WO2008059935A1

WO2008059935A1 - Photocurable/thermosetting resin composition, cured product and printed wiring board

Info

Publication number: WO2008059935A1
Application number: PCT/JP2007/072218
Authority: WO
Inventors: Nobuhito Itoh; Yoko Shibasaki; Kenji Kato; Masao Arima
Original assignee: Taiyo Ink Mfg. Co., Ltd.
Priority date: 2006-11-15
Filing date: 2007-11-15
Publication date: 2008-05-22

Abstract

Disclosed is a photocurable/thermosetting resin composition which is excellent in surface curability and deep-section curability. This resin composition can be patterned by a laser light having a wavelength of 350-410 nm, and is usable as a solder resist for laser direct imaging. This composition contains (A) a carboxylic acid-containing resin, (B) an oxime ester photopolymerization initiator such as 2-(acetyloxyiminomethyl)thioxanthene-9-one, (C) a photopolymerization initiator other than (B) such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and (E) a sulfur compound such as 2-mercaptobenzothiazole.

Description

Specification

Photo curable · Thermosetting resin composition, cured product and printed wiring board

Technical field

The present invention particularly relates to a photocurable / thermosetting resin composition suitable for use in direct drawing with a laser beam as a solder resist application, a cured product, and a printed wiring pattern formed using the same. Regarding the board.

Background art

[0002] Conventionally, laser direct imaging technology that draws an image with a laser directly from CAD data for alignment accuracy in the formation of a solder resist in the production of printed wiring boards has attracted attention. However, the conventional solder resists on the market require very high exposure energy of 200mJ and 500mJ, and the problem is that it takes a lot of time when performing direct exposure.

[0003] In order to solve this problem, conventionally, a photopolymerization initiator capable of exhibiting high photopolymerization ability and a composition using the photopolymerization initiator have been proposed (for example, Patent Document 1). : JP-A-2001-235858 and Patent Document 2: International Publication WO02 / 096969). These technologies are capable of exhibiting sufficient photopolymerization capability even with only volatiles such as 350 to 370 nm. However, since the photopolymerization rate is very high, sufficient depth and surface hardenability cannot be obtained, and furthermore, the sensitivity decreases significantly due to deactivation of the photopolymerization initiator on the circuit after heat treatment. , Have a problem that peeling occurs on the copper circuit.

Disclosure of the invention

[0004] The present invention is capable of exhibiting a high photopolymerization ability with respect to ultraviolet light and laser light, and at the same time, sufficient deep-part curability is obtained, and further, photocuring / thermosetting resin having excellent thermal stability. This composition is used for direct writing with laser light, especially for solder resist applications. V. Suitable photocurable and thermosetting resin compositions, and cured products, and uses them to form patterns. It is an object to provide a printed wiring board.

[0005] In order to achieve this object, the present inventors paid attention to a sulfur compound having a (1 SH) mercapto group known as a chain transfer agent (Patent Document 3: Japanese Patent Application Laid-Open No. 2006-010793 to Permission document 4: Japanese Patent Laid-Open No. 2006-071890). However, it has been found that when a composition containing these sulfur compounds is used as a solder resist, it reacts quickly with copper and remains as a development residue in a portion that should be developed and removed. Therefore, as a result of further earnest research, the present inventors, as photopolymerization initiators, other than oxime ester photopolymerization initiators such as phosphine oxide photopolymerization initiators together with oxime ester photopolymerization initiators. In combination with the above photopolymerization initiator, the above-mentioned sulfur compound is added, and (-SH) Sulfur compound power having a mercapto group S, the mercapto group has poor reactivity at the copper interface and is stable. It was found that deactivation and delamination due to contact between the heat of the compound and copper were reduced, and the finished coating film had excellent adhesion and improved properties such as electroless gold plating.

[0006] The present invention has been made based on the above findings, and has the following configuration.

[0007] (1) (A) a carboxylic acid-containing resin,

(B) an oxime ester photopolymerization initiator containing an oxime ester group represented by the following general formula (I):

[Chemical 1…)

(In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or a phenyl group, and R ² represents an alkyl group having 1 to 7 carbon atoms or a phenyl group. Represents.)

(C) Photopolymerization initiator other than the above (B)

(D) a compound having two or more ethylenically unsaturated groups in the molecule,

(E) Sulfur compounds represented by the following general formula (Π)

[Chemical 2]

[0009] A photocurable thermosetting resin composition capable of alkali development, comprising: (2) Photopolymerization initiator (C)

A group consisting of an aminoacetophenone photopolymerization initiator containing a structure represented by the following general formula (III), and an acyl phosphine oxide photopolymerization initiator containing a structure represented by the following general formula (IV) The photocurable thermosetting resin composition according to (1), which comprises one or a mixture selected from the group consisting of:

[Chemical 3]

[0011] In the general formulas (III) to (IV),

R ³ and R ⁴ each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group,

R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or R ⁵ and R ⁶ may be bonded to form a cyclic alkyl ether group.

R ⁷ and R ⁸ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group (a norogen atom, an alkyl group, or an alkoxy group). Or R—C (═O) — group (where R is a carbon group;! -20 hydrocarbon group). However, this excludes the case where both R ⁷ and R ⁸ are R—C (= 〇) -groups.

(3) The oxime ester photopolymerization initiator (B)

The photocurable / thermosetting resin composition according to (1), which is a photopolymerization initiator represented by the following formula (V):

[In the formula, R is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentanol group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, or a C 2-12 alkyl group. Lucanoyl group, alkoxycarbonyl group having 2 to 12 carbon atoms (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and in the middle of the alkyl chain) Which may have one or more oxygen atoms) or a phenoxycarbonyl group.

[0014] R and R are each independently a phenyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group,

twenty four

Or substituted with a halogen atom! /, May! /,), An alkyl group having 1 to 20 carbon atoms (one or more in the middle of the alkyl chain which may be substituted with one or more hydroxyl groups) Which may have an oxygen atom), a cycloalkyl group having 5 to 8 carbon atoms, an alkanol group having 2 to 20 carbon atoms or a benzoyl group (substituted with an alkyl group or phenyl group having 1 to 6 carbon atoms). Moyo! /,)

[0015] R represents a hydrogen atom, a phenyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom).

Three

1 or more oxygen atoms in the middle of an alkyl chain that may be substituted with one or more hydroxyl groups. A cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (substituted with an alkyl group or phenyl group having 1 to 6 carbon atoms! /, O!), Indicating o))

(4) The oxime ester photopolymerization initiator (B) is represented by the following general formula (VI)

[0016] The photocurable 'thermosetting resin composition according to claim 1, which is a photopolymerization initiator.

[0017] (5) The photocurable 'thermosetting resin composition according to (1), further comprising (G) a thermosetting component.

[0018] (6) In the photocurable thermosetting resin composition according to the above (1), the absorbance of the dried coating film with respect to the light source is 0.4 to 25 per 111; Curing / thermosetting resin composition.

[0019] (7) The curing is possible with a laser oscillation light source having a maximum wavelength of 350 to 410 nm.

1. The photocurable / thermosetting resin composition according to 1.

[0020] (8) A photocurable / thermosetting dry film obtained by applying the photocurable 'thermosetting resin composition described in (1) above to a carrier film and drying.

[0021] (9) A cured product obtained by photocuring a dry film of the photocurable thermosetting resin composition according to (1) above on copper.

[0022] (10) A cured product obtained by photocuring the dry film according to (8) above on copper.

