KR102073440B1 - Alkaline-developable thermosetting resin composition and printed circuit board - Google Patents

Abstract

This invention suppresses generation | occurrence | production of a crack, and provides the alkali developing type thermosetting resin composition and printed wiring board which can obtain the resin layer which is favorable in the B stage state in the form of a dry film. Negative pattern formation by alkali development by containing alkali developable resin, a thermally reactive compound, a polymeric resin, and a photobase generator, and addition reaction of the said alkali developable resin and the said thermally reactive compound by selective light irradiation. It becomes an alkali developing type thermosetting resin composition characterized by the above-mentioned.

Description

Thermosetting resin composition of alkali development type, printed wiring board {ALKALINE-DEVELOPABLE THERMOSETTING RESIN COMPOSITION AND PRINTED CIRCUIT BOARD}

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

In recent years, as a material of the soldering resist for a printed wiring board and a flexible printed wiring board, in consideration of environmental problems, the alkali developing type photocurable resin composition which uses aqueous alkali solution as a developing solution is becoming mainstream. As such an alkali developing type photocurable resin composition, as described in Patent Documents 1 and 2, an epoxy acrylate-modified resin (hereinafter sometimes abbreviated as epoxy acrylate) induced by modification of an epoxy resin is included. The resin composition to be used is generally used.

As a formation method of the soldering resist using such a photocurable resin composition, a photocurable resin composition is apply | coated and dried to a base material, and a resin layer is formed, and it irradiates with a pattern shape with respect to the resin layer, and then forms by developing with alkaline developing solution. There is a way.

In addition, a printed wiring board and a flexible printed wiring board are mounted and used for various apparatuses. For this reason, it is required to be resistant to sudden changes in the environment such as temperature. Therefore, high temperature change resistance is required also for a soldering resist.

Moreover, when the difference in the coefficient of linear expansion (CTE) between a thermosetting resin and a base material, base material, copper, and underfill, etc. is large, there exists a problem that a crack generate | occur | produces a resist in TCT (thermal cycle test).

On the other hand, matching the CTE of a thermosetting resin with the CTE of a peripheral member material is performed widely recently. For example, it is common to reduce CTE by suppressing hardening shrinkage by high filling an inorganic filler with a thermosetting resin.

Japanese Patent Laid-Open No. 61-243869 (patent claims) Japanese Patent Laid-Open No. 3-250012 (Patent Claims)

However, in order to suppress hardening shrinkage, when filling an inorganic filler, when there is much filling amount of an inorganic filler, a crack arises in a resin layer (dry coating film) in the B stage state (semi-curing state) of a thermosetting resin composition. There is a problem that throws away.

Moreover, since the conventional photocurable resin composition hardens | cures by the radical chain reaction by light, hardening shrinkage is large and there existed a problem that a crack generate | occur | produced, but mix | blending a polymeric resin suppresses hardening shrinkage and produces a crack, Was suppressing. However, further suppression of curing shrinkage is desired.

Accordingly, an object of the present invention is to provide an alkali-developed thermosetting resin composition and a printed wiring board which can suppress the occurrence of cracks and obtain a resin layer having good stability in a B stage state in the form of a dry film. have.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discovered that the said subject can be solved by setting it as the following structure, and came to complete this invention.

That is, the alkali developing type thermosetting resin composition of this invention contains alkali developable resin, a thermoreactive compound, a polymeric resin, and a photobase generator,

The alkali developable resin and the thermally reactive compound are reacted by selective light irradiation, whereby negative pattern formation by alkali development is possible.

It is preferable that the alkali developing type thermosetting resin composition of this invention contains 1 or more types of said polymer resin chosen from the group which consists of a block copolymer, an elastomer, a rubber particle, and a binder polymer.

In addition, the alkali developing type thermosetting resin composition of this invention produces an exothermic peak in DSC measurement by light irradiation, or the exothermic starting temperature in DSC measurement of the alkali developing type thermosetting resin composition which irradiated light was inadequate. The exothermic peak temperature in the DSC measurement of the alkali developing type thermosetting resin composition which is lower than the exothermic onset temperature in DSC measurement of the alkali developing type thermosetting resin composition of irradiation, or the light irradiation is the non-irradiating alkali developing type thermosetting resin. It is preferable that it is lower than exothermic peak temperature in DSC measurement of a composition.

The printed wiring board of this invention has a pattern layer containing the said alkali developing type thermosetting resin composition, It is characterized by the above-mentioned.

By this invention, generation | occurrence | production of a crack can be suppressed and the alkali developing type thermosetting resin composition which can obtain the resin layer which is excellent in stability in B-stage state in the form of a dry film can be provided. Moreover, according to this invention, the alkali developing type thermosetting resin composition which can obtain the pattern layer excellent in curability and cold-heat cycle characteristics can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows an example of the pattern formation method using the alkali developing type thermosetting resin composition of this invention.
It is a figure which shows the DSC chart concerning the resin layer containing the alkali developing type thermosetting resin composition of Example 1 of this invention.
It is a figure which shows an example of the pattern formation method using the alkali developing type thermosetting resin composition of this invention.

The alkali developing type thermosetting resin composition (hereinafter may be abbreviated as "thermosetting resin composition") of the present invention contains an alkali developing resin, a thermally reactive compound, a polymer resin, and a photobase generator, and is optional. The alkali-developable resin and the thermally reactive compound react by light irradiation, whereby negative pattern formation by alkali development is enabled. Here, pattern formation means forming the hardened | cured material of a pattern shape, ie, a pattern layer.

In the resin layer containing a thermosetting resin composition, a base generate | occur | produces on the surface by light irradiation. This generated base destabilizes the photobase generator, and further generates a base. By generating a base in this way, it is thought that it grows chemically to the deep part of a resin layer. And since a base acts as a catalyst when alkali-developable resin and a thermally reactive compound add reaction, since addition reaction advances to the core part, in a light irradiation part, a resin layer hardens to a core part.

Therefore, after irradiating a thermosetting resin composition to pattern shape, alkali development may be carried out, and a non-irradiated part can be removed and a pattern can be formed.

In addition, the thermosetting resin composition of the present invention is curable by addition reaction of the alkali developable resin and the thermoreactive compound, and includes a polymer resin, so that a pattern layer having less deformation and curing shrinkage can be obtained than the photocurable resin composition. . Therefore, in this invention, since generation | occurrence | production of a crack can be suppressed, it is excellent in the cold heat cycling characteristics, for example.

Moreover, in this invention, handling becomes favorable by containing a polymeric resin, the generation | occurrence | production of the crack of the coating film in B-stage state is suppressed, and the pattern layer excellent in flexibility can be obtained.

