TWI778003B - Negative photocurable resin composition, dry film, cured product, and printed wiring board - Google Patents

Abstract

(式中，n表示1以上之整數)The present invention can provide a negative photocurable resin composition capable of forming a cured product with 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 cured product having the cured product. printed wiring board. The negative-type photocurable resin composition of the present invention is characterized by comprising (A) an alkali-soluble resin, (B) an organosiloxane compound having a cyclosiloxane skeleton with six or more membered rings, and (C) a light The polymerization initiator, the aforementioned (B) organosiloxane compound having a cyclic siloxane skeleton with six or more members, has a skeleton represented by the following 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 photocurable resin composition, a dry film, a cured product and a printed wiring board.

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

In addition, the resin layer of the above-mentioned printed wiring board is required to have high heat resistance and high elongation rate from the viewpoint of reliability, etc., but heat resistance and elongation rate are in a trade-off relationship, so they cannot be simultaneously established. Prior Art Documents Patent Documents

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 Inventions"

Therefore, the object of the present invention is to provide a negative photocurable resin composition capable of forming a cured product with excellent resolution, high heat resistance and high elongation, a dry film having a resin layer obtained from the composition, and the cured product and a printed wiring board having the cured product. "Means to Solve Problems"

The inventors of the present invention have made careful examinations in view of the above, and found that the above-mentioned problems can be solved by mixing an organosiloxane compound having a cyclosiloxane skeleton with a 6-membered ring or more into a negative photocurable resin composition. The subject has been solved, and the present invention has been completed.

(式中，n表示1以上之整數)。That is, the negative type photocurable resin composition of the present invention is characterized by comprising (A) an alkali-soluble resin, (B) an organosiloxane compound having a cyclic siloxane skeleton with six or more membered rings, and ( C) The photopolymerization initiator, the organosiloxane compound having a cyclosiloxane skeleton having a 6-membered ring or more, which is the aforementioned (B), has a skeleton represented by the following general formula.

(In the formula, n represents an integer of 1 or more).

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

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

In the negative photocurable resin composition of the present invention, the organosiloxane compound (B) having a cyclic siloxane skeleton having a 6-membered ring or more preferably has 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 further contains a compound having an ethylenically unsaturated group.

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

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

A cured product of the present invention is characterized by being obtained 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 above-mentioned hardened material. Invention effect

According to the present invention, there can be provided a negative photocurable resin composition capable of forming a cured product with excellent resolution, high heat resistance and high elongation, a dry film having a resin layer obtained from the composition, a cured product thereof, and the like. A printed wiring board having the cured product. The form in which the invention is carried out

(式中，n表示1以上之整數)。 　　詳細機構雖不明，但是藉由調配(B)具有6員環以上之環狀矽氧烷骨架的有機矽氧烷化合物，意外地可使取捨關係的耐熱性與延伸率同時成立。又，因光暈受抑制，故解析性也良好。The negative-type photocurable resin composition of the present invention is characterized by comprising (A) an alkali-soluble resin, (B) an organosiloxane compound having a cyclosiloxane skeleton of 6 or more membered rings, and (C) a light A polymerization initiator, wherein the aforementioned (B) organosiloxane compound having a cyclic siloxane skeleton having a 6-membered ring or more 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 preparing (B) an organosiloxane compound having a cyclosiloxane skeleton having a 6-membered ring or more, unexpectedly, the trade-off relationship between heat resistance and elongation can be established at the same time. In addition, since the halo is suppressed, the resolution is also good.

Each component of the negative photocurable resin composition of the present invention will be described below.

[(A) Alkali-Soluble Resin] The (A) alkali-soluble resin contains one or more functional groups among phenolic hydroxyl groups, mercapto groups, sulfo groups, and carboxyl groups, and is soluble in an alkali solution. Compounds having two or more phenolic hydroxyl groups, carboxyl group-containing resins, compounds having phenolic hydroxyl groups and carboxyl groups, compounds having two or more mercapto groups, and compounds having sulfo groups. (A) Alkali-soluble resin, more preferably a carboxyl group-containing resin. The aforementioned carboxyl group-containing resin preferably has an ethylenically unsaturated group in the molecule in addition to the carboxyl group from the viewpoint of photocurability or development resistance, but may be a carboxyl group-containing resin that does not have an ethylenically unsaturated group. The ethylenically unsaturated groups are preferably those derived from (meth)acrylic acid or their derivatives. In addition, here, (meth)acrylic acid is collectively referred to as the term of acrylic acid, methacrylic acid, and the mixture of these, and other similar descriptions are also the same. (A) Alkali-soluble resin can be used individually by 1 type or in combination of 2 or more types.

Specific examples of the carboxyl group-containing resin include compounds listed below (which may be either an oligomer or a polymer).

(1) Obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene, etc. The carboxyl-containing resin. 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) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, etc. and carboxyl group-containing two such as dimethylolpropionic acid, dimethylolbutyric acid, etc. Alcohol compounds, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, Carboxyl group-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 diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, etc., and polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyols Urethanes obtained by polyaddition reaction of olefin-based polyols, acrylic-based polyols, bisphenol A-based alkylene oxide adduct diols, and diol compounds having phenolic and alcoholic hydroxyl groups A urethane resin containing a terminal carboxyl group obtained by reacting the terminal 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, the diol compound, and the acid anhydride may have an aromatic ring.

(4) By diisocyanate and, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol A epoxy resin, bisphenol A epoxy resin , The photosensitivity obtained by the polyaddition reaction of bifunctional epoxy resins such as biphenol-type epoxy resins (meth)acrylates or their partial acid anhydride modifications, carboxyl-containing diol compounds and diol compounds Carboxylic urethane resin. When this photosensitive carboxyl group-containing urethane resin has an aromatic ring, diisocyanate, (meth)acrylate of bifunctional epoxy resin or its partial acid anhydride modified product, 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 groups in the molecule, such as hydroxyalkyl (meth)acrylate, is added, and the Terminal (meth)acrylated carboxyl-containing urethane resin. When this photosensitive carboxyl group-containing urethane resin has an aromatic ring, the compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule may have an aromatic ring.

(6) In the resin synthesis of the above (2) or (4), a molar reaction product such as isophorone diisocyanate and pentaerythritol triacrylate is added, and a molecule having one isocyanate group and one or more (methyl) A carboxyl group-containing urethane resin with terminal (meth)acrylation. When this photosensitive carboxyl group-containing urethane resin has an aromatic ring, the compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule may have an aromatic ring.

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

(8) The hydroxyl group of the bifunctional epoxy resin is then epoxidized with epichlorohydrin to react with (meth)acrylic acid, and the resulting hydroxyl group is added to the photosensitive carboxyl group of the dibasic acid anhydride. resin. When this photosensitive carboxyl group-containing resin has an aromatic ring, at least one of the bifunctional epoxy resin and the dibasic acid anhydride may have an aromatic ring.

(9) Polyfunctional oxetane resin is reacted with dicarboxylic acid, and a carboxyl group-containing polyester resin is added to a dibasic acid anhydride to a primary hydroxyl group. When the photosensitive carboxyl group-containing polyester resin has an aromatic ring, at least one of the polyfunctional oxetane resin, the dicarboxylic acid, and the 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 an alkylene oxide such as ethylene oxide and propylene oxide, and a reaction product obtained by reacting with an unsaturated group-containing monocarboxylic acid , and then react with polybasic acid anhydride to obtain the photosensitive resin containing carboxyl group.