[0023] (11) A cured product obtained by photocuring the photocurable thermosetting resin composition described in (1) with a laser oscillation light source.

[0024] (12) A cured product obtained by photocuring the dry film according to (8) with a laser oscillation light source.

[0025] (13) Printed wiring obtained by photocuring the photocurable thermosetting resin composition according to (1) above with a laser beam having a maximum wavelength of 350 to 410 nm, followed by thermosetting Board.

[0026] (14) A printed wiring board obtained by photocuring the dry film according to (8) above with a laser beam having a maximum wavelength of 350 to 410 nm, followed by thermosetting.

[0027] The present invention has the following effects by providing the above configuration. [0028] The photocurable thermosetting resin composition of the present invention exhibits excellent photocurability with respect to a laser oscillation light source having a maximum wavelength of 350 nm to 420 nm. One direct imaging system can be used, and there is no positional displacement due to the expansion and contraction of the photomask and glass substrate that has occurred in the conventional exposure method. Furthermore, there is no pattern loss due to foreign matter adhering to the photomask. High development is possible.

[0029] In addition, the use of a laser 'direct' imaging device eliminates the need for a photomask, simplifies the transfer of design power to production, and further reduces the product cost by reducing the defect rate. .

[0030] In particular, as a photopolymerization initiator, an oxime ester photopolymerization initiator and a phosphine oxide photopolymerization initiator are used in combination, and the sulfur compound according to the present invention is further blended to deepen the portion. It is excellent in curability and can have a cross-sectional shape as designed, and a solder resist with excellent surface curability, heat stability, and ball height can be obtained.

Brief Description of Drawings

[0031] [Fig. 1] Fig. 1 is a schematic diagram of a cross-sectional shape of a resin composition obtained by exposure and development, and A to E show different evaluation shapes.

BEST MODE FOR CARRYING OUT THE INVENTION

[0032] Hereinafter, each component of the photocurable thermosetting resin composition of the present invention will be described in detail.

[0033] (A) Carboxylic acid-containing resin

As the carboxylic acid-containing resin (A) contained in the photocurable thermosetting resin composition of the present invention, a known and commonly used resin compound containing a carboxyl group in the molecule can be used. Further, a carboxyl group-containing photosensitive resin (Α ′) force having an ethylenically unsaturated double bond in the molecule is more preferable from the viewpoint of development resistance. Specific examples include the resins listed below.

[0034] (1) A carboxylic acid-containing resin obtained by copolymerization with an unsaturated carboxylic acid such as (meth) acrylic acid and one or more other compounds having an unsaturated double bond,

(2) Copolymers of unsaturated carboxylic acids such as (meth) acrylic acid and one or more other compounds having unsaturated double bonds to glycidyl (meth) atarylate or 3, 4— Yepo Containing carboxyl group obtained by adding an ethylenically unsaturated group as a pendant with an epoxy group such as xyloxymethyl (meth) acrylate and an unsaturated double bond, or (meth) acrylic acid chloride An unsaturated carboxylic acid such as (meth) acrylic acid is added to a copolymer of a photosensitive resin, a compound having an epoxy group and an unsaturated double bond such as a rate, and another compound having an unsaturated double bond. A carboxyl group-containing photosensitive resin obtained by reacting and reacting a polybasic acid anhydride with the generated secondary hydroxyl group,

(4) 2-hydroxyethyl (meth) acrylate, etc., as a copolymer of an acid anhydride having an unsaturated double bond such as maleic anhydride and other compounds having an unsaturated double bond Carboxyl group-containing photosensitive resin obtained by reacting a compound having an unsaturated double bond with a hydroxyl group of

(5) a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting the resulting hydroxyl group with a saturated or unsaturated polybasic acid anhydride,

(6) Compounds having an epoxy group and an unsaturated double bond in one molecule after reacting a saturated or unsaturated polybasic acid anhydride with a hydroxyl group-containing polymer such as a polybutyl alcohol derivative. Hydroxyl and carboxyl group-containing photosensitive resin obtained by reacting

(7) A polyfunctional epoxy compound, an unsaturated monocarboxylic acid, a compound having at least one alcoholic hydroxyl group in one molecule and one reactive group other than an alcoholic hydroxyl group that reacts with an epoxy group A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a saturated or unsaturated polybasic acid anhydride,

(8) —Saturated or unsaturated polybasic to the primary hydroxyl group in the modified oxetane resin obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional oxetane compound having at least two oxetane rings in the molecule A carboxyl group-containing photosensitive resin obtained by reacting an acid anhydride, and

(9) After reacting unsaturated monocarboxylic acid with polyfunctional epoxy resin, polybasic acid anhydride A carboxyl group-containing photosensitive resin obtained by reacting a carboxylic acid-containing resin obtained by reacting a compound with a compound having one oxysilane ring and one or more ethylenically unsaturated groups in the molecule, etc. However, it is not limited to these.

Among these examples, the carboxyl group-containing photosensitive resins (2) and (3) are preferable from the viewpoints of photocurability and baking properties.

[0036] In the present specification, the term "(meth) atalylate" is a general term for atalylate, metatalate, and a mixture thereof, and the same applies to other similar expressions.

[0037] Since the carboxylic acid-containing resin (A) as described above has a number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.

[0038] The acid value of the carboxylic acid-containing resin (A) is in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g. If the acid value of the carboxylic acid-containing resin is less than S40 mgKOH / g, alkali development becomes difficult.On the other hand, if it exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary. Depending on the case, the exposed portion and the unexposed portion may be dissolved and separated by a developer without distinction, and it becomes difficult to draw a normal resist pattern.

[0039] The weight-average molecular weight of the carboxylic acid-containing resin (A) varies depending on the resin skeleton, and generally ranges from 2,000 to 150,000, more preferably from 5,000 to 100,000. If the weight average molecular weight is less than 2,000, the tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, the film may be reduced during development, and the resolution may be greatly inferior. On the other hand, if the weight average molecular weight exceeds 150,000, the developability may be remarkably deteriorated and the storage stability may be inferior.

[0040] The amount of the carboxylic acid-containing resin (A) is preferably 10 to 80% by mass, more preferably 15 to 50% by mass, based on the total composition. If the blending amount is too small, the coating film strength decreases, which is not preferable. On the other hand, when the amount is too large, the viscosity becomes high, and the coating property and the like are deteriorated.

[0041] (B) An oxime ester photopolymerization initiator containing an oxime ester group

In the photocurable thermosetting resin composition of the present invention, it is essential to use, as a photopolymerization initiator, an oxime photopolymerization initiator (B) having a functional group represented by the above general formula (I). [0042] Examples of such compounds include 1,2-octanedione 1 [4- (phenylthio) 2- (O benzoyloxime)], ethanone 1 [9-ethyl 6- (2 methylbenzoyl) 9H, and rubazole. 3-yl] 1- (O acetyloxyme), a compound represented by the above formula (IV), 2 (acetyloxyiminomethyl) thioxanthen 9 -one, and the like. Among these, the compounds represented by the above formulas (V) and (IV), ethanone 1 [9-ethyl 6- (2 methylbenzoyl) 9H force rubazol 3 yl] 1 (O-acetylyl), 2-(acetilo) Ximinomethyl) thixanthen 9-one is particularly preferred. Examples of commercially available compounds include CGI 325, OXE 02, and OXE 01 manufactured by Ciba 'Specialty' Chemicals.

