JP6010340B2 - Printed wiring board and printed wiring board manufacturing method - Google Patents

Description

  The present invention relates to a printed wiring board and a method for manufacturing a printed wiring board.

Conventionally, as a material used for a solder resist of a printed wiring board, a photocurable resin composition that can be developed with an alkaline aqueous solution has been used. For example, Patent Documents 1 and 2 disclose resin compositions containing an epoxy acrylate-modified resin (hereinafter sometimes abbreviated as epoxy acrylate) derived by modification of an epoxy resin.
As a method for forming a solder resist using such a photocurable resin composition, a photocurable resin composition is applied to a substrate and dried to form a resin layer, and the resin layer is patterned. There is a method of forming by developing with an alkali developer after light irradiation.
In Patent Document 3, a solder resist layer made of a thermosetting resin composition is formed on one surface of a printed wiring substrate, and a solder resist layer made of a photocurable resin composition is formed on the other surface. It is disclosed to form. In Patent Document 3, an opening having a relatively small opening diameter is formed by a laser in a solder resist layer made of a thermosetting resin composition, and the solder resist layer made of a photocurable resin composition is opened by photolithography. It is disclosed that an opening having a relatively large aperture is formed.

JP 61-243869 (Claims) Japanese Patent Laid-Open No. 3-250012 (Claims) JP 2010-258147 A

  However, in the thermosetting resin composition as in Patent Document 3, the light irradiation portion cannot be selectively cured by light irradiation as in the photocurable resin composition. A layer cannot be formed. Therefore, it is conceivable to form a pattern layer by laser processing, but in this case, the task time becomes long, for example, the number of shots increases.

  Therefore, an object of the present invention is to provide a printed wiring board having a pattern layer formed with a short task time and an opening, and a method for manufacturing the same.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-described problems can be solved by adopting the following configuration, and have completed the present invention.

That is, the printed wiring board of the present invention comprises a pattern layer formed by irradiating and developing a negative resin layer composed of an alkali development type thermosetting resin composition containing a photobase generator;
It has an opening formed by laser processing in the same layer as this pattern layer or in another layer.

  In the printed wiring board of the present invention, the pattern layer forms a resin layer formed by applying and drying the alkali-developing thermosetting resin composition, and the alkali-developing-type heat is irradiated by pattern-shaped light irradiation. It is preferable that the photobase generator contained in the curable resin composition is activated and an unirradiated portion is removed by development to form a negative pattern.

The method for producing a printed wiring board of the present invention includes a step (A) of forming a resin layer formed by applying and drying an alkali development type thermosetting resin composition containing a photobase generator on a substrate.
A step (B) of activating the photobase generator contained in the alkali-developable thermosetting resin composition by pattern-shaped light irradiation to cure the light-irradiated portion, and removing the unirradiated portion by alkali development. A step (C) of forming a negative pattern layer, and
A step (D) of performing laser processing on the pattern layer.

  The method for producing a printed wiring board of the present invention preferably further includes a desmear process.

  According to the present invention, it is possible to provide a printed wiring board having a pattern layer formed with a short task time and an opening, and a manufacturing method thereof. Further, the pattern layer of the present invention is excellent in curing characteristics.

FIG. 1 is a diagram showing a DSC chart for a resin layer made of an alkali development type thermosetting resin composition of Example 1 of the present invention. FIG. 2 is a diagram showing an example of a method for manufacturing a printed wiring board according to the present invention. FIG. 3 is a diagram showing an example of a method for manufacturing a printed wiring board according to the present invention.

The printed wiring board of the present invention has a resin layer made of an alkali developing type thermosetting resin composition containing a photobase generator (hereinafter sometimes abbreviated as “thermosetting resin composition”) on a negative. The pattern has a pattern layer formed by light irradiation and development on the mold, and an opening formed in the same layer as this pattern layer or in another layer by laser processing.
Here, the pattern layer forms a resin layer made of a thermosetting resin composition, and the photobase generator contained in the thermosetting resin composition is activated by irradiating the pattern with light, and the unirradiated part is developed by development. It is preferable that the film is removed to form a negative pattern.
In the resin layer made of the thermosetting resin composition, a base is generated on the surface by light irradiation. The generated base destabilizes the photobase generator and further generates a base. The generation of the base in this way is considered to cause chemical multiplication up to the deep part of the resin layer. And since an addition reaction advances to a deep part, a base acts as a catalyst at the time of addition reaction of an alkali developable resin and a heat-reactive compound, a resin layer hardens | cures to a deep part in a light irradiation part.
Therefore, after irradiating the thermosetting resin composition in a pattern, it is possible to easily form the pattern layer by removing the non-irradiated portion by alkali development.
Thus, in this invention, since light irradiation and a development process are possible like the case where a photocurable resin composition is used, a pattern layer can be formed in a short task time.
Then, by performing laser processing on the same layer or another layer with the pattern layer, a minute opening can be easily formed.
Moreover, since hardening of the thermosetting resin composition of this invention advances by thermal reaction, distortion and hardening shrinkage | contraction can be suppressed compared with the case where it advances by photoreaction.

  The thermosetting resin composition may be a composition that does not cure even when heated in an unirradiated state and that can be cured by heat only after irradiation with light.

In the thermosetting resin composition, an exothermic peak occurs in DSC measurement by light irradiation, or the heat generation starting temperature in DSC measurement of the thermosetting resin composition irradiated with light is unirradiated thermosetting resin composition The exothermic peak temperature in the DSC measurement of the uncured thermosetting resin composition is lower than the exothermic peak temperature in the DSC measurement of the thermosetting resin composition irradiated with light. It is preferable.
In addition, the thermosetting resin composition is also referred to as a temperature difference (ΔT start) of heat generation start temperature in DSC measurement between a light-irradiated thermosetting resin composition and an unirradiated thermosetting resin composition) or The temperature difference between the exothermic peak temperatures (also referred to as ΔT peak) is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, and even more preferably 30 ° C. or higher.
Here, ΔT start is a thermosetting resin composition having the same composition, one is irradiated with light, and the other is not irradiated with light, and the DSC (Differential Scanning Calorimetry) is left as it is. Each measurement is performed, and refers to the temperature difference between the heat generation start temperature indicating the start of the curing reaction of the resin composition irradiated with light and the heat generation start temperature of the unirradiated resin composition. ΔT peak refers to the temperature difference between the exothermic peak temperatures of the resin composition irradiated and unirradiated when DSC measurement is similarly performed.
In addition, the irradiation amount in the DSC measurement of the thermosetting resin composition irradiated with light increases the irradiation amount, and the exothermic peak temperature shift due to light irradiation of the thermosetting resin composition does not occur (saturation). is there.
When ΔT start or ΔT peak is 10 ° C. or higher, it is possible to suppress the occurrence of so-called fogging in which the unirradiated part remains due to alkali development and so-called biting in which the light irradiated part is removed by alkali development. it can. Further, when ΔT start or ΔT peak is 10 ° C. or higher, it is possible to widen the range of heating temperatures that can be taken in the heating step (B1) described later.