The thermosetting resin composition may not be cured even when heated in a non-irradiated state, but may be a composition which enables curing by heat as a ratio when light is irradiated.

The thermosetting resin composition of this invention generate | occur | produces an exothermic peak in DSC measurement by light irradiation, or the exothermic start temperature in the DSC measurement of the thermosetting resin composition which irradiated light is the DSC measurement of the unirradiated thermosetting resin composition. It is preferable that the exothermic peak temperature in the DSC measurement of the thermosetting resin composition lower than the exothermic onset temperature or light irradiation is lower than the exothermic peak temperature in the DSC measurement of the non-irradiated thermosetting resin composition.

In addition, the thermosetting resin composition of this invention is the temperature difference of the heat generation start temperature (also called ΔT start) or the temperature difference of the heat generation peak temperature (ΔT peak) in the DSC measurement between the light-curable thermosetting resin composition and the unirradiated thermosetting resin composition. It is preferable that it is 10 degreeC or more, It is more preferable that it is 20 degreeC or more, It is still more preferable that it is 30 degreeC or more.

Here, with ΔT start, a thermosetting resin composition having the same composition is prepared, and after one side is irradiated with light, the other side is subjected to DSC (differential scanning calorimetry, Differential scanning calorimetry) measurement without being irradiated with light, and irradiated with light. The temperature difference between the exothermic onset temperature indicating the start of the curing reaction of the composition and the unexposed resin composition exothermic onset temperature is indicated. (DELTA) T peak says the temperature difference of the light composition and the unexposed resin composition exothermic peak temperature at the time of carrying out DSC measurement similarly.

In addition, the amount of light irradiation in the DSC measurement of the thermosetting resin composition which irradiated light is the amount of light irradiation which raises the amount of light irradiation and does not produce the shift of the exothermic peak temperature by the light irradiation of the thermosetting resin composition (saturation).

When the ΔT start or ΔT peak is 10 ° C. or more, it is possible to suppress the occurrence of so-called overwriting in which the unilluminated portion remains due to alkali development and so-called erosion in which the light irradiated portion is removed by alkali development. Moreover, when (DELTA) T start or (DELTA) T peak is 10 degreeC or more, it becomes possible to take wide the range of the heating temperature which can be taken in the heating process (B1) mentioned later.

Hereinafter, each component of a thermosetting resin composition is demonstrated in detail.

[Alkali Developable Resin]

Alkali-developable resins are resins which contain at least one functional group among phenolic hydroxyl groups, thiol groups and carboxyl groups, and are developable with an alkaline solution, preferably compounds having two or more phenolic hydroxyl groups, carboxyl group-containing resins and phenolic compounds. The compound which has a hydroxyl group and a carboxyl group, and the compound which has two or more thiol groups are mentioned.

As a compound which has two or more phenolic hydroxyl groups, a phenol novolak resin, an alkylphenol novolak resin, bisphenol A novolak resin, a dicyclopentadiene type phenol resin, a Xylok type phenol resin, a terpene modified phenol resin, Known conventional phenol resins, such as polyvinyl phenol, bisphenol F, bisphenol S-type phenol resin, poly-p-hydroxy styrene, the condensate of naphthol and aldehydes, and the condensate of dihydroxy naphthalene and aldehydes, are mentioned.

Moreover, as a phenol resin, the compound which has a biphenyl skeleton, a phenylene skeleton, or both skeletons, and 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 And phenol resins having various skeletons synthesized using 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, phloroglucinol and the like can also be used.

These may be used individually by 1 type and may be used in combination of 2 or more type.

As carboxyl group-containing resin, resin containing a well-known carboxyl group can be used. By presence of a carboxyl group, a resin composition can be made alkaline developable. Moreover, in addition to a carboxyl group, although the compound which has an ethylenically unsaturated bond in a molecule | numerator can also be used, in this invention, as carboxyl group-containing resin, the carboxyl group-containing number which does not have ethylenically unsaturated double bond like following (1), for example. It is preferable to use only.

As a specific example of carboxyl group-containing resin which can be used for this invention, the compound (any of an oligomer and a polymer) listed below may be mentioned.

(1) Carboxyl group-containing resin obtained by copolymerization of unsaturated carboxylic acids, such as (meth) acrylic acid, and unsaturated group containing compounds, such as styrene, (alpha) -methylstyrene, lower alkyl (meth) acrylate, and isobutylene. In addition, 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; and polycarbonate-based polyols and polyethers. Carboxyl group-containing by polyaddition reaction of diol compounds, such as a compound polyol, a polyester polyol, a polyolefin polyol, an acryl polyol, a bisphenol A alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group Urethane resin.

(3) diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol Terminal carboxyl group-containing urethane resin which makes acid anhydride react with the terminal of the urethane resin by the polyaddition reaction of diol compounds, such as the compound which has a bisphenol-A alkylene oxide adduct diol, a phenolic hydroxyl group, and alcoholic hydroxyl group, etc. .

(4) bifunctional epoxy resins such as diisocyanate, 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, and biphenol type epoxy resin Carboxyl group-containing urethane resin by the polyaddition reaction of the (meth) acrylate or its partial acid anhydride modified | denatured product, a carboxyl group-containing dialcohol compound, and a 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 to the terminal ( (Meth) acrylated carboxyl group-containing urethane resin.

(6) Having one isocyanate group and one or more (meth) acryloyl groups in the molecule, such as equimolar reactants of isophorone diisocyanate and pentaerythritol triacrylate during synthesis of the resin of the above (2) or (4) The carboxyl group-containing urethane resin which added the compound and was terminal (meth) acrylated.

(7) Unsaturated monocarboxylic acids, such as (meth) acrylic acid, are made to react with the polyfunctional (solid) epoxy resin mentioned above, and the hydroxyl group which exists in a side chain, such as phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, etc. Carboxyl group-containing resin which added two base acid anhydride.

(8) A saturated monocarboxylic acid is reacted with a polyfunctional (solid) epoxy resin as described above to add a dibasic acid anhydride such as phthalic anhydride, tetrahydro phthalic anhydride and hexahydro phthalic anhydride to a hydroxyl group present in the side chain. Carboxyl group-containing resin.

(9) A carboxyl group-containing resin in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin in which the hydroxyl group of a bifunctional (solid) epoxy resin is further epoxidized with epichlorohydrin, and added dibasic anhydride to the generated hydroxyl group.