[0043] The amount of such oxime-based photopolymerization initiator (B) is preferably 0.0;! To 20 parts by mass with respect to 100 parts by mass of the carboxylic acid-containing resin (A). The ratio is preferably 0.0;! To 5 parts by mass. If the amount of the oxime-based photopolymerization initiator (B) is too small relative to 100 parts by mass of the carboxylic acid-containing resin (A), it is not preferable because sufficient photocurability cannot be obtained. On the other hand, if the amount is too large, the thick film curability is lowered and the cost of the product is increased.

[0044] (C) Photopolymerization initiator other than oxime ester photopolymerization initiator such as phosphine oxide photopolymerization initiator

When an oxime ester photopolymerization initiator is used alone, it may react with copper atoms at the interface with the copper foil, and the function as a photopolymerization initiator may be deactivated. Phosphine oxide photopolymerization initiator, etc. By using a photoinitiator other than the oxime ester photoinitiator, this problem can be solved. Therefore, the photocurable 'thermosetting resin composition of the present invention has, as a photopolymerization initiator, an aminoacetophenone photopolymerization initiator represented by the above general formula (III), the above general formula (IV) acylphosphine. It is preferable to use the phosphine oxide photopolymerization initiator (C) having a functional group having an oxide photopolymerization initiator in order to improve the thermal stability of the oxime ester photopolymerization initiator.

[0045] As the photopolymerization initiator (C) other than the oxime ester photopolymerization initiator such as the phosphine oxide photopolymerization initiator, 2, 4, 6 trimethylbenzoyldiphenylphosphine is used. Acinolephosphine such as fin oxide, bis (2, 4, 6 trimethylbenzoyl) phenyl phosphine oxide, bis (2, 6 dimethoxybenzoinole) 1, 2, 4, 4 trimethyl monopentylphosphine oxide Oxide-based photopolymerization initiator and 2-methylolene 1

[4 (Methylthio) phenyl] 2-morpholinopropane 1-one, 2-benzenole — 2 dimethylamino-1- (4-morpholinophenyl) butanone 1 and the like α-aminoacetophenone photoinitiators. Commercially available products include BASF's Lucillin®PO, Chino 'Specialty' Chemicals' Irgacure 1 819, 907, Irgacure 1 369, and Irgacure 1 379.

[0046] The blending amount of the photopolymerization initiator (C) other than the oxime ester photopolymerization initiator, such as the phosphine oxide photopolymerization initiator, is 100 parts by mass of the carboxylic acid-containing resin (A). The ratio is 60 parts by mass or less, preferably 50 parts by mass or less. When the blending amount of the photopolymerization initiator (C) other than the oxime ester-based photopolymerization initiator exceeds 60 parts by mass, the thick film curability is lowered and the cost of the product is increased, which is not preferable.

[0047] (Other photoinitiators, photoinitiators, sensitizers)

The composition of the present invention can be used in combination with a known and commonly used photopolymerization initiator, photoinitiator assistant, and sensitizer, if necessary. Specifically, in the composition of the present invention, photopolymerization initiators other than the above-mentioned compounds, photopolymerization initiation assistants, and sensitizers can be used. For example, benzoin compounds, acetophenone compounds, And anthraquinone compounds, thixanthone compounds, ketal compounds, benzophenone compounds, xanthone compounds, and tertiary amine compounds.

[0048] Specific examples of the benzoin compound include, for example, benzoin, benzoin methyl ethereol, benzoin ethinoreethenore, and benzoin isopropinoreethenore.

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

[0049] Specific examples of anthraquinone compounds include, for example, 2 methylanthraquinone, and 2 [0050] Specific examples of thixanthone compounds include, for example, 2,4 dimethylthioxanthone. 2, 4 Jetylthioxanthone, 2 Black mouth thixanthone, 2, 4 Diisopropyl thixanthone.

[0051] Specific examples of the ketal compound include, for example, acetophenone dimethyl ketal and benzinoresimethinoreketanol.

[0052] Specific examples of the benzophenone compound include, for example, benzophenone, 4 benzoyl diphenyl sulfide, 4 benzoyl rho 4'-methyldiphenyl sulfide, 4 benzoinoleure 4, Tildiphenylsulfide, 4 benzoyl 4 'propyldiphenylsulfide.

[0053] Specific examples of the tertiary amine compound include, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4, 4'-dimethylaminobenzobenzoenone (Nisso-Cure I MABP manufactured by Nippon Soda Co., Ltd.), 4, 4 Dialkylaminobenzophenones such as' -jetylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), dialkyl such as 7- (jetylamino) -4 -methyl-2H—1-benzopiran 2one (7 (jetylamino) 4 methylcoumarin) Amino group-containing coumarin compounds, 4-dimethylaminobenzoic acid ethyl (Nippon Kayaku Co., Ltd., CACURE EPA), 2-dimethylaminobenzoic acid ethyl (International Bio Synthetics Quantacure DMB), 4-dimethylaminobenzoic acid (n-butoxy) ) Echiru (International Bio-Synthetic Quantacure BEA), p Dimethylaminobenzoic acid isoamylethyl ester (Nippon Kayaku Co., Ltd. DMBI), 4-Dimethylaminobenzoic acid 2-ethylhexyl (Van Dyk Esolol 507), 4, 4'-Jetylaminobe Nzofuenone (Hoabaya Chemical EAB).

Of the above, thixanthone compounds and tertiary amine compounds are preferred. Thioxanthone compounds such as 2,4 dimethylenolechixanthone, 2,4 jetinolecidate xanthone, 2,4 dithioxanthone, 2,4-diisopropylthioxanthone, etc. are preferred because of their deep curability. Is preferred.

[0055] The mixing ratio of such a thixanthone compound is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). If the compounding ratio of thixanthone compound is too high, the thick film curability will decrease and the product This leads to an increase in cost.

[0056] As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferred, and among them, a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferred. Les. As the dialkylaminobenzophenone compound, 4,4′-jetylaminobenzophenone has low toxicity and is preferable. Dialkylamino group-containing coumarin compounds having a maximum absorption wavelength in the range of 350 to 410 nm have a maximum absorption wavelength in the ultraviolet region, so that not only a colorless and transparent photosensitive composition with little coloration but also a color pigment is used. A colored solder resist film reflecting the color can be provided. In particular, 7- (Jetylamino) -4-methyl 2H-1-benzopyran 2 -on is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

[0057] The blending ratio of such a tertiary amine compound is preferably 0.;! To 20 parts by mass, more preferably 0. to 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). ! ~ 10 parts by mass. When the compounding ratio of the tertiary amine compound is less than 0.1 part by mass, a sufficient sensitizing effect tends not to be obtained. When the amount exceeds 20 parts by mass, light absorption on the surface of the dry calendar resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease.

Yes

[0058] These photopolymerization initiator, photopolymerization initiation assistant and sensitizer can be used alone or as a mixture of two or more.