  The thermosetting resin composition preferably contains an alkali-developable resin, a thermoreactive compound, and a photobase generator. Hereinafter, each component of the thermosetting resin composition will be described.

[Alkali developable resin]
The alkali-developable resin is a resin that contains one or more functional groups among phenolic hydroxyl groups, thiol groups, and carboxyl groups and that can be developed with an alkaline solution, preferably a compound having two or more phenolic hydroxyl groups, carboxyl Examples thereof include a group-containing resin, a compound having a phenolic hydroxyl group and a carboxyl group, and a compound having two or more thiol groups.

Examples of the compound having two or more phenolic hydroxyl groups include phenol novolac resin, alkylphenol volac resin, bisphenol A novolac resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene modified phenol resin, polyvinylphenols, bisphenol F, Examples thereof include known and commonly used phenol resins such as bisphenol S-type phenol resin, poly-p-hydroxystyrene, a condensate of naphthol and aldehydes, and a condensate of dihydroxynaphthalene and aldehydes.
In addition, as a phenol resin, a compound having a biphenyl skeleton or a phenylene skeleton, or both, and as a phenolic hydroxyl group-containing compound, phenol, orthocresol, paracresol, metacresol, 2,3-xylenol, 2,4- Xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, phloroglucinol You may use the phenol resin which synthesize | combined using these and which have various frame | skeletons.
These may be used alone or in combination of two or more.

  As the carboxyl group-containing resin, a known resin containing a carboxyl group can be used. Due to the presence of the carboxyl group, the resin composition can be made alkali developable. In addition to the carboxyl group, a compound having an ethylenically unsaturated bond in the molecule may be used, but in the present invention, as the carboxyl group-containing resin, for example, ethylenically unsaturated as shown in (1) below. It is preferable to use only a carboxyl group-containing resin having no double bond.

  Specific examples of the carboxyl group-containing resin that can be used in the present invention include the compounds listed below (any of oligomers and polymers).

  (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. The lower alkyl refers to an alkyl group having 1 to 5 carbon atoms.

  (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 compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems Terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with the terminal of urethane resin by polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group

  (4) 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 ( Carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its partial acid anhydride modified product, carboxyl group-containing dialcohol compound and diol compound.

  (5) During the synthesis of the resin of the above (2) or (4), 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 urethane resin.

  (6) During the synthesis of the resin of (2) or (4) above, one isocyanate group and one or more (meth) acryloyl groups are present in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. The carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.

(7) An unsaturated monocarboxylic acid such as (meth) acrylic acid is reacted with the polyfunctional (solid) epoxy resin as described above, and phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride is added to the hydroxyl group present in the side chain. A carboxyl group-containing resin to which a dibasic acid anhydride such as an acid is added.
(8) A dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is reacted with a saturated monocarboxylic acid on the polyfunctional (solid) epoxy resin as described above, and the hydroxyl group present in the side chain. A carboxyl group-containing resin to which is added.

  (9) A carboxyl obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin and adding a dibasic acid anhydride to the resulting hydroxyl group Group-containing resin.

  (10) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin as described later with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.

  (11) A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide. Non-photosensitive carboxyl group-containing resin that does not contain.

  (12) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide is reacted with a saturated monocarboxylic acid. A carboxyl group-containing resin obtained by reacting a basic acid anhydride.

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

  (14) A reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, with a saturated monocarboxylic acid. A non-photosensitive carboxyl group-containing resin that does not contain a carboxyl group-containing resin obtained by reacting a polybasic acid anhydride.

  (15) A carboxyl group obtained by reacting a polybasic acid anhydride with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate. Containing resin.

  (16) 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 resin obtained by reacting a reaction product with a polybasic acid anhydride.

  (17) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and a saturated monocarboxylic acid React with acid and react with polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid etc. to the alcoholic hydroxyl group of the resulting reaction product Carboxyl group-containing resin obtained by making it.

  (18) An epoxy compound having a plurality of epoxy groups in one molecule is reacted with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol; Carboxyl groups obtained by reacting polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid with the alcoholic hydroxyl group of the obtained reaction product Containing resin.

  (19) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth) Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and then reacting with the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride such as an acid.

  (20) One epoxy group and one or more (meth) acryloyl in a molecule such as glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate and the like in any one of the resins (1) to (19) above A carboxyl group-containing resin formed by adding a group-containing compound.

Such an alkali-developable resin has a large number of carboxyl groups, hydroxyl groups, and the like in the side chain of the backbone polymer, so that development with an alkaline aqueous solution becomes possible.
In addition, the hydroxyl group equivalent or carboxyl group equivalent of the carboxyl group-containing resin is 80 to 900 g / eq. And more preferably 100 to 700 g / eq. It is. Hydroxyl group equivalent or carboxyl group equivalent is 900 g / eq. If it exceeds 1, the adhesion of the pattern layer may not be obtained, or alkali development may be difficult. On the other hand, the hydroxyl group equivalent or the carboxyl group equivalent is 80 g / eq. In the case of less than, because the dissolution of the light irradiation part by the developer proceeds, the line becomes thinner than necessary, or in some cases, the light irradiation part and the unirradiated part are dissolved and peeled off with the developer, This is not preferable because it may be difficult to draw a normal resist pattern. Further, it is preferable that the carboxyl group equivalent or the phenol group equivalent is large because development is possible even when the content of the alkali-developable resin is small.

  Moreover, although the weight average molecular weight of alkali developable resin used by this invention changes with resin frame | skeletons, the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. If the weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the resin layer after light irradiation 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.

  In this specification, (meth) acrylate is a general term for acrylate, methacrylate and mixtures thereof, and the same applies to other similar expressions.

  Examples of the compound having a thiol group include trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, ethylene glycol bisthioglycolate, 1,4-butanediol bisthioglycolate, trimethylolpropane. Tristhioglycolate, pentaerythritol tetrakisthioglycolate, di (2-mercaptoethyl) ether, 1,4-butanedithiol, 1,3,5-trimercaptomethylbenzene, 1,3,5-trimercaptomethyl -2,4,6-trimethylbenzene, terminal thiol group-containing polyether, terminal thiol group-containing polythioether, thiol compound obtained by reaction of epoxy compound with hydrogen sulfide, reaction of polythiol compound with epoxy compound Thiol compounds having terminal thiol group obtained Te are exemplified.