(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 an unsaturated group-containing monocarboxylic acid and then react with polybasic acid anhydride to obtain carboxyl group-containing photosensitive resin.

(12) Compounds having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as an epoxy compound having a plurality of epoxy groups in one molecule, and a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group, such as p-hydroxyphenethyl alcohol, and (meth)acrylic acid, etc. The alcoholic hydroxyl group of the reaction product obtained by the reaction of the unsaturated group-containing monocarboxylic acid, and the polyvalent of maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc. Carboxyl-containing photosensitive resin obtained by acid anhydride reaction. When the photosensitive carboxyl group-containing polyester resin has an aromatic ring, at least one of an epoxy compound, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, an unsaturated group-containing monocarboxylic acid and a polybasic acid anhydride Only one type has an aromatic ring.

(13) Add glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, etc. to any of the above resins (1) to (12), and have 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 this photosensitive carboxyl group-containing urethane resin has an aromatic ring, the compound having one epoxy group and one or more (meth)acryloyl groups in the molecule may 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 one epoxy group and an unsaturated double bond in one molecule and a compound having an unsaturated double bond, respectively, reacts with an unsaturated monocarboxylic acid to make the generated secondary hydroxyl group and saturated or The photosensitive carboxyl group-containing resin obtained by the reaction of unsaturated polybasic acid anhydrides.

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

The above-mentioned carboxyl group-containing resin has many carboxyl groups in the main chain and the side chain of the polymer, so it can be developed by an alkaline aqueous solution.

Moreover, the alkali-soluble resin which has an amide imide structure represented by at least one of following formula (2) or (3) can also be used suitably as an alkali-soluble resin. Since it contains a cyclohexane ring or a resin having an imide bond directly bonded to a benzene ring, a cured product with stronger toughness and excellent heat resistance can be obtained. In particular, the amide imide resin having the structure represented by the following (2) is excellent in light transmittance, so that the resolution of the resin composition can be further improved. The alkali-soluble resin having an amide imide structure represented by at least one of the following formulas (2) or (3) is preferably transparent. For example, in a dry coating film of 25 μm, the transmittance of light with a wavelength of 365 nm is More than 70% is better.

The content of the structures of the formulae (2) and (3) in the alkali-soluble resin having the above-mentioned amide imide structure is preferably 10 to 70 mass %. By using this resin, it is possible to obtain a cured product which is excellent in solvent solubility, and excellent in physical properties such as heat resistance, tensile strength and elongation, and dimensional stability. Preferably it is 10-60 mass %, More preferably, it is 20-50 mass %.

(式(4A)及(4B)中，各自R為1價之有機基，以H、CF₃ 或CH₃ 為佳，X為直接鍵結或2價有機基，以直接鍵結、CH₂ 或C(CH₃ )₂ 等之伸烷基為佳)表示之構造的樹脂，因拉伸強度或伸度等之物性及尺寸安定性優異，故較佳。就溶解性或機械物性的觀點，具有式(2)之構造的醯胺醯亞胺樹脂，可適合使用具有10~100質量%之式(4A)及(4B)之構造的樹脂。更佳為20~80質量%。Alkali-soluble resins having an amide imide structure represented by the formula (2), especially those having 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, with a direct bond, CH ₂ or A resin having a structure represented by an alkylene group such as C(CH ₃ ) ₂ is preferable) is preferable because it is excellent in physical properties such as tensile strength and elongation and dimensional stability. From the viewpoint of solubility or mechanical properties, as the amide imide resin having the structure of formula (2), resins having the structure of formula (4A) and (4B) in an amount of 10 to 100 mass % can be suitably used. More preferably, it is 20-80 mass %.

In addition, as the amide imide resin having the structure of the formula (2), it is preferable to use an amide containing 5 to 100 mol% of the structure of the formula (4A) and (4B) from the viewpoint of solubility and mechanical properties. Amine imide resin. More preferably, it is 5-98 mol %, still more preferably 10-98 mol %, and still more preferably 20-80 mol %.

(式(5A)及(5B)中，各自R為1價有機基，以H、CF₃ 或CH₃ 為佳，X為直接鍵結或2價有機基，以直接鍵結、CH₂ 或C(CH₃ )₂ 等之伸烷基為佳)表示之構造的樹脂，因可得到拉伸強度或伸度等之機械物性優異之硬化物，故較佳。就溶解性或機械物性的觀點，具有式(3)之構造的醯胺醯亞胺樹脂，較佳為使用含有10~100質量%之式(5A)及(5B)之構造的樹脂。更佳為20~80質量%。Moreover, the alkali-soluble resin having the amide imide structure represented by the formula (3), in particular, has the formula (5A) or (5B)

(In formula (5A) and (5B), each R is a monovalent organic group, preferably H, _CF3 or _CH3 , X is a direct bond or a divalent organic group, with a direct bond, _CH2 or C A resin having a structure represented by an alkylene group such as (CH ₃ ) ₂ is preferable) is preferable because a cured product having excellent mechanical properties such as tensile strength and elongation can be obtained. From the viewpoint of solubility or mechanical properties, the amide imide resin having the structure of formula (3) is preferably a resin containing 10 to 100 mass % of the structure of formula (5A) and (5B). More preferably, it is 20-80 mass %.

For the amide imide resin having the structure of the formula (3), it is preferable to use an amide imide resin containing 2 to 95 mol% of the structure of the formula (5A) and (5B) for the reason of exhibiting good mechanical properties. Amine resin. More preferably, it is 10-80 mol%.

The alkali-soluble resin having an amide imide structure can be obtained by a known method. The amide imide resin having the structure of the formula (2) can be obtained, for example, by using a diisocyanate compound having a biphenyl skeleton and a cyclohexane polycarboxylic acid anhydride.

Diisocyanate compounds having a biphenyl skeleton include 4,4'-diisocyanate-3,3'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-3,3'-diphenyl Ethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-diphenyl 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, etc. can also be used.

Cyclohexane polycarboxylic acid anhydride, cyclohexane tricarboxylic acid anhydride, cyclohexane tetracarboxylic acid anhydride, etc. are mentioned.

Moreover, the amide imide resin which has the structure of Formula (3) can be obtained, for example by using the diisocyanate compound which has the said biphenyl skeleton, and the polycarboxylic acid anhydride which has two acid anhydride groups.

Polycarboxylic anhydrides having two acid anhydride groups include pyromellitic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and 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)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 2,2-bis(2,3-dicarboxyphenyl) ) propane dianhydride, 2,3-bis(3,4-dicarboxyphenyl) propane dianhydride, bis(3,4-dicarboxyphenyl) bis(3,4-dicarboxyphenyl) bis(3,4-dicarboxyphenyl) Ether dianhydride, ethylene glycol bis-trimellitic anhydride, etc., alkylene glycol bis-trimellitic anhydride, etc.

Moreover, as a specific example of the alkali-soluble resin which has the said amide imide structure, the UNIDIC V-8000 series by DIC Corporation and SOXR-U by Nippon Advanced Paper Industries are mentioned.