[0059] The total amount of such photopolymerization initiator, photopolymerization initiation assistant, and sensitizer is within a range of 35 parts by mass or less with respect to 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). Preferably it is. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

[0060] (D) Compound having two or more ethylenically unsaturated groups in the molecule

The compound (D) having two or more ethylenically unsaturated groups in the molecule used in the photocurable / thermosetting resin composition of the present invention is photocured by irradiation with active energy rays, The ethylenically unsaturated group-containing carboxylic acid-containing resin (A) is insolubilized or assists insolubilization in an alkaline aqueous solution. Such compounds include ethylene glycol, meso Diacrylates of glycols such as toxitetraethylene glycolol, polyethylene glycolol, propylene glycol; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or these Polyvalent acrylates such as ethyloxide adducts or propylene oxide adducts; phenoxy acrylate, bisphenol A diatalylate, and ethylene oxide adducts or propylene oxide of these phenols

Examples include glycidyl ether polyvalent acrylates such as nurate; and melamine acrylate, and / or metatalates corresponding to the acrylate.

[0061] Furthermore, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol nopolac-type epoxy resin, and further a hydroxy acrylate such as pentaerythritol triacrylate with a hydroxyl group of the epoxy acrylate resin. rate and isophorone Epoki reacted a half urethane compound Jiisoshianeto such Jiisoshianeto urethane Atari rate such compound forces ^s, and the like. Such an epoxy acrylate resin can improve photocurability without reducing touch dryness.

[0062] The compounding amount of the compound (D) having two or more ethylenically unsaturated groups in such a molecule is based on 100 parts by mass of the ethylenically unsaturated group-containing carboxylic acid-containing resin (A). 5 to; 100 parts by mass, more preferably;! To 70 parts by mass. When the blending amount is less than 5 parts by mass, the photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays, which is not preferable. On the other hand, when the amount exceeds 100 parts by mass, the solubility in an alkaline aqueous solution is lowered, and the coating film becomes brittle.

[0063] (E) a sulfur compound represented by the above general formula (Π)

As the sulfur compound represented by the general formula (Π), a compound of the formula (VII) can be used.

[Chemical 6]

(In the formula, R ³ represents an alkyl group, an aryl group or a substituted aryl group, R ⁴ represents a hydrogen atom or an alkyl group, and R ³ and R ⁴ are bonded to each other to form oxygen, Non-metallic atom group necessary to form a 5- to 7-membered ring that may contain a heteroatom selected from sulfur and nitrogen atoms.

These sulfur compounds are tautomers and exist as both SH and NH groups. In the case of the present invention, a carboxylic acid-containing resin is included, and it is presumed that the interaction stabilizes the NH group (base). Since the SH group is highly reactive to copper, the force that prevents development is possible. The NH group is inert to copper and does not impair the developability.

[0065] Examples of the sulfur compound (E) include mercaptobenzothiazole, 3 mercapto-4 methyl 4H—1, 2, 4-triazolene, 5-methyl-1,3,4-thiadiazole 2-thiol, 1 phenyl 5- Examples include mercapto 1H-tetrazole.

[0066] (Fila I)

In the present invention, a known and commonly used inorganic or organic filler can be blended. In particular, sodium sulfate and spherical silica are preferably used. Furthermore, NANOCRYL (trade name) XP 0396 manufactured by Hanse-Chemie, in which nanosilica is dispersed in the compound (D) having two or more ethylenically unsaturated groups described above and the polyfunctional epoxy resin (F-1) described later. , XP 0596, XP 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 104 5 (all product grade names), NANOPOX (trade name) XP 0516, XP 0525 from Hanse-Chemie XP 0314 (product grade names) can also be used.

[0067] These may be used alone or in combination of two or more. These fillers suppress hardening shrinkage of the coating film and improve basic properties such as adhesion and hardness, as well as allow active energy rays to pass through the photocurable resin composition. It is used for the purpose of suppressing interference with light reflection and refraction.

[0068] The amount of these fillers to be added is 0.1% with respect to 100 parts by mass of the carboxylic acid-containing resin (A).

! ~ 300 parts by mass, more preferably 0.;! ~ 150 parts by mass. If the amount of the filler blended is too small, the cured coating film properties such as solder heat resistance and galling resistance deteriorate, which is not preferable. On the other hand, if the amount is too large, the viscosity of the composition becomes high and printability is lowered, or the cured product becomes brittle, which is not preferable. [0069] Thermosetting component (G)

In the present invention, a thermosetting component can be blended. Examples of the thermosetting component used in the present invention include amino resins such as melamine resins and benzoquamine resins, block isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, and episulfide resins. A thermosetting resin can be used. Among these, heat having two or more cyclic ether groups and / or cyclic thioether groups in a molecule such as a polyfunctional epoxy compound (G-l), a polyfunctional oxetane compound (G-2), and episulfide resin. A curable component (hereinafter abbreviated as a cyclic (thio) ether compound) is particularly preferred.

[0070] Examples of the polyfunctional epoxy compound (G-1) include Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, Epiclon 840, Epiclone 840, and Epiclone manufactured by Dainippon Ink & Chemicals, Japan Epoxy Resin. 850, Epiclon 1050, Epiclon 20 55, EPO made by Tohto Kasei Co., Ltd. YD— 011, YD— 013, YD— 127, YD— 128, DU 317, DER 331, DER 661, DER 664, Chinoku. Specialty Chemicals' Araludide 6071, Alanoredide 6084, Aral Dyed GY250, Alanoredide GY260, Sumitomo Chemical's Sumie Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei AER 330, A. ER 331, AER 661, AER 664, etc. (all trade names) bisphenol A type epoxy resin; Epoxy Coat YL903, Japan Epoxy Resin Co., Ltd. Epiclon 152, Epiclon 165 manufactured by Ink Chemical Industry Co., Ltd., Epototo YDB—400, YDB—500 manufactured by Toto Kasei Co., Ltd., DER 542 manufactured by Dow Chemical Company, Allano Redide 8011 manufactured by Chino “Specialty” Chemicals, Sumitomo Chemical Co., Ltd. Bromy epoxy resins such as Sumie Epoxy ESB-400, ESB-700 manufactured by Kogyo Co., Ltd., AER 711, AER 714 manufactured by Asahi Kasei Kogyo Co., Ltd. (all trade names); Epicoat 152, Epicoat 154, Japan Epoxy Resin Co., Ltd. DEN 431, DEN 438 manufactured by Daukemika Nore, Epiclon N- 730, Epiclon N- 770, Epiclon N- 770 manufactured by Dainippon Ink & Chemicals, Epotote YDCN- 701, YDCN- 704 manufactured by Tohto Kasei Chiral 'Specialty'Chemicals' ALAL DIDE ECN1235, ARALDIDE ECN1273, ARALDIDE ECN1299, ARALDIDE X PY307, Nippon Kayaku EPPN-201, EOCN-1025, EOCN-1020, EOC N-104S, RE-306, Sumitomo Chemical Sumitomo Epoxy ESCN-195X, ESC N-220, Asahi Kasei ERECN-235, ECN-299, etc. (all trade names) nopolac-type epoxy resins; Epiclon 830, manufactured by Dainippon Ink & Chemicals, Epicoat 807, manufactured by Japan Epoxy Resin, manufactured by Toto Kasei Epototo YDF—170, YDF175, YDF—2004, Bisphenol F-type epoxy resin such as Araldide ダイ 30 6 manufactured by Chino 'Specialty' Chemicals (all trade names); Epototo S Τ 2004, ST— Hydrogenated bisphenolate type epoxy resin such as 2007, ST-3000 (trade name); Epicoat 604 manufactured by Japan Epoxy Resin Co., Epotote YH 434 manufactured by Tohto Kasei Co., Ltd., Aralda manufactured by Chino 'Specialty' Chemicals MY720, Sumitomo Chemical Co., Ltd. Sumie Epoxy ELM-120, etc. (all trade names) glycidylamine type epoxy resin; Ciba 'Specialty Chemikanorez Co., Ltd. Araludide CY- 350 (trade name), etc. Type epoxy resin; Daicel Chemical Industries 'Celoxide 2021, Ciba's Special. Chemicals' Araludide CY175, CY179, etc. (both trade names); YL-933, Japan Epoxy Resin Co., Ltd. Trihydroxyphenyl methane type epoxy resin such as TEN, EPPN-501, EPPN-502, etc. (all trade names) manufactured by Dow Chemical Company; YL-6056, YX-4000, YL-6121 manufactured by Japan Epoxy Resin All are trade names such as bixylenol type or biphenol type epoxy resins, or mixtures thereof; Nippon Kayaku EBPS-200, Asahi Denka Kogyo EPX— 30, Dai Nippon Ink Chemical Co., Ltd. EXA-1514 (trade name) and other bisphenol S type epoxy resins; Japan Epoxy Resin Epicoat 157S (trade name) and other bisphenol A nopolak type epoxy resins; Resin Epicoat YL-931, Ciba 'Specialty' Chemicals Co., Ltd.'s Araldide 163, etc. (both trade names) Tetraphenol diethane type epoxy resin; Chinoku. Specialty.

