JP2018036651A - Alkali development type thermosetting resin composition and printed wiring board - Google Patents

Abstract

An alkali development type thermosetting resin composition capable of forming a pattern by development and a printed wiring board are provided. At least one selected from a black colorant, a white colorant and a yellow colorant, comprising an alkali-developable resin, a heat-reactive compound, a photobase generator, and a colorant. An alkali developing type characterized in that a negative pattern can be formed by alkali development by an addition reaction between the alkali developing resin and the thermally reactive compound by heating after selective light irradiation. Thermosetting resin composition. [Selection figure] None

Description

  The present invention relates to an alkali development type thermosetting resin composition and a printed wiring board.

Conventionally, as a material used for a solder resist of a printed wiring board, there is a photocurable resin composition that can be developed with an alkaline aqueous solution. For example, Patent Documents 1 and 2 use a photocurable resin composition 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.

  On the other hand, Patent Document 3 discloses a composition in which desmear resistance is improved by not including a thermosetting resin having a secondary hydroxyl group. In this composition, a solder resist is formed by, for example, screen printing.

JP 61-243869 (Claims) Japanese Patent Laid-Open No. 3-250012 (Claims) JP 2004-240233 A (Claims)

  However, in the thermosetting resin composition as in Patent Document 3, the light irradiation part cannot be selectively cured by light irradiation as in the photocurable resin composition, so that the pattern layer can be formed by development. Can not. Accordingly, there is a problem that the formation of the pattern layer of the thermosetting resin composition is limited to a printing method such as screen printing or formation by laser processing.

  Accordingly, an object of the present invention is to provide an alkali development type thermosetting resin composition and a printed wiring board capable of forming a pattern by development.

  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 alkali-developable thermosetting resin composition of the present invention includes an alkali-developable resin, a heat-reactive compound, a photobase generator, and a colorant, and the colorant is a black colorant, white A negative pattern by alkali development, which is at least one selected from a colorant and a yellow colorant, and the alkali-developable resin and the heat-reactive compound undergo an addition reaction by heating after selective light irradiation. It can be formed.

  The alkali development type thermosetting resin composition of the present invention preferably contains no (meth) acrylate-derived photopolymerizable monomer.

Further, the cured product of the present invention is characterized by curing the above alkali development type thermosetting resin composition.
Furthermore, the printed wiring board of the present invention is characterized by having the above cured product.

  According to the present invention, an alkali development type thermosetting resin composition and a printed wiring board capable of forming a pattern layer by development can be provided. Moreover, since the pattern layer of this invention consists of thermosetting resins, it can be anticipated that it is excellent in curability and suppresses curing shrinkage.

FIG. 1 is a diagram showing a DSC chart of a light irradiated part or an unirradiated part of a layer made of the thermosetting resin composition of Example 1 of the present invention. FIG. 2 is a diagram showing a DSC chart of the light irradiated portion or the non-irradiated portion of the layer made of the thermosetting resin composition of Example 9 of the present invention. FIG. 3 is a diagram showing a DSC chart of the light irradiated portion or the non-irradiated portion of the layer made of the thermosetting resin composition of Example 32 of the present invention. FIG. 4 is a diagram showing a DSC chart for the light irradiated portion or the non-irradiated portion of the layer made of the thermosetting resin composition of Example 36 of the present invention. FIG. 5 is a diagram showing a DSC chart of a light irradiated part or an unirradiated part of a layer made of the thermosetting resin composition of Example 50 of the present invention. FIG. 6 is a schematic view showing a method for forming a pattern layer of the present invention. FIG. 7 is a diagram showing an example of a pattern forming method using the alkali development type thermosetting resin composition of the present invention.

The alkali developing type thermosetting resin composition of the present invention (hereinafter sometimes abbreviated as “thermosetting resin composition”) includes an alkali developing resin, a thermoreactive compound, and a photobase generator. In addition, a negative pattern can be formed by alkali development by an addition reaction between the alkali-developable resin and the heat-reactive compound by selective light irradiation. Here, pattern formation means forming a patterned cured product, that is, a pattern layer.
In the resin layer made of this 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 the thermosetting resin composition is irradiated with light in a pattern, the pattern can be formed by removing the unirradiated portion by alkali development.
Moreover, since the thermosetting resin composition of the present invention cures by an addition reaction between an alkali-developable resin and a thermoreactive compound, it does not proceed to a photo-chain reaction like a photocurable resin composition, so that distortion and curing A pattern layer with little shrinkage can be obtained.
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.

The thermosetting resin composition of the present invention generates a heat generation peak in DSC measurement by light irradiation, or the heat generation start temperature in DSC measurement of the light-cured thermosetting resin composition is an unirradiated thermosetting resin. 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 that is lower than the exothermic start temperature in the DSC measurement of the composition or is irradiated with light. Is also preferably low.
In addition, the thermosetting resin composition of the present invention is also referred to as a temperature difference (ΔT start) of the heat generation starting temperature in DSC measurement between the light-irradiated thermosetting resin composition and the non-irradiated thermosetting resin composition. ) Or the exothermic peak temperature difference (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 light irradiation amount in DSC measurement of the thermosetting resin composition irradiated with light increases the light irradiation amount, and the shift of the exothermic peak temperature due to the light irradiation of the thermosetting resin composition does not occur (saturation). Irradiation amount.
When ΔT start or ΔT peak is 10 ° C. or higher, 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 is suppressed. be able to. Further, when ΔT start or ΔT peak is 10 ° C. or more, it is possible to widen the range of heating temperatures that can be taken in the heating step (B1) described later.

  Hereinafter, each component of the thermosetting resin composition will be described in detail.

[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 polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A 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. .

  (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 carboxyl group-containing resin obtained by reacting with 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 tris. Thioglycolate, 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 and hydrogen sulfide, reaction of polythiol compound and epoxy compound Thiol compounds, and the like with terminal thiol groups to be.

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, development can be performed with a weak alkaline aqueous solution as compared with the case of a phenolic resin. Examples of the weak alkaline aqueous solution include a solution in which sodium carbonate or the like is dissolved. By developing with weak alkaline aqueous solution, it can suppress that a light irradiation part will be developed. Moreover, the light irradiation time in the following process (B) and the heating time in the 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. A naphthalene group-containing epoxy resin is preferable because it can suppress the thermal expansion of the cured product.

The epoxy resin preferably has an epoxy equivalent of 200 or more. When the epoxy equivalent is 200 or more, the warp of the cured film is suppressed, and the developability is excellent even when left under high humidity for a long time.
As an epoxy resin having an epoxy equivalent of 200 or more, DIC Corporation HP-4770 (naphthalene type, equivalent 205 g / eq), HP-7200 (dicyclopentadiene skeleton-containing novolak epoxy, 255 g / eq) EXA-4850-150 ( Soft epoxy containing liquid epoxy, 440 g / eq) EXA-4850-1000 (340 g / eq), HP-820 (aralkylphenol epoxy, 225 g / eq), Nippon Kayaku Co., Ltd. EOCN-104S (cresol novolak epoxy, 210 g / eq), NC-7000 (Naphthalene skeleton-containing novolak epoxy, 230 g / eq), Osaka Gas Chemical Co., Ltd. PG-100 (fluorene skeleton-containing epoxy, 250 g / eq), EG-200 (flexible epoxy, 292 g / eq) , Mitsubishi Chemical Corporation Bis-A type linear epoxy such as 1001 (475 g / eq), 1002 (650 g / eq), Bis-F type linear epoxy such as 4004P (900 g / eq), 4005P (1075 g / eq), 157S70 (Bis- A novolac epoxy, 210 g / eq), Nippon Steel & Sumikin Chemical Co., Ltd. ESN-475V (naphthol aralkyl type, 325 g / eq),
Biphenyl aralkyl type epoxy resin (Nippon Kayaku Co., Ltd., NC3000: Epoxy equivalent = 275 g / eq), Biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. NC-3000H: Epoxy equivalent = 215 g / eq), softening point 69.2 ° C.), phenol aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000H: epoxy equivalent = 289 g / eq), phenol biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000) -FH, epoxy equivalent: 320 g / eq.), NC-2000L (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 238 g / eq, NC-3100 (manufactured by Nippon Kayaku, epoxy equivalent 258 g / eq.), NC- 3000S (Nippon Kayaku Co., Ltd., epoxy equivalent 284 g / eq), NC-3000S-H (Nippon Kayaku Co., Ltd.) , Epoxy equivalent 290 g / eq) and the like.
The compounding amount of the epoxy resin having an epoxy equivalent of 200 or more can be the same as the compounding amount of the thermosetting component.