(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 making the acid value of the (A) alkali-soluble resin in the above-mentioned range, favorable alkali development can be achieved, and a pattern of a normal cured 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 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 dry coating film, the moisture resistance of the coating film after exposure are good, and the resolution is also more favorable. 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 to 100,000.

(式中，n表示1以上之整數) 　　又，環狀矽氧烷骨架為6~12員環(亦即通式(1)中之n為1~4之整數)為佳，6~8員環(亦即通式(1)中之n為1或2)更佳。[(B) Organosiloxane compound having a cyclosiloxane skeleton with 6 or more membered rings] (B) Organosiloxane compound having a cyclic siloxane skeleton with 6 or more membered rings (hereinafter also referred to as "" (B) "Organosiloxane compound"), a known and conventional compound having a cyclosiloxane skeleton of 6 or more membered 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 a 6-12-membered ring (that is, n in the general formula (1) is an integer of 1-4), and 6-8 membered rings are preferred. Ring (ie, n in formula (1) is 1 or 2) is more preferred.

The organosiloxane compound (B) preferably has a thermosetting reactive group. When it has a thermosetting reactive group, it is preferable to improve adhesion. The thermosetting reactive group includes a hydroxyl group, a carboxyl group, an isocyanate group, an amino group, an imino group, an epoxy group, an oxetanyl group, a mercapto group, a methoxymethyl group, a methoxyethyl group, and an ethoxy group. Methyl, ethoxyethyl, oxazoline group (Oxazoline Group) and the like. Among them, an epoxy group is preferable. Moreover, from the viewpoint of storage stability (lifetime), it is more preferable to have an epoxy group as a cyclohexene oxide group. Moreover, when the (B) organosiloxane compound has a thermosetting reactive group, the functional group number of the thermosetting reactive group is preferably 1-6, more preferably 1-4.

(B) The organosiloxane compound may have a photosensitive group. When it has a photosensitive group, it can prevent bleeding (bleed), so it is preferable. The photosensitive group includes ethylenically unsaturated groups such as vinyl, styryl, methacryloyl, and acryl. Among them, vinyl group, styryl group, methacryloyl group, and acryl group are preferable. (B) When the organosiloxane compound has a photosensitive group, the number of functional groups of the photosensitive group is preferably 1-6, more preferably 1-4.

(B) The organosiloxane compound may have both a thermosetting reactive group and a photosensitive group. When both are present, the improvement of heat resistance, adhesiveness, and bleed prevention can be achieved in a well-balanced manner.

The thermosetting reactive group and the photosensitive group are preferably bonded to the Si atom of the 6-membered or more cyclic siloxane skeleton represented by the general formula (1), either directly or via an organic group. The aforementioned organic group may be branched, may have a substituent such as a hydroxyl group, 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-tris, manufactured by Wako Pure Chemical Industries, Ltd. Vinyl-1,3,5-trimethylcyclotrisiloxane, etc.

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

(B) The organosiloxane compound may be used alone or in combination of two or more. (B) The compounding quantity of an organosiloxane compound is 1-200 mass parts with respect to 100 mass parts of (A) alkali-soluble resin, More preferably, it is 5-100 mass parts.

[(C) Photopolymerization initiator] The (C) photopolymerization initiator can be used as long as it is a known photopolymerization initiator or a 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 oxide (BASF JAPAN company, IRGACURE819) and other bis-phosphoryl phosphine oxides; 2,6-dimethoxybenzyl diphenylphosphine oxide compound, 2,6-dichlorobenzyldiphenylphosphine oxide, methyl 2,4,6-trimethylbenzylphenylphosphonate, 2-methylbenzyldiphenyl Phosphine oxide, isopropyl trimethylacetylphenylphosphonate, 2,4,6-trimethylbenzyldiphenylphosphine oxide (manufactured by BASF JAPAN, DAROCUR TPO), etc. Phosphine oxides; 1-Hydroxy-cyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one , 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy- Hydroxyacetophenones such as 2-methyl-1-phenylpropan-1-one; benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin In isopropyl ether, benzoin n-butyl ether and other benzoins; benzoin alkyl ethers; benzophenone, p-methyl benzophenone, Michler's ketone, methyl diphenylmethane Ketones, 4,4'-dichlorobenzophenone, 4,4'-bis-diethylaminobenzophenone and other benzophenones; acetophenone, 2,2-dimethoxy- 2-Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenone, 2-methyl-1 -[4-(Methylsulfanyl)phenyl]-2-morpholinyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butyl Keto-1 (manufactured by BASF JAPAN, IRGACURE369), 2-(dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4-morpholino)benzene Acetophenones such as]-1-butanone, N,N-dimethylaminoacetophenone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2, 4-Dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and other thioxanthones; anthraquinone, chloroanthracene Anthraquinones such as quinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, etc.; Acetophenone dimethyl acetal, Acetals such as benzyl dimethyl acetal; ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, p-dimethylbenzene Parabens such as ethyl formate; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzyl oxime)], ethyl ketone, 1-[9 -Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyloxyoxime) (manufactured by BASF JAPAN, IRGACURE OXE-02) Oxime esters such as; bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium (Cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyrrol-1-yl)ethyl)phenyl]titanocenes such as titanium; phenyl disulfide 2-Nitropyridine, Butyroin, Anisoin ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc. (C) A photopolymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more types.

(C) The compounding quantity of a photopolymerization initiator is a solid content conversion, Preferably it is 0.01-50 mass parts with respect to 100 mass parts of (A) alkali-soluble resin, More preferably, it is 0.1-30 mass parts.

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

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

The photopolymerizable vinyl monomers 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; acrylamide, methacrylamide, N-hydroxymethyl acrylamide, N -(Meth)acrylamides such as hydroxymethyl methacrylamide, N-methoxymethacrylamide, N-ethoxymethacrylamide, N-butoxymethacrylamide, etc. Amines; allyl compounds of triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, etc.; 2-ethylhexyl (meth)acrylate, Lauryl (meth)acrylate, Tetrahydrofurfuryl (Furfuryl) (meth)acrylate, Isobornyl (meth)acrylate, Phenyl (meth)acrylate, Phenoxyethyl (meth)acrylate ) (meth)acrylic acid esters such as acrylates; hydroxyalkyl (methyl) hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, etc. ) acrylates; methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate and other alkoxyalkylene glycol mono (meth)acrylates; ethylene glycol di ( Meth)acrylates, butanediol di(meth)acrylates, neopentyl glycol di(meth)acrylates, 1,6-hexanediol di(meth)acrylates, trimethylolpropane Alkylene polyol poly(meth)acrylates of tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.; diethylene glycol di(meth)acrylate Polyoxyalkane diacrylates of acrylates, triethylene glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri(meth)acrylate, etc. Alcohol poly(meth)acrylates; poly(meth)acrylates such as neopentyl glycol hydroxypivalate di(meth)acrylate; tris[(meth)acryloyloxyethyl] Isocyanurate (isocyanurate) type poly(meth)acrylates etc., such as isocyanurate.