Heterocyclic epoxy resins such as T810, TEPIC manufactured by Nissan Chemical Industries (all trade names); diglycidyl phthalate resins such as Blemmer DGT manufactured by Nippon Oil &Fats; Tetraglycidylxylenoxy such as ΖΧ1063 manufactured by Tohto Kasei Co., Ltd. Luetan resin: Nippon Steel Chemical Co., Ltd. ESN-190, Ε SN-360, Dainippon Ink & Chemicals, Inc. HP-4032, EXA-4750, EXA-4700 Naphthalene group-containing epoxy resins such as Dainippon Ink & Chemicals, Inc. HP-7200, HP-7200H and other dicyclopentagen skeletons; Nippon Yushi Co., Ltd. CP 50S, CP-50M and other glycidyl methacrylate Copolymerized epoxy resin; Further, copolymerized epoxy resin of hexylmaleimide and daricidylmethacrylate, epoxy-modified polybutadiene rubber derivative (eg PB-3600 manufactured by Daicel Chemical Industries), CTBN-modified epoxy resin (eg, Tokyo Metropolitan Government) Examples include: YR-102 and YR-450 manufactured by Kasei Co., Ltd. These epoxy resins can be used alone or in combination of two or more. Of these, nopolac-type epoxy resins, heterocyclic epoxy resins, bisphenol A-type epoxy resins or mixtures thereof are particularly preferred.

[0071] Examples of the polyfunctional oxetane compound (G2) include bis [(3methyl-3-oxetaninoremethoxy) methinore] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4bis [ (3-Methyl-3-oxetanylmethoxy) methinole] benzene, 1,4bis [(3-Ethyl3-oxetanylmethoxy) methinole] benzene, (3-Methyl-3-oxetanyl) methyl acrylate, (3-Ethylate) Of 3-functional oxetanes such as (3-oxetanyl) methyl attalylate, (3-methyl-3-oxetanyl) methyl metatalylate, (3-ethyl-3-oxetanyl) methyl metatalylate and oligomers or copolymers thereof. Others, oxetane and nopolac resins, poly (p-hydroxystyrene), hardened bisphenols, calixarenes, Box resorcin arenes, or the like ethers of a resin having a hydroxyl group such as Shirusesuki Okisan the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

[0072] Examples of the compound having two or more cyclic thioether groups in the molecule include force S such as Bisphenol A-type episulfide resin YL7000 manufactured by Japan Epoxy Resin Co., Ltd. In addition, episulfide resin in which the oxygen atom of the epoxy group of the nopolac-type epoxy resin is replaced with a sulfur atom can be used by using the same synthesis method.

[0073] The amount of such a cyclic (thio) ether compound contains the ethylenically unsaturated group. The cyclic (thio) ether group is in the range of 0.6 to 2.0 equivalents, preferably 0.8 to 1.5 equivalents with respect to 1 equivalent of the carboxyl group of the carboxylic acid-containing resin. When the blending amount of the cyclic (thio) ether compound is less than the above range, the carboxyl group remains, which is not preferable because the heat resistance, alkali resistance, electrical insulation and the like are lowered. On the other hand, when the above range is exceeded, the low molecular weight cyclic hydrocarbon ether group remains, which is not preferable because the strength of the coating film is lowered.

(Thermosetting catalyst)

When the cyclic (thio) ether compound is used as the thermosetting component, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2 methylenoremidazolene, 2 ethenoreidamidole, 2 ethenorei 4-methinoreidamidazonore, 2-phenylimidazole, 4 phenylimidazole. 1-cyanethyl-2-phenolinoreidazonole, 1- (2-cyanethinore) 2 ethinolei 4-methinoreimidazolene imidazole derivatives; dicyandiamide, benzyldimethylamine, 4 (dimethylamino) N, N dimethylbenzylamine Amine compounds such as 4-methoxy N, N dimethylbenzylamine, 4-methyl-N, N dimethylbenzylamine, hydrazine compounds such as adipic hydrazide and sebacic acid hydrazide; phosphorus compounds such as triphenylphosphine, For example, Shikoku Kasei 2MZ—A, 2M Z OK, 2ΡΗΖ, 2Ρ4ΒΗΖ, 2Ρ4ΜΗΖ (all trade names of imidazole compounds) manufactured by Kogyo Co., U—CAT3503N, U—CAT3502T (both dimethylamine amine block isocyanate compounds) Product names), DBU, DBN, U—CATSA102, U—CA T5002 (both bicyclic amidine compounds and salts thereof). In particular, the thermal curing catalyst for epoxy resins and oxetane compounds that are not limited to these, or those that promote the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups may be used alone or in combination of two or more. Even if you use it, it does not turn. Guanamine, acetoguanamine, benzoguanamine, melamine, 2, 4 diamino-6 methacryloyloxychetyl S triazine, 2-bulu 4, 6, diamino 1 S triazine, 2 vinylol 4 , 6 Diamino 1 S Triazine 'isocyanuric acid adduct, 2, 4 Diamino 6-methacryloyloxychetyl S Triazine and isocyanuric acid adduct, etc. These s-triazine derivatives can also be used, and preferably a compound that also functions as an adhesion-imparting agent is used in combination with the thermosetting catalyst.

[0075] The amount of the thermosetting catalyst to be blended is usually a normal quantitative ratio, and for example, it is preferably 0 with respect to 100 parts by mass of the ethylenically unsaturated group-containing carboxylic acid-containing resin (A) or thermosetting component. ! ~ 20 parts by mass, more preferably 0.5-15.0 parts by mass.

[0076] (Other ingredients)

Further, the photocurable / thermosetting resin composition of the present invention is applied for synthesis of the ethylenically unsaturated group-containing potent rubonic acid-containing resin (A), adjustment of the composition, or on a substrate or a carrier film. An organic solvent can be used to adjust the viscosity.