The alkali developable resin is preferably a carboxyl group-containing resin or a compound having a phenolic hydroxyl group.
The alkali-developable resin is preferably non-photosensitive without a photocurable structure such as epoxy acrylate. Such a non-photosensitive alkali-developable resin does not have an ester bond derived from epoxy acrylate, and therefore has high resistance to desmear liquid. Therefore, a pattern layer having excellent curing characteristics can be formed. Moreover, since it does not have a photocurable structure, curing shrinkage can be suppressed.
When the alkali-developable resin is a carboxyl group-containing resin, it can be developed with a weak alkali as compared with the case of a phenolic resin. Examples of the weak alkali include sodium carbonate. By developing with weak alkali, it can suppress that a light irradiation part will be developed. Moreover, the light irradiation time in a process (B) and the heating time in a process (B1) can be shortened.

[Heat-reactive compound]
The thermoreactive compound is a resin having a functional group that can be cured by heat. An epoxy resin, a polyfunctional oxetane compound, etc. are mentioned.

  The epoxy resin is a resin having an epoxy group, and any known one can be used. Examples thereof include a bifunctional epoxy resin having two epoxy groups in the molecule, and a polyfunctional epoxy resin having many epoxy groups in the molecule. In addition, a hydrogenated bifunctional epoxy compound may be used.

  Polyfunctional epoxy compounds include bisphenol A type epoxy resin, brominated epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, alicyclic ring Epoxy resin, trihydroxyphenylmethane type epoxy resin, bixylenol type or biphenol type epoxy resin or mixtures thereof, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylolethane type epoxy resin, heterocyclic epoxy Resin, diglycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin, epoxy resin having dicyclopentadiene skeleton, glycidyl meta Acrylate copolymer epoxy resins, copolymerized epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, and a CTBN modified epoxy resin.

  Other liquid bifunctional epoxy resins include vinylcyclohexene diepoxide, (3 ′, 4′-epoxycyclohexylmethyl) -3,4-epoxycyclohexanecarboxylate, and (3 ′, 4′-epoxy-6′-methyl). And alicyclic epoxy resins such as (cyclohexylmethyl) -3,4-epoxy-6-methylcyclohexanecarboxylate.

  Said epoxy resin may be used individually by 1 type, and may use 2 or more types together.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene), cardo-type bisphenol Le ethers, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.
Here, it is preferable that the heat-reactive compound has a benzene skeleton because heat resistance is improved. Moreover, when a thermosetting resin composition contains a white pigment, it is preferable that a thermoreactive compound is an alicyclic skeleton. Thereby, photoreactivity can be improved.

  As a compounding quantity of the said heat-reactive compound, it is preferable that equivalent ratio (alkali-developable resin: heat-reactive compound) with alkali-developable resin is 1: 0.5-1: 10. Since development will become difficult when it remove | deviates from such a compounding ratio, it is more preferable that it is 1: 0.5-1: 5.

[Photobase generator]
One or more photobase generators can function as a catalyst for the polymerization reaction of the above-described thermoreactive compound by changing the molecular structure upon irradiation with light such as ultraviolet rays or visible light, or by cleaving the molecules. It is a compound that produces a basic substance. Examples of basic substances include secondary amines and tertiary amines.
Examples of photobase generators include α-aminoacetophenone compounds, oxime ester compounds, acyloxyimino groups, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzyl carbamate groups, and alkoxyoxybenzyl carbamates. And compounds having a substituent such as a group.

  The α-aminoacetophenone compound has a benzoin ether bond in the molecule, and when irradiated with light, cleavage occurs in the molecule to produce a basic substance (amine) that exhibits a curing catalytic action. Specific examples of the α-aminoacetophenone compound include (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, manufactured by BASF Japan Ltd.) and 4- (methylthiobenzoyl) -1-methyl. -1-morpholinoethane (Irgacure 907, trade name, manufactured by BASF Japan Ltd.), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl]- A commercially available compound such as 1-butanone (Irgacure 379, trade name, manufactured by BASF Japan Ltd.) or a solution thereof 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−ジイルで表し、ｎは０か１の整数である。） As the oxime ester compound, any compound that generates a basic substance by light irradiation can be used. Examples of oxime ester compounds include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, NCI-831 manufactured by Adeka, and the like as commercially available products. Moreover, the compound 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), And Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon number 1). Alkyl group having 1 to 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) Group 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, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms, or Represents an anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, and 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.

（式中、Ｒ^１は、炭素原子数１〜４のアルキル基、または、ニトロ基、ハロゲン原子もしくは炭素原子数１〜４のアルキル基で置換されていてもよいフェニル基を表す。Ｒ^２は、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、または、炭素原子数１〜４のアルキル基もしくはアルコキシ基で置換されていてもよいフェニル基を表す。Ｒ^３は、酸素原子または硫黄原子で連結されていてもよく、フェニル基で置換されていてもよい炭素原子数１〜２０のアルキル基、炭素原子数１〜４のアルコキシ基で置換されていてもよいベンジル基を表す。Ｒ^４は、ニトロ基、または、Ｘ−Ｃ（＝Ｏ）−で表されるアシル基を表す。Ｘは、炭素原子数１〜４のアルキル基で置換されていてもよいアリール基、チエニル基、モルホリノ基、チオフェニル基、または、下記式で示される構造を表す。）

Moreover, the compound which can be represented by the following general formula can also be mentioned as a preferable carbazole oxime ester compound.

(In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms, or a phenyl group optionally substituted with a nitro group, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. R ² represents , An alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group, R ³ represents , Which may be linked with an oxygen atom or a sulfur atom, may be substituted with a phenyl group, may be substituted with an alkyl group having 1 to 20 carbon atoms, or may be substituted with an alkoxy group with 1 to 4 carbon atoms R ⁴ represents a nitro group or an acyl group represented by X—C (═O) —, where X is an aryl optionally substituted with an alkyl group having 1 to 4 carbon atoms. Group, thienyl group, morpholino A group, a thiophenyl group, or a structure represented by the following formula:

  In addition, JP-A-2004-359639, JP-A-2005-097141, JP-A-2005-220097, JP-A-2006-160634, JP-A-2008-094770, JP-A-2008-509967, Specific examples include carbazole oxime ester compounds described in JP2009-040762A and JP2011-80036A.

  Specific examples of the compound having an acyloxyimino group include O, O'-diacetphenone oxime succinate, O, O'-dinaphthophenone oxime succinate, benzophenone oxime acrylate-styrene copolymer, and the like.