  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.

  The blending amount of the heat-reactive compound is preferably such that the equivalent ratio to the alkali-developable resin (heat-reactive group: alkali-developable group) is 1: 0.1 to 1:10, and 1: 0 More preferably, it is 2 to 1: 5. When the ratio is within such a range, the development is good.

[Photobase generator]
One or more photobase generators can function as a catalyst for the addition reaction of the above-mentioned thermoreactive compound when the molecular structure is changed by irradiation with light such as ultraviolet rays or visible light, or when the molecule is cleaved. 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.

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,
It is represented by 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.

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-anthrylmethylN, N'-diethylcarbamate), WPBG-027 (Product name: (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine), WPBG-082 ( Trade names: 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 JP 2007-86763 A, JP 2007-231235 A, JP 2008-3581 A, JP 2008-3582 A, JP 2009-280785 A, JP 2009-080452, JP 2010-. No. 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. Publication, JP2010-222586A JP 2010-084144, 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 of the present invention may contain 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 (maleimide group: alkali developable group) with alkali-developable resin is 1: 0.1-1: 10, and 1: 0.2-1: 5. It is more preferable that With such a blending ratio, development is facilitated.

[Colorant]
Furthermore, a coloring agent can be mix | blended with the thermosetting resin composition of this invention.
Conventionally, at the edge of a copper circuit on a printed wiring board, if the coloring power of the pattern layer is insufficient, the copper color changes in the thermal history after the pattern layer is formed, and only the thin part appears to change in appearance. It was. Typical thermal history includes marking thermosetting, warping, preheating before mounting, mounting, and the like.
For this reason, conventionally, a problem has been solved that only the edge portion of the copper circuit looks discolored by adding a large amount of colorant to the pattern layer to enhance the coloring power.
However, since the colorant has light absorptivity, it prevents light from penetrating to the deep part. As a result, in the composition containing a colorant, undercut is likely to occur, and there is a problem that sufficient adhesion cannot be obtained.
On the other hand, in the thermosetting resin composition of the present invention, as described above, the base can be sufficiently cured to the deep part of the resin layer by chemically growing the base to the deep part.
Therefore, in the thermosetting resin composition of the present invention, even when a colorant is contained, a pattern layer having excellent copper circuit concealing property and excellent adhesion can be formed.
Further, in the present invention, even when the content of the colorant is increased, undercuts can be suppressed and good via holes and lines can be formed.

  As the colorant, conventionally known colorants such as red, blue, green, yellow, white, and black can be used, and any of pigments, dyes, and pigments may be used. Specific examples include those with the following color index numbers (CI: issued by The Society of Dyer's and Colorists). However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.

Red colorant:
Examples of red colorants include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. It is done.
Monoazo: PigmentRed 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: PigmentRed 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: SolventRed 135, Solvent Red 179, PigmentRed 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 systems: PigmentRed 220, Pigment Red 144, PigmentRed 166, Pigment Red 214, PigmentRed 220, Pigment Red 221, and PigmentRed 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: PigmentRed 122, Pigment Red 202, PigmentRed 206, Pigment Red 207, PigmentRed 209.

Blue colorant:
Examples of blue colorants include phthalocyanine and anthraquinone, and pigments include compounds classified as Pigments, specifically, PigmentBlue 15 and Pigment Blue 15: 1, PigmentBlue 15: 2, Pigment Blue 15: 3, PigmentBlue 15: 4, Pigment Blue 15: 6, PigmentBlue 16, and Pigment Blue 60.
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. are used as the dye system. be able to. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
Of the blue colorants, phthalocyanine is preferable because it is excellent in laser processability.

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 type: PigmentYellow 93, Pigment Yellow 94, PigmentYellow 95, Pigment Yellow 128, PigmentYellow 155, Pigment Yellow 166, PigmentYellow 180.
Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.
Monoazo: PigmentYellow 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 series: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152,170, 172, 174,176, 188, 198.

White colorant:
In the present invention, a white colorant can also be used as the (B) colorant. Examples of the white colorant include titanium oxide. Titanium oxide may be rutile titanium oxide or anatase titanium oxide, but rutile titanium is preferably used. Anatase-type titanium oxide, which is the same titanium oxide, has higher whiteness compared to rutile-type titanium oxide and is often used as a white pigment. The emitted light may cause discoloration of the resin in the insulating resin composition. In contrast, rutile-type titanium oxide is slightly inferior to anatase-type in whiteness, but has almost no photoactivity, so that the resin is deteriorated by light due to the photoactivity of titanium oxide (yellowing). Is remarkably suppressed and is stable against heat. For this reason, when it is used as a white pigment in the insulating layer of the printed wiring board on which the LED is mounted, a high reflectance can be maintained over a long period of time.

  A well-known thing can be used as a rutile type titanium oxide. There are two types of production methods for rutile titanium oxide, a sulfuric acid method and a chlorine method. In the present invention, those produced by any of the production methods can be suitably used. Here, the sulfuric acid method uses ilmenite ore or titanium slag as a raw material, dissolves this in concentrated sulfuric acid, separates iron as iron sulfate, and hydrolyzes the solution to obtain a hydroxide precipitate. A production method in which rutile titanium oxide is taken out by baking at a high temperature. On the other hand, the chlorine method uses synthetic rutile or natural rutile as a raw material, reacts with chlorine gas and carbon at a high temperature of about 1000 ° C to synthesize titanium tetrachloride, and oxidizes this to extract rutile titanium oxide. Say. Among them, rutile-type titanium oxide produced by the chlorine method is particularly effective in suppressing the deterioration (yellowing) of the resin due to heat, and is more preferably used in the present invention.

Among these titanium oxides, it is particularly preferable to use titanium oxide whose surface is treated with hydrous alumina or aluminum hydroxide from the viewpoints of dispersibility in the composition, storage stability, and flame retardancy.
Moreover, it is preferable that the Y value is 70 or more, and, as for the cured coating film formed with the composition containing a titanium oxide, it is more preferable that it is 75 or more.