(10) The carboxyl group-containing polyester resin which made dicarboxylic acid react with the polyfunctional oxetane resin as mentioned later, and added dibasic acid anhydride to the primary hydroxyl group which generate | occur | produced.

(11) Carboxyl group-containing resin obtained by making polybasic acid anhydride react with the reaction product obtained by making compound which has a some phenolic hydroxyl group, and alkylene oxide, such as ethylene oxide and a propylene oxide, react in 1 molecule.

(12) A saturated monocarboxylic acid is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with alkylene oxides such as ethylene oxide and propylene oxide, and a polybasic anhydride is reacted with the reaction product obtained. Carboxyl group containing resin obtained by making it react.

(13) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with alkylene oxides such as ethylene oxide and propylene oxide, and the resulting polybasic acid. Carboxyl group-containing resin obtained by making anhydride react.

(14) A reaction product obtained by reacting a saturated monocarboxylic acid with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with cyclic carbonate compounds such as ethylene carbonate and propylene carbonate. Carboxyl group-containing resin obtained by making polybasic acid anhydride react.

(15) Carboxyl group-containing resin obtained by making polybasic acid anhydride react with the reaction product obtained by making compound which has a some phenolic hydroxyl group, and cyclic carbonate compounds, such as ethylene carbonate and a propylene carbonate, react in 1 molecule.

(16) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with cyclic carbonate compounds such as ethylene carbonate and propylene carbonate. Carboxyl group-containing resin obtained by making polybasic acid anhydride react with a reaction product.

(17) A compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and saturated monocarboxylic acid are reacted with an epoxy compound having a plurality of epoxy groups in one molecule. The carboxyl group-containing resin obtained by making polybasic acid anhydrides, such as maleic anhydride, tetrahydro phthalic anhydride, trimellitic anhydride, a pyromellitic anhydride, adipic anhydride, react with the alcoholic hydroxyl group of the obtained reaction product.

(18) An alcohol compound of the reaction product obtained by reacting an epoxy compound having a plurality of epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol and the like Carboxyl group-containing resin obtained by making polybasic acid anhydrides, such as maleic anhydride, tetrahydro phthalic anhydride, trimellitic anhydride, a pyromellitic anhydride, adipic anhydride, react with a hydroxyl group.

(19) Unsaturated compounds, such as a compound which has at least 1 alcoholic hydroxyl group and 1 phenolic hydroxyl group in 1 molecule, such as p-hydroxy phenethyl alcohol, to the epoxy compound which has several epoxy groups in 1 molecule, and (meth) acrylic acid Carboxyl group obtained by making group-containing monocarboxylic acid react, and making polybasic acid anhydrides, such as maleic anhydride, tetrahydro phthalic anhydride, trimellitic anhydride, a pyromellitic anhydride, adipic anhydride, react with the alcoholic hydroxyl group of the obtained reaction product. Containing resin.

(20) One epoxy group or one or more (meth) groups in a molecule such as glycidyl (meth) acrylate or α-methylglycidyl (meth) acrylate in any one of the above (1) to (19). Carboxyl group-containing resin formed by further adding the compound which has acryloyl group.

Since the above-mentioned alkali developable resin has many carboxyl groups, hydroxyl groups, etc. in the side chain of a backbone polymer, image development by aqueous alkali solution is attained.

The hydroxyl group equivalent or carboxyl group equivalent of the carboxyl group-containing resin is preferably 80 to 900 g / eq., More preferably 100 to 700 g / eq. When hydroxyl group equivalent or carboxyl group equivalent exceeds 900 g / eq., The adhesiveness of a pattern layer may not be obtained or alkali development may become difficult. On the other hand, the hydroxyl group equivalent or the carboxyl group equivalent was 80 g / eq. If less, the dissolution of the light irradiated portion by the developing solution proceeds, so that the line becomes thinner than necessary or, in some cases, is melted and peeled off with the developing solution without distinguishing between the light irradiating portion and the unilluminated portion, and it is difficult to draw a normal resist pattern. It is not preferable because it may be reduced. Moreover, when carboxyl group equivalent or phenol group equivalent is large, since even if content of alkali developable resin is small, since image development becomes possible, it is preferable.

Moreover, although the weight average molecular weight of alkali-developable resin used by this invention changes with resin skeleton, the range of 2,000-150,000, Furthermore, 5,000-100,000 are preferable. If the weight average molecular weight is less than 2,000, the adhesion-free performance may be inferior, the moisture resistance of the resin layer after light irradiation is bad, the film decreases at the time of image development, and the resolution may fall large. On the other hand, when a weight average molecular weight exceeds 150,000, developability may remarkably worsen and storage stability may be inferior.

In the present specification, (meth) acrylate is a term that generically refers to acrylate, methacrylate and mixtures thereof, and the same also applies to other similar expressions.

As a compound which has a thiol group, for example, a trimethylol propane tristyropropionate, a pentaerythritol tetrakistyropropionate, ethylene glycol bisthioglycolate, 1, 4- butanediol bisthioglycolate, trimethylol propane trithio Glycolate, pentaerythritol tetrakisthioglycolate, di (2-mercaptoethyl) ether, 1,4-butanedithiol, 1,3,5-trimercaptomethylbenzene, 1,3,5-trimercaptomethyl -2,4,6-trimethylbenzene, terminal thiol group-containing polyether, terminal thiol group-containing polythioether, thiol compound obtained by reaction of epoxy compound with hydrogen sulfide, obtained by reaction of polythiol compound and epoxy compound The thiol compound which has a terminal thiol group, etc. are mentioned.

It is preferable that alkali developable resin is a compound which has carboxyl group-containing resin and phenolic hydroxyl group. Moreover, it is preferable that alkali developable resin is non-photosensitive, which does not have photocurable structures, such as an epoxy acrylate. Since such non-photosensitive alkali developable resin does not have an ester bond derived from epoxy acrylate, it is highly resistant to desmear liquid. Therefore, the pattern layer excellent in hardening characteristic can be formed. Moreover, since it does not have a photocurable structure, hardening shrinkage can be suppressed.

When alkali developable resin is carboxyl group-containing resin, it can develop with weakly alkaline aqueous solution compared with the case of phenol resin. As a weak alkaline aqueous solution, what melt | dissolved sodium carbonate etc. is mentioned. By developing with a weakly alkaline aqueous solution, it can suppress that a light irradiation part is developed. Moreover, the light irradiation time in a process (B) and the heating time in a process (B1) can be shortened.

[Thermally reactive compound]

A thermally reactive compound is resin which has a functional group which can harden reaction by heat. Epoxy resin, a polyfunctional oxetane compound, etc. are mentioned.