The compound having an ethylenically unsaturated group is preferably a compound having a (meth)acryloyl group, that is, a (meth)acrylate compound. Moreover, since the heat resistance of a (meth)acrylate compound is more favorable, it is preferable that it is bifunctional or more. In addition, when the acryl group equivalent of the (meth)acrylate compound is 100 or more, the elongation is better, the halo can be suppressed more, and the warpage of the cured product is less likely to occur, so it is preferable.

式中，R¹ 為氫原子、碳數1~20之有機基，可相同或相異，R² 為選自由碳數1~10之烷基、碳數1~10之伸烷基、及伸苯基所成群中之至少1種的官能基， 　　R³ 表示氫原子或碳數1~4之烷基， 　　R⁴ 表示氫原子或碳數1~4之烷基， 　　R⁵ 表示氫原子或甲基， 　　p表示1~5之整數，q表示3以上之整數， 　　m表示1~4之整數，n表示1~10之整數。 　　較佳的態樣係前述(甲基)丙烯酸酯化合物為使(a)1分子中具有3個以上之酚性羥基的化合物與(b)環狀醚化合物或環狀碳酸酯化合物反應，所生成的羥基與(c)具有乙烯性不飽和基的化合物反應所得的丙烯酸酯化合物。此時，較佳為上述1分子中具有3個以上之酚性羥基的化合物(a)為具有室溫以上的軟化點之具有酚性羥基的化合物，又，上述具有乙烯性不飽和基的化合物(c)係以甲基丙烯酸為佳。Moreover, as a compound which has an ethylenically unsaturated group, the (meth)acrylate compound represented by following General formula (6) can also be used.

In the formula, R ¹ is a hydrogen atom, an organic group with 1 to 20 carbon atoms, which may be the same or different, and R ² is selected from an alkyl group with 1 to 10 carbon atoms, an alkyl group with 1 to 10 carbon atoms, and an alkyl group with 1 to 10 carbon atoms. A functional group of at least one of the phenyl groups, R ³ represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, R ⁴ represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, and R ⁵ represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. For methyl group, 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. In a preferred aspect, 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. An 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 a phenolic hydroxyl group having three or more phenolic hydroxyl groups in one molecule is a compound having a phenolic hydroxyl group having a softening point of room temperature or higher, and the compound having an ethylenically unsaturated group. The system (c) is preferably methacrylic acid.

The compound which has an ethylenically unsaturated group may be used individually by 1 type, and may be used in combination of 2 or more types. The compounding quantity of the compound which has an ethylenically unsaturated group is 1-80 mass parts with respect to 100 mass parts of (A) alkali-soluble resin, More preferably, it is 2-70 mass parts.

(Thermosetting component) The negative photocurable resin composition of the present invention may contain a thermosetting component. By thermally curing the photocured composition, the properties of the cured product such as heat resistance and insulation reliability can be improved. As thermosetting components, amine-based resins, melamine resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, epoxy compounds, polyfunctional oxetane compounds, Known and usual thermosetting resins such as episulfide resins. In the present invention, an epoxy compound, an oxetane compound, and a maleimide compound can be suitably used, or these compounds can be used in combination.

As the above-mentioned epoxy compound, a known and usual compound having one or more epoxy groups can be used, and among them, a compound having two or more epoxy groups is preferable. For example, monoepoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and 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 polyglycidyl ether, phenyl-1,3- Diglycidyl ether, biphenyl-4,4'-diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitan Glycidyl ether, tris(2,3-epoxypropyl)isocyanurate, triglycidyltris(2-hydroxyethyl)isocyanurate, etc. have 2 in one molecule Compounds with more than one epoxy group.

The compound having two or more epoxy groups, specifically, jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, EPICLON840, EPICLON850, EPICLON1050, EPICLON2055 manufactured by Nippon Steel & Sumitomo Chemical Corporation, manufactured by DIC Corporation EPOTOHTOYD-011, YD-013, YD-127, YD-128, D.E.R.317, D.E.R.331, D.E.R.661, D.E.R.664, manufactured by Dow Chemical Japan, Sumi-epoxyESA-011, ESA-014, ELA manufactured by Sumitomo Chemical -115, ELA-128, A.E.R.330, A.E.R.331, A.E.R.661, A.E.R.664 and other bisphenol A epoxy resins manufactured by Asahi Kasei Industries; EPOTOHTO YDB-400, YDB-500 manufactured by Sumitomo Metal Chemical Co., Ltd., D.E.R.542 manufactured by Dow Chemical Japan, Sumi-epoxyESB-400, ESB-700 manufactured by Sumitomo Chemical Corporation, A.E.R.711, A.E.R.714 manufactured by Asahi Kasei Industries, etc. The brominated epoxy resin; jER152, jER154 manufactured by Mitsubishi Chemical Corporation, D.E.N.431, D.E.N.438 manufactured by Dow Chemical Japan Corporation, EPICLONN-730, EPICLONN-770, EPICLONN-865 manufactured by DIC Corporation, Nippon Steel & Sumitomo Metal Chemical Corporation EPOTOHTOYDCN-701, YDCN-704 manufactured by Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumi-epoxyESCN-195X manufactured by Sumitomo Chemical Corporation , ESCN-220, A.E.R.ECN-235, ECN-299 manufactured by Asahi Kasei Industry Co., Ltd., YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7 manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. , YDCN-700-10, YDCN-704, YDCN-704A, EPICLONN-680, N-690, N-695 made by DIC company novolak epoxy resin; EPICLON830 made by DIC company, jER807 made by Mitsubishi Chemical company, EPOTOHTO YDF-170, YDF-175, YDF-2004 and other bisphenol F-type epoxy resins manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.; new Hydrogenated bisphenol A epoxy resins such as EPOTOHTO ST-2004, ST-2007, ST-3000 manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation; jER604 manufactured by Mitsubishi Chemical Corporation, EPOTOHTO YH-434 manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation; Epoxypropylamine type epoxy resins such as Sumi-epoxyELM-120 manufactured by Sumitomo Chemical Co., Ltd.; Hydantoin type epoxy resins; Alicyclic epoxy resins such as CELLOXID 2021 manufactured by DAICEL Corporation; Mitsubishi Chemical Corporation YL-933, T.E.N., EPPN-501, EPPN-502 made by Dow Chemical Japan Co., Ltd. of trihydroxyphenylmethane type epoxy resin; YL-6056, YX-4000, YL-6121 made by Mitsubishi Chemical Co., Ltd. Bis-xylenol-type or biquinol-type epoxy resins or their mixtures; bisphenol S-rings such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by ADEKA Corporation, EXA-1514 manufactured by DIC Corporation, etc. Oxygen resin; bisphenol A novolak type epoxy resin such as jER157S manufactured by Mitsubishi Chemical Corporation; tetrahydroxyphenyl ethane type epoxy resin such as jERYL-931 manufactured by Mitsubishi Chemical Corporation; TEPIC manufactured by Nissan Chemical Industry Corporation, etc. Heterocyclic epoxy resins; Diglycidyl phthalate resins such as Blenmer DGT manufactured by NOF Corporation; Tetraglycidyl xylyl ethyl acetate such as ZX-1063 manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. Alkane resins; ESN-190, ESN-360 manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by DIC Corporation and other epoxy resins containing naphthyl groups; HP-7200, HP manufactured by DIC Corporation Epoxy resin with dicyclopentadiene skeleton such as -7200H; glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by NOF Corporation; Copolymerized epoxy resin of imide and glycidyl methacrylate; CTBN modified epoxy resin (such as YR-102, YR-450 manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), etc., but not limited to this Wait.

