JP5466522B2 - Photocurable resin composition, dry film and cured product thereof, and printed wiring board using them - Google Patents

Description

  The present invention relates to a photocurable resin composition used as a solder resist or the like for a printed wiring board, a dry film and a cured product thereof, and a printed wiring board using them.

  In recent years, solder resists are required to have higher workability and higher performance in response to the increase in the density of printed wiring boards accompanying the reduction in the size of electronic devices. Recently, along with the downsizing, lightening, and high performance of electronic devices, downsizing of semiconductor packages and increasing the number of pins have been put into practical use, and mass production is progressing. In response to this high density, BGA (ball grid array), CSP (chip) instead of IC packages called QFP (quad flat pack package), SOP (small outline package), etc. An IC package called “Scale Package” has appeared. As a solder resist used for such a package substrate or an in-vehicle printed wiring board, various photocurable resin compositions have been conventionally proposed (for example, see Patent Document 1).

  Insulating materials such as solder resists are required to have high insulation reliability. For example, in order to obtain high reliability in semiconductor packages such as BGA (ball grid array) and CSP (chip size package). In particular, PCT (pressure cooker test) resistance, which should also be referred to as moisture and heat resistance, is required.

  On the other hand, from the viewpoint of productivity, in the dry film type solder resist, (1) suppressing the generation of handling cracks, (2) not generating cracks when cutting the dry film sheet, (3) when cutting the film It is required to eliminate the scattering of resin. However, when a dry film type solder resist is prepared from a conventional photocurable resin composition, cracks occur during handling, cracks occur when cutting a dry film sheet, and resin scatter occurs during film cutting. There was a problem that it was easy to do.

JP 61-243869 (Claims)

Therefore, the object of the present invention is to suppress the generation of handling cracks when a dry film is prepared, the generation of cracks when cutting a dry film sheet, and the scattering of resin when the film is cut, and the swelling of the solder resist that occurs during PCT In addition to these characteristics, heat resistance, adhesion, resolution, and electroless plating required for conventional solder resists for printed wiring boards and interlayer insulation materials for multilayer wiring boards Hardened film with improved properties such as resistance and PCT resistance and excellent properties such as elasticity and toughness especially required for IC packages can be obtained, and can be used for high-density printed circuit boards and surface mounting. An object of the present invention is to provide a photocurable resin composition that can be developed with an alkali.
Furthermore, the object of the present invention is to obtain a dry film and a cured product excellent in various properties as described above obtained by using such a photocurable resin composition, and to cure a solder resist or the like with the dry film or the cured product. It is providing the printed wiring board by which a membrane | film | coat is formed.

To achieve the above object, according to the present invention, a composition comprising a carboxyl group-containing resin, a photopolymerization initiator, a filler, and an elastomer, wherein the filler content is the total amount of nonvolatile components in the composition. The photo-curable resin that can be developed with an alkaline solution, wherein the content of the elastomer is in the range of filler: elastomer = 90: 10 to 70:30 (mass ratio). A composition is provided.
In a preferred embodiment, the elastomer has an unsaturated double bond, and in this case, the photocurable resin composition further contains an antioxidant. In another preferred embodiment, the carboxyl group-containing resin is a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond.

Moreover, according to this invention, the dry film obtained by apply | coating and drying the said photocurable resin composition to a film is provided. Furthermore, the photocurable resin composition is applied to a base material, or a dry film obtained by applying and drying the photocurable resin composition to a film is laminated on the base material, and irradiated with active energy rays. A cured product obtained by photocuring, particularly a cured product obtained by photocuring on copper, and a cured product obtained by photocuring in a pattern are also provided.
Furthermore, according to the present invention, a coating film formed by applying the photocurable resin composition on a substrate, or a dry film obtained by applying and drying the photocurable resin composition on a film is used as a substrate. There is also provided a printed wiring board characterized by having a cured film obtained by photocuring a coating film formed by laminating on a film.

  The photocurable resin composition of the present invention is a composition containing a carboxyl group-containing resin, a photopolymerization initiator, a filler, and an elastomer, and the content of the filler is 25 to 40 of the total amount of nonvolatile components of the composition. Since the content ratio of the elastomer is in the range of filler: elastomer = 90: 10 to 70:30 (mass ratio), generation of handling cracks when a dry film is prepared, and cutting of the dry film sheet The generation of cracks at the time, the scattering of the resin at the time of film cutting can be suppressed, and it has high sensitivity, and in its cured product, for example, when used for a printed wiring board or a semiconductor package, excellent resolution, PCT resistance and high reliability can be obtained.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have blended a filler together with an elastomer so that the filler, which is an essential component of the composition, has a high content in the range of 25 to 40% by volume. It discovered that it could mix | blend and that the glass transition temperature Tg of the hardened | cured material obtained from the photocurable resin composition of this invention rose, and PCT tolerance improved. Furthermore, it has been found that by using an elastomer together with a filler in a well-balanced manner, cracks that occur when cutting a dry film sheet are eliminated and handling cracks are not generated, and the present invention has been completed. That is, according to the present invention, the above excellent characteristics can be exhibited, the workability is good, the sensitivity is high, and the cured product is used for, for example, a printed wiring board or a semiconductor package. In this case, it is possible to provide a photocurable resin composition that can be developed with an alkaline solution that can exhibit excellent PCT resistance, crack resistance, and resolution.
Further, according to the study by the present inventors, it has been found that the heat resistance is improved when the elastomer has an unsaturated double bond. In this case, it is preferable to add an antioxidant for the reason of preventing coating film deterioration due to oxidation and decomposition of the elastomer.