Black colorant:
As the black colorant used in the present invention, a known and commonly used black colorant can be used. Examples of black colorants include carbon black pigments such as CIPigmentblack 6, 7, 9 and 18; graphite pigments such as CIPigment black 8, 10 and the like; CIPigmentblack 11, 12 and 27; Pigment Brown 35 and the like. Iron oxide pigments: For example, iron oxide of KN-370 manufactured by Toda Kogyo Co., Ltd., 13M titanium black manufactured by Mitsubishi Materials Co., Ltd., an anthraquinone pigment represented by CIPigmentblack 20, etc., CIPigment black 13, 25 and 29 Cobalt oxide pigments such as CIPigmentblack 15 and 28, etc., manganese pigments such as CIPigment black 14 and 26, antimony oxide pigments such as CIPigmentblack 23, CIPigment Nickel oxide pigment represented by black 30 etc., perylene pigment represented by CI Pigment black 31, 32, PigmentBlac Examples of suitable pigments include aniline pigments represented by k1, molybdenum sulfide and bismuth sulfide. These pigments are used alone or in appropriate combination. Particularly preferred is carbon black. For example, carbon black, M-40, M-45, M-50, MA-8, MA-100 manufactured by Mitsubishi Chemical Corporation, and perylene pigments are organic pigments. Among these, it is effective for reducing halogen.
Carbon black is preferable because it is excellent in circuit concealment.

In addition, a colorant such as purple, orange or brown may be added for the purpose of adjusting the color tone.
For example, 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 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 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 and the like.

It is preferable that the compounding quantity of the coloring agent in the thermosetting resin composition of this invention shall be 0.1-10 mass parts with respect to 100 mass parts of said thermoreactive compounds. More preferably, it is 0.8-10 mass parts, More preferably, it is 1-5 mass parts.
In addition, when a colorant is white, it is preferable that the compounding quantity of a white colorant shall be 20 mass parts or more and 70 mass parts or less with respect to 100 mass parts of said thermoreactive compounds, More preferably, it is 20 mass parts. The amount is 60 parts by mass or less.

[Polymer resin]
In the thermosetting resin composition of the present invention, a conventionally known polymer resin can be blended for the purpose of improving the flexibility and dryness of the touch of the resulting cured product. Examples of the polymer resin include cellulose-based, polyester-based, phenoxy-resin-based, polyvinyl acetal-based, polyvinyl butyral-based, polyamide-based, polyamide-imide-based binder polymers, block copolymers, elastomers, and rubber particles. A binder polymer may be used individually by 1 type, and may use 2 or more types together.
By blending the polymer resin, the melt viscosity of the thermosetting resin composition is increased, and the fluidity of the resin in the through-hole portion can be suppressed during post-exposure heating. As a result, a flat substrate that is not recessed on the through hole can be manufactured.

  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, those in which A or A ′ is highly compatible with the heat-reactive compound are preferable, and B is the above-mentioned 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.

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 intended 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.
As a polymer resin, a block copolymer is preferable because it is excellent in crack resistance during a thermal cycle and can suppress warping after curing. The block copolymer is particularly preferable because it can suppress a dent on the through hole and form a substrate having a flat surface. Moreover, it is excellent in the crack tolerance at the time of a thermal cycle by combining an inorganic filler.

(Elastomer)
An elastomer having a functional group can be added to the thermosetting resin composition of the present invention. 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.

(Rubber particles)
The rubber particles may be any particles as long as they are formed from organic substances such as polymers having a crosslinked structure. For example, as a copolymer of acrylonitrile butadiene, a crosslinked acrylonitrile and butadiene are copolymerized. NBR particles: Copolymerized acrylonitrile, butadiene and carboxylic acid such as acrylic acid; cross-linked polybutadiene, cross-linked silicon rubber, or cross-linked rubber particles having a so-called core-shell structure using NBR as a core layer and cross-linked acrylic resin as a shell layer (Also referred to as “core-shell rubber particles”).
Among these, from the viewpoint of dispersibility control and particle size stability, a core-shell structured crosslinked rubber particle is preferable. Particles are more preferred.
The cross-linked NBR particles are particles obtained by partially cross-linking at the stage of copolymerizing and copolymerizing acrylonitrile and butadiene. It is also possible to obtain carboxylic acid-modified crosslinked NBR particles by copolymerizing together carboxylic acids such as acrylic acid and methacrylic acid.
Cross-linked butadiene rubber-cross-linked acrylic resin core-shell rubber particles can be obtained by a two-stage polymerization method in which butadiene particles are polymerized by emulsion polymerization, followed by addition of monomers such as acrylic acid ester and acrylic acid. .
Cross-linked silicone rubber-cross-linked acrylic resin core-shell rubber particles can be obtained by a two-stage polymerization method in which silicon particles are polymerized by emulsion polymerization, followed by addition of monomers such as acrylic acid ester and acrylic acid. .
The size of the rubber particles is 1 μm or less in terms of primary average particle diameter, and is preferably 50 nm to 1 μm. If the primary average particle diameter exceeds 1 μm, the adhesive strength is lowered and the insulation reliability in fine wiring is impaired. The “primary average particle diameter” here refers to the aggregated particle diameter, that is, the secondary particle diameter, not the aggregated single particle diameter.
The primary average particle diameter can be determined by measuring with a laser diffraction particle size distribution meter, for example.
The rubber particles as described above may be used alone or in combination of two or more.
The content of the rubber particles is preferably 50% by mass or less and more preferably 1 to 30% by mass in the resin composition.
For example, as a commercially available product of carboxylic acid-modified acrylonitrile butadiene rubber particles, XER-91 manufactured by Nippon Synthetic Rubber Co., Ltd. may be mentioned. Examples of the core-shell particles of butadiene rubber-acrylic resin include Paraloid EXL2655 manufactured by Rohm and Haas Co., Ltd. and AC-3832 manufactured by Gantz Kasei Kogyo Co., Ltd. Examples of the core-shell rubber particles of the crosslinked silicone rubber-acrylic resin include GENIOPERLP52 manufactured by Asahi Kasei Wacker Silicone Co., Ltd.
By using rubber particles, it is possible to improve the crack resistance during the cooling and heating cycle.

[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. Although the lower limit of the average particle diameter (D50) of the inorganic filler is not particularly limited, it is, for example, 0.01 μm or more. Here, the average particle diameter (D50) means an average primary particle diameter.
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 curability. 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 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 80% by mass or less based on the total solid content of the thermosetting resin composition. When the blending ratio of the inorganic filler exceeds 80% by mass, the viscosity of the composition increases, and the applicability may decrease or the cured product of the thermosetting resin composition may become brittle.
In a composition in which curing proceeds due to radical reaction, when the content of the inorganic filler increases, the resolution decreases, but in the present invention, since it is a curing reaction by the generated base, the inclusion of the inorganic filler Even when the amount is increased, good resolution can be maintained.
Moreover, it is preferable that the specific gravity of an inorganic filler is 3 or less, More preferably, it is 2.8 or less, More preferably, it is 2.5 or less. When the specific gravity of the inorganic filler is 3 or less, thermal expansion can be suppressed. Examples of the inorganic filler of 3 or less include silica and aluminum hydroxide, and silica is particularly preferable.
Examples of the shape of the inorganic filler include an indeterminate shape, a needle shape, a disc shape, a scale piece, a spherical shape, and a hollow shape. Here, the spherical shape is preferable because it can be blended in the composition at a high ratio. In order to improve moisture resistance, the inorganic filler is more preferably treated with a surface treatment agent such as a silane coupling agent.
Moreover, the crack tolerance at the time of a thermal cycle can be improved by containing an inorganic filler. By containing a large amount of the inorganic filler, warping after curing can be suppressed.
In this invention, it is preferable that the thermal expansion coefficient (CTE) of hardened | cured material is 40 ppm or less, More preferably, it is 30 ppm or less, More preferably, it is 20 ppm or less.