(式中，R⁶ 表示氫原子或碳數1~6之烷基)表示之氧雜環丁烷環之氧雜環丁烷化合物的具體例，可列舉3-乙基-3-羥基甲基氧雜環丁烷(東亞合成公司製OXT-101)、3-乙基-3-(苯氧基甲基)氧雜環丁烷(東亞合成公司製OXT-211)、3-乙基-3-(2-乙基己氧基甲基)氧雜環丁烷(東亞合成公司製OXT-212)、1,4-雙{[(3-乙基-3-氧雜環丁烷基( oxetanyl) 甲氧基]甲基}苯(東亞合成公司製OXT-121)、雙(3-乙基-3-氧雜環丁烷基甲基)醚(東亞合成公司製OXT-221)等。此外，也可列舉苯酚酚醛清漆型的氧雜環丁烷化合物等。氧雜環丁烷化合物也可與上述環氧化合物併用，也可單獨使用。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 Toagosei Co., Ltd.), 3-ethyl-3-(phenoxymethyl)oxetane (OXT-211 manufactured by Toagosei Corporation), 3-ethyl-3 -(2-Ethylhexyloxymethyl)oxetane (OXT-212 manufactured by Toagosei Co., Ltd.), 1,4-bis{[(3-ethyl-3-oxetanyl ( oxetanyl) ) methoxy]methyl}benzene (OXT-121 manufactured by Toagosei Corporation), bis(3-ethyl-3-oxetanylmethyl) ether (OXT-221 manufactured by Toagosei Corporation), etc. In addition , and phenol novolac-type oxetane compounds, etc. The oxetane compounds may be used in combination with the above-mentioned epoxy compounds, or may be used alone.

The above-mentioned maleimide compound includes polyfunctional aliphatic/alicyclic maleimide and polyfunctional aromatic maleimide. A maleimide compound having two or more functions (polyfunctional maleimide compound) is preferable. Polyfunctional aliphatic/alicyclic maleimide, for example, N,N´-methylenebismaleimide, N,N´-ethylidenebismaleimide, bis(hydroxyl) Ethyl) isocyanurate) and aliphatic/alicyclic maleimide carboxylic acid, the maleimide compound of isocyanurate skeleton obtained by dehydration esterification; see (carbamic acid) Ester (carbamate) hexyl) isocyanurate and aliphatic/alicyclic maleimide alcohol, maleimide carbamic acid of isocyanurate skeleton obtained by urethane esterification Isocyanuric (isocyanuric) skeleton polymaleimides of ester compounds, etc.; isophorone biscarbamate bis(N-ethylmaleimide), triethylene glycol bis( Maleimide ethyl carbonate), aliphatic/alicyclic maleimine carboxylic acid and various aliphatic/alicyclic polyols, dehydrated esterification, or aliphatic/alicyclic maleimide Aliphatic/alicyclic polymaleimide ester compounds obtained by transesterification of imine carboxylate with various aliphatic/alicyclic polyols; aliphatic/alicyclic maleimide carboxylate Aliphatic/alicyclic polymaleimide ester compounds obtained by ether ring-opening reaction between acid and various aliphatic/alicyclic polyepoxides; aliphatic/alicyclic maleimide alcohol and Various aliphatic/alicyclic polyisocyanates, aliphatic/alicyclic polymaleimide urethane compounds obtained by urethane reaction, etc.

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

A thermosetting component may be used individually by 1 type, or may be used in combination of 2 or more types. The blending amount of the thermosetting component is calculated in terms of solid content, and is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 100 parts by mass, and more preferably 1 to 60 parts by mass relative to 100 parts by mass of the (A) alkali-soluble resin. share. When blending the maleimide compound as a thermosetting component, the blending amount of the maleimide compound is preferably 0.1 to 50 parts by mass based on 100 parts by mass of the (A) alkali-soluble resin, in terms of solid content, More preferably, it is 0.2-20 mass parts. 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 can be used - imidazole derivatives of 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.; dicyandiamide, benzyldimethylamine, 4-(dimethylamine) amino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc. Amine compounds, hydrazine compounds such as adipic acid dihydrazine, sebacate dihydrazine, etc.; phosphorus compounds such as triphenylphosphine, etc.

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

In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2, 4-Diamino-S-triazine, 2-Vinyl-4,6-diamino-S-triazine･Isocyanuric acid adduct, 2,4-Diamino-6-methyl S-triazine derivatives such as acryloxyethyl-S-triazine, isocyanuric acid adducts, etc. Preferably, these compounds that function as adhesion imparting agents are used together with a thermosetting catalyst .

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

(Polymerization inhibitor) It is preferable that the negative photocurable resin composition of the present invention contains a polymerization inhibitor, which can suppress halo.

The polymerization inhibitor is not particularly limited, and a photopolymerization inhibitor or a thermal polymerization inhibitor can be used. Examples of photopolymerization inhibitors include p-benzoquinone, naphthoquinone, di-t-butyl-p-cresol, hydroquinone monomethyl ether, α-naphthol, acetamidine acetate, and hydrazine hydrochloride. , benzyltrimethylammonium chloride, dinitrobenzene, picric acid, quinone dioxime, pyrogallol, tannic acid, resorcinol, cupferron ), phenothiazine, etc. Thermal polymerization inhibitors, such as 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methylmethane Oxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, tetrachlorobenzoquinone, naphthylamine, beta-naphthol, 2,6-di-t-butyl-4 -Cresol, 2,2'-methylidenebis(4-methyl-6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper Reactants with organic chelating agents, methyl salicylate, phenothiazine, nitroso compounds, chelate compounds of nitroso compounds and Al, etc. The polymerization inhibitor is preferably a photopolymerization inhibitor, and 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 quantity of a polymerization inhibitor is 0.005-20 mass parts with respect to 100 mass parts of (A) alkali-soluble resin, More preferably, it is 0.01-10 mass parts.

(Leveling agent) The negative photocurable resin composition of the present invention may contain a leveling agent. The leveling agent is not particularly limited, and examples thereof include polyacrylate-based polymers, polyether-modified dimethylpolysiloxane copolymers, polyester-modified dimethylpolysiloxane copolymers, and polyether-modified dimethylpolysiloxane copolymers. Methyl alkyl polysiloxane copolymers, aralkyl modified methyl alkyl polysiloxane copolymers and polyether modified methyl alkyl polysiloxane copolymers, etc. Commercially available flattening agents include BYK-350, -352, -354, -356, -361N, -392 manufactured by BYK-Chemie Japan, and polyflow series manufactured by Kyōeisha Chemical Co., Ltd., for example. A leveling agent may be used individually by 1 type, or may be used in combination of 2 or more types.