The photocurable resin composition of the present invention can impart alkali developability by using a carboxyl group-containing resin. As the carboxyl group-containing resin, various conventionally known carboxyl group-containing resins having a carboxyl group in the molecule can be used. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is more preferable in terms of photocurability and development resistance. And the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof. In the case of using only a carboxyl group-containing resin having no ethylenically unsaturated double bond, in order to make the composition photocurable, a compound having a plurality of ethylenically unsaturated groups in the molecule described below, That is, it is necessary to use a photopolymerizable monomer in combination.
As specific examples of the carboxyl group-containing resin, compounds listed below (any of oligomers and polymers) can be suitably used.

  (1) A carboxyl group-containing resin 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, and isobutylene.

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

  (3) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

  (4) During the synthesis of the resin of (2) or (3), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic carboxyl group-containing photosensitive urethane resin.

  (5) During the synthesis of the resin of (2) or (3), one isocyanate group and one or more (meth) acryloyl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. A carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal (meth) acrylate.

  (6) Carboxyl group-containing photosensitivity in which (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin as described later and a dibasic acid anhydride is added to the hydroxyl group present in the side chain. Resin.

  (7) A polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group. Added carboxyl group-containing photosensitive resin.

  (8) A dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid is reacted with a bifunctional oxetane resin as described later, and the resulting primary hydroxyl group is phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride. A carboxyl group-containing polyester resin to which a dibasic acid anhydride such as

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

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

(11) In addition to the resins (1) to (10) above, one epoxy group and one or more (meth) acryloyl groups in one molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate A carboxyl group-containing photosensitive resin obtained by adding a compound having the following.
In addition, in this specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

Since the carboxyl group-containing resin as described above has a large number of carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.
The acid value of the carboxyl group-containing resin is suitably in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value 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 are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.

  Moreover, although the weight average molecular weight of the said carboxyl group containing resin changes with resin frame | skeletons, what is generally in the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. When the weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, film thickness may be reduced during development, and resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.

  The amount of such a carboxyl group-containing resin is 20 to 60% by mass, preferably 30 to 50% by mass in the entire composition. When the amount of the carboxyl group-containing resin is less than the above range, the film strength is lowered, which is not preferable. On the other hand, when the amount is larger than the above range, the viscosity of the composition is increased or the coating property is lowered, which is not preferable.

  These carboxyl group-containing resins can be used without being limited to those listed above, and can be used singly or in combination. In particular, among the carboxyl group-containing resins, resins having an aromatic ring are preferable because they have a high refractive index and excellent resolution, and the carboxyl group-containing resins having a novolak structure are not only high in resolution. It is preferable because it is excellent in PCT and crack resistance. Also, carboxyl group-containing resins such as carboxyl group-containing resins (9) and (10) that use a phenol compound as a starting material are also preferable because PCT is improved. This is because water absorption tends to occur at the interface between the filler and the resin due to an increase in the filler component, whereas carboxyl group-containing resins such as (9) and (10) having a novolac structure are Even if the filler component increased, the PCT resistance was very excellent. This is because the former is improved in hydrophobicity by the structure of novolac, while the latter is a carboxyl group-containing resin (6), (7) that can form a similar structure, whereas the epoxy acrylate structure has a hydroxyl group. Thus, it is considered that the carboxyl group-containing resins (9) and (10) have no hydroxyl groups and have significantly improved hydrophobicity.

  The photopolymerization initiator includes at least one light selected from the group consisting of an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. A polymerization initiator can be used.

（式中、Ｘは、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、フェニル基、フェニル基（炭素数1〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）を表し、Ｙ、Ｚはそれぞれ、水素原子、炭素数1〜１７のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、結合か、炭素数１〜１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５−ピロール−ジイル、４，４’−スチルベン−ジイル、４，２’−スチレン−ジイルを表し、ｎは０か１の整数である。 Examples of commercially available oxime ester photopolymerization initiators include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Japan, N-1919, and NCI-831 manufactured by Adeka. Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.

(In the formula, X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms) A group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms), Represents an amino group, an alkylamino group having a C 1-8 alkyl group or a dialkylamino group, and Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, and a carbon number of 1 Alkyl group having ˜8 alkoxy group, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkyl group having 1 to 8 carbon atoms) Or substituted with a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkyl group) Anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar is a bond or alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, Anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, and n is an integer of 0 or 1.