[Organic solvent]
In the thermosetting resin composition of the present invention, 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)
(Latent base)
In the present invention, a latent base can be blended. By containing the latent base, the heating time after light irradiation can be shortened. Examples of the latent base include imidazole series.
Examples of the imidazole compound (B) include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2- Phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1- Cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate 2,4-diamino-6- (2′-methylimidazolyl- (1 ′))-ethyl-s-triazine, 2,4-diamino-6- (2′-undecylimidazolyl) -ethyl-s-triazine 2,4-diamino-6- (2'-ethyl-4-methylimidazolyl- (1 '))-ethyl-s-triazine, 2,4-diamino-6- (2'methylimidazolyl- (1') ) -Ethyl-striazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 -Hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di (2-cyanoethoxy) methylimidazole, 2-methylimidazo 2-phenylimidazoline, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenylimidazole hydrochloride, 1-benzyl-2-phenylimidazolium trimellitate (1B2PZ), 2,4-diamino-6-vinyl-s-triazine, 2,4-diamino-6-methacryloyloxy-s-triazine, 2,4-diamino-6-vinyl-1,3,5-triazine isocyanuric acid adduct 2,4-diamino-6-methacryloyloxy-1,3,5-triazine isocyanuric acid adducts or organic acid salts thereof.
The content of the latent base is preferably 0.1 to 10% by mass, more preferably 0.1 to 7% by mass, based on 100 parts by mass of the total solid content of the composition.
In the present invention, in addition to the imidazole compound, for example, triethylamine, tributylamine, dimethylbenzylamine, diethylbenzylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N , Tertiary amines such as 4-methyl-N, N-dimethylbenzylamine,
Quaternary ammonium salts such as benzyltrimethylammonium chloride, benzyltriethylammonium chloride,
Phosphines such as triethylphosphine and triphenylphosphine,
phosphonium salts such as n-butyltriphenylphosphonium bromide,
Organic acid salts,
Guantamines such as acetoguanamine and benzoguanamine can be used, and together with these, amines, acid anhydrides, aminopolyamide resins, polysulfide resins, boron trifluoride amine complexes, novolac resins, dicyandiamide, acid hydrazides, carboxyl group-containing compounds Etc. can be used in combination.

(Thiol compound)
In the present invention, a thiol compound can be blended. By containing a thiol compound, a cured film having excellent adhesion to a copper circuit on the substrate can be obtained.
As thiol compound, 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.
A polyfunctional mercaptan-based compound can also be used as the thiol compound. Examples of the polyfunctional mercaptan compound include aliphatic thiols such as hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide, xylylene dimercaptan, 4,4. Aromatic thiols such as' -dimercaptodiphenyl sulfide, 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate) , Trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythritol tetrakis (mercaptoacetate), dipen Poly (mercaptoacetate) polyhydric alcohols such as erythritol hexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate), propylene glycol bis (3- Mercaptopropionate), glycerol tris (3-mercaptopropionate), trimethylol ethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) And poly (3-mercaptopropionate) of polyhydric alcohols such as dipentaerythritol hexakis (3-mercaptopropionate); 1,4-bis (3-mercaptobutyryl) Oxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3- And poly (mercaptobutyrate) s such as mercaptobutyrate).
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).

  Moreover, the heterocyclic compound which has a mercapto group as a thiol compound can also be used. Examples of the heterocyclic compound having a mercapto group 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-mercap -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 Chemical Co., Ltd .: trade name Disnet F), 2-dibutylamino-4,6-dimercapto-s-triazine (manufactured by Sankyo Chemical Co., Ltd .: trade name Disnet DB), and 2 -Anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name Disnet AF)

In particular, since the developability of the curable resin composition is not impaired, mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, 5-methyl-1,3,4- Thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole is preferred. These thiol compounds may be used individually by 1 type, and may use 2 or more types together.
In addition, 3-mercaptopropylmethylmethoxysilane (KBM-802, Shin-Etsu Chemical Co., Ltd.) and 3-mercaptopropyltrimethoxysilane (KBM-803, Shin-Etsu Chemical Co., Ltd.) may be used.
0.1-30 mass parts is preferable with respect to 100 mass parts of thermoreactive compounds, as for the compounding quantity of a thiol compound, 0.5-20 mass parts is more preferable, and 1-15 mass parts is still more preferable.

The thermosetting resin composition of the present invention may further contain components such as a mercapto compound, an adhesion promoter, an antioxidant, and an ultraviolet absorber as necessary. 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, it is possible to increase Tg and obtain a cured product having excellent HAST resistance 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. 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 of the present invention 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.

[Pattern formation method]
The pattern forming method in which the thermosetting resin composition of the present invention can be suitably used includes the step (A) of forming a resin layer made of a thermosetting resin composition on a substrate, and a negative pattern-shaped light irradiation. Activating the photobase generator contained in the thermosetting resin composition in step (B) to cure the light-irradiated part, and forming a negative pattern layer by removing the unirradiated part by development ( C).
A light irradiation part is hardened by generating a base in the light irradiation part of a thermosetting resin composition by pattern-shaped light irradiation. Then, by developing with an organic solvent or an aqueous alkali solution, the unirradiated part is removed, and a negative pattern layer is formed.
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)]
The pattern forming method will be described with reference to FIG. 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 a light irradiator used for light irradiation, for example, a direct drawing apparatus capable of irradiating laser light, lamp light, and LED light can be used. 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. Moreover, the light irradiation amount varies depending on the film thickness, etc., 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)]
The pattern forming method preferably further includes an ultraviolet irradiation step (D) after the step (C). By further irradiating with ultraviolet rays after the step (C), the photobase generator remaining without being activated at the time of light irradiation can be activated. The wavelength of ultraviolet rays and the light irradiation amount (exposure amount) in the ultraviolet irradiation step (D) after the step (C) may be the same as or different from those in the step (B). A suitable light irradiation amount (exposure amount) is 150 to 2000 mJ / cm ² .

[Step (E)]
The pattern formation method preferably further includes a thermosetting (post-cure) step (E) after the step (C).
When performing a process (D) and a process (E) together after a process (C), it is preferable to perform a process (E) after a process (D).
In the step (E), the pattern layer is sufficiently heat-cured by the base generated from the photobase generator in the step (B) or the steps (B) and (D). Since the unirradiated portion has already been removed at the time of the step (E), the step (E) can be performed at a temperature equal to or higher than the curing reaction start temperature of the unirradiated thermosetting resin composition. Thereby, a pattern layer can fully be thermosetted. The heating temperature is, for example, 160 ° C. or higher.

[Step (F)]
The pattern forming method may further include a laser processing step (F). Fine openings can be formed by laser processing. As the laser, a known laser such as a YAG laser, a CO2 laser, or an excimer laser can be used.
The step (F) is preferably performed after the step (C) or after the steps (D) and (E) when the step (F) includes the steps (D) and (E).

[Step (G)]
The pattern forming method of the present invention preferably further includes a desmear process (G) after the process (F).
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 and a comparative example demonstrate this invention further in detail, this invention is not restrict | limited by these Examples and a comparative example.