The said epoxy resin is resin which has an epoxy group, and all well-known thing can be used. The bifunctional epoxy resin which has two epoxy groups in a molecule | numerator, the polyfunctional epoxy resin which has many epoxy groups in a molecule | numerator, etc. are mentioned. Moreover, the hydrogenated bifunctional epoxy compound may be sufficient.

Examples of the polyfunctional epoxy compound include bisphenol A type epoxy resins, brominated epoxy resins, novolac type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol A type epoxy resins, glycidylamine type epoxy resins, hydantoin type epoxy resins, Alicyclic 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, complex Cyclic epoxy resin, diglycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group containing epoxy resin, epoxy resin with dicyclopentadiene frame | skeleton, glycidyl methacrylate copolymer type epoxy resin, cyclohexyl malee Copolymerized epoxy resin of mid and glycidyl methacrylate, CTBN modified epoxy water And the like.

Other liquid bifunctional epoxy resins include vinylcyclohexene diepoxide, (3 ', 4'-epoxycyclohexylmethyl) -3,4-epoxycyclohexanecarboxylate, (3', 4'-epoxy- And alicyclic epoxy resins such as 6'-methylcyclohexylmethyl) -3,4-epoxy-6-methylcyclohexanecarboxylate. A naphthalene group containing epoxy resin is preferable because it can suppress the thermal expansion of hardened | cured material.

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) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate In addition to polyfunctional oxetanes such as oligomers or copolymers thereof, oxetane alcohols and novolac resins, poly (p-hydroxystyrene), cardo type bisphenols, calix arenes, calyx resorcinrenes, or Ether ether with resin which has hydroxyl groups, such as a silsesquioxane, etc. are mentioned. In addition, the copolymer of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate etc. are mentioned.

Here, when a heat reactive compound has a benzene frame | skeleton, since heat resistance improves, it is preferable. In addition, when a thermosetting resin composition contains a white pigment, it is preferable that a thermoreactive compound is an alicyclic skeleton. Thereby, photoreactivity can be improved.

As a compounding quantity of the said thermoreactive compound, it is preferable that it is 1: 0.1-1: 10, and, as for the equivalence ratio (thermal reactive group: alkali developing group) with alkali developable resin, it is more preferable that it is 1: 0.2-1: 5. When it exists in the range of such a compounding ratio, image development becomes favorable.

[Photobase Generator]

A photobase generator is a compound which produces | generates 1 or more basic substances which can function as a catalyst of the addition reaction of the said thermally reactive compound by molecular structure change by the irradiation of light, such as an ultraviolet-ray or visible light, or a molecule | numerator cleaves. to be. As a basic substance, secondary amine and tertiary amine are mentioned, for example.

As a photobase generator, For example, (alpha)-amino acetophenone compound, an oxime ester compound, an acyloxyimino group, N-formylated aromatic amino group, N-acylated aromatic amino group, nitrobenzyl carbamate group, alkoxybenzylcar The compound which has substituents, such as a barmate group, etc. are mentioned.

The α-aminoacetophenone compound has a benzoin ether bond in the molecule, and when irradiated with light, cleavage occurs in the molecule to generate a basic substance (amine) that exhibits a curing catalyst action. Specific examples of the α-aminoacetophenone compound include (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, manufactured by BASF Japan) and 4- (methylthiobenzoyl)- 1-methyl-1-morpholinoethane (Irgacure907, a brand name, the BASF Japan company make), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4- Commercially available compounds, such as morpholinyl) phenyl] -1-butanone (Irgacure 379, a brand name, the BASF Japan company make), or its solution can be used.

As an oxime ester compound, all the compounds which produce a basic substance by light irradiation can be used. Examples of commercially available oxime ester compounds include CGI-325 manufactured by BASF Japan, Irgacure-OXE01, Irgacure-OXE02, Adeka's N-1919, NCI-831, and the like. 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 by a following formula is mentioned.

Wherein X represents a hydrogen atom, an alkyl group of 1 to 17 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group of 1 to 17 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, an amino group, an alkyl group of 1 to 8 carbon atoms) Substituted with an alkylamino 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 1 to 8 carbon atoms or a dialkylamino group) And Y and Z each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, and a phenyl group (an alkyl group having 1 to 17 carbon atoms, having 1 to 8 carbon atoms). Substituted by an alkoxy group, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, a group having 1 to 8 carbon atoms) Substituted with an alkoxy group, an amino group, an alkylamino group or a dialkylamino group having an alkyl group having 1 to 8 carbon atoms), an anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, and Ar represents a bond or 1 carbon atom. Alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4'-stilbene -Diyl, 4,2'-styrene-diyl, n is an integer of 0 or 1)

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

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

(Wherein R ¹ represents a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, or 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 which may be substituted with an alkyl group or alkoxy group having 1 to 4 carbon atoms, and R ³ represents an oxygen atom or sulfur Benzyl group which may be connected by the atom and may be substituted by the C1-C20 alkyl group and the C1-C4 alkoxy group which may be substituted by the phenyl group, R <^4> represents a nitro group or XC ( Represents an acyl group represented by = O)-, X represents an aryl group, thienyl group, morpholino group, thiophenyl group, or a structure represented by the following formula, which may be substituted with an alkyl group having 1 to 4 carbon atoms)

In addition, Japanese Patent Laid-Open No. 2004-359639, Japanese Patent Laid-Open No. 2005-097141, Japanese Patent Laid-Open No. 2005-220097, Japanese Patent Laid-Open No. 2006-160634, and Japanese Patent Laid-Open No. 2008-094770 The carbazole oxime ester compound of Unexamined-Japanese-Patent No. 2008-509967, Unexamined-Japanese-Patent No. 2009-040762, Unexamined-Japanese-Patent No. 2011-80036, etc. are mentioned.

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

As a specific example of a compound which has N-formylated aromatic amino group and N-acylated aromatic amino group, For example, di-N- (p-formylamino) diphenylmethane, di-N (p-acetylamino) diphenylmethane , Di-N- (p-benzoamide) diphenylmethane, 4-formylaminotoluene, 4-acetylaminotoluene, 2,4-diformylaminotoluylene, 1-formylaminonaphthalene, 1-acetylamino Naphthalene, 1,5-diformylaminonaphthalene, 1-formylaminoanthracene, 1,4-diformylaminoanthracene, 1-acetylaminoanthracene, 1,4-diformylaminoanthraquinone, 1,5- Diformylaminoanthraquinone, 3,3'-dimethyl-4,4'-diformylaminobiphenyl, 4,4'-diformylaminobenzophenone, and the like.