[0077] Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methylcetosolve, butylcetosolve, carbitol, methylcarbide Tonore, Butinorecanorebitonore, Propylene Glycole Monomethinoreatenore, Dipropylene Glyconore Monomethinoreatenore, Dipropylene Glycoleo Regina Pretenore, Triecirene Glyconore Monoceno Reteinore, etc. Dichloropropylene glycolate: Dipropylene glycolenomethineate acetate, Propyleneglycolenomethineate acetate, Propylene glycolenoleatenoacetate, Propylene glycolenobutyinoate acetate Glycol ether acetates such as: Ethyl acetate, butyl acetate and esters such as acetic acid ester of the above glycol ethers; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane Petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

[0078] Such an organic solvent is used alone or as a mixture of two or more.

[0079] The photo-curable 'thermosetting resin composition of the present invention further contains phthalocyanine as required.

'Blue, phthalocyanine' green, Iodine 'green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc. Colorants, known and conventional thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol and funothiazine, known conventional thickeners such as finely divided silica, organic bentonite and montmorillonite, silicones and fluorines Additives such as antifoaming agents and / or leveling agents such as polymers, silane coupling agents such as imidazole, thiazole and triazole, antioxidants, antifungal agents, etc. Touch with force S.

[0080] (Use of composition of the present invention)

The photocurable / thermosetting resin composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the organic solvent, and is formed on the circuit-formed substrate by a dip coating method, a flow coating method, a mouth coating method, a bar coating method, or the like. It is applied by a method such as the one-tar method, screen printing method, curtain coating method, etc., and the organic solvent contained in the composition is evaporated and dried (temporary drying) at a temperature of about 60-100 ° C. A film can be formed. In addition, a resin insulation layer can be formed by applying the composition described above onto a carrier finolene, and drying and winding the film as a film on a circuit-formed substrate. After that, the contact type (or non-contact type) is selectively exposed with active energy rays through a photomask with a pattern formed, and the unexposed part is diluted with a dilute alkaline aqueous solution (for example, 0.3 to 3% sodium carbonate aqueous solution). As a result, a resist pattern is formed. Furthermore, for example, by heating to a temperature of about 140 to 180 ° C and thermosetting, the carboxyl group of the ethylenically unsaturated group-containing carboxylic acid-containing resin (A) reacts with the thermosetting component (G). In addition, a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics can be formed.

[0081] In the case of the dry film, the substrates are laminated on a substrate using a hot roll laminator or the like (bonded so that the photosensitive resin composition layer and the substrate are in contact with each other). In the case of a dry film provided with a peelable cover film in the form of the photosensitive resin composition of the film, after the cover film is peeled off, a hot roll is made so that the photosensitive resin composition is in contact with the substrate. Paste using a laminator.

[0082] As the base material used for the above substrate, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine polyethylene, ポリエチレンCopper clad product for high frequency circuits using cyanate ester, etc. All grades (FR-4, etc.) of copper-clad laminates, other polyimide films, PET films, glass substrates, ceramic substrates, wafer plates, etc. can be used.

[0083] Volatile drying performed after the photocurable / thermosetting resin composition of the present invention is applied may be a hot-air circulating drying oven, an IR oven, a hot plate, a competition oven, or the like (for an air heating method using steam). This method can be carried out by using a method equipped with a heat source to bring the hot air in the dryer into countercurrent contact and a method of spraying on a support from a nozzle.

[0084] After applying the photocurable resin composition of the present invention and evaporating and drying it as described below, the obtained coating film is exposed (irradiated with active energy rays). In the coating film, the exposed portion (the portion irradiated by the activated energy line) is cured.

[0085] As the exposure apparatus used for the active energy ray irradiation, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) can be used. As the active energy ray, either a gas laser or a solid-state laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. Also, the amount of exposure varies depending on the film thickness etc. Generally 5 to 200m

Preferably 5~; 100mj / cm ^2, still more preferably be force S in the range of 5~80mj / cm ^2. As the direct drawing device, for example, a device manufactured by Nippon Orbotech, manufactured by Pentax, manufactured by Hitachi Via Mechanitas, or manufactured by Ball Semiconductor Corporation can be used. Good. Also, a known ultraviolet exposure machine can be used.

[0086] The developing method may be a dating method, a shower method, a spray method, a brush method, or the like. The developer may be potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, key. Alkaline aqueous solutions such as sodium acid, ammonia and amines can be used.

[0087] Examples

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples.

[0088] Synthesis example A 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube was added to a cresol nopolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN 104S) 92. C, epoxy equivalent 220) 660 g, Canolebi monoacetate 421.3 g, and solvent naphtha 180 · 6 g were introduced, heated to 90 ° C., stirred and dissolved. Next, it is once cooled to 60 ° C, 216 g of acrylic acid, 4.0 g of triphenylphosphine, 1.3 g of methylhydroquinone are added and reacted at 100 ° C for 12 hours, and the acid value is 0.2 mgKOH / g. A reaction product was obtained. This was charged with 241.7 g of tetrahydrophthalic anhydride, heated to 90 ° C and reacted for 6 hours. As a result, a solution of a carboxylic acid-containing resin (A) having an acid value of 50 mgKOH / g, a double bond equivalent (g weight of resin per mole of unsaturated groups) of 400, and a weight average molecular weight of 7,000 was obtained. Hereinafter, this carboxylic acid-containing resin solution is referred to as A-1 varnish.

[0089] Specific examples

Using the resin solution of Synthesis Example 1 above, blended in the proportions (parts by mass) shown in Tables 1 and 2 together with various components shown in Tables 1 and 2, premixed with a stirrer, The mixture was kneaded to prepare a photosensitive resin composition for solder resist. Here, when the degree of dispersion of the obtained photosensitive resin composition was evaluated by particle size measurement using a grindometer manufactured by Eriksen Co., it was 15 ^ m or less.

[0090] Here, Examples 1 to 8 in Tables 1 and 2 are compositions of the present invention, Comparative Examples 1 and 4 do not contain a phosphine oxide photopolymerization initiator, and Comparative Examples 2 and 5 are sulfur compounds. Comparative Example 3 departs from the present invention in that the sulfur compound contains a sulfur compound different from the sulfur compound of the present invention.

[table 1]

Examples and comparative examples of solder resist for 355nm laser

Examples Comparative examples

2 3 4 2 3

A— 1 Varnish 154 54 154 154 154 154 154 Photopolymerization initiator (B— 1 ¹

Photoinitiator (B-2) 0.2 0.5 0.5 Photoinitiator (C-1) 0.5

Sulfur compounds (E—I) * '0.3 0.3 0.3 0.3 0.3

Sulfur compound (E— 2) ^{+ ί} 0.3 Compound (D— 1 ⁶ 20 20 20 20 20 20 20 Filler * 130 130 130 130 130 130 130 Thermosetting component (G— 1Γ ⁸ 15 15 15 15 15 15 15 Heat Curing component (G-2) 30 30 30 30 30 30 30 Thermosetting catalyst * ¹ ° 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Phthalocyanine ^; Lay 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Yellow pigment " ¹ 0.75 0.75 0.75 0.75 0.75 0.75 0.75 Silicone antifoam 3

DP '5 5 5 5 5 5

# 150 ^"3 5 5 5 5 5 5

* 1: 2— (Aceteroxyiminomethyl) thixanthene

* 2: Ethanone, 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazolsole-3-yl]-, 1-(0-Acetyloxime)

* 3: 2,4,6-trimethylbenzoyldiphenylphenylphosphine oxide

* 4: 2—Mercaptobenzothiazol

* 5: Trimethylolpropane tris (3-mercaptopropionate)

* 6: Dipentaerythritol hexaacrylate

* 7: Barium sulfate

* 8: Phenolic nopolac epoxy resin

* 9: Boxylenol type epoxy resin

* 10 Dicyandiamide

* 11 Anthraquinone yellow pigment

* 12 Dipropylene glycol methyl ether acetate

* 13 Aromatic organic solvent manufactured by Idemitsu Petrochemical Co., Ltd.