  In particular, in the above general formula, X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, and Ar is a bond, phenylene, naphthylene, thiophene or thienylene. It is preferable.

  It is preferable that the compounding quantity of such an oxime ester system photoinitiator shall be 0.01-5 mass parts with respect to 100 mass parts of carboxyl group-containing resin. When it is less than 0.01 parts by mass, the photocurability on copper is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are deteriorated. On the other hand, when it exceeds 5 parts by mass, light absorption on the surface of the solder resist coating film becomes violent, and the deep curability tends to decrease. More preferably, it is 0.5-3 mass parts.

  As the α-aminoacetophenone photopolymerization initiator, specifically, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N , N-dimethylaminoacetophenone and the like. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Japan.

  Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Commercially available products include Lucilin TPO manufactured by BASF, Irgacure 819 manufactured by Ciba Japan.

  The blending amount of these α-aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. If it is less than 0.01 parts by mass, the photo-curability on copper is similarly insufficient, the coating film peels off, and the coating properties such as chemical resistance deteriorate. On the other hand, when the amount exceeds 15 parts by mass, the effect of reducing the outgas cannot be obtained, the light absorption on the surface of the solder resist coating film becomes intense, and the deep curability tends to be lowered. More preferably, it is 0.5-10 mass parts.

  Here, as the photopolymerization initiator to be used, the oxime ester-based initiator is preferable because the addition amount is small and outgassing is suppressed. Further, it is particularly preferable to use an acylphosphine oxide photopolymerization initiator in combination with the oxime ester initiator, since a good shape can be obtained in terms of resolution.

  In addition, as a photopolymerization initiator, a photoinitiator assistant and a sensitizer that can be suitably used for the photocurable resin composition of the present embodiment, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, Examples include benzophenone compounds, tertiary amine compounds, and xanthone compounds.

These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.
The total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the carboxylic acid-containing resin. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

  In addition, since these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, in some cases, the sensitivity is lowered, and the photopolymerization initiator, the photoinitiator assistant, and the sensitizer may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as necessary to improve the photoreactivity of the surface, change the resist line shape and opening to vertical, tapered, reverse taper, and processing accuracy of line width and opening diameter Can be improved.

  The photo-curable resin composition of the present invention contains a filler, but as a result of detailed examination of the amount of the filler, 25 to 40% by volume of the total amount of nonvolatile components in the composition is added. Thus, it was found that Tg was increased despite the combined use of the elastomer, and crack resistance and PCT resistance were improved. Furthermore, it has been found that the warpage occurring during curing is suppressed.

  Examples of fillers that can be used in the present invention include known and commonly used inorganic fillers such as silica, barium sulfate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, boehmite, mica powder, and hydrotalcite. Can be used. Among these, barium sulfate (refractive index: 1.64), talc (refractive index: 1.57), aluminum hydroxide (refractive index: 1.57), boehmite (refractive index: 1.62), hydrotalcite (Refractive index: 1.50), a compound composed of spherical silica and plate-shaped kaolinite called silitin or silicocolloid and its surface such as aminosilane, vinylsilane, methacrylsilane, epoxysilane, mercaptosilane, alkylsilane A treated product with a treating agent (refractive index: 1.55) (trade name Actidil, manufactured by HOFFMAN MINEAL) is preferable. Furthermore, since the refractive index is close to the resin having an aromatic ring excellent in PCT resistance and the resolution is excellent, a filler having a refractive index in the range of 1.52 to 1.59 is particularly preferable.

  The total amount of the filler is suitably in the range of 25 to 40% by volume of the total amount of nonvolatile components of the composition. When the filler content is less than 25% by volume, no increase in Tg is observed in the cured product of the photocurable resin composition, and the PCT resistance deteriorates. On the other hand, if it exceeds 40% by volume, the viscosity of the composition increases, the coating and moldability deteriorates, and the water absorption also increases, so the PCT resistance and crack resistance deteriorate, which is not preferable. Moreover, these fillers can be used individually or in combination of 2 or more types.

Furthermore, the photocurable resin composition of the present invention is characterized by containing an elastomer together with the filler. By adding this elastomer in a well-balanced manner together with the filler, specifically, handling cracks are generated by setting the elastomer content in the range of filler: elastomer = 90: 10 to 70:30 (mass ratio). It was found that the scattering of the resin can be eliminated without generating cracks when cutting the dry film sheet. Furthermore, it has also been found that the use of the filler in the range of 25 to 40% by volume of the total amount of nonvolatile components suppresses warpage that occurs during curing and improves PCT resistance.
It has also been found that heat resistance is improved when the elastomer has an unsaturated double bond.