As a specific example of the compound which has a nitrobenzyl carbamate group and the alkoxy benzyl carbamate group, bis {{((2-nitrobenzyl) oxy} carbonyl} diaminodiphenylmethane, 2,4-di {{( 2-nitrobenzyl) oxy} toluene, bis {{((2-nitrobenzyloxy) carbonyl} hexane-1,6-diamine, m-xyldine {{(2-nitro-4-chlorobenzyl) oxy} amide } And the like.

As a photobase generator, an oxime ester compound and the (alpha)-amino acetophenone compound are preferable. Especially as an alpha-amino acetophenone compound, what has two or more nitrogen atoms is preferable.

As other photobase generators,

WPBG-018 (brand name: 9-anthrylmethyl N, N'-diethylcarbamate), WPBG-027 (brand name: (E) -1- [3- (2-hydroxyphenyl) -2-prope Noyl] piperidine), WPBG-082 (brand name: guanidinium 2- (3-benzoylphenyl) propionate), WPBG-140 (brand name: 1- (anthraquinone-2-yl) ethyl imidazole carboxyl Rate) or the like.

Japanese Patent Laid-Open No. 11-71450, International Publication 2002/051905, International Publication 2008/072651, Japanese Patent Publication No. 2003-20339, Japanese Patent Publication No. 2003-212856, Japanese Patent Publication 2003-344992, Japanese Patent Publication No. 2007-86763, Japanese Patent Publication No. 2007-231235, Japanese Patent Publication No. 2008-3581, Japanese Patent Publication No. 2008-3582, Japanese Patent Publication 2009-280785, Japanese Patent Publication No. 2009-080452, Japanese Patent Publication No. 2010-95686, Japanese Patent Publication No. 2010-126662, Japanese Patent Publication No. 2010-185010, Japanese Patent Publication No. 2010-185036 Japanese Patent Laid-Open No. 2010-186054, Japanese Patent Laid-Open No. 2010-186056, Japanese Patent Laid-Open No. 2010-275388, Japanese Patent Laid-Open No. 2010-222586, Japanese Patent Laid-Open No. 2010-084144, Japanese Patent Publication 2011-107199, Japanese Patent Publication No. 2011-236416, Japan The photobase generating agent described in the literature, such as Patent Publication No. 2011-080032 may be used.

The said photobase generator may be used individually by 1 type, and may be used in combination of 2 or more type. The compounding quantity of the photobase generator in a thermosetting resin composition becomes like this. Preferably it is 1-50 mass parts with respect to 100 mass parts of thermally reactive compounds, More preferably, it is 1-40 mass parts. When it is less than 1 mass part, since image development becomes difficult, it is not preferable.

(Maleimide compound)

The thermosetting resin composition of this invention may contain a maleimide compound.

Examples of the maleimide compound include polyfunctional aliphatic / alicyclic maleimide and polyfunctional aromatic maleimide. Preferred are bifunctional or higher maleimide compounds (polyfunctional maleimide compounds). Examples of the polyfunctional aliphatic / alicyclic maleimide include N, N'-methylenebismaleimide, N, N'-ethylenebismaleimide, tris (hydroxyethyl) isocyanurate and aliphatic / alicyclic maleimide Maleimide ester compound of the isocyanurate frame | skeleton obtained by dehydrating esterification of carboxylic acid; Isocyanur skeleton polymaleimide, such as the maleimide urethane compound of the isocyanurate frame | skeleton obtained by urethanating a tris (carbamate hexyl) isocyanurate and an aliphatic / alicyclic maleimide alcohol; Dehydration esterification of isophoronebisurethanebis (N-ethylmaleimide), triethyleneglycolbis (maleimideethylcarbonate), aliphatic / alicyclic maleimidecarboxylic acid and various aliphatic / alicyclic polyols, or aliphatic / alicyclic Aliphatic / alicyclic polymaleimide ester compounds obtained by transesterifying a group maleimide carboxylic acid ester with various aliphatic / alicyclic polyols; Aliphatic / alicyclic polymaleimide ester compounds obtained by ether ring opening reaction of aliphatic / alicyclic maleimide carboxylic acid and various aliphatic / alicyclic polyepoxides; And aliphatic / alicyclic polymaleimide urethane compounds obtained by urethane-forming aliphatic / alicyclic maleimide alcohols and various aliphatic / alicyclic polyisocyanates.

As a polyfunctional aromatic maleimide, Aromatic polymaleimide ester compounds obtained by dehydrating esterification of maleimide carboxylic acid and various aromatic polyols, or transesterifying maleimide carboxylic acid ester and various aromatic polyols; Aromatic polymaleimide ester compounds obtained by ether ring-opening reaction of maleimide carboxylic acid and various aromatic polyepoxides; Aromatic polyfunctional maleimide, such as aromatic polymaleimide urethane compounds obtained by carrying out urethanation reaction of a maleimide alcohol and various aromatic polyisocyanate, etc. are mentioned.