  Specific examples of the compound having an N-formylated aromatic amino group and an N-acylated aromatic amino group include, for example, di-N- (p-formylamino) diphenylmethane, di-N (p-aceethylamino). Diphenylmelane, di-N- (p-benzamido) diphenylmethane, 4-formylaminotoluylene, 4-acetylaminotoluylene, 2,4-diformylaminotoluylene, 1-formylaminonaphthalene, 1-acetylaminonaphthalene, 1,5-diformylaminonaphthalene, 1-formylaminoanthracene, 1,4-diformylaminoanthracene, 1-acetylaminoanthracene, 1,4-diformylaminoanthraquinone, 1,5-diformylaminoanthraquinone, 3, 3′-dimethyl-4,4′-diformylaminobipheny And 4,4'-formylamino benzophenones.

  Specific examples of the compound having a nitrobenzyl carbamate group or an alkoxybenzyl carbamate group include, for example, bis {{(2-nitrobenzyl) oxy} carbonyl} diaminodiphenylmethane, 2,4-di {{(2-nitrobenzyl) Oxy} toluylene, bis {{(2-nitrobenzyloxy) carbonyl} hexane-1,6-diamine, m-xylidine {{(2-nitro-4-chlorobenzyl) oxy} amide} and the like.

  As a photobase generator, an oxime ester compound and an α-aminoacetophenone compound are preferable. As the α-aminoacetophenone compound, those having two or more nitrogen atoms are particularly preferable.

As other photobase generators,
WPBG-018 (Product name: 9-anthrylmethyl N, N'-diethylcarbamate), WPBG-027 (Product name: (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine), WPBG-082 A photobase generator such as (trade name: guanidinium 2- (3-benzoylphenyl) propionate), WPBG-140 (trade name: 1- (anthraquinon-2-yl) ethyl imidazolecarboxylate) can also be used.
Also, JP-A-11-71450, WO2002 / 051905, WO2008 / 072651, JP2003-20339, JP2003-212856, JP2003-344992, JP 2007-86763, JP 2007-23315, JP 2008-3581, JP 2008-3582, 2009-280785, JP 2009-080452, JP 2010-95686, JP 2010-126662 A, JP 2010-185010 A, JP 2010-185036 A, JP 2010-186054 A, JP 2010-186056 A, JP 2010-275388 A, JP 2010-222586, JP2010-0 4144, JP 2011-107199, JP 2011-236416, it is also possible to use a photobase generator described in the literature such as JP-2011-080032.

  The said photobase generator may be used individually by 1 type, and may be used in combination of 2 or more type. The compounding amount of the photobase generator in the thermosetting resin composition is preferably 1 to 50 parts by mass, and more preferably 1 to 40 parts by mass with respect to 100 parts by mass of the thermoreactive compound. When the amount is less than 1 part by mass, development may be difficult, which is not preferable.

[Maleimide compound]
The thermosetting resin composition may include a maleimide compound.
Examples of maleimide compounds include polyfunctional aliphatic / alicyclic maleimides and polyfunctional aromatic maleimides. Bifunctional or higher maleimide compounds (polyfunctional maleimide compounds) are preferred. Examples of the polyfunctional aliphatic / alicyclic maleimide include N, N′-methylene bismaleimide, N, N′-ethylene bismaleimide, tris (hydroxyethyl) isocyanurate, and aliphatic / alicyclic maleimide carboxylic acid. Isocyanurate skeleton maleic ester compound obtained by urethanizing isocyanurate skeleton maleimide ester compound obtained by urethanization of tris (carbamate hexyl) isocyanurate and aliphatic / alicyclic maleimide alcohol Maleimides; isophorone bisurethane bis (N-ethylmaleimide), triethylene glycol bis (maleimidoethyl carbonate), aliphatic / alicyclic maleimide carboxylic acid and various aliphatic / alicyclic polyols dehydrated or esterified / Alicyclic maleimide carboxylic acid esters and aliphatic / alicyclic polymaleimide ester compounds obtained by transesterification of various aliphatic / alicyclic polyols; aliphatic / alicyclic maleimide carboxylic acids and various fats Aliphatic / alicyclic polymaleimide ester compounds obtained by ether ring-opening reaction of aliphatic / alicyclic polyepoxides; urethanization of aliphatic / alicyclic maleimide alcohols and various aliphatic / alicyclic polyisocyanates Examples include aliphatic / alicyclic polymaleimide urethane compounds obtained by reaction.

  As polyfunctional aromatic maleimide, aromatic polymaleimide ester compounds obtained by dehydrating esterification of maleimide carboxylic acid and various aromatic polyols, or transesterification reaction of maleimide carboxylic acid ester and various aromatic polyols; Aromatic polymaleimide ester compounds obtained by ether ring-opening reaction of carboxylic acid and various aromatic polyepoxides; Aromatic polymaleimide urethane compounds obtained by urethanization reaction of maleimide alcohol and various aromatic polyisocyanates, etc. And aromatic polyfunctional maleimides.

  Specific examples of the polyfunctional aromatic maleimide include, for example, N, N ′-(4,4′-diphenylmethane) bismaleimide, N, N′-2,4-tolylene bismaleimide, N, N′-2, 6-tolylene bismaleimide, 1-methyl-2,4-bismaleimide benzene, N, N′-m-phenylene bismaleimide, N, N′-p-phenylene bismaleimide, N, N′-m-toluylene Bismaleimide, N, N′-4,4′-biphenylenebismaleimide, N, N′-4,4 ′-[3,3′-dimethyl-biphenylene] bismaleimide, N, N′-4,4′- [3,3′-dimethyldiphenylmethane] bismaleimide, N, N′-4,4 ′-[3,3′-diethyldiphenylmethane] bismaleimide, N, N′-4,4′-diphenylmethane bismale N, N′-4,4′-diphenylpropane bismaleimide, N, N′-4,4′-diphenyl ether bismaleimide, N, N′-3,3′-diphenylsulfone bismaleimide, N, N ′ -4,4'-diphenylsulfone bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-t-butyl-4- (4-maleimidophenoxy) phenyl ] Propane, 2,2-bis [3-s-butyl-4- (4-maleimidophenoxy) phenyl] propane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] decane, 1,1-bis [2-Methyl-4- (4-maleimidophenoxy) -5-t-butylphenyl] -2-methylpropane, 4,4′-cyclohexylidene-bis [1- (4 Maleimidophenoxy) -2- (1,1-dimethylethyl) benzene], 4,4′-methylene-bis [1- (4-maleimidophenoxy) -2,6-bis (1,1-dimethylethyl) benzene] 4,4′-methylene-bis [1- (4-maleimidophenoxy) -2,6-di-s-butylbenzene], 4,4′-cyclohexylidene-bis [1- (4-maleimidophenoxy) -2-cyclohexylbenzene, 4,4′-methylenebis [1- (maleimidophenoxy) -2-nonylbenzene], 4,4 ′-(1-methylethylidene) -bis [1- (maleimidophenoxy) -2,6 -Bis (1,1-dimethylethyl) benzene], 4,4 '-(2-ethylhexylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4'-(1 -Methylheptylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4′-cyclohexylidene-bis [1- (maleimidophenoxy) -3-methylbenzene], 2,2-bis [4 -(4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-methyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4- Maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3,5-dimethyl-4- (4- Maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-ethyl-4- (4-maleimidophenoxy) phenyl] propa 2,2-bis [3-ethyl-4- (4-maleimidophenoxy) phenyl] hexafluoropropane, bis [3-methyl- (4-maleimidophenoxy) phenyl] methane, bis [3,5-dimethyl- ( 4-maleimidophenoxy) phenyl] methane, bis [3-ethyl- (4-maleimidophenoxy) phenyl] methane, 3,8-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo [5.2.1. 02,6] decane, 4,8-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo [5.2.1.02,6] decane, 3,9-bis [4- (4-maleimidophenoxy) ) Phenyl] -tricyclo [5.2.1.02,6] decane, 4,9-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo [5 2.1.02,6] decane, 1,8-bis [4- (4-maleimidophenoxy) phenyl] menthane, 1,8-bis [3-methyl-4- (4-maleimidophenoxy) phenyl] menthane, Examples include 1,8-bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] menthane.