[Table 2] Examples and comparative examples of solder resist for 405nm laser

[0091] The performance (depth curing, cross-sectional shape, surface curing, thermal stability and absorbance) of the thus prepared photosensitive resin composition for solder resist was evaluated according to the following criteria.

[0092] High Deep Curability>

The photo-curing / thermosetting resin compositions of Examples and Comparative Examples were screen printed using a circuit pattern board with 300/300 line / space and copper thickness of 35 m after buffing, washing with water and drying. And dry for 30 minutes in a hot air circulating drying oven at 80 ° C. After drying, exposure was performed using a direct drawing apparatus for each wavelength. The exposure pattern used was a pattern to draw 20/30/40/50/60/70/80/90/100 μm lines in the space. Active energy rays were irradiated so that the exposure amount was 40 mj / cm ² on the photosensitive resin composition. After the exposure, development was performed with a 1% by mass aqueous sodium carbonate solution at 30 ° C to draw a pattern, and a cured coating film was obtained by heat curing at 150 ° C for 60 minutes.

[0093] Counting was performed using an optical microscope in which the minimum remaining line of the cured coating film of the obtained photocurable 'thermosetting resin composition was adjusted to 200 times. The results of evaluation are shown in Tables 3 and 4.

[0094] Cross-sectional shape>

The photocurable thermosetting resin compositions of the examples and comparative examples were obtained by polishing a circuit pattern substrate having a line / space of 300/300 and a copper thickness of 50 m, washing with water and drying. Apply by screen printing and dry for 30 minutes in a hot air circulation drying oven at 80 ° C. After drying, exposure was performed using a direct drawing apparatus for each wavelength. The exposure pattern used was a pattern for drawing lines with a space of 20/30/40/50/60/70/80/90/100 μm. The active energy line was irradiated so that the exposure amount was 40 mj / cm ² on the photosensitive resin composition. After exposure, development was performed with an aqueous sodium carbonate solution to form a pattern. After irradiating with 1000 mj / cm ² of ultraviolet light with a high-pressure mercury lamp, heat curing was performed at 150 ° C. for 60 minutes to obtain a cured coating film. Design value of the cured coating film The cross section of the 100 m line section was observed.

[0095] This shape was evaluated in five stages of A to E as shown in the schematic diagram in the drawing. The figure shows a schematic diagram when the following phenomenon occurs. In the figure, la is the design value of the line width, lb is the resin composition after exposure and development, and lc is the substrate.

[0096] In particular, in the case of evaluation A, the deviation from the design value was assumed to be within 5 m at both the upper and lower parts of the line. The results of evaluation are shown in Tables 3 and 4.

[0097] A evaluation: Ideal state according to design width

B evaluation: Surface layer erosion due to insufficient development resistance

C evaluation: Undercut state

D evaluation: Line thickening due to noise etc.

E evaluation: Surface layer thickening and undercut Here, not only A evaluation, but also C evaluation and D evaluation are levels that can be used as solder resist. On the other hand, those with B evaluation have insufficient surface curability and inferior appearance and electrical characteristics, and those with E evaluation are at a level where the line and undercut parts peel off and cannot be used as a solder resist immediately. .

[0098] Surface Hardness>

The photo-curable / thermosetting resin compositions of the above Examples and Comparative Examples were subjected to screen printing after the circuit pattern substrate having a line / space force of ¾00 / 300 and a copper thickness of 35 m was buffed, washed with water and dried. And dry for 60 minutes in a hot air circulating drying oven at 80 ° C. After drying, exposure was performed using a direct drawing apparatus for each wavelength. The exposure pattern used was an overall exposure pattern. The active energy line was irradiated so that the exposure amount was 40 mj / cm ² on the photosensitive resin composition. After exposure, development (30 ° C, 0.2 MPa, 1% by weight aqueous sodium carbonate solution) was performed in 60 seconds to draw a pattern, and a cured coating film was obtained by heat curing at 150 ° C for 60 minutes.

[0099] The surface curability of the cured coating film thus obtained was evaluated for the glossiness at 60 ° using a gloss meter Micro Trigloss (manufactured by Big Gardner). The evaluation criteria were a glossiness of 50 or higher after development as good and a glossiness of less than 50 as poor. The evaluation results are shown in Tables 3 and 4.

[0100] High thermal stability>

The optical microscope in which the presence or absence of peeling of the cured coating film on copper of the photocurable and thermosetting resin compositions of the Examples and Comparative Examples obtained in the same manner as the surface curing property was adjusted 1000 times. It confirmed using. The evaluation criteria were good when no delamination occurred and bad when delamination occurred regardless of size and number. The results of evaluation are shown in Tables 3 and 4.

[0101] Absorbance>

For the measurement of absorbance, an ultraviolet-visible spectrophotometer (Ubest-V-570DS manufactured by JASCO Corporation) and an integrating sphere device (ISN-470 manufactured by JASCO Corporation) were used. Examples:! To 8 and Comparative Examples 1 to 5 Photo-curable. After applying a thermosetting resin composition to a glass plate and applying it to an applicator, it was dried at 80 ° C for 30 minutes using a hot-air circulating drying oven. A dry coating film of a photocurable / thermosetting resin composition was prepared on a glass plate. UV-visible spectrophotometer and integration Using a ball apparatus, an absorbance baseline at 500 to 300 nm was measured with the same glass plate as the glass plate coated with the photocurable / thermosetting resin composition. The absorbance of the produced glass plate with the dried coating film was measured, and the absorbance of the dried film with the baseline force could be calculated, and the absorbances at the target wavelengths of 355 nm and 405 nm were obtained. In order to prevent deviations in absorbance due to deviations in coating film thickness, this operation is performed with the applicator changing the coating thickness in four stages, and graphs of the coating thickness and absorbance at 355 nm and 405 nm are created. The absorbance of the dried coating film of 25 ΐη was calculated and taken as the respective absorbance. The evaluation results are shown in Tables 3 and 4.

[Table 3]

Evaluation results of solder resist for 355nm laser

[Table 4] Table 4 Evaluation results of solder resist for one 405 nm laser

Examples Comparative examples

5 6 7 8 4 5 Minimum line width

Deep curing 50 30 30 60 100 120 m

Cross-sectional shape D A A C B B Surface hardening 60 ° Gloss Good Good Good Good No S Bad thermal stability Peeling on circuit Good Good Good Good Good Good

405nm

Absorbance 0.38 0.63 0.65 1.22 0.45 0.44

25 Um thickness [0102] Next, the compositions prepared in the blending examples described in the examples and comparative examples in the table below were applied to a copper clad laminate formed with a circuit pattern, dried at 80 ° C for 30 minutes, and then subjected to a high-pressure mercury lamp. Exposed at 20mJ using ORRC EXP-2021 equipped with, developed with sodium carbonate aqueous solution in the same way as the previous example to form a pattern, and after irradiation with UV light of lOOOmj / cm ² with a high-pressure mercury lamp A printed wiring board on which a solder resist was formed was obtained by thermosetting at 150 ° C. for 60 minutes.