As a specific example of polyfunctional aromatic maleimide, N, N '-(4,4'- diphenylmethane) bismaleimide, N, N'-2,4-tolylene bismaleimide, N, N', for example -2,6-tolylenebismaleimide, 1-methyl-2,4-bismaleimidebenzene, N, N'-m-phenylenebismaleimide, N, N'-p-phenylenebismaleimide, N, N'-m-toluylenebismaleimide, N, N'-4,4'-biphenylenebismaleimide, N, N'-4,4 '-[3,3'-dimethyl-biphenyl Len] bismaleimide, N, N'-4,4 '-[3,3'-dimethyldiphenylmethane] bismaleimide, N, N'-4,4'-[3,3'-diethyldi Phenylmethane] bismaleimide, N, N'-4,4'-diphenylmethanebismaleimide, N, N'-4,4'-diphenylpropanebismaleimide, N, N'-4,4 ' -Diphenyletherbismaleimide, N, N'-3,3'-diphenylsulfonbismaleimide, N, N'-4,4'-diphenylsulfonbismaleimide, 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane, 2,2-bis [3-t-butyl-4- (4-maleimidephenoxy) phenyl] propane, 2,2 -Bis [3-s-butyl-4- (4-maleimidephenoxy) phenyl] propane, 1,1-bis [4- (4-maleimidephenoxy) phenyl] decane, 1,1-bis [2 -Methyl-4- (4-maleimidephenoxy) -5-t-butylphenyl] -2-methylpropane, 4,4'-cyclohexylidene-bis [1- (4-maleimidephenoxy)- 2- (1,1-dimethylethyl) benzene], 4,4'-methylene-bis [1- (4-maleimidephenoxy) -2,6-bis (1,1-dimethylethyl) benzene], 4 , 4'-methylene-bis [1- (4-maleimidephenoxy) -2,6-di-s-butylbenzene], 4,4'-cyclohexylidene-bis [1- (4-maleimide Phenoxy) -2-cyclohexylbenzene, 4,4'-methylenebis [1- (maleimidephenoxy) -2-nonylbenzene], 4,4 '-(1-methylethylidene) -bis [1 -(Maleimide phenoxy) -2,6-bis (1,1-dimethylethyl) benzene], 4,4 '-(2-ethylhexylidene) -bis [1- (maleimide phenoxy) -benzene ], 4,4'- (1-methylheptylidene) -bis [1- (maleimide phenoxy) -benzene], 4,4'- cyclohexylidene-bis [1- (maleimide phenoxy)] 3-M Benzene], 2,2-bis [4- (4-maleimidephenoxy) phenyl] hexafluoropropane, 2,2-bis [3-methyl-4- (4-maleimidephenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-maleimidephenoxy) phenyl] hexafluoropropane, 2,2-bis [3,5-dimethyl-4- (4-maleimidephenoxy) phenyl ] Propane, 2,2-bis [3,5-dimethyl-4- (4-maleimidephenoxy) phenyl] hexafluoropropane, 2,2-bis [3-ethyl-4- (4-maleimidephenoxy Phenyl] propane, 2,2-bis [3-ethyl-4- (4-maleimidephenoxy) phenyl] hexafluoropropane, bis [3-methyl- (4-maleimidephenoxy) phenyl] methane , Bis [3,5-dimethyl- (4-maleimidephenoxy) phenyl] methane, bis [3-ethyl- (4-maleimidephenoxy) phenyl] methane, 3,8-bis [4- (4- Maleimidephenoxy) phenyl] -tricyclo [5.2.1.02,6] decane, 4,8-bis [4- (4-maleimidephenoxy) phenyl] -tricyclo [5.2.1.02,6] decane, 3 , 9-bis [4- (4-maleimide Phenoxy) phenyl] -tricyclo [5.2.1.02,6] decane, 4,9-bis [4- (4-maleimidephenoxy) phenyl] -tricyclo [5.2.1.02,6] decane, 1,8 -Bis [4- (4-maleimidephenoxy) phenyl] mentane, 1,8-bis [3-methyl-4- (4-maleimidephenoxy) phenyl] mentan, 1,8-bis [3,5 -Dimethyl-4- (4-maleimidephenoxy) phenyl] mentan etc. are mentioned.

As a compounding quantity of a maleimide compound, it is preferable that the equivalence ratio (maleimide group: alkali developing group) with alkali developable resin is 1: 0.1-1: 10, and it is more preferable that it is 1: 0.2-1: 5. By setting it as such a compounding ratio, image development becomes easy.

[Polymer resin]

The thermosetting resin composition of this invention can mix | blend a conventionally well-known high polymer resin for the purpose of the improvement of the flexibility of hardened | cured material obtained, and a touch-drying property. Examples of the polymer resin include cellulose, polyester, phenoxy resin, polyvinyl acetal, polyvinyl butyral, polyamide, polyamideimide binder polymer, block copolymer, elastomer, rubber particles and the like. Polymeric resin may be used individually by 1 type, and may use two or more types together.

By mix | blending a polymeric resin, the melt viscosity of a thermosetting resin composition rises and the resin fluidity of a through-hole part can be suppressed at the time of post-exposure heating. As a result, the flat board | substrate with which a recessed part is not seen can be manufactured on a through hole.

The addition amount of the said polymeric resin becomes like this. Preferably it is 50 mass parts or less with respect to 100 mass parts of said thermally reactive compounds, More preferably, it is 1-30 mass parts, Especially preferably, it is 5-30 mass parts. When the compounding quantity of a polymer resin exceeds 50 mass parts, since deterioration of the desmear tolerance of a thermosetting resin composition is concerned, it is unpreferable.

(Block copolymer)

A block copolymer is a copolymer of a molecular structure in which two or more kinds of polymers having different properties are covalently linked to form a long chain.

As a block copolymer used by this invention, A-B-A or A-B-A 'type block copolymer is preferable. Among the ABA or AB-A 'type block copolymers, the central B is a soft block and the glass transition point Tg is low, preferably less than 0 ° C, and both outer As or A's are hard blocks, and Tg is high. Preferably, it is comprised by the polymer unit of 0 degreeC or more. The glass transition point Tg is measured by differential scanning calorimetry (DSC).

Further, among the ABA or AB-A 'type block copolymers, a block copolymer in which A or A' includes a polymer unit having a Tg of 50 ° C or more and B contains a polymer unit having a Tg of -20 ° C or less is more preferable. .

Moreover, it is preferable that A or A 'is high in compatibility with the said heat reactive compound among A-B-A or A-B-A' type block copolymers, and it is preferable that B is low in compatibility with the said heat reactive compound. Thus, it is thought that the block of both ends is compatible with a matrix, and the center block becomes a block copolymer incompatible with a matrix, and it becomes easy to show a specific structure in a matrix.

As A or A ', it is preferable to contain polymethyl (meth) acrylate (PMMA), polystyrene (PS), etc., and as B, it contains polyn-butylacrylate (PBA), polybutadiene (PB), etc. It is preferable. In addition, a hydrophilic unit having excellent 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, or the like is introduced into a part of the A or A 'component. It is possible to further improve compatibility.

Moreover, as a block copolymer used for this invention, a block copolymer of three or more members is preferable, and the block copolymer by which the molecular structure synthesize | combined by the living polymerization method is precisely controlled is more preferable in obtaining the effect of this invention. It is thought that this is because the block copolymer synthesized by the living polymerization method has a narrow molecular weight distribution and the characteristics of each unit become clear. 3 or less are preferable, as for the molecular weight distribution (Mw / Mn) of the block copolymer to be used, 2.5 or less are more preferable, More preferably, it is 2.0 or less.

The block copolymer containing such a (meth) acrylate polymer block is, for example, the methods described in Japanese Patent Application Laid-Open No. 2007-516326 and Japanese Patent Laid-Open No. 2005-515281, in particular, the following general formulas (1) to ( After polymerizing Y unit using the alkoxy amine compound represented by any one of 4) as an initiator, it can obtain suitably by polymerizing X unit.