  As a compounding quantity of a maleimide compound, it is preferable that equivalent ratio (alkali developable resin: maleimide compound) with alkali developable resin is 1: 0.5-1: 10. If it is out of such a mixing ratio, development may be difficult. The equivalent ratio is more preferably 1: 0.5 to 1: 5.

[Polymer resin]
The thermosetting resin composition can be blended with a conventionally known polymer resin for the purpose of improving the flexibility and dryness of the touch of the resulting cured product. Examples of the polymer resin include cellulose, polyester, phenoxy resin, polyvinyl acetal, polyvinyl butyral, polyamide, polyamideimide binder polymer, block copolymer, elastomer and the like. A binder polymer may be used individually by 1 type, and may use 2 or more types together.

  The addition amount of the polymer resin is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, and particularly preferably 5 to 30 parts by mass with respect to 100 parts by mass of the thermoreactive compound. When the amount of the polymer resin exceeds 50 parts by mass, there is a concern about deterioration of desmear resistance of the thermosetting resin composition, which is not preferable.

(Block copolymer)
The block copolymer is a copolymer having a molecular structure in which two or more kinds of polymers having different properties are connected by a covalent bond to form a long chain.

The block copolymer used in the present invention is preferably an ABA or ABA ′ type block copolymer. Among the ABA and ABA ′ type block copolymers, the central B is a soft block and has a low glass transition point Tg, preferably less than 0 ° C., both outer sides A or A ′. Is a hard block and has a high Tg, and is preferably composed of polymer units of 0 ° C. or higher. The glass transition point Tg is measured by differential scanning calorimetry (DSC).
Further, among the ABA and ABA 'type block copolymers, A or A' is composed of polymer units having a Tg of 50 ° C or higher, and B is a polymer unit having a Tg of -20 ° C or lower. More preferred is a block copolymer of
Of the ABA and ABA 'type block copolymers, A or A' is preferably highly compatible with the heat-reactive compound, and B is the heat-reactive compound. Those having low compatibility are preferred. Thus, it is considered that a specific structure in the matrix can be easily shown by using a block copolymer in which the blocks at both ends are compatible with the matrix and the central block is incompatible with the matrix.

  A or A 'preferably includes polymethyl (meth) acrylate (PMMA), polystyrene (PS) or the like, and B preferably includes poly n-butyl acrylate (PBA) or polybutadiene (PB). Further, a hydrophilic unit excellent in compatibility with the matrix described above represented by a styrene unit, a hydroxyl group-containing unit, a carboxyl group-containing unit, an epoxy-containing unit, an N-substituted acrylamide unit, etc. as part of the A or A ′ component It becomes possible to introduce and further improve the compatibility.

  The block copolymer used in the present invention is preferably a ternary or more block copolymer, and a block copolymer having a precisely controlled molecular structure synthesized by a living polymerization method is effective for obtaining the effects of the present invention. More preferred. This is considered to be because the block copolymer synthesized by the living polymerization method has a narrow molecular weight distribution, and the characteristics of each unit have been clarified. The molecular weight distribution (Mw / Mn) of the block copolymer used is preferably 3 or less, more preferably 2.5 or less, and still more preferably 2.0 or less.

（式中、ｎは２を表し、Ｚは、２価の有機基を表し、好ましくは、１，２−エタンジオキシ、１，３−プロパンジオキシ、１，４−ブタンジオキシ、１，６−ヘキサンジオキシ、１，３，５−トリス（２−エトキシ）シアヌル酸、ポリアミノアミン、例えばポリエチレンアミン、１，３，５−トリス（２−エチルアミノ）シアヌル酸、ポリチオキシ、ホスホネートまたはポリホスホネートの中から選択されるものである。Ａｒは２価のアリール基を表す。） The block copolymer containing the (meth) acrylate polymer block as described above is, for example, a method described in JP-A-2007-516326 and JP-A-2005-515281, particularly, the following formulas (1) to (4). After the Y unit is polymerized using the alkoxyamine compound represented by any of the above as an initiator, it can be suitably obtained by polymerizing the X unit.

Wherein n represents 2 and Z represents a divalent organic group, preferably 1,2-ethanedioxy, 1,3-propanedioxy, 1,4-butanedioxy, 1,6-hexanedi Selected from among oxy, 1,3,5-tris (2-ethoxy) cyanuric acid, polyaminoamines such as polyethyleneamine, 1,3,5-tris (2-ethylamino) cyanuric acid, polythioxy, phosphonate or polyphosphonate Ar represents a divalent aryl group.)

  The weight average molecular weight of the block copolymer is preferably in the range of 20,000 to 400,000, more preferably 50,000 to 300,000. When the weight average molecular weight is less than 20,000, the desired toughness and flexibility effects cannot be obtained, and when the thermosetting resin composition is formed into a dry film or applied to a substrate and temporarily dried. Inferior to tackiness. On the other hand, when the weight average molecular weight exceeds 400,000, the viscosity of the thermosetting resin composition becomes high, and the printability and processability may be remarkably deteriorated. When the weight average molecular weight is 50000 or more, an excellent effect is obtained in terms of relaxation against external impact.