[0103] Each of the obtained printed wiring boards was subjected to electroless clinging treatment at Ei Kogyo Co., Ltd., and the presence or absence of peeling was confirmed with a cello tape (registered trademark) peel. As a result, the composition described in Example 18 did not show any peeling at all, whereas Comparative Example 15 showed slight peeling of the line on the thin line.

As can be seen from these results, the photocurable / thermosetting resin compositions of the examples according to the present invention can exhibit high photopolymerization ability with respect to ultraviolet light and laser light. A composition with sufficient deep-curing properties and excellent surface curability and thermal stability, especially for solder resist applications that require electroless gold plating and for direct writing with laser light It is possible to provide a photocurable / thermosetting resin composition suitable for the present invention, and a printed wiring board patterned using the composition.

[0105] In particular, as can be seen from the results shown in Table 4, the photocurable thermosetting resin composition of the present invention can exhibit a high photopolymerization ability with respect to 350 to 410 nm laser light and is sufficient. It is a composition that provides deep curability, and has excellent surface curability and thermal stability, especially for solder resist applications that require electroless gold plating, and with a laser beam of 350 to 410 nm. It is possible to provide a photocurable / thermosetting resin composition suitable for use in direct drawing by the use of the resin, and a printed wiring board patterned using the composition.

[0106] Other Examples

A test in which the photopolymerization initiator (C) was replaced with another type of photopolymerization initiator (C) was conducted on Example 1 in Table 1 relating to a solder resist compatible with a 355 nm laser.

[0107] Photopolymerization initiator (C) of Example 1, 2,4,6 Trimethylbenzoyldifluorophosphine oxide Irg907 (Cibas) which is an aminoacetophenone photopolymerization initiator instead of 1 part The test was carried out using 6 chemical specialty chemicals). Same as Example 1 The same result was obtained. However, 40mj / cm ² is not enough for the exposure amount when creating the substrate, and 50 mj / cm is necessary.

[0108] A test was conducted by replacing the sulfur compound (D) with another type of photopolymerization initiator (D) for Example 1 in Table 1 relating to a solder resist compatible with a 355 nm laser.

[0109] For Example 1, the sulfur compound (D) was converted from mercaptobenzothiazole to 3 mercapto.

— 4 Methyl 4H— 1, 2, 4 Triazole was used in the experiment, and the exposure dose was 3

The same results as in Examples were obtained at OmJ / cm ² .

[0110] For Example 1, the sulfur compound (D) was converted from mercaptobenzothiazole to 5-methyl-

1, 3, 4 Thiadiazole-2 When the experiment was carried out in place of thiol, the same results as in Examples were obtained with an exposure dose of 30 mj / cm ² .

[0111] For Example 1, the sulfur compound (D) is converted from mercaptobenzothiazole to 1 phenol.

When the experiment was conducted with 5-mercapto 1H-tetrazole, the exposure was 40 mJ / cm.

² gave the same results as in the example.

[0112] Next, a test using a dry film was performed.

[0113] The photosensitive resin composition prepared in accordance with Example 1 was diluted with methyl ethyl ketone, applied onto a carrier film, dried by heating in a hot air dryer at 80 ° C for 30 minutes, and a thickness of 20 m. A photosensitive resin composition layer was formed. Further, a cover film was laminated thereon to obtain a dry film. After that, the cover film is peeled off, the film is heat-laminated on the patterned copper foil substrate, and then exposed in the same manner. After the exposure, the carrier film is peeled off and developed with a 1% aqueous sodium carbonate solution at 30 ° C for 60 seconds to form a film. Formed. Then, heat curing was performed for 60 minutes with a 150 ° C hot air dryer to prepare a test substrate. The test substrate having the cured film thus obtained was subjected to an evaluation test of each characteristic by the test method and the evaluation method described above. The result was equivalent to Example 1.

Claims

Claims (A) Carboxylic acid-containing resin, (B) An oxime ester photopolymerization initiator containing an oxime ester group represented by the following general formula (I):

[Chemical 1]

—— C = N— 0— C— R ²

L II…

R ¹ ○

(In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or a phenyl group, and R ² represents an alkyl group having 1 to 7 carbon atoms or a phenyl group.)

(C) Photopolymerization initiator other than the above (B)

(E) Sulfur compounds represented by the following general formula (Π)

[Chemical 2]

A photocurable / thermosetting resin composition that can be developed with a dilute alkaline solution. Photopolymerization initiator (C)

From the group consisting of an aminoacetophenone photopolymerization initiator containing a structure represented by the following general formula (III) and an acyl phosphine oxide photopolymerization initiator containing a structure represented by the following general formula (IV) The alkali-developable photocurable thermosetting resin composition according to claim 1, comprising one or a mixture of two or more selected from:

[Chemical 3]

In general formulas (III) to (IV),

2. The photocurable / thermosetting resin composition according to claim 1, wherein the oxime ester photopolymerization initiator (B) is a photopolymerization initiator represented by the following formula (V).

[Chemical 4]

(In the formula, R is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkyl group having 2 to 12 carbon atoms; , An alkoxycarbonyl group having 2 to 12 carbon atoms (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and one in the middle of the alkyl chain. It may have the above oxygen atoms) or a phenoxycarbonyl group.

R and R are each independently a phenyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group, Or substituted with a halogen atom! /, May! /,), An alkyl group having 1 to 20 carbon atoms (one or more in the middle of the alkyl chain which may be substituted with one or more hydroxyl groups) Which may have an oxygen atom), a cycloalkyl group having 5 to 8 carbon atoms, an alkanol group having 2 to 20 carbon atoms or a benzoyl group (substituted with an alkyl group or phenyl group having 1 to 6 carbon atoms). Moyo! /,)

R represents a hydrogen atom, a phenyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom).

Three

1 or more oxygen atoms in the middle of an alkyl chain that may be substituted with one or more hydroxyl groups. A cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (substituted with an alkyl group or phenyl group having 1 to 6 carbon atoms! /, Show me! /,) )

The oxime ester photoinitiator (B) 1S, represented by the following general formula (VI)

[Chemical 5]

2. The photocurable / thermosetting resin composition according to claim 1, which is a photopolymerization initiator.

[5] The photocurable / thermosetting resin composition according to claim 1, further comprising (G) a thermosetting component.

[6] The photocurable thermosetting resin composition according to claim 1, wherein the absorbance of the dried coating film to the light source is 0.4 to 25 per 25 111; Curable resin composition.

[7] The photocurable thermosetting resin composition according to [1], which can be cured by a laser oscillation light source having a maximum wavelength of 350 to 410 nm.

[8] The photocurable thermosetting resin composition according to claim 1 is applied to a carrier film. Photo-curing / thermo-curing dry film obtained by drying.

[9] A cured product obtained by photocuring the dry film of the photocurable / thermosetting resin composition according to claim 1 on copper.

[10] A cured product obtained by photocuring the dry film according to claim 8 on copper.

[11] A cured product obtained by photocuring the photocurable thermosetting resin composition according to claim 1 with a laser oscillation light source.

[12] A cured product obtained by photocuring the dry film according to claim 8 with a laser oscillation light source.

[13] A printed wiring board obtained by photocuring the photocurable thermosetting resin composition according to claim 1 with a laser beam having a maximum wavelength of 350 to 410 nm, followed by thermosetting.

[14] A printed wiring board obtained by photocuring the dry film according to claim 8 with a laser beam having a maximum wavelength of 350 to 410 nm, followed by thermosetting.