(Wherein n represents 2, Z represents a divalent organic group, preferably 1,2-ethanedioxy, 1,3-propanedioxy, 1,4-butanedioxy, 1,6-hexane Dioxy, 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. If the weight average molecular weight is less than 20,000, the desired effect of toughness and flexibility cannot be obtained, and the adhesiveness when the thermosetting resin composition is dry filmed or when it is applied to a substrate and dried is also inferior. On the other hand, when a weight average molecular weight exceeds 400,000, the viscosity of a thermosetting resin composition may become high and printability and workability may remarkably worsen. When the weight average molecular weight is 50000 or more, an excellent effect is obtained in the relaxation against impact from the outside.

As a polymer resin, a block copolymer is preferable because it is excellent in crack resistance at the time of a cold cycle, and can suppress the curvature after hardening. The block copolymer is particularly preferable because it can suppress the recessed portion on the through hole and can produce a substrate having a flat surface. Moreover, by combining an inorganic filler, it is also excellent in crack resistance at the time of cold heat cycle.

(Elastomer)

The elastomer which has a functional group can be added to the thermosetting resin composition of this invention. By adding an elastomer having a functional group, it is possible to improve the coating property and to improve the strength of the coating film. In addition, polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyesteramide elastomers, acrylic elastomers, olefin elastomers, and the like can be used. Moreover, the resin etc. which modified | denatured the epoxy group of one part or all part of the epoxy resin which has a various skeleton with both terminal carboxylic acid modified type butadiene- acrylonitrile rubber can also be used. Furthermore, epoxy-containing polybutadiene-based elastomers, acrylic-containing polybutadiene-based elastomers, hydroxyl-containing polybutadiene-based elastomers, hydroxyl-containing isoprene-based elastomers, and the like can also be used. In addition, this elastomer may be used individually by 1 type, and may use two or more types together.

(Rubber particles)

The rubber particles may be any particle-shaped one formed from an organic substance such as a polymer having a crosslinked structure. Examples of the rubber particles include crosslinked NBR particles obtained by copolymerizing acrylonitrile and butadiene as copolymers of acrylonitrile butadiene; Copolymers of acrylonitrile, butadiene and carboxylic acids such as acrylic acid; The so-called core-shell structured crosslinked rubber particles (also referred to as "core-shell rubber particles") in which crosslinked polybutadiene, crosslinked silicone rubber, or NBR is used as a core layer and a crosslinked acrylic resin is used as a shell layer may be mentioned.

Among them, from the viewpoint of control of dispersibility and stability of particle size, a crosslinked rubber particle having a core shell structure is preferable, and a core shell structure having a crosslinked acrylic resin as a shell layer and a crosslinked polybutadiene or crosslinked silicone rubber as a core layer. Crosslinked rubber particles are more preferred.

Crosslinked NBR particles are those obtained by copolymerizing acrylonitrile and butadiene and partially crosslinking in the step of copolymerizing to form a particulate. It is also possible to obtain carboxylic acid-modified crosslinked NBR particles by copolymerizing carboxylic acids such as acrylic acid and methacrylic acid together.

The core-shell rubber particles of the crosslinked butadiene rubber-crosslinked acrylic resin can be obtained by a two-step polymerization method in which the butadiene particles are polymerized by emulsion polymerization, and then monomers such as acrylic acid ester and acrylic acid are added to continue the polymerization.

The core-shell rubber particles of the crosslinked silicone rubber-crosslinked acrylic resin can be obtained by a two-step polymerization method in which the silicon particles are polymerized by emulsion polymerization, and then monomers such as acrylic acid ester and acrylic acid are added to continue the polymerization.

The size of a rubber particle is 1 micrometer or less in primary average particle diameter, and it is preferable to set it as 50 nm-1 micrometer. When 1 micrometer exceeds 1 micrometer in primary mean particle diameter, adhesive force falls and the insulation reliability in a micro wiring is impaired. The "primary average particle diameter" here means not the aggregated particle diameter, ie, the secondary particle diameter, but the particle diameter in the single body which is not aggregated.

In addition, the primary average particle diameter can be measured and calculated | required with a laser diffraction type particle size distribution meter, for example.

Such rubber particles may be used alone or in combination of two or more thereof.

It is preferable that it is 50 mass% or less in a resin composition, and, as for content of a rubber particle, it is more preferable that it is 1-30 mass%.

For example, XER-91 by Nippon Kosei Rubber Co., Ltd. is mentioned as a commercial item of a carboxylic acid modified acrylonitrile butadiene rubber particle. Examples of the core shell particles of butadiene rubber-acrylic resin include Paraloid EXL2655 manufactured by Rohm and Haas Co., Ltd. and AC-3832 of Gantsu Kasei Kogyo Co., Ltd. As for the core-shell rubber particle | grains of crosslinked silicone rubber-acrylic resin, Asahi Kasei Barker Silicone Co., Ltd. product GENIOPERLP52 is mentioned.

By using rubber particles, crack resistance at the time of cold heat cycle can be improved.

[Inorganic Filler]

It is preferable that the said thermosetting resin composition contains an inorganic filler. An inorganic filler is used in order to suppress hardened | cured material hardening shrinkage of a thermosetting resin composition, and to improve characteristics, such as adhesiveness and hardness. Examples of the inorganic fillers 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, Neuburg Silius Earth, and the like. Can be mentioned.

It is preferable that the average particle diameter (D50) of an inorganic filler is 1 micrometer or less, It is more preferable that it is 0.7 micrometer or less, It is further more preferable that it is 0.5 micrometer. When the average particle diameter exceeds 1 µm, the pattern layer may be cloudy, which is not preferable. Although the lower limit of the average particle diameter (D50) of an inorganic filler is not specifically limited, For example, it is 0.01 micrometer or more. Here, the average particle diameter (D50) means an average primary particle diameter.

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 closer to the resin component, the transmittance is improved, and the generation efficiency of the base from the photobase generator by light irradiation is increased. It is preferable that the refractive index difference of an inorganic filler and alkali developable resin is 0.3 or less. By setting the refractive index difference to 0.3 or less, scattering of light can be suppressed and good core hardening characteristics can be obtained. Here, it is preferable that the refractive index of an inorganic filler is 1.4 or more and 1.8 or less. In addition, the refractive index of an inorganic filler can be measured based on JISK7105.

20 mass% or more and 80 mass% or less are preferable based on the total solid of the said thermosetting resin composition, and, as for the compounding ratio of an inorganic filler, More preferably, they are 30 mass% or more and 80 mass% or less. When the compounding ratio of an inorganic filler exceeds 80 mass%, the viscosity of a composition may become high, applicability | paintability may fall, or the hardened | cured material of a thermosetting resin composition may become brittle.