  Examples of elastomers that can be used in the present invention include R-45HT, Poly bd HTP-9 (manufactured by Idemitsu Kosan Co., Ltd.), Epolide PB3600 (manufactured by Daicel Chemical Industries, Ltd.), Denarex R-45EPT (manufactured by Nagase ChemteX Corporation), Ricon 130, Ricon 131, Ricon 134, Ricon 142, Ricon 150, Ricon 152, Ricon 153, Ricon 154, Ricon 156, Ricon 157, Ricon 100, Ricon 18 Ricon 184, Ricon 130MA8, Ricon 130MA13, Ricon 130MA20, Ricon 131MA5, Ricon 131MA10, Ricon 131MA17, Ri con 131MA20, Ricon 184MA6, Ricon 156MA17 (above, manufactured by Sartomer). Polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyesteramide elastomers, acrylic elastomers, and olefin elastomers can be used. Moreover, the resin etc. which modified the one part or all part of the epoxy resin which has various frame | skeleton with the both-ends carboxylic acid modified butadiene-acrylonitrile rubber | gum can be used. Furthermore, epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers, and the like can also be used. These elastomers can be used alone or in combination of two or more. Furthermore, in order to prevent decomposition of the elastomer due to oxidation, it is preferable to add an antioxidant described later. In particular, when the elastomer has an unsaturated double bond, the antioxidant should be used.

A mercapto compound can be added to the photocurable resin composition of the present invention.
Examples of the mercapto compound include mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof such as 1-butanethiol, butyl-3-mercaptopropionate, methyl-3- Mercaptopropionate, 2,2- (ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclopentanethiol, cyclohexanethiol , Thioglycerol, 4,4-thiobisbenzenethiol and the like.
Examples of these commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PMP, DPMP, and TEMPIC (above, manufactured by Sakai Chemical Industry Co., Ltd.), Karenz MT-PE1, Karenz MT-BD1, And Karenz-NR1 (manufactured by Showa Denko KK).

Further, examples of the mercapto compound having a heterocyclic ring include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, and 2-mercapto-4-ethyl-4. -Butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butyrolactam, N-methyl- 2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) ethyl-2-mercapto- 4-butyrolactam, 2-mercapto-5-valerolactone, 2-mer Pto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto-5-valerolactam N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, 2-mercaptobenzothiazole, 2-mercapto-5-methylthio-thiadiazole, 2-mercapto-6-hexanolactam, 2,4,6 -Trimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name Disnet F), 2-dibutylamino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name Disnet DB) , And 2-anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name DISNET AF).
Among these, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (manufactured by Kawaguchi Chemical Co., Ltd .: trade name Accel M), 3-mercapto-4-methyl-4H-1,2, 4-Triazole, 5-methyl-1,3,4-thiadiazole-2-thiol and 1-phenyl-5-mercapto-1H-tetrazole are preferred.

  The blending amount of such a mercapto compound is suitably 0.01 parts by weight or more and 10.0 parts by weight or less, more preferably 0.05 parts by weight or more, with respect to 100 parts by weight of the carboxyl group-containing resin. 5 parts by mass or less. If it is less than 0.01 part by mass, the improvement in adhesion as an effect of adding a mercapto compound is not confirmed. On the other hand, if it exceeds 10.0 parts by mass, the development failure of the photocurable resin composition and the decrease in the dry management width will be confirmed. This is not preferable because it may cause These mercapto compounds can be used alone or in combination of two or more.

  A thermosetting component can be added to the photocurable resin composition of the present invention. Examples of thermosetting components used in the present invention include amino resins such as melamine resins, benzoguanamine resins, melamine derivatives, benzoguanamine derivatives, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, bismaleimides. Well-known thermosetting resins such as carbodiimide resins can be used. Particularly preferred is a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.

  As for the compounding quantity of the thermosetting component which has a some cyclic | annular (thio) ether group in such a molecule | numerator, 0.6-2.5 equivalent is preferable with respect to 1 equivalent of carboxyl groups of carboxyl group-containing resin. When the blending amount is less than 0.6, a carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulation and the like are lowered. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, thereby reducing the strength of the coating film. More preferably, it is 0.8-2.0 equivalent.

  When using the thermosetting component which has a some cyclic | annular (thio) ether group in a molecule | numerator, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with a thermosetting catalyst.

  The blending amount of these thermosetting catalysts is sufficient in a normal quantitative ratio. For example, preferably 100 parts by mass of the thermosetting component having a carboxyl group-containing resin or a plurality of cyclic (thio) ether groups in the molecule. It is 0.1-20 mass parts, More preferably, it is 0.5-15.0 mass parts.

  Furthermore, in the photocurable resin composition of this invention, a coloring agent can be mix | blended. As the colorant, conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body. Specific examples include those with the following color index numbers (CI; issued by The Society of Dyers and Colorists).