(Elastomer)
An elastomer having a functional group can be added to the thermosetting resin composition. By adding an elastomer having a functional group, it is expected that the coating property is improved and the strength of the coating film is also improved. Further, polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyester amide elastomers, acrylic elastomers, olefin elastomers, and the like 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. Moreover, these elastomers may be used individually by 1 type, and may use 2 or more types together.

[Inorganic filler]
The thermosetting resin composition preferably contains an inorganic filler. The inorganic filler is used for suppressing the curing shrinkage of the cured product of the thermosetting resin composition and improving the properties such as adhesion and hardness. Examples of the inorganic filler include barium sulfate, amorphous silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, boron nitride, and Neuburg Examples include rich earth.

The average particle size (D50) of the inorganic filler is preferably 1 μm or less, more preferably 0.7 μm or less, and even more preferably 0.5 μm. When the average particle diameter exceeds 1 μm, the pattern layer may become cloudy, which is not preferable. The average particle diameter (D50) can be measured by a laser diffraction / scattering method. When the average particle diameter is in the above range, the refractive index is close to that of the resin component, the permeability is improved, and the generation efficiency of the base from the photobase generator by light irradiation is increased. The difference in refractive index between the inorganic filler and the alkali developable resin is preferably 0.3 or less. By setting the difference in refractive index to 0.3 or less, it is possible to suppress light scattering and obtain good deep-curing characteristics. Here, the refractive index of the inorganic filler is preferably 1.4 or more and 1.8 or less. In addition, the refractive index of an inorganic filler can be measured based on JISK7105.
The blending ratio of the inorganic filler is preferably 75% by mass or less, more preferably 0.1 to 60% by mass based on the total solid content of the thermosetting resin composition. When the blending ratio of the inorganic filler exceeds 75% by mass, the viscosity of the composition is increased, the applicability may be lowered, and the cured product of the thermosetting resin composition may be brittle.

[Organic solvent]
In the thermosetting resin composition, an organic solvent can be used for preparing the resin composition or adjusting the viscosity for application to a substrate or a carrier film.

  Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. Such an organic solvent may be used individually by 1 type, and may be used as a 2 or more types of mixture.

[Photopolymerizable monomer]
The thermosetting resin composition of the present invention may contain a photopolymerizable monomer as long as the effects of the present invention are not impaired.
Photopolymerizable monomers include alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate; hydroxyalkyl such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate (Meth) acrylates; mono- or di (meth) acrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, Polyhydric alcohols such as trishydroxyethyl isocyanurate or polyvalent (meth) acrylates of these ethylene oxide or propylene oxide adducts (Meth) acrylates of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol A; glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl (Meth) acrylates of glycidyl ether such as isocyanurate; and melamine (meth) acrylate.
The blending amount of the photopolymerizable monomer is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably based on the solid content excluding the solvent of the thermosetting resin composition. 15 mass% or less. When the blending amount of the photopolymerizable monomer exceeds 50% by mass, the curing shrinkage increases, so that the warpage may increase. When the photopolymerizable monomer is derived from (meth) acrylate, it contains an ester bond. In this case, since the ester bond is hydrolyzed by the desmear treatment, the electrical characteristics may be deteriorated.

(Other optional ingredients)
If necessary, the thermosetting resin composition may further contain components such as a mercapto compound, an adhesion promoter, a colorant, an antioxidant, and an ultraviolet absorber. As these, those known in the field of electronic materials can be used. In addition, the thermosetting resin composition includes a known and commonly used thickening agent such as finely divided silica, hydrotalcite, organic bentonite, and montmorillonite, an antifoaming agent such as silicone, fluorine, and polymer, and / or Known and commonly used additives such as a leveling agent, a silane coupling agent, and a rust preventive agent can be blended.
Moreover, you may mix | blend well-known and usual thermosetting resins, such as a block isocyanate compound, an amino resin, a benzoxazine resin, a carbodiimide resin, a cyclocarbonate compound, an episulfide resin, etc. as a thermosetting component.
Furthermore, by containing a phenol resin as the alkali-developable resin and an epoxy resin as the heat-reactive compound, a Tg can be increased, and a cured product having excellent HAST resistance can be obtained without depending on the softening point of the raw material. It can be set as a resin composition. In addition, a photopolymerizable monomer (a low molecular compound compounded to promote photocuring in a photocurable resin composition containing an ethylenically unsaturated group in the molecule and containing a carboxyl group-containing resin as a main component) When it is set as the composition which does not mix | blend, it can be set as the resin composition excellent in tackiness.
In the conventional photocurable resin composition, since the photocuring reaction occurs at room temperature, the Tg of the resin composition rises at the time of curing. As a result, the curing reaction may stop, and the Tg of the resin composition may be lowered. There was a need to design. On the other hand, the alkali development type thermosetting resin composition of the present invention is not limited to Tg before the curing reaction, and can be expected to have a high Tg. Further, the alkali development type thermosetting resin composition of the present invention can be expected to be cured without being inhibited by oxygen.

  The thermosetting resin composition is useful for forming a pattern layer of a printed wiring board, and is particularly useful as a material for a solder resist or an interlayer insulating layer.

[Method of manufacturing printed wiring board]
The method for producing a printed wiring board of the present invention includes a step (A) of forming a resin layer formed by applying and drying an alkali development type thermosetting resin composition containing a photobase generator on a substrate, and a pattern. A step (B) of activating the photobase generator contained in the alkali development type thermosetting resin composition by irradiation with a shaped light to cure the light irradiated portion, removing the unirradiated portion by alkali development, It includes a step (C) of forming a pattern layer of a mold and a step (D) of performing laser processing on the pattern layer.

By irradiating the resin layer with light in a pattern, the photobase generator in the resin layer of the light irradiation part is activated, and a basic substance is generated from the photobase generator. Then, the light irradiation part is cured by the generated basic substance. And by developing with alkaline aqueous solution, a negative pattern layer can be formed by removing an unirradiated part.
Here, in this invention, it is preferable to have the process (B1) of heating a resin layer after a process (B). Thereby, a resin layer can fully be hardened and the pattern layer excellent in the hardening characteristic can be obtained.

[Step (A)]
A process (A) is a process of forming the resin layer which consists of a thermosetting resin composition in a base material. The resin layer is formed by a method in which a liquid thermosetting resin composition is applied and dried on a substrate, or a method in which a thermosetting resin composition is formed into a dry film and laminated on the substrate. be able to.