(Reference Examples 1 to 10)
<Preparation of thermosetting resin composition>
In accordance with the formulation shown in Table 1 below, the materials described in the reference examples were respectively blended, 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 alkali developability (patterning) evaluation>
The substrate provided with the resin layer obtained above was irradiated with a negative pattern with an aperture design size of 100 μm by ORC HMW680GW (metal halide lamp, scattered light). The light irradiation amount was set as shown in Table 1 below with reference to the exothermic peak temperature by DSC. Next, heat treatment was performed for 60 to 80 minutes under the temperature conditions described in Table 1. Thereafter, the substrate was immersed in a 3 wt% TMAH / 5 wt% ethanolamine mixed aqueous solution at 35 ° C. and developed for 3 minutes, and development and patterning were evaluated according to the following criteria. The results obtained are shown in the table.
(Evaluation method)
A: Development is possible with a sodium carbonate aqueous solution in place of the TMAH / 5 wt% ethanolamine mixed aqueous solution. No damage from the developer on the surface of the light-irradiated area, and no development residue on the non-irradiated area. X: The development residue was confirmed in the non-irradiated 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.
XXX: Undercut was observed in the deep part of the opening

(Desmear resistance)
The base material produced by the same method as the base material for which the formation of the opening pattern 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 subjected to Table 1 in a hot air circulation drying furnace. It hardened | cured for 60 minutes at the post-cure temperature of -3 (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.
Conditions: Aperture (mask diameter): 3.1 mm / pulse width 20 μsec / output 2 W / frequency 5 kHz / number of shots: burst 3 shots For the substrate subjected to the above laser processing, desmear is further carried out by a permanganate desmear aqueous solution (wet method). Processed. 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>
The base material provided with the resin layer obtained above was irradiated with a negative pattern with ORC HMW680GW (metal halide lamp, scattered light). For each substrate, light irradiation was performed two patterns where the light irradiation amount is ^{500mJ / cm 2, 1000mJ / cm} 2. After light irradiation, the resin layer is scraped off from the base material and immediately heated to 30-300 ° C. at a temperature increase rate of 5 ° C./min in Seiko Instruments Inc. DSC-6200. DSC measurement was performed. About each, exothermic peak temperature was calculated | required from the obtained DSC chart. The results are shown in Table 2 below. FIG. 1 shows a DSC chart of the resin layer of Reference Example 1 and FIG. 2 shows a resin layer of Reference Example 9. Each figure is a DSC chart of an unirradiated resin layer and a resin layer with a light irradiation amount of 1000 mJ / cm ² . In the resin layer of Reference Example 1, the peak shifted to the low temperature side by light irradiation. Further, in the resin layer of Reference Example 9, a peak was first exhibited by light irradiation.

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.

In Reference Examples 1 and 9, the DSC measurement as described above was performed on the pattern layer immediately after the ultraviolet irradiation and before the post cure. Specifically, DSC measurement was performed on the pattern layer which was irradiated with ultraviolet light at 1000 mJ / cm 2 after the pattern layer was irradiated with light at a light irradiation amount of 1000 mJ / cm ² .
About the pattern layer of the reference examples 1 and 9, the exothermic peak temperature was calculated | required from the obtained DSC chart. FIG. 1 shows a DSC chart of the pattern layer of Reference Example 1 and FIG. 2 shows a pattern layer of Reference Example 9.
It can be seen that the heat curing reaction proceeded more efficiently because the amount of heat generation increased in the pattern layer of Reference Example 1 by ultraviolet irradiation. In addition, it can be seen that the heat curing reaction proceeds more efficiently because the amount of heat generation is increased and the peak is shifted to the low temperature side in the pattern layer of Reference Example 9 by ultraviolet irradiation.

* 828: Bis-A type liquid epoxy resin (equivalent 190 g / eq), Mitsubishi Chemical Corporation * HP-4032: naphthol type epoxy resin (equivalent 150 g / eq), DIC * HP-7200H60: dicyclopentadiene type epoxy resin ( Equivalent 265 g / eq), DIC was dissolved in cyclohexanone. 60% solids
* HF-1M H60: phenol novolak, Meiwa Kasei Co., Ltd. dissolved in cyclohexanone. Solid content 60%. Solid OH equivalent 100 g / eq
* Johncrill 68 H60: Styrene acrylic acid copolymer resin, Mw = 10000, acid value 195, Johnson Polymer Co., Ltd., solid equivalent 287 g / eq
* Irg907: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, BASF Japan Ltd. * Irg369: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1, BASF Japan Ltd. * Irg379: 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) ethane-1-one, BASF Japan Ltd. * OXE-02: Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), BASF Japan Ltd. * TPO: Lucillin TPO, BASF Japan Ltd.

* 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
* 4: In Examples 9 and 10, no exothermic peak was observed when not irradiated, but an exothermic peak was expressed by light irradiation.

(Comparative Examples 1-4)
A thermosetting resin composition having the composition shown in Table 4 below was prepared in the same manner as in the above Reference Example and applied to the base material to prepare a base material provided with a resin layer made of the thermosetting resin composition. The results of DSC measurement are shown in Table 5 below.
In Comparative Example 1, evaluation was performed in the same manner as in Reference Example 1 except that no photobase generator was added.
In Comparative Example 2, evaluation was performed in the same manner as in Reference Example 1 except that lucillin TPO was blended in place of the photobase generator.
In Comparative Examples 3 and 4, the first light irradiation was not performed, and the heat treatment was performed at the temperature shown in Table 6 for 30 minutes. Further, subsequent ultraviolet irradiation and post-cure were not performed. About the comparative example 4, the desmear process was performed similarly to the above, and the hardening characteristic was evaluated. The obtained results are shown in Table 6 below.

  From the results of Tables 3 and 6 above, in Reference Examples 1 to 10, by using a thermosetting resin composition comprising a thermoreactive compound, an alkali developable resin, and a photobase generator, curing such as desmear resistance. It was found that the characteristics were excellent and pattern formation by development was possible. On the other hand, in Comparative Examples 1-4, pattern formation was difficult.

(Examples 1-7, Reference Examples 11-66, Comparative Examples 5-9)
In Examples 1-7, Reference Examples 11-66, and Comparative Examples 5-9 shown in Tables 7-15, thermosetting resin compositions were prepared in the same manner as in Reference Example 1.
In Reference Example 11, as in Reference Example 1, a liquid thermosetting resin composition was directly applied to a printed wiring board, dried, light irradiated, heat treatment, alkali development, ultraviolet irradiation, and heat curing were sequentially performed.

  In Examples 1 to 7, Reference Examples 12 to 66, and Comparative Examples 5 to 9, a dry film was prepared using a thermosetting resin composition as described below, laminated on a printed wiring substrate, and printed. A wiring board was produced. The obtained results are shown in Tables 7 to 15 below.

<Production of dry film>
As a carrier film, a thermosetting resin composition was applied on a PET film having a thickness of 38 μm using an applicator, and then dried at 90 ° C. for 30 minutes to prepare a dry film. The coating amount was adjusted so that the thickness of the thermosetting resin composition was about 20 μm after drying. Thereafter, the obtained dry film was slit to a predetermined size.

<Laminate>
A double-sided printed wiring board having a copper thickness of 15 μm and a circuit formed thereon was prepared, and a pre-processed printed wiring board using MEC CZ-8100 was used, using a well-known company vacuum laminator MVLP-500 A dry film was laminated on the printed wiring board substrate to obtain a printed wiring board having a resin layer. Lamination conditions were temperature 80 ° C., was conducted at a pressure ^5kg / cm 2 / 60sec.

<Evaluation of the B stage state (handling during formation on the substrate)>
The B stage state (semi-cured state) of DF (dry film) was evaluated. Slit processing was performed to a predetermined size of the DF on which the obtained thermosetting resin composition was formed, and the state of the DF was confirmed by the following method.
(Evaluation method)
A: Cracking of the resin layer and resin powder falling were not confirmed after the slit processing. B: Slight cracking of the resin layer was confirmed after the slit processing. Resin powder-off was not confirmed. Δ: After slitting, cracking of resin layer and resin powder-off were confirmed.