Red colorant:
Examples of red colorants include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. It is done.
Monoazo: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.
Disazo: Pigment Red 37, 38, 41.
Monoazo lakes: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1,68.
Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.
Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.
Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.
Condensed azo series: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and Pigment Red 242.
Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.
Kinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:
Blue colorants include phthalocyanine-based and anthraquinone-based pigments, and pigment-based compounds such as Pigment Blue 15 and Pigment Blue 15 are listed below. : 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, and Pigment Blue 60.
The dye systems include Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:
Similarly, green colorants include phthalocyanine, anthraquinone, and perylene. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. are used. be able to. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:
Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
Isoindolinone type: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.
Condensed azo series: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.
Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.
Monoazo: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169, 182, 183.
Disazo: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

In addition, a colorant such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone.
Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black And the like.

  The colorant as described above can be appropriately blended, but is preferably 10 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin or the thermosetting component. More preferably, it is 0.1-5 mass parts.

  The photocurable resin composition of the present invention can contain a compound having a plurality of ethylenically unsaturated groups in the molecule. The compound having a plurality of ethylenically unsaturated groups in the molecule used in the photocurable resin composition of the present invention is photocured by irradiation with active energy rays, and the photosensitive compound of the present invention or the carboxyl group-containing photosensitivity. The insoluble resin is insolubilized in the aqueous alkali solution or helps insolubilization. As such a compound, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and urethane (meth) acrylate can be used. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethylacrylamide, Acrylamides such as N-methylolacrylamide and N, N-dimethylaminopropylacrylamide; N, N-dimethylaminoethyl acrylate, N, -Aminoalkyl acrylates such as dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethylisocyanurate or their ethylene oxide adducts, propylene oxide adducts, Or polyvalent acrylates such as ε-caprolactone adduct; phenoxy acrylate, bisphenol A diacrylate, and polyvalent acrylates such as ethylene oxide adduct or propylene oxide adduct of these phenols; glycerin diglycidyl ether, glycerin tri Glycidyl such as glycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate Polyvalent acrylates of ethers: not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols, or urethane acrylates via diisocyanates, and And / or methacrylates corresponding to the acrylate.

  Furthermore, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. The epoxy urethane acrylate compound etc. which made the half urethane compound react are mentioned. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

Such compounds having a plurality of ethylenically unsaturated groups can be used singly or in combination of two or more. In particular, a compound having 4 to 6 ethylenically unsaturated groups in one molecule is preferable from the viewpoint of photoreactivity and resolution, and a compound having two ethylenically unsaturated groups in one molecule is used. When the Tg of the cured product is increased and the coefficient of linear expansion is further decreased, it has been found that the occurrence of cracks during the thermal cycle test is reduced.
As for the compounding quantity of the compound which has several ethylenically unsaturated groups in such a molecule | numerator, 5-100 mass parts is preferable with respect to 100 mass parts of carboxyl group-containing resin. When the blending amount is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays. On the other hand, when it exceeds 100 mass parts, the solubility with respect to dilute alkali aqueous solution falls, and a coating film becomes weak. More preferably, it is 1-70 mass parts.

Furthermore, the photocurable resin composition of the present invention may use an organic solvent for the synthesis of the carboxyl group-containing resin, the preparation of the composition, or the viscosity adjustment for application to a substrate or a carrier film. it can.
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, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

  It is preferable to add a radical scavenger or / and an antioxidant to the photocurable resin composition of the present invention. It was confirmed that the PCT resistance and the crack resistance were improved by adding a radical scavenger or / and an antioxidant. This is because in the resin composition (1) a radical scavenger that invalidates the generated radicals and / or (2) the generated peroxide is decomposed into harmless substances so that no new radicals are generated. This is probably because the oxidation of the elastomer in the resin composition was suppressed by the addition of an antioxidant such as a peroxide decomposer.

  Examples of the antioxidant acting as a radical scavenger include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2 -Methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2 , 4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′-di-t-butyl-4-hydroxybenzyl)- Phenolic compounds such as S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6,6-tetramethyl-4 -Piperidyl) -amine compounds such as sebacate and phenothiazine.

  The radical scavenger may be commercially available, for example, ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (all manufactured by Asahi Denka), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, all manufactured by TINUVIN 5100 ) And the like.

Examples of the antioxidant acting as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3′-thiodipro Sulfur compounds such as pionate can be mentioned.
The peroxide decomposing agent may be commercially available, and examples thereof include ADK STAB TPP (manufactured by Asahi Denka Co., Ltd.), Mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd.), and Sumilizer TPS (manufactured by Sumitomo Chemical Co., Ltd.). It is done. Such antioxidant can be used individually by 1 type or in combination of 2 or more types.

In addition to the antioxidant, an ultraviolet absorber can be used in the photocurable resin composition of the present invention.
Examples of such ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like.

  Examples of the benzophenone derivatives include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and 2 , 4-dihydroxybenzophenone and the like.

  Examples of the benzoate derivative include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl- Examples include 4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate.

  Examples of the benzotriazole derivatives include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) enzotriazole, 2- (2′- Hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, Examples include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole.