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

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

Red colorants include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridine. Ketones, etc. Blue colorants include metal-substituted or unsubstituted phthalocyanines and anthraquinones, and pigments include compounds classified as pigments. Green colorants also include metal-substituted or unsubstituted phthalocyanines, anthraquinones, and perylenes. The yellow coloring agent includes monoazo-based, disazo-based, condensed-azo-based, benzimidazolone-based, isoindolinone-based, anthraquinone-based, and the like. As a white coloring agent, titanium oxide, such as a rutile type and anatase type, etc. are mentioned. Examples of black colorants include titanium black-based, carbon black-based, graphite-based, iron oxide-based, anthraquinone-based, cobalt oxide-based, copper oxide-based, manganese-based, antimony oxide-based, nickel oxide-based, perylene-based, and aniline-based pigments , molybdenum sulfide, bismuth sulfide, etc. In addition, colorants such as purple, orange, and brown may be added for the purpose of adjusting the color tone.

A coloring agent can be used individually by 1 type or in combination of 2 or more types. The blending amount of the colorant is not particularly limited, but is preferably 10 parts by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin. More preferably, it is 0.1-5 mass parts.

(Organic Solvent) The negative-type photocurable resin composition of the present invention may contain an organic solvent for the purpose of preparation of the composition or adjustment of the viscosity when it is applied to a substrate or a carrier film. As organic solvents, ketones such as methyl ethyl ketone and cyclohexanone can be used; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, etc.; cellosolve, methyl cellosolve, butyl cellosolve, card Biol, 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 Esters of acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate, etc.; aliphatic hydrocarbons such as octane and decane; petroleum-based solvents such as petroleum ether, naphtha, solvent naphtha, etc. organic solvent. These organic solvents may be used alone or in combination of two or more.

In addition, other well-known and conventional additives 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, antiaging agents, antibacterial and antifungal agents, antifoaming agents, organic fillers, inorganic fillers, tackifiers agent, adhesion imparting agent, thixotropy imparting agent, photoinitiating aid, sensitizer, hardening accelerator, mold release agent, surface treating agent, dispersing agent, wetting dispersing agent, dispersing aid, surface modifier , stabilizers, phosphors, etc.

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

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

The carrier film can be a plastic film, such as a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyimide film, a polypropylene film, a polystyrene film, etc. . There is no particular limitation on the thickness of the carrier film, and it can generally 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, in order to prevent dust from adhering to the surface of the film, a cover film that can be peeled off the surface of the film is preferred . As a peelable cover film, for example, polyethylene film or polytetrafluoroethylene film, polypropylene film, surface-treated paper and the like can be used. The cover film may be one that is smaller than the adhesive force between the resin layer and the carrier film when the cover film is peeled off.

In addition, in the present invention, the negative photocurable resin composition of the present invention may be applied on the cover film, and dried to form a resin layer, and a carrier film may be formed on the surface thereof. That is, in the present invention, when producing a dry film, the film to which the curable resin composition of the present invention is applied may use either a carrier film or a cover film.

When the negative photocurable resin composition of the present invention is used as a photocurable thermosetting resin composition, the resin layer obtained by coating the composition, volatilizing and drying the solvent, is exposed to light (light irradiation). The exposure part (the part irradiated with light) is hardened. Specifically, by a contact or non-contact method, through a mask with a pattern formed thereon, selective exposure by active energy rays or direct pattern exposure by a laser direct exposure machine is performed, and the unexposed part is exposed to alkali with alkali. An aqueous solution (for example, a 0.3-3 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. for thermal curing (post-curing), a cured film ( hardened material).

When the negative-type photocurable resin composition of the present invention is used as a photocurable resin composition, the composition is applied, the solvent is volatilized and dried, and then the exposed portion (irradiated with light) is exposed by exposure (light irradiation). part) hardened, and a hardened film (hardened product) can be formed.

The negative photocurable resin composition of the present invention is, for example, adjusted to the viscosity suitable for the coating method using the above-mentioned organic solvent, and is applied to the substrate by dip coating method, flow coating method, roll coating method, coating bar method After coating by methods such as screen printing method, screen printing method, curtain coating method, etc., the organic solvent contained in the composition is volatilized and dried at a temperature of about 60~100 ° C (temporary drying), which can form a non-sticky Resin layer of the hand. In addition, when the above-mentioned composition is applied on 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 base material by a laminator or the like, and is attached to the base material After being applied, a resin layer can be formed by peeling off the carrier film.

As the above-mentioned substrate, in addition to a printed wiring board or a flexible printed wiring board in which a circuit is first formed of copper or the like, phenolic paper, epoxy paper, epoxy glass cloth, glass polyimide, glass Cloth/epoxy non-woven fabric, glass cloth/epoxy resin paper, epoxy resin synthetic fiber, fluororesin・polyethylene・polyphenylene ether, polyphenylene ether・cyanate etc. For materials, all grades (FR-4, etc.) copper-clad laminates, other metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafers board etc.

For the above-mentioned volatilization drying or thermal curing, hot air circulation drying furnace, IR furnace, hot plate, convection oven, etc. can be used (those using a heat source equipped with an air heating method by steam, the method of contacting the hot air in the dryer with convection and the The nozzle is blown towards the support).

The exposure machine used for the above-mentioned active energy ray irradiation may be a device equipped with a high-pressure mercury-vapor lamp, an ultra-high-pressure mercury-vapor lamp, a metal halide lamp, a short-arc mercury lamp, etc. to irradiate ultraviolet rays in the range of 350 to 450 nm, and a direct drawing device may also be used. (For example, a laser direct imaging apparatus that draws images directly with a laser using CAD data from a computer. The light source or laser light source of the direct plotter's light is in the range of 350~410nm maximum wavelength That is, the exposure amount for image formation varies depending on the film thickness, etc., but is generally within the range of 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 developer can use potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines etc. alkaline aqueous solution.

The negative-type photocurable resin composition of the present invention can be used to form a pattern layer of a permanent film of a printed wiring board as a solder resist, a coating layer, an interlayer insulating layer, etc., and especially 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) the formation of the redistribution layer. The negative 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, it is possible to suppress difficulty in high temperature processing. adverse effects of the material.

Example

The present invention is specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples and Comparative Examples. In addition, below, "part" and "%" are the quality standards unless otherwise stated.

[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 (manufactured by DIC Corporation, EPICLON N-695, softening point 95°C, epoxy equivalent 214, average number of functional groups 7.6) 1070g (number of glycidyl groups (total number of aromatic rings): 5.0 moles) , 360 g (5.0 moles) of acrylic acid, and 1.5 g of hydroquinone were heated to 100° C. for stirring and uniformly dissolved. Next, 4.3 g of triphenylphosphine was put in, heated to 110° C., and reacted for 2 hours, then the temperature was raised to 120° C., and the reaction was further performed for 12 hours. In the prepared reaction solution, 415 g of aromatic hydrocarbon (o-cresol 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added, and reacted at 110° C. for 4 hours. A solution of unsaturated 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 amide imide resin)) In a 4-neck flask equipped with a stirring device, a thermometer and a condenser, put diethylene glycol monohydrate 103.5 parts by weight of 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 from 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. 166.4 parts by weight of diethylene glycol monoethyl ether acetate, 1.0 part by weight of methylhydroquinone were added, and 58.4 parts by weight of butanol was added thereto, 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. The molecular weight distribution measurement by GPC showed that the number average molecular weight was 934 in terms of polystyrene, and the weight average molecular weight was 1420 in terms of polystyrene. In addition, the acid value was 63.2 KOH-mg/g (solid content conversion).