<Evaluation of dent on through hole>
As shown in FIG. 7, a double-sided printed wiring substrate having a thickness of 0.3 mm in which copper plated through holes are formed at intervals of 300 μm in diameter and 1 mm in pitch is prepared using MEC CZ-8100. Pretreatment was performed. Thereafter, the dry film having a thickness of 50 μm produced by the method shown in the paragraph for producing a dry film is simultaneously dried on both sides of a printed wiring board on which through holes are formed using a vacuum laminator MVLP-500, a well-known company. The film was laminated. Lamination conditions were temperature 80 ° C., was conducted at a pressure ^5kg / cm 2 / 60sec. After that, the entire surface of the base material provided with the thermosetting resin layer was irradiated with ORC HMW680GW (metal halide lamp, scattered light) on the entire surface with a solid exposure. The light irradiation amount was set as described in Tables 7 to 15 with reference to the exothermic peak temperature by DSC. Next, the substrate was vertically applied for 60 to 80 minutes under the temperature conditions shown in Tables 7 to 15 for heat treatment. Further, UV irradiation was carried out with an energy amount of 1 J / cm ² using an ORC UV irradiation device, followed by longitudinal curing at 170 ° C./60 min in a hot air circulating drying furnace to complete curing. Then, the amount of dents on the through hole was confirmed using a surface roughness measuring instrument SE-700 (manufactured by Kosaka Laboratory).
(Evaluation method)
○: The maximum dent on the through hole is 5 μm or less.
Δ: The maximum recess on the through hole exceeds 5 μm

<Evaluation of formation of opening pattern>
The substrate provided with the resin layer obtained above was irradiated with a negative pattern with an aperture design size of 100 μm by ORC HMW680GW (metal halide lamp, scattered light). The light irradiation amount was set as described in Tables 7 to 15 below with reference to the exothermic peak temperature by DSC. Next, heat treatment was performed for 60 to 80 minutes under the temperature conditions shown in Tables 7 to 15. Thereafter, the substrate was immersed in a 3 wt% TMAH / 5 wt% ethanolamine mixed aqueous solution at 35 ° C. and developed for 3 minutes, and development and patterning were evaluated according to the following criteria. The results obtained are shown in the table.
(Evaluation method)
A: Development is possible with a sodium carbonate aqueous solution in place of the TMAH / 5 wt% ethanolamine mixed aqueous solution. No damage from the developer on the surface of the light-irradiated area, and no development residue on the non-irradiated area. X: The development residue was confirmed in the non-irradiated 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.
XXX: Undercut was observed in the deep part of the opening

<Line pattern formation>
The substrate provided with the resin layer obtained above was irradiated with a negative pattern having a design value of line / space = 100/100 μm using ORC HMW680GW (metal halide lamp, scattered light). The light irradiation amount was set as described in Tables 7 to 15 below with reference to the exothermic peak temperature by DSC. Next, heat treatment was performed for 60 to 80 minutes under the temperature conditions shown in Tables 7 to 15. Thereafter, the substrate was immersed in a 3 wt% TMAH / 5 wt% ethanolamine mixed aqueous solution at 35 ° C. and developed for 3 minutes, and the obtained linear pattern having a design value of 100 μm was evaluated according to the following criteria. The results obtained are shown in the table.
(Evaluation method)
○: The top length of the line was 100 μm and the bottom length was 100 μm, and a pattern as designed was obtained.
Δ: The top length of the line was 100 μm and the bottom length was 60 μm or more and less than 100 μm, and a slight undercut was observed.
X: The top length of the line was 100 μm, the bottom length was less than 60 μm, and a large undercut was observed at the bottom.

<Evaluation of warpage after curing>
The glossy surface of 18 μm copper foil obtained by cutting a dry film having a thickness of 20 μm, prepared by the method shown in the section of dry film production, into a square of 50 mm × 50 mm size using a vacuum laminator MVLP-500 Laminated on one side. Lamination conditions were temperature 80 ° C., was conducted at a pressure ^5kg / cm 2 / 60sec. Thereafter, the copper foil provided with the thermosetting resin layer was irradiated with light on the entire surface by ORC HMW680GW (metal halide lamp, scattered light). The light irradiation amount was set as described in Tables 7 to 15 with reference to the exothermic peak temperature by DSC. Next, the substrate was heat-treated for 60 to 80 minutes under the temperature conditions shown in Tables 7 to 15. Further, UV irradiation was performed with an energy amount of 1 J / cm ² using an ORC UV irradiation device, followed by curing at 170 ° C./60 min in a hot air circulating drying oven to obtain a copper foil having a thermosetting resin composition on one side. It was. Thereafter, as an evaluation of the warped state of the obtained cured product, the amount of warpage at four end portions was measured with a caliper.
(Evaluation method)
A: The warp is hardly seen. The amount of warpage of the maximum warp portion among the four end portions is less than 5 mm. Of the four end portions, the warp amount of the maximum warp portion is 5 mm or more and less than 20 mm. O: The warp amount of the maximum warp portion of the four end portions is 20 mm or more. Δ: The cured product contracted into a cylindrical shape. The amount of warp at the end could not be measured with calipers

<CTE measurement>
Each dry film having a thickness of 40 μm was prepared in accordance with the method described in the section of dry film preparation. Thereafter, a dry film was laminated on the glossy surface side of the 18 μm copper foil using a vacuum laminator MVLP-500 from Meiki. Lamination conditions were temperature 80 ° C., was conducted at a pressure ^5kg / cm 2 / 60sec. Thereafter, the entire surface was exposed with ORC HMW680GW (metal halide lamp, scattered light). The light irradiation amount was set as described in Tables 7 to 15 below with reference to the exothermic peak temperature by DSC. Next, heat treatment was performed for 60 to 80 minutes under the temperature conditions shown in Tables 7 to 15. Thereafter, UV irradiation was performed with an energy amount of 1 J / cm ² using an ORC UV irradiation device, and then complete curing was performed at 170 ° C./60 min in a hot-air circulating drying furnace. Then, it peeled from copper foil and obtained the resin composition as described in an Example, a reference example, and a comparative example. Thereafter, the obtained resin composition was cut into a strip shape having a width of 3 mm and a length of 10 mm, and the evaluation of CTE (coefficient of thermal expansion) was evaluated by the TMA method (tensile method) described in JIS-C-6481. I did it. The rate of temperature increase was 5 ° C./min, and the thermal expansion coefficient of Tg or less was evaluated. The thermal expansion coefficient was an average thermal expansion coefficient in the temperature range of 25 ° C. to 100 ° C., and the unit was ppm.
The obtained CTE values are shown in the table.

<Method of measuring refractive index of heat-reactive compound, maleimide compound, and alkali-developable resin>
Measuring apparatus: Appe refractometer Measuring conditions: Wavelength 589.3 nm, temperature 25 ° C.