Examples of the triazine derivative include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.
Ultraviolet absorbers may be commercially available, for example, TINUVI PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460. , TINUVIN 479 (both manufactured by Ciba Japan). Such ultraviolet absorbers can be used singly or in combination of two or more, and can be used in combination with an antioxidant to stabilize the molded product obtained from the photocurable resin composition of the present invention. Can be achieved.

  The photo-curable resin composition of the present invention may further include a known thickener such as a known thermal polymerization inhibitor, fine silica, organic bentonite, and montmorillonite, a silicone-based, a fluorine-based, a polymer-based, etc., if necessary. Known additives such as antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, antioxidants, rust inhibitors, and the like can be blended.

  The thermal polymerization inhibitor can be used for preventing thermal polymerization or polymerization with time of the polymerizable compound. Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

  In the photocurable resin composition of the present invention, an adhesion promoter can be used in order to improve adhesion between layers or adhesion between the formed resin insulation layer and the substrate. Examples of such adhesion promoters include, for example, benzimidazole, benzoxazole, benzothiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione. , Triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent and the like.

After the photocurable resin composition of the present invention configured as described above is prepared to a predetermined composition, it is adjusted to a viscosity suitable for a coating method with an organic solvent, for example, on a substrate, a dip coating method, a flow The coating method is a coating method, a roll coating method, a bar coater method, a screen printing method, a curtain coating method, or the like.
And the organic solvent contained in a composition is volatilized and dried (temporary drying) at the temperature of about 60-100 degreeC, and a tack-free coating film (resin insulating layer) is formed. At this time, the volatile drying is performed by using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (using a method having a heat source of an air heating method using steam in a countercurrent contact with hot air in the dryer) A method of spraying on a support).

Moreover, you may form a resin insulating layer by forming a dry film from a photocurable resin composition and bonding this on a base material.
The dry film has, for example, a structure in which a carrier film such as polyethylene terephthalate, a resin insulating layer such as a solder resist layer, and a peelable cover film used as necessary are laminated in this order.

  A resin insulation layer is a layer obtained by apply | coating and drying a photocurable resin composition to a carrier film or a cover film. For such a resin insulation layer, the photo-curable resin composition of the present invention is uniformly applied to a carrier film with a thickness of 10 to 150 μm using a blade coater, a lip coater, a comma coater, a film coater, etc., and dried. Formed. And a dry film is formed by laminating | stacking a cover film further as needed. At this time, the carrier film may be laminated after the photocurable resin composition is applied to the cover film and dried.

As the carrier film, for example, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm is used.
As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but a cover film having a smaller adhesive force than the solder resist layer is preferable.

  If such a dry film is used and the cover film is used, after peeling off the cover film, the resin insulation layer and the base material are stacked and bonded together using a laminator or the like, so that the resin insulation layer is formed on the base material. It is formed. In addition, what is necessary is just to peel a carrier film before or after the exposure mentioned later.

  At this time, as a base material on which a coating film is formed or a dry film is laminated, paper-phenol resin, paper-epoxy resin, glass cloth--in addition to a printed circuit board and a flexible printed circuit board in which circuits are formed in advance Epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin, glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, all grades using composite materials such as fluororesin / polyethylene / PPO / cyanate ester ( FR-4 etc.) copper-clad laminate, polyimide film, PET film, glass substrate, ceramic substrate, wafer plate and the like.

Further, the pattern is exposed by an active energy beam or directly by a laser direct exposure machine through a photomask having a pattern formed by a contact method (or non-contact method). In the coating film, the exposed portion (the portion irradiated by the active energy ray) is cured.
As an exposure machine used for active energy ray irradiation, a direct drawing device (for example, a laser direct imaging device that draws an image directly with a laser using CAD data from a computer), an exposure device equipped with a metal halide lamp, and an (ultra) high-pressure mercury lamp It is possible to use an exposure machine mounted, an exposure machine equipped with a mercury short arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (super) high pressure mercury lamp.

As the active energy ray, it is preferable to use laser light having a maximum wavelength in the range of 350 to 410 nm. By setting the maximum wavelength within this range, radicals can be efficiently generated from the photopolymerization initiator. If a laser beam in this range is used, either a gas laser or a solid laser may be used. Further, the exposure amount varies depending the thickness or the like, generally 5~500mJ / cm ^2, preferably be in the range of 10 to 300 mJ / cm ^2.

  As the direct drawing device, for example, a device manufactured by Nippon Orbotech, manufactured by Pentax, or the like can be used, and any device that oscillates laser light having a maximum wavelength of 350 to 410 nm may be used. .

And by exposing in this way, an exposed part (part irradiated with the active energy ray) is hardened, and an unexposed part is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3 wt% sodium carbonate aqueous solution). Thus, a cured product (pattern) is formed.
At this time, as a developing method, a dipping method, a shower method, a spray method, a brush method, or the like can be used. Further, as the developer, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used.