As a method for applying the thermosetting resin composition to the substrate, a known method such as a blade coater, a lip coater, a comma coater, or a film coater can be appropriately employed. Also, the drying method is a method using a hot-air circulation type drying furnace, IR furnace, hot plate, convection oven, etc., equipped with a heat source of the heating method by steam, and the hot air in the dryer is counter-contacted and supported by the nozzle Known methods such as a method of spraying on the body can be applied.
As the substrate, in addition to a printed wiring substrate and a flexible printed wiring substrate in which a circuit is formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy Resin, glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminates of all grades (FR-4 etc.) using polyimide, polyethylene, PPO, cyanate ester, etc., polyimide film, A PET film, a glass substrate, a ceramic substrate, a wafer substrate and the like can be used.

[Step (B)]
Step (B) is a step of irradiating light in a negative pattern and activating the photobase generator contained in the thermosetting resin composition to cure the light irradiated portion. In the step (B), it is considered that the photobase generator is destabilized by the base generated in the light irradiation part, and further the base is generated. In this way, the base can be sufficiently cured to the deep part of the light irradiation part by chemically growing.
As the light irradiator used for light irradiation, a direct drawing device (for example, a laser direct imaging device that directly draws an image with a laser using CAD data from a computer), a light irradiator equipped with a metal halide lamp, and an (ultra) high pressure mercury lamp It is possible to use an on-board light irradiation machine, a light irradiation 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 patterned light irradiation mask, a negative mask can be used.

As the active energy ray, it is preferable to use laser light or scattered light having a maximum wavelength in the range of 350 to 410 nm. By setting the maximum wavelength within this range, the thermal reactivity of the thermosetting resin composition can be improved efficiently. If a laser beam in this range is used, either a gas laser or a solid laser may be used. Further, the irradiation amount varies depending the thickness or the like, generally 100~1500mJ / cm ^2, preferably be in the range of 300~1500mJ / 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. .

[Step (B1)]
In the step (B1), the light irradiation part is cured by heating. Step (B1) can be cured to a deep portion by the base generated in step (B).
The heating temperature is preferably a temperature at which the light-irradiated portion of the thermosetting resin composition is thermally cured, but the non-irradiated portion is not thermally cured.
For example, in the step (B1), the heat generation start temperature or the heat generation peak temperature of the unirradiated thermosetting resin composition is lower than the heat generation start temperature or the heat generation peak temperature of the light irradiated thermosetting resin composition. Heating at a high temperature is preferred. By heating in this way, only the light irradiation part can be selectively cured.
Here, the heating temperature is, for example, 80 to 140 ° C. By setting the heating temperature to 80 ° C. or higher, the light irradiation part can be sufficiently cured. On the other hand, by setting the heating temperature to 140 ° C. or lower, only the light irradiation part can be selectively cured. The heating time is, for example, 10 to 100 minutes. The heating method is the same as the drying method.
In the unirradiated portion, no base is generated from the photobase generator, so that thermosetting is suppressed.

[Step (C)]
Step (C) is a step of forming a negative pattern layer by removing unirradiated portions by development. As a developing method, a known method such as a dipping method, a shower method, a spray method, or a brush method can be used. Developers include potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines such as ethanolamine, and alkalis such as tetramethylammonium hydroxide aqueous solution (TMAH). An aqueous solution or a mixed solution thereof can be used.

[Step (D)]
Step (D) is a step of performing laser processing on the pattern layer. Thereby, a fine opening can be formed. As the laser, a known laser such as a YAG laser, a CO2 laser, or an excimer laser can be used.
The step (D) is preferably performed after the step (C) or after the step (F) when the following step (F) is included.

[Step (E)]
The method for producing a printed wiring board of the present invention preferably further includes an ultraviolet irradiation step (E) after the step (C).
In the step (E), the photobase generator remaining without being activated at the time of light irradiation in the step (B) is activated to sufficiently generate a base.
The wavelength of ultraviolet rays and the irradiation amount (irradiation amount) in the step (E) may be the same as or different from those in the step (B). The irradiation amount (irradiation amount) is, for example, 150 to 2000 mJ / cm ² .

[Step (F)]
The method for producing a printed wiring board of the present invention preferably further includes a thermosetting (post-cure) step (F) after the step (C).
In the step (F), the pattern layer is sufficiently heat-cured by the step (B) or the base generated from the photobase generator in the step (B) and the step (E). Since the unirradiated portion has already been removed at the time of the step (F), the step (F) is performed at a temperature equal to or higher than the heat generation start temperature or the heat generation peak temperature in the DSC measurement of the unirradiated thermosetting resin composition. be able to. Thereby, a pattern layer can fully be thermosetted. The heating temperature is, for example, 160 ° C. or higher.

[Step (G)]
The pattern forming method of the present invention preferably further includes a desmear process (G) after the process (D).
Step (G) includes a smear swelling step for swelling smear to facilitate removal, a removal step for removing smear, and a neutralization step for neutralizing sludge generated from the desmear liquid used in the removal step.
The swelling step is performed using an alkali chemical such as sodium hydroxide, and facilitates smear removal with a desmear chemical.
In the removing step, smear is removed using an acidic chemical solution containing an oxidizing agent such as dichromic acid or permanganic acid.
In the neutralization step, the oxidizing agent used in the removal step is reduced and removed using an alkaline chemical such as sodium hydroxide.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples.

(Example 1 and Comparative Example 1)
<Preparation of thermosetting resin composition>
Each material was blended according to the formulation shown in Table 1 below, premixed with a stirrer, and then kneaded with a three-roll mill to prepare a thermosetting resin composition. The values in the table are parts by mass unless otherwise specified.

<Preparation of a printed wiring board provided with a resin layer>
A double-sided printed wiring substrate having a copper thickness of 15 μm and a circuit formed thereon having a thickness of 0.4 mm was prepared, and pretreated using MEC CZ-8100. Thereafter, using a roll coater (Furness Co., Ltd.), the thermosetting resin composition was applied to the pre-treated printed wiring board so as to have a thickness of 20 μm after drying. Then, it dried at 90 degreeC / 30min with the hot air circulation type drying furnace, and formed the resin layer which consists of a thermosetting resin composition.

<Preparation of substrate for evaluation of developability and curing characteristics>
(Evaluation of alkali developability / patterning)
The base material provided with the resin layer obtained above was irradiated with a negative pattern with ORC HMW680GW (metal halide lamp, scattered light). The irradiation amount was set as described in Table 2 below with reference to the exothermic peak temperature by DSC. Subsequently, it heated for 70 minutes on the temperature conditions of Table 2. Thereafter, the substrate was immersed in a 3 wt% TMAH / 5 wt% ethanolamine mixed aqueous solution at 35 ° C. and developed for 3 minutes to obtain a pattern layer. The developability and patterning of the pattern layer were evaluated according to the following criteria. The obtained results are shown in Table 2 below.
○: No damage from the developer on the surface of the light-irradiated part, and no development residue is observed in the non-irradiated part ×: Development residue was confirmed in the unirradiated part Alternatively, the unexposed area could not be developed.
XX: A state where both the light irradiated part and the unirradiated part are completely dissolved.

