C and 180 ° C or higher were evaluated as 0, those who did not reach 180 ° C and 170 ° C or higher were evaluated as △, and those who did not reach 170 ° C were evaluated as ×.

(Elongation (Tensile Breaking)) Elongation (Tensile Breaking Extension) is a tensile tester (Shimadzu Corporation AGS-G100W), based on JISK7127, at a tensile speed of 1.0 mm / min at 23 ° C measuring.

(Warpage) Based on the above evaluation substrate manufacturing conditions, a 20 μm thick resist was formed on a 35 μm thick copper foil, and the total amount of warpage of the four squares after curing was evaluated in specific steps. A total of 20 mm or more and less than 25 mm was evaluated as ◎, a 25 mm or more and less than 30 mm was evaluated as 0, and a 30 mm or more was evaluated as ×.

(Analytical (halation)) The negative-type photocurable resin compositions of each of the obtained examples and comparative examples were completely coated on silicon wafers for evaluation with an arbitrary film thickness using a spin coater Above, dry at 80 ° C for 20 minutes and let cool to room temperature. Then, for the obtained silicon wafer for evaluation, using an exposure device equipped with a high-pressure mercury lamp, with an exposure amount of 300 mJ / cm ² and a resist coating thickness of 10-15 μm, a resist pattern with a design opening diameter of 20 μm, Exposure was carried out through a negative mask, using 2.38% by mass of TMAH (tetramethylammonium = hydroxide) developing solution, and development was carried out for 30 seconds under the condition of a spray pressure of 0.15 MPa. Then, the obtained silicon wafer for evaluation was irradiated with ultraviolet rays using a UV conveyor belt furnace under the condition of a total exposure of 1000 mJ / cm ² , and then cured by heating at 180 ° C. for 60 minutes. According to the above silicon wafer fabrication conditions for evaluation, when the resist coating thickness is 10 to 15 μm and the design opening diameter is 20 μm, the measured value is 20 to 19 μm, that is, the halo is within 1 μm. The evaluation is ◎. Also based on the measured values, the halo exceeds 1 μm and 2 μm or less is evaluated as ○, and the halo exceeds 2 μm is evaluated as ×.

As shown in the above table, it can be seen that the negative-type photocurable resin composition of the present invention is excellent in resolution and can form a cured product with high heat resistance and high elongation.

Claims (11)

A negative-type photocurable resin composition characterized by containing (A) an alkali-soluble resin, (B) an organic siloxane compound having a cyclic siloxane skeleton of 6 or more rings, and (C) photopolymerization A starting agent, wherein the aforementioned (B) organic siloxane compound having a cyclic siloxane skeleton of 6 or more rings has a skeleton represented by the following general formula (1), (In the formula, n represents an integer of 1 or more). The negative type photocurable resin composition according to claim 1, wherein the aforementioned (B) organic siloxane compound having a cyclic siloxane skeleton of 6 or more rings has a thermosetting reactive group. The negative photocurable resin composition according to claim 2, wherein the aforementioned thermosetting reactive group is an epoxy group. The negative photocurable resin composition according to claim 1, wherein the aforementioned (B) organic siloxane compound having a cyclic siloxane skeleton of 6 or more rings has a photosensitive group. The negative photocurable resin composition according to claim 4, wherein the photosensitive group is an ethylenically unsaturated group. The negative photocurable resin composition according to claim 1, which further contains a compound having an ethylenically unsaturated group. The negative photocurable resin composition according to claim 6, wherein the compound having an ethylenically unsaturated group is a (meth) acrylate compound having at least two functions. The negative photocurable resin composition according to claim 6, wherein the compound having an ethylenically unsaturated group is a (meth) acrylate compound having an acrylic equivalent of 100 or more. A dry film characterized by having a resin layer obtained by applying the negative photocurable resin composition of claim 1 to the film and drying it. A hardened product characterized by hardening the negative photocurable resin composition of any one of claims 1 to 8 or the resin layer of the dry film of claim 9. A printed wiring board characterized by the hardened product of claim 10.