  Further, when a thermosetting component is added, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxyl group-containing resin and, for example, a plurality of cyclic ether groups and / or cyclic groups in the molecule A thermosetting component having a thioether group reacts to form a cured product (pattern) excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics. In addition, even when it does not contain a thermosetting component, by performing heat treatment, the ethylenically unsaturated bond of the photocurable component remaining in an unreacted state at the time of exposure undergoes thermal radical polymerization, and the coating film characteristics are improved. Therefore, heat treatment (thermosetting) may be performed depending on the purpose and application.

  Thus, in the photocurable resin composition of the present invention, by containing a carboxyl group-containing resin, a photopolymerization initiator, a filler, an elastomer, more preferably a thermosetting resin, and an antioxidant, the curing thereof is achieved. It is possible to obtain reliability such as thermal cycle resistance and PCT resistance without impairing the heat resistance required when used in electronic parts. And it becomes possible by using such hardened | cured material for a printed wiring board etc. to obtain high reliability.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following description, “parts” and “%” are based on mass unless otherwise specified.

Synthesis example 1
A novolac-type cresol resin (trade name “Shonol CRG951”, manufactured by Showa Polymer Co., Ltd., OH equivalent: 119.4) is added to an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device. 4 parts, 1.19 parts of potassium hydroxide and 119.4 parts of toluene were charged, the system was purged with nitrogen while stirring, and the temperature was raised. Next, 63.8 parts of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
293.0 parts of an alkylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 part of methylhydroquinone and 252.9 parts of toluene were mixed with a stirrer and a temperature. A reactor equipped with a meter and an air blowing tube was charged, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring. 12.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 parts of the obtained novolak acrylate resin solution and 1.22 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was supplied at a rate of 10 ml / min. While blowing and stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added, reacted at 95 to 101 ° C. for 6 hours, cooled and taken out. In this way, a solution (hereinafter abbreviated as A-1) of a carboxyl group-containing photosensitive resin having a non-volatile content of 65% and a solid acid value of 87.7 mgKOH / g was obtained.

Synthesis example 2
Add 330 g of cresol novolac type epoxy resin (Epiclon N-695, manufactured by DIC Corporation, epoxy equivalent 220) to a flask equipped with a gas introduction tube, a stirrer, a cooling tube and a thermometer, add 340 g of carbitol acetate, The mixture was dissolved by heating, and 0.46 g of hydroquinone and 1.38 g of triphenylphosphine were added. This mixture was heated to 95 to 105 ° C., 108 g of acrylic acid was gradually added dropwise, and reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C., 68 g of tetrahydrophthalic anhydride was added, reacted for 8 hours, and cooled. In this way, a solution (hereinafter abbreviated as A-4) of a carboxyl group-containing photosensitive resin having a solid acid value of 50 mgKOH / g and a nonvolatile content of 60% was obtained.

Examples 1-21 and Comparative Examples 1-7
Using the resin solution of the above synthesis example, blended in the proportions (parts by mass) shown in Tables 1 and 2 together with various components shown in Tables 1 and 2 below, premixed with a stirrer, The mixture was kneaded to prepare a photosensitive resin composition for solder resist.

The meanings of the suffixes in Tables 1 and 2 are as follows.
* 1: ZFR-1401H (nonvolatile content: 65.0%, solid content acid value: 100 mgKOH / g, manufactured by Nippon Kayaku Co., Ltd.)
* 2: ZCR-1601H (nonvolatile content 65.0%, solid content acid value 100 mgKOH / g, manufactured by Nippon Kayaku Co., Ltd.)
* 3: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] 1,1- (O-acetyloxime) (manufactured by Ciba Japan)
* 4: Lucillin TPO (BASF)
* 5: Nippon Talc Co., Ltd. SG-2000
* 6: Sakai Chemical Industry Co., Ltd. B-33
* 7: Showa Denko Hijilite H-42M
* 8: Sakai Chemical Industry Co., Ltd. MGZ-3
* 9: ACTILOX400SM manufactured by Nabaltec
* 10: Admatechs SO-E2
* 11: Made by HOFFMANN MINALAL (treated with aminosilane coupling material of silitin, a compound composed of spherical silica and plate-shaped kaolinite)
* 12: DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd.
* 13: Epoxidized polybutadiene (molecular weight: 3000, epoxy equivalent: 200, manufactured by Daicel Chemical Industries, Ltd.)
* 14: Hydroxyl-terminated polybutadiene (made by Idemitsu Kosan Co., Ltd.)
* 15: 2-mercaptobenzothiazole (manufactured by Kawaguchi Chemical Industry Co., Ltd.)
* 16: 2,4,6-trimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd.)
* 17: 1,4-bis (3-mercaptobutyryloxy) butane (manufactured by Showa Denko KK)
* 18: Bixylenol type epoxy resin (Japan Epoxy Resin Co., Ltd.)
* 19: Bisphenol type epoxy resin (manufactured by Toto Kasei)
* 20: Antioxidant (Ciba Japan)
* 21: Block isocyanate (manufactured by Asahi Kasei Chemicals Corporation)
* 22: CIPigment Blue 15: 3
* 23: CIPigment Yellow 147
* 24: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
* 25: Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

Characteristic test:
The compositions of Examples and Comparative Examples were applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Using this exposure apparatus equipped with a high-pressure mercury lamp on this substrate, the solder resist pattern is exposed at an optimum exposure amount, and developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 90 seconds. Obtained. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 160 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

<Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.
A: Peeling is not observed even after 10 seconds of immersion for 6 or more times.
○: No peeling is observed even if the immersion for 10 seconds is repeated 3 times or more.
(Triangle | delta): It peels for a while when immersion for 10 seconds is repeated 3 times or more.
X: The resist layer swells and peels off within 3 times for 10 seconds.