[Synthesis of Alkali-Soluble Resin] (Synthesis Example 3: Alkali-Soluble Resin A-3 (Alkali-Soluble Acrylate-Added Amidoimide Resin)) In a 4-neck flask equipped with a stirring device, a thermometer and a condenser, put into 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 from 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 parts by weight of methylhydroquinone, and add 234.7 parts by weight of Aronix M-305 (made by Toagosei, hydroxyl value 120KOH-mg/g), while paying attention to heat, The temperature was raised to 80°C. 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 the molecular weight distribution measurement by GPC, the number average molecular weight was 1084 in terms of polystyrene, and the weight average molecular weight was 1524 in terms of polystyrene. In addition, the acid value was 68.3 KOH-mg/g (solid content conversion).

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

[Synthesis of Alkali-Soluble Resin] (Synthesis Example 5: Alkali-Soluble Resin A-5 (Copolymerized Acrylate-Added Alkali-Soluble Resin)) 325.0 parts by mass of dipropylene glycol monomethyl ether as a solvent was heated to 110° C., 174.0 parts by mass of base 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 -butylperoxy 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 over 3 hours, The polymerization catalyst was deactivated by stirring at 110° C. for 3 hours 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 gave 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 having ethylenically unsaturated group] (Synthesis example 6: phenol-initiated alkylene oxide modified acrylate) 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, and 100 parts of toluene/methyl isobutyl ketone (mass ratio = 2/1) were put and stirred At the same time, nitrogen substitution was carried out in the system, followed by heating and heating, and 60 parts of propylene oxide was gradually introduced at 150° C. and 8 kg/cm ² to react. The reaction was continued for about 4 hours until the gauge pressure reached 0.0 kg/cm ² and then cooled to room temperature. To this reaction solution, 3.3 parts of a 36% aqueous hydrochloric acid solution was added and mixed to neutralize sodium hydroxide. The neutralization reaction product was diluted with toluene, washed three times with water, and desolvated with an evaporator to obtain an alkylene oxide adduct of a novolak-type phenol resin having a hydroxyl equivalent of 164 g/eq. This is 1 equivalent of hydroxyl group, and an average of 1 mole of alkylene oxide is added. 164 parts of alkylene oxide adducts of the obtained novolak-type resol phenol resin, 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 put into a mixer equipped with a thermometer and air. It was made to react at 90 degreeC for 12 hours, blowing in the air, and stirring in the reactor which was blown into the tube. After the water produced by the reaction started to distill out as an azeotrope with toluene, the reaction was continued for 5 hours and cooled to room temperature. The obtained reaction solution was washed with 5% NaCl aqueous solution, toluene was distilled off with an evaporator, and carbitol acetate was added to obtain a resin solution of phenol-initiated alkylene oxide modified acrylate with a solid content of 70%.

(Examples 1 to 15, Comparative Example 1) Each component was prepared according to the mixing ratio shown in Tables 1 and 2 below, and after preliminary mixing with a mixer, dispersion was carried out with a three-roll mill, and curable resins were prepared by kneading. composition. In addition, the compounding quantity in a table|surface is a mass part.

*1：上述合成例1合成之感光性酚醛清漆型含羧基之樹脂的樹脂溶液A-1(固體成分65%) *2：上述合成例2合成之鹼可溶性醯胺醯亞胺樹脂的樹脂溶液A-2(固體成分45%) *3：上述合成例3合成之鹼可溶性丙烯酸酯加成醯胺醯亞胺樹脂的樹脂溶液A-3(固體成分42%) *4：上述合成例4合成之苯酚起始型鹼可溶性樹脂的樹脂溶液A-4(固體成分65%) *5：上述合成例5合成之共聚合丙烯酸酯加成鹼可溶性樹脂的樹脂溶液A-5(固體成分46%) *6：BASF JAPAN公司製IRGACURETPO(氧化磷系光聚合起始劑) *7：BASF JAPAN公司製IRGACUREOXE02(肟系光聚合起始劑) *8：甲基乙基酮 *9：四國化成公司製1B2PZ(咪唑系硬化觸媒；1-苄基-2-苯基咪唑) *10：四國化成公司製2PHZ(咪唑系硬化觸媒；2-苯基-4,5-二羥基甲基咪唑) *11：川崎化成工業公司製QS-30(醌系光聚合抑制劑) *12：BYK公司製BYK-361N(聚丙烯酸酯系表面調整劑) *13：新中村化學工業公司製A-DCP(2官能；三環癸烷二甲醇二丙烯酸酯；分子量304) *14：BASF JAPAN公司製Laromer LR 8863(3官能；環氧乙烷加成三羥甲基丙烷三丙烯酸酯；分子量約340) *15：根上工業公司製UN9200A(2官能；具有非芳香族系之聚碳酸酯骨架之聚碳酸酯系胺基甲酸酯丙烯酸酯；分子量15000) *16：二季戊四醇六丙烯酸酯(6官能；分子量578；丙烯醯基當量未達100) *17：新中村化學工業公司製A-TMPT(3官能；三羥甲基丙烷三丙烯酸酯；分子量296；丙烯醯基當量未達100) *18：大阪有機化學工業公司製IBXA(單官能；丙烯酸異冰片酯；分子量208；丙烯醯基當量208) *19：上述合成例6合成之苯酚起始型環氧烷改質丙烯酸酯的樹脂溶液(固體成分70%) *20：Designer Molecules公司製BMI-1500(液狀雙馬來醯亞胺：雙馬來醯亞胺寡聚物、60℃、5rpm下，以圓錐平板型黏度計(東機產業公司製TVH-33H)進行測量的黏度：20,000±10,000cp) *21：DIC公司製HP-7200L(脂環式環氧化合物；卡必醇乙酸酯之稀釋品、固體成分85%) *22：信越SILICONES公司製X-40-2670(具有環狀有機矽氧烷8員環骨架之4官能脂環環氧化合物) *23：信越SILICONES公司製X-40-2678(具有環狀有機矽氧烷8員環骨架之2官能脂環環氧化合物) *24：DMI公司製CS-783(具有環狀有機矽氧烷8員環骨架之環氧丙醚丙烯酸酯) *25：和光純藥公司製(具有環狀有機矽氧烷6員環骨架之3官能乙烯基化合物) *26：DIC公司製850-S(Bis-A骨架環氧化合物)