(Laser processability)
The base material on which the developability (patterning) was evaluated was further irradiated with ultraviolet rays at an energy amount of 1 J / cm ² using an ORC ultraviolet irradiation device, and then cured at 170 ° C. for 60 minutes in a hot air circulation drying oven. (Post cure).
Then, laser processing was performed on the light irradiation surface. The light source was processed with a CO 2 laser (Hitachi Via Mechanics, light source 10.6 μm). Evaluation was made according to the following criteria. In order to give superiority or inferiority in workability, laser processing was performed under the same conditions.
The target of the processing diameter is a top diameter of 65 μm / bottom of 50 μm.
Condition: Aperture (mask diameter): 3.1 mm / pulse width 20 μsec / output 2 W / frequency 5 kHz / number of shots: burst 3 shots ○: difference from target processing diameter is less than ± 2 μm ×: difference from target processing diameter is ± 2μm or more

(Desmear resistance)
About the base material which performed the said laser processing, the desmear process was further performed with the permanganate desmear aqueous solution (wet method). As evaluation of desmear resistance, confirmation of the surface roughness of the substrate surface and the state around the laser opening were evaluated according to the following criteria. For confirmation of the surface roughness, each surface roughness Ra was measured by a laser microscope VK-8500 (Keyence Corporation, measurement magnification 2000 times, Z-axis direction measurement pitch 10 nm). The laser aperture was observed with an optical microscope.
About chemicals (Rohm & Haas)
Swelling MLB-211 Temperature 80 ° C / hour 10min
Permanganic acid MLB-213 Temperature 80 ℃ / hour 15min
Reduction MLB-216 Temperature 50 ° C / hour 5min
Evaluation method A: Surface roughness Ra after permanganate desmear is less than 0.1 μm, and the difference from the processed diameter after laser processing is 2 μm or less ○: Surface roughness Ra after permanganate desmear is 0.1 ~ 0.3μm or less, and the difference from the processed diameter after laser processing is 2-5μm
×: Surface roughness Ra after permanganate desmear exceeds 0.3 μm and the difference from the processed diameter after laser processing is 5 μm or more

<DSC measurement>
(DSC measurement immediately after light irradiation)
After irradiating the resin layer on the base material in a pattern at 1000 mJ / cm ² , the light irradiated part and the non-irradiated part were shaved from the base material, and immediately at a Seiko Instruments DSC-6200, the temperature rising rate was 5 ° C. / The temperature was raised to 30 to 300 ° C. in min, and DSC measurement was performed for each of the light irradiated part and the non-irradiated part. The exothermic peak temperature was determined from the obtained DSC chart.

(DSC measurement immediately after UV irradiation)
After the pattern layer on the substrate was irradiated with ultraviolet rays at 1000 mJ / cm ² , the pattern layer was shaved off from the substrate, and immediately, at Seiko Instruments DSC-6200, the temperature increased from 30 ° C. to 300 ° C. at a rate of 5 ° C./min. After raising the temperature, DSC measurement was performed for light irradiation. The exothermic peak temperature was determined from the obtained DSC chart.
Figure 1 is a non-irradiated portion, the light irradiation section irradiating light at 1000 mJ / cm ^2, a DSC chart of the ultraviolet radiation pattern layer 1000 mJ / cm ^2.
In the light irradiation part of Example 1, the peak shifted to the low temperature side by light irradiation.
It can also be seen that the heat curing reaction proceeds more efficiently in the pattern layer immediately after the ultraviolet irradiation because the calorific value increased.

From the DSC chart obtained by the above method, the exothermic peak temperature T peak 1 of the light-irradiated portion and the exothermic peak temperature of the non-irradiated portion were defined as T peak 2 and ΔT peak was defined as follows.
ΔT peak = T peak 2−T peak 1
From the above definition, when ΔT peak is positive (positive value), it indicates that the exothermic peak of the light irradiation part is shifted to the low temperature side, and the photobase generator is activated by light irradiation. I express that.

※１：光照射部の発熱ピーク温度
※２：未照射部の発熱ピーク温度
※３：Ｔ ｐｅａｋ ２−Ｔ ｐｅａｋ １

* 1: Exothermic peak temperature of the light-irradiated part * 2: Exothermic peak temperature of the non-irradiated part * 3: T peak 2-T peak 1

  It turned out that a pattern layer can be easily formed by irradiating the resin layer which consists of a thermosetting resin composition of Example 1 with a negative type, and also developing. It was also found that the pattern layer of Example 1 had excellent curing characteristics and laser processability.

(Comparative Example 2)
A double-sided printed wiring substrate having a copper thickness of 15 μm and a circuit formed thereon having a thickness of 0.4 mm was prepared, and pretreated using MEC CZ-8100. Thereafter, a product name PSR-4000G23K (Taiyo Ink Manufacturing Co., Ltd., a photocurable resin composition containing an alkali-developable resin having an epoxy acrylate structure) was applied by screen printing so that it would be 20 μm after drying. I did it. Next, after drying at 80 ° C./30 min in a hot air circulating drying oven, the film was irradiated with a negative pattern at an irradiation amount of 300 mJ / cm 2 with ORC HMW680GW (metal halide lamp, scattered light). Thereafter, development was performed with a 1 wt% sodium carbonate aqueous solution for 60 seconds, followed by heat treatment at 150 ° C./60 min using a hot-air circulating drying oven to obtain a patterned cured coating film.
Thereafter, laser processability and desmear resistance were evaluated in the same manner as in Example 1. As a result, the laser processability was “◯”, but the desmear resistance was “x”.

Claims (2)

Step (A) of forming a resin layer formed by applying and drying an alkali development type thermosetting resin composition containing a photobase generator on a substrate, and heating the alkali development type heat by pattern light irradiation Activating the photobase generator contained in the curable resin composition to cure the light-irradiated part (B), curing the light-irradiated part to the deep part by heating (B1), alkali-developing the unirradiated part It is removed to form a patterned layer of negative type (C), and the pattern layer and the same layer, or printing including the step (D) to form the facilities and opening the laser processing in a separate layer A method of manufacturing a wiring board,
Wherein comprises an alkali developing type thermosetting resin composition of the alkali-developable resin and thermally reactive compound, characterized in that the alkali developable resin is an alkali developable resin having no epoxy acrylate structure method for producing a print circuit board. Further, a method for manufacturing a printed wiring board according to claim 1, characterized in that it comprises a desmear process.

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