<Evaluation of thermal cycle characteristics>
The printed wiring board subjected to the permanganate desmear treatment as described above was further subjected to conditions of nickel 0.5 μm and gold plating 0.03 μm using a commercially available electroless nickel plating bath and electroless gold plating bath. Plating was performed, and the pattern layer was gold-plated. About the obtained printed wiring board, the thermal cycle characteristic evaluation was performed. The processing conditions are as follows: -65 ° C for 30 min, 150 ° C for 30 min, heat history is added, and after 2000 cycles, the surface of the pattern layer and the periphery are observed with an optical microscope, and cracks are observed according to the following criteria. Was evaluated. The number of observation patterns was 100 holes.
(Evaluation method)
◎ ○: No cracks are generated on the surface and the periphery of the pattern layer ◎: Crack generation rate of the periphery of the pattern layer is less than 10% ○: Crack occurrence rate of the periphery of the pattern layer is 10% or more and less than 30% Over 30% crack generation rate in the peripheral area

(Basic configuration)

(Basic configuration)

(Colorant combination)

(Filler combination)

(Filler combination)

(With polymer resin)

(With polymer resin)

(Filler + polymer resin combination, maleimide compound)

(Comparative example)

The materials used for the thermosetting resin compositions in Tables 7 to 15 are as follows. Note that the description of the materials already described in Table 1 is omitted here to avoid redundant description.
(Maleimide compound)
UVT-302: acrylic polymer having maleimide group in side chain (equivalent 320), Toagosei Co., Ltd. DIC maleimide MIA-200: DIC, maleimide oligomer, Mw: about 1000, equivalent: 500 g / eq
BMI-3000: Air Brown, long chain alkyl bismaleimide oligomer, Mw: 3000
(Alkali developable resin)
MEH-7851M H60: Biphenyl / phenol novolak, Meiwa Kasei Co., Ltd. dissolved in cyclohexanone. Solid content 60%. Solid hydroxyl equivalent 210g / eq
Jonkrill 586 H60: Styrene acrylic acid copolymer resin, Mw = 3100, solid content acid value = 108 mgKOH / g, Johnson polymer was dissolved in cyclohexanone. Solid content 60%. Solid equivalent 519 g / eq.
(Photobase generator)
WPBG-140: 1- (anthraquinone-2-yl) ethylimidazole carboxylate, Wako Pure Chemical Industries, Ltd. (polymer resin)
MAM M52 H30: MMA / nBA / MMA triblock copolymer, Arkema Co. dissolved in cyclohexanone. Solid content 30%
PB-3600: Epoxidized polybutadiene Mn = 5900, Daicel Chemical Company KS-10 H30: Polyvinyl butyral, Sekisui Chemical Co. dissolved in cyclohexanone. Solid content 30%
XER-91: particulate crosslinked rubber particles (NBR, functional group carboxylic acid), JSR Paraloid EXL2655: core-shell particles of butadiene-acrylic resin, Rohm and Haas Japan YX8100 BH30: phenoxy resin. Mitsubishi Chemical Corporation. Solid content 30%
(Inorganic filler)
SO-C2: spherical silica, D50 = 0.5 μm, refractive index = 1.45, 2.2 g / cm ³ , Admatech AO-502: spherical alumina, D50 = 0.7 μm, refractive index = 1.76,3. 9 g / cm ³ , Admatex Hygielite H-42M: amorphous, aluminum hydroxide, D50 = 1.0 μm, refractive index = 1.65, 2.4 g / cm ³ , Showa Denko B-30: barium sulfate D50 = 0.3 μm, refractive index = 1.64, 4.3 g / cm ³ , Sakai Chemical Co., Ltd. DAW-10: amorphous, alumina, D50 = 10 μm, refractive index = 1.76, 3.9 g / cm ³ Electrochemical industry US-10: spherical, silica, D50 = 10 μm, refractive index = 1.45, 2.2 g / cm ³ , Tatsumori Co., Ltd. (colorant)
Phthalocyanine blue: C.I. I. Pigment Blue 15: 3
Carbon MA-50 Carbon black: Mitsubishi Chemical Corporation CR58 rutile titanium oxide: D50 = 0.28 μm, 4.2 g / cm ³ , Ishihara Sangyo Chromophthal Yellow: C.I. I. Pigment Yellow 147
(Other)
Ralomer LR8863: Trifunctional acrylate monomer, BASF R-2000: Cresol novolak, acrylic acid, THPA-modified resin (solid content 61%, solid content acid value 87 mgKOH / g, DIC)
DPHA: dipentaerythritol hexaacrylate Nippon Kayaku Co., Ltd. IRG-184: 1-hydroxycyclohexyl-phenyl ketone_Ciba Japan Co., Ltd. (Reference Examples A, A1, Examples A1, A2)
The following evaluation was performed on the thermosetting resin compositions of Reference Examples A and A1, Examples A1 and A2 shown in Table 16.
<Laser workability>
The substrate having the same developability (patterning) evaluation as described above was further irradiated with ultraviolet rays at an energy amount of 1 J / cm ² using an ORC ultraviolet irradiation device, and then 170 ° C./60 min in a hot air circulating drying furnace. Cured (post cure).
Thereafter, laser processing was performed on the same 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 / shot number: burst 3 shots ◎: Target machining diameter is less than top ± 2 μm, bottom +2 μm or more ○: Target machining diameter Difference between top and bottom is less than ± 2 μm x: Difference from target machining diameter is -2 μm or more for both top and bottom <Concealment of circuit substrate>
The board | substrate which has a circuit pattern in which the thermosetting resin composition was formed was further heat-processed at 200 degreeC for 1 hour. Then, it was visually confirmed whether the color of the copper circuit of the coated part was discolored by heating.
○: No copper circuit discoloration △: Copper circuit discoloration <Reflectance measurement>
About each test board | substrate, K value of XYZ color system was measured using Konica Minolta Co., Ltd. color difference meter CR-400. The results were evaluated according to the following criteria. The Y value is the Y value of the XYZ color system, and the higher the value, the higher the reflectance.
○: Y value is 70 or more Δ: Y value is less than 70

The obtained results are shown in Table 16.
As can be seen from the comparison between Reference Example A and Reference Example A1, although phthalocyanine blue was an absorption aid for CO ₂ laser and there was no change in the top processing diameter size, compared to the case where no phthalocyanine blue was contained, The bottom machining diameter could be increased.
Moreover, the bottom processing diameter at the time of laser processing can be enlarged by containing a blue colorant.
As can be seen from the comparison between Reference Example A and Example A1, the concealability can be improved by containing a black colorant.
As can be seen from a comparison between Reference Example A and Example A2, the reflectance can be increased by containing a white colorant.
(Reference examples B, B1, B2)
The following evaluation was performed on the thermosetting resin compositions of Reference Examples B, B1, and B2 shown in Table 17.
<Evaluation of shortening PEB time (Effect when using latent base)>
Prepare a double-sided printed wiring board with a copper thickness of 15 μm and a circuit formed on it, and print it on a base material that has been pretreated using MEC CZ-8100, using a vacuum laminator MVLP-500 A dry film was laminated on the plate. Lamination conditions were temperature 80 ° C., was conducted at a pressure ^5kg / cm 2 / 60sec. The substrate provided with the resin layer obtained above was irradiated with 750 mJ / cm ² in a negative pattern with ORC HMW680GW (metal halide lamp, scattered light). Then, the board | substrate which performed the heat processing for 40 and 80 minutes at 120 degreeC was produced, respectively. Next, the substrate was immersed in a 3 wt% TMAH / 5 wt% ethanolamine mixed aqueous solution at 35 ° C. and developed for 3 minutes, and the developability in each heat treatment time was evaluated according to the following criteria.
○: In both 40 min and 80 min, the surface of the light-irradiated part was not damaged by the developer, and no development residue was observed in the unirradiated part.
Δ: A pattern could not be formed in 40 min. On the other hand, at 80 min, the surface of the light irradiated part was not damaged by the developer, and no development residue was found on the unirradiated part.