*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 A-3 (solid content 42%) of the alkali-soluble acrylate-addition imide resin synthesized in Synthesis Example 3 above *4: Synthesized in Synthesis Example 4 above Resin solution A-4 of phenol-initiated alkali-soluble resin (solid content 65%) *5: Resin solution A-5 of copolymerized acrylate-added alkali-soluble resin synthesized in Synthesis Example 5 above (solid content 46%) *6: IRGACURETPO (phosphorus oxide-based photopolymerization initiator) manufactured by BASF JAPAN Corporation *7: IRGACUREOXE02 (oxime-based photopolymerization initiator) manufactured by BASF JAPAN Corporation *8: Methyl ethyl ketone *9: Shikoku Chemical Co., Ltd. 1B2PZ (imidazole-based hardening catalyst; 1-benzyl-2-phenylimidazole) *10: 2PHZ (imidazole-based hardening catalyst; 2-phenyl-4,5-dihydroxymethylimidazole) manufactured by Shikoku Chemical Co., Ltd. ) *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 Co., Ltd. (Difunctional; Tricyclodecane dimethanol diacrylate; Molecular weight: 304) *14: Laromer LR 8863, manufactured by BASF JAPAN (Trifunctional; Trimethylolpropane triacrylate added with ethylene oxide; Molecular weight about 340) *15: UN9200A manufactured by Negami Kogyo Co., Ltd. (2-functional; polycarbonate-based urethane acrylate having a non-aromatic polycarbonate skeleton; molecular weight: 15,000) *16: Dipentaerythritol hexaacrylate (6-functional; Molecular weight 578; Acryloyl equivalent weight less than 100) *17: A-TMPT (tri-functional; trimethylolpropane triacrylate; molecular weight 296; Acryloyl equivalent weight less than 100) *18: IBXA (monofunctional; isobornyl acrylate; molecular weight 208; acryloyl equivalent 208) *19: Resin solution of phenol-initiated alkylene oxide-modified acrylate synthesized in Synthesis Example 6 above (solid Composition 70%) *20: BMI-1500 manufactured by Designer Molecules (liquid bismaleimide: bismaleimide oligomer, 60°C, 5 rpm, in a cone-plate viscometer (Toki Sangyo). Viscosity measured by company TVH-33H): 20,000±10,000cp) *21: DIC company HP-7200L (alicyclic epoxy compound; carbitol acetate dilution, solid content 85%) *22 : X-40-2670 made by Shin-Etsu Silicones Co., Ltd. (with a ring 4-functional alicyclic epoxy compound with 8-membered organosiloxane skeleton) *23: X-40-2678 (bifunctional alicyclic epoxy compound with 8-membered cyclic organosiloxane skeleton) manufactured by Shin-Etsu Silicones Co., Ltd. *24: CS-783 manufactured by DMI Corporation (glycidyl ether acrylate with 8-membered cyclic organosiloxane skeleton) *25: manufactured by Wako Pure Chemical Industries Ltd. (with 6-membered cyclic organosiloxane skeleton) Trifunctional vinyl compound) *26: 850-S (Bis-A skeleton epoxy compound) manufactured by DIC Corporation

The negative photocurable resin compositions of the obtained Examples and Comparative Examples were evaluated as follows. The results are shown in the above table.

(Preparation of Cured Film for Evaluation) The obtained negative photocurable resin composition of each Example and Comparative Example was coated on the entire surface of the copper foil substrate for evaluation of pattern formation with an arbitrary film thickness by screen printing , dried at 80°C for 20 minutes, and allowed to cool to room temperature. Then, about the obtained board|substrate, using the exposure apparatus equipped with a high pressure mercury lamp, the resist pattern was exposed with the exposure amount of 500mJ/cm< ² >. Then, the obtained substrate was irradiated with ultraviolet rays using a UV conveyor furnace on the condition of an accumulated exposure amount of 1000 mJ/cm ² , and then heated at 180° C. for 60 minutes for curing. From the cured coating film obtained above, the copper foil was peeled off to obtain a single cured film. About the obtained cured film, the characteristic was evaluated as follows.

(Heat resistance (glass transition temperature Tg)) Tg is measured by the DMA method in accordance with IPC TM-650, under the conditions of a heating rate of 5°C/min and a stretching mode. Those with Tg of 190°C or more were evaluated as ⊚, those less than 190°C and 180°C or more were evaluated as 0, those less than 180°C and 170°C or more were evaluated as Δ, and those less than 170°C were evaluated as ×.

(Elongation ratio (tensile failure)) The elongation ratio (tensile failure elongation) was measured using a tensile tester (AGS-G100W, manufactured by Shimadzu Corporation), according to JISK7127, at a tensile speed of 1.0 mm/min and 23°C. Measurement.

(Warpage) According to the above evaluation substrate production conditions, a 20μm thick resist was formed on a 35μm thick copper foil, and the evaluation was performed by the total amount of warpage of the four squares after curing in a specific step. A total of 20 mm or more, less than 25 mm was evaluated as ⊚, 25 mm or more, and less than 30 mm were evaluated as 0, and those of 30 mm or more were evaluated as ×.

(Analytical (halation)) The obtained negative photocurable resin composition of each Example and Comparative Example was fully coated on a silicon wafer for evaluation with a spin coater with an arbitrary film thickness dried at 80°C for 20 minutes, and allowed to cool to room temperature. Then, using an exposure apparatus equipped with a high-pressure mercury lamp for the obtained silicon wafer for evaluation, 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 was obtained. Exposure was performed through a negative mask, and development was performed for 30 seconds under the conditions of a spray pressure of 0.15 MPa using a 2.38 mass % TMAH (tetramethylammonium=hydroxide) developer. Then, the obtained silicon wafer for evaluation was irradiated with ultraviolet rays using a UV conveyor furnace on the condition of an accumulated exposure amount of 1000 mJ/cm ² , and then heated at 180° C. for 60 minutes for curing. Based on the above silicon wafer fabrication conditions for evaluation, when the resist coating thickness is 10-15 μm and the designed opening diameter is 20 μm, the measured value is 20-19 μm, that is, those with halo within 1 μm are evaluated as ◎. Also according to the actual measurement value, when the halo exceeds 1 μm and 2 μm or less, it is evaluated as ◯, and when the halo exceeds 2 μm, it is evaluated as ×.

As shown in the above table, it was found 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 (9)

A negative photocurable resin composition characterized by containing (A) an alkali-soluble resin, (B) having a skeleton represented by the following general formula (1), and two or more of the following general formula (1) are different An organosiloxane compound having a cyclosiloxane skeleton with a 6-12-membered ring and having a thermosetting reactive group or a photosensitive group on the silicon atom, and (C) a photopolymerization initiator, wherein the aforementioned (B) organosilicon The oxane compound is the aforementioned (B) organosiloxane compound having both the aforementioned thermosetting reactive group and the aforementioned photosensitive group, or the aforementioned (B) organosiloxane compound having the aforementioned thermosetting reactive group and the aforementioned (B) organosiloxane compound having the aforementioned thermosetting reactive group. The aforementioned (B) organosiloxane compound of the aforementioned photosensitive group,

(In the formula, n represents an integer from 1 to 4). The negative photocurable resin composition according to claim 1, wherein the thermosetting reactive group is an epoxy group. The negative photocurable resin composition according to claim 1, wherein the photosensitive group is an ethylenically unsaturated group. As the negative photocurable resin composition of any one of claims 1 to 3, Among them, a compound having an ethylenically unsaturated group is further contained. The negative photocurable resin composition according to claim 4, wherein the compound having an ethylenically unsaturated group is a (meth)acrylate compound having two or more functions. The negative-type photocurable resin composition according to claim 4, wherein the compound having an ethylenically unsaturated group is a (meth)acrylate compound having an acrylamide equivalent of 100 or more. A dry film characterized by having a resin layer obtained by coating the negative photocurable resin composition of any one of claims 1 to 6 on the film and drying it. A cured product obtained by curing the negative photocurable resin composition of any one of Claims 1 to 6, or the resin layer of the dry film of Claim 7. A printed wiring board characterized by having the cured product of claim 8.