<Electroless gold plating resistance>
Using commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 0.5 μm and gold 0.03 μm, and the tape peeling causes the presence or absence of resist layer peeling or plating penetration. After evaluating the presence or absence, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
A: No soaking or peeling is observed.
○: Slight penetration is confirmed after plating, but does not peel off after tape peeling.
Δ: Slight penetration after plating and peeling after tape peel.
X: There is peeling after plating.

<PCT resistance>
It was placed in a high-pressure, high-temperature, high-humidity tank at 121 ° C., 2 atm and 100% humidity for 168 hours, and the state change of the cured coating film was evaluated. Evaluation was made according to the following evaluation criteria.
A: No noticeable swelling or discoloration.
X: Remarkable swelling and discoloration.

<Crack resistance>
Thermal history was added for 30 minutes at -55 ° C and 30 minutes at 125 ° C, and after 1000 cycles, observation with an optical microscope was performed.
(Double-circle): There is no crack generation.
Δ: Cracks occurred.
X: Crack generation is remarkable.

<Resolution>
A negative pattern having a via opening diameter of 60 μm was used as a negative mask for resolution evaluation, and the bottom diameter of the solder resist opening was observed and measured with a scanning electron microscope (SEM) of 1000 times. evaluated.
A: Bottom diameter is 55-60 μm
○: Bottom diameter is 50 to 55 μm
X: Bottom diameter is less than 50 μm

<Linear expansion coefficient and glass transition temperature (Tg)>
A tensile coating of a 3 mm × 10 mm cured coating film was performed in a temperature range of 0 ° C. to 260 ° C. at a constant temperature increase rate while applying a 10 g load with TMA6100 manufactured by Seiko Instruments Inc. Tg was measured.

<Confirmation of status when cutting out>
The obtained photocurable resin composition was coated on a 16 μm thick PET film so that the film thickness after drying with an applicator was about 20 μm, preliminarily dried at 80 ° C. for 30 minutes, and 10 cm with a cutter knife. When cut into corners, the occurrence of scattering and cracking of the photocurable resin composition was visually evaluated.
A: No resin scattering or cracking.
Δ: Resin scattering and cracking occurred.
X: Resin scattering and cracking are remarkable.

<Verification of bendability>
The obtained photocurable resin composition was coated on a 16 μm-thick PET film so that the film thickness after drying with an applicator was about 20 μm, and pre-dried at 80 ° C. for 30 minutes, and then obtained. The dried film was bent 180 ° with the PET film surface inside, and the presence or absence of cracks was confirmed.
(Double-circle): There is no crack generation.
Δ: Cracks occurred.
X: Crack generation is remarkable.

<Confirmation of reworkability>
The obtained photocurable resin composition was coated on a 16 μm-thick PET film so that the film thickness after drying with an applicator was about 20 μm, and pre-dried at 80 ° C. for 30 minutes, and then obtained. The dry film was checked for the presence or absence of reworkability when the dry film was superimposed on the test substrate with the PET film surface as the upper surface so that the resin composition layer was in contact.
◎: Rework possible ×: Rework impossible

The results of the above tests are summarized in Tables 3 and 4.

Claims (5)

  A composition containing a carboxyl group-containing resin, a photopolymerization initiator, a filler, and an elastomer, wherein the content of the filler is 25 to 40% by volume of the total amount of nonvolatile components of the composition, and the content of the elastomer is Filler: elastomer = 90: 10 to 70:30 (mass ratio) The range of the photocurable resin composition that can be developed with an alkaline solution.   The photocurable resin composition according to claim 1, further comprising an antioxidant, wherein the elastomer has an unsaturated double bond.   The dry film obtained by apply | coating and drying the photocurable resin composition of Claim 1 or 2 on a film.   The photocurable resin composition according to claim 1 or 2 is applied to a substrate, or a dry film obtained by applying the photocurable resin composition to a film and drying is laminated on the substrate, and active. A cured product obtained by photocuring by irradiation with energy rays.   A coating film formed by applying the photocurable resin composition according to claim 1 or 2 on a substrate, or a dry film obtained by applying and drying the photocurable resin composition on a film as a substrate A printed wiring board comprising a cured film obtained by photocuring a coating film formed by laminating on a pattern.