Table 17 shows the obtained results.
By containing the latent base, the heating time after light irradiation can be shortened.
(Reference examples C, C1, C2)
The following evaluation was performed on the thermosetting resin compositions of Reference Examples C, C1, and C2 shown in Table 18.
<Adhesion with copper (effect when using thiol)>
The entire copper-clad substrate on which the thermosetting resin composition was formed was treated for 168 hours under the conditions of 121 ° C., saturation, and 0.2 MPa using a PCT apparatus (manufactured by Espec, HAST SYSTEM TPC-412MD). . Then, according to the crosscut method described in JIS K5600, the adhesiveness with the base copper surface was evaluated. For the treatment of the base copper surface, a substrate on which a profile was formed by etching 1 μm with Mec CZ-8100 was used. Thereafter, in order to form a mesh on the resin surface, a cutter and a dedicated guide jig were used to produce a mesh so that the scratches reached the copper surface. The cut interval was 10 squares in length and breadth at an interval of 1 mm to produce a total of 100 squares. Then, the cellophane adhesive tape was affixed, the peeling test was done, and it evaluated in accordance with the judgment criteria shown below.
The overall copper-clad substrate on which the thermosetting resin composition was formed was evaluated for adhesion to the underlying copper surface according to the cross-cut method described in JIS K5600.
Evaluation was performed according to the following criteria.
○: No deposits were observed on the surface of the cellophane adhesive tape after peeling. Δ: Deposits were found on the surface of the cellophane adhesive tape after peeling.

The obtained results are shown in Table 18.
By containing a thiol compound, a cured film having excellent adhesion to a copper circuit on the substrate can be obtained.
(Reference examples D, D1, 2)
The following evaluation was performed on the thermosetting resin compositions of Reference Examples D, D1, and D2 shown in Table 19.
<Evaluation of warpage on thin plate (Effect when using epoxy with epoxy equivalent of 200 or more)>
Hitachi Chemical Co., Ltd. MCL with a thickness of 100 μm obtained by cutting a dry film with a thickness of 20 μm produced by the method shown in the section of dry film production into a square with a size of 50 mm × 50 mm using a vacuum laminator MVLP-500 -E-679FGR laminated on an etch-out substrate. Conditions were temperature 80 ° C., was conducted at a pressure ^5kg / cm 2 / 60sec. Thereafter, the etch-out substrate provided with the thermosetting resin layer was irradiated with 750 mJ / cm ² by ORC HMW680GW (metal halide lamp, scattered light) with a full surface exposure. Then, the board | substrate which performed the heat processing for 40 and 80 minutes at 120 degreeC was produced, respectively. After that, UV irradiation is performed with an energy amount of 1 J / cm ² using an ORC UV irradiation apparatus, followed by curing at 170 ° C./60 min in a hot-air circulating drying furnace, and etching out with a thermosetting resin composition on one side. A substrate was obtained. Thereafter, as an evaluation of the warped state of the obtained cured product, the amount of warpage at four end portions was measured with a caliper.
(Evaluation method)
○: Slight warping was observed. Of the four end portions, the warp amount of the maximum warp portion is 5 mm or more and less than 20 mm. Δ: The warp amount of the maximum warp portion of the four end portions is 20 mm or more <Life Evaluation>
A double-sided printed wiring board with a copper thickness of 15 μm and a circuit formed thereon is prepared, and printing is performed on a base material that has been pretreated using MEC CZ-8100, using a vacuum machine laminator MVLP-500 A dry film was laminated on the wiring board. Lamination conditions were temperature 80 ° C., was conducted at a pressure ^5kg / cm 2 / 60sec. Then, the board | substrate which laminated the thermosetting resin composition in the constant temperature and humidity chamber of temperature 23 degreeC and humidity 65% RH was stored for 72 hours. Then, 750 mJ / cm ^{2 was} irradiated in a negative pattern with ORC HMW680GW (metal halide lamp, scattered light). Next, heat treatment was performed at 120 ° C. for 60 minutes. Thereafter, the substrate was immersed in a 3 wt% TMAH / 5 wt% ethanolamine mixed aqueous solution at 35 ° C. and developed for 3 minutes, and development and patterning were evaluated according to the following criteria.

○: No damage from the developer on the surface of the light-irradiated part and no development residue on the non-irradiated part. Δ: No damage from the developer on the surface of the light-irradiated part. It was.

The obtained results are shown in Table 19.
By containing an epoxy resin having an epoxy equivalent of 200 or more, curling of the cured film is suppressed, and the developability is excellent even when left under high humidity for a long time.

(Developable conditions due to temperature / time differences in Reference Examples 1, 3, 8, 9, and E)
As a detailed evaluation of developability / patterning property, the printed wiring boards prepared in Reference Examples 1, 3, 8, 9 and Reference Example E below were further evaluated for the heating temperature and heating time after light irradiation. It was. The table shows the range of heating time that can be developed. Reference Example E is the same as Reference Example 1 except that the number of parts of the photobase generator in Reference Example 1 is reduced to 10 parts by mass.

As shown in Table 20, in Reference Examples 1 and 8, the development was good when heated at 120 ° C. for 20 to 40 minutes. That is, in Reference Examples 1 and 8, the range of the heating time that can be developed was 20 minutes. In Reference Example 3, the development was good when heated at 120 ° C. for 80 to 100 minutes. That is, also in Reference Example 3, the range of the heating time that can be developed was 20 minutes. In Reference Examples 9 and E, development was good only when heated at 120 ° C. for 60 or 40 minutes.
Accordingly, the photobase generator having a plurality of nitrogen atoms in the molecular structure used in Reference Examples 1, 3, and 8 has a longer development time range than that of Reference Example 9, so that the printed wiring board is manufactured. Was found to be easier.
Also, by blending the polymer resin, the melt viscosity of the thermosetting resin composition is increased, and the flow of the resin in the through-hole portion can be suppressed during heating after exposure. As a result, a flat substrate that is not recessed on the through hole can be manufactured.
On the other hand, in the photoradical composition of Comparative Example 3, pattern formation by alkali development became difficult. The line shape was also poor. Furthermore, it was inferior in curability at the time of a cold-heat cycle.

<DSC measurement immediately after light irradiation>
The base material provided with the resin layer obtained in Examples 1 and 5 and Reference Example 43 was irradiated with a negative pattern by ORC HMW680GW (metal halide lamp, scattered light). About each base material, the light irradiation amount of light was set to 1000 mJ / cm < ² >, and the pattern light irradiation was performed. After light irradiation, the resin layer is scraped off from the base material and immediately heated to 30-300 ° C. at a temperature increase rate of 5 ° C./min in Seiko Instruments Inc. DSC-6200. DSC measurement was performed. Moreover, DSC measurement was similarly performed with respect to the cured layer which consists of a thermosetting resin composition immediately after ultraviolet irradiation and before postcure.
3-5, in each embodiment 1,5,43, unirradiated portions, the light irradiation portion of the light irradiation amount 1000 mJ / cm ^2, a light irradiation amount 1000 mJ / cm ² at a further 1000 mJ / cm ² after irradiation It is a DSC chart figure of the light irradiation part irradiated with the ultraviolet-ray.
In the light irradiation parts of Examples 1 and 5 and Reference Example 43, the heat generation peak shifted to the low temperature side due to light irradiation.

(Comparative Example 10)
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 circulation drying furnace, the film was irradiated in a negative pattern with ORC HMW680GW (metal halide lamp, scattered light) at a light irradiation amount of 300 mJ / cm ² . 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, desmear resistance was evaluated in the same manner as in Reference Example 11. As a result, the desmear resistance was “x”.

Claims (4)

An alkali-developable resin, a heat-reactive compound, a photobase generator, and a colorant,
The colorant is at least one selected from a black colorant, a white colorant and a yellow colorant;
Alkaline development type thermosetting characterized in that a negative pattern can be formed by alkali development by an addition reaction between the alkali developable resin and the heat-reactive compound by heating after selective light irradiation. Resin composition.   The alkali-developable thermosetting resin composition according to claim 1, which does not contain a photopolymerizable monomer derived from (meth) acrylate.   A cured product obtained by curing the alkali developing type thermosetting resin composition according to claim 1.   A printed wiring board comprising the cured product according to claim 3.