In the composition which hardens | cures by a radical reaction, resolution will fall when content of an inorganic filler increases, but in this invention, since it is a hardening reaction by the base which generate | occur | produced, it maintains favorable resolution even when content of an inorganic filler increases. Can be.

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. As an inorganic filler of 3 or less, silica and aluminum hydroxide are mentioned, for example, and silica is especially preferable.

Examples of the shape of the inorganic filler include irregular shapes, needle shapes, disc shapes, scale pieces, spherical shapes, hollow shapes, and the like. Here, spherical shape is preferable from the point which can be mix | blended in a high ratio in a composition. And in order to improve moisture resistance, it is more preferable that an inorganic filler is processed by surface treating agents, such as a silane coupling agent.

Moreover, by containing an inorganic filler, crack resistance at the time of a cold heat cycle can be improved. By containing a large amount of inorganic filler, the curvature after hardening can also 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 this invention, an organic solvent can be used for manufacture of a resin composition, or the viscosity adjustment for apply | coating to a base material or a carrier film.

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

[Photopolymerizable monomer]

The thermosetting resin composition of this invention may contain the photopolymerizable monomer in the range which does not impair the effect of this invention.

As a photopolymerizable monomer, Alkyl (meth) acrylates, such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; Mono or di (meth) acrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol; Polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, trishydroxyethyl isocyanurate, or polyhydric (meth) acrylates of ethylene oxide or propylene oxide adduct Ryu; (Meth) acrylates of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol A; (Meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; And melamine (meth) acrylate etc. are mentioned.

It is preferable that the compounding quantity of a photopolymerizable monomer is 50 mass% or less on the basis of solid content except the solvent of a thermosetting resin composition, More preferably, it is 30 mass% or less, More preferably, it is 15 mass% or less. When the compounding quantity of a photopolymerizable monomer exceeds 50 mass%, since curing shrinkage becomes large, there exists a possibility that curvature may become large. Moreover, when a photopolymerizable monomer is derived from (meth) acrylate, it contains an ester bond. In this case, since desmear treatment causes hydrolysis of the ester bond, there is a possibility that the electrical properties may be reduced.

(Other optional ingredients)

In the thermosetting resin composition of this invention, components, such as a mercapto compound, an adhesion promoter, a coloring agent, antioxidant, and a ultraviolet absorber, can be mix | blended further as needed. These can use a well-known thing in the field of an electronic material.

In particular, in the present invention, even when the content of the colorant is increased, the undercut can be suppressed to form good via holes and lines.

Further, in the thermosetting resin composition, known conventional thickeners such as finely divided silica, hydrotalcite, organic bentonite and montmorillonite, antifoaming agents and / or leveling agents such as silicone, fluorine and polymers, imidazole, thiazole and tria Known conventional additives such as silane coupling agents such as sol-based and rust inhibitors can be blended.

Moreover, you may mix | blend well-known conventional thermosetting resins, such as a block isocyanate compound, an amino resin, a benzoxazine resin, a carbodiimide resin, a cyclocarbonate compound, an episulfide resin, as a thermosetting component.

In addition, by containing a phenol resin as the alkali developable resin and an epoxy resin as the thermally reactive compound, the Tg can be made high and a cured product having excellent HAST resistance can be obtained without depending on the softening point of the raw material. have. In addition, when it is set as the composition which does not mix | blend a photopolymerizable monomer (the low molecular compound mix | blended in the photocurable resin composition which contains an ethylenically unsaturated group in a molecule and has a carboxyl group-containing resin as a main component, and promotes photocuring), It can be set as the resin composition excellent in the property.

In addition, in the conventional photocurable resin composition, since the photocuring reaction occurs at room temperature, as a result of the increase in the Tg of the resin composition at the time of curing, the curing reaction may be stopped, and the Tg of the resin composition needs to be designed low. There was. On the other hand, the alkali developing type thermosetting resin composition of this invention does not have a restriction | limiting in Tg before hardening reaction, and can be expected to set it as high Tg. In addition, the alkali developing thermosetting resin composition of the present invention can be expected to be cured without being subjected to oxygen inhibition.

The thermosetting resin composition of this invention is useful for formation of the pattern layer of a printed wiring board, and is especially useful as a material of a soldering resist and an interlayer insulation layer.

[Pattern Forming Method]

The pattern formation method which can use suitably the thermosetting resin composition of this invention is a process (A) of forming the resin layer containing a thermosetting resin composition on a base material, and is irradiated with a negative pattern shape, and is contained in a thermosetting resin composition. The step (B) of activating a photobase generator and hardening a light irradiation part, and the process (C) of forming a negative pattern layer by removing a non-irradiation part by alkali image development are included.

A light irradiation part can be hardened by generating a base in the light irradiation part of a thermosetting resin composition by light irradiation of a pattern shape. Thereafter, by developing with an aqueous alkali solution, the unilluminated portion is removed to form a negative pattern layer.

Here, in this invention, it is preferable to have a process (B1) which heats a resin layer after a process (B). Thereby, a resin layer can fully be hardened and the pattern layer excellent in further hardening characteristic can be obtained.

[Step (A)]

The pattern formation method is demonstrated, referring FIG. Process (A) is a process of forming the resin layer containing a thermosetting resin composition in a base material. The method of forming a resin layer can be based on the method of apply | coating and drying a liquid thermosetting resin composition on a base material, and the method of laminating on a board | substrate what used the thermosetting resin composition as a dry film.

As a coating method of a thermosetting resin composition to a board | substrate, well-known methods, such as a blade coater, a lip coater, a comma coater, and a film coater, can be employ | adopted suitably. In addition, the drying method is a method of hot air circulation type drying furnace, which is provided with a heat source of a heating method using steam such as a hot plate, a convection oven, or the like in a countercurrent direction, and a method of countercurrently contacting the hot air in the dryer, and the support from the nozzle. A well-known method, such as a method of spraying on, can be applied.

As a base material, in addition to the printed wiring base material and flexible printed wiring base material which were previously formed in a circuit, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass polyimide, glass cloth / nonwoven fabric-epoxy resin, glass cloth / paper- Copper clad laminates of all grades (such as FR-4) using composite materials such as epoxy resins, synthetic fiber-epoxy resins, fluororesins, polyethylene, PPO, and cyanate esters, polyimide films, PET films, glass substrates, ceramic substrates, wafers Base materials and the like can be used.

[Step (B)]

Process (B) is a process of hardening a light irradiation part by activating the photobase generator contained in a thermosetting resin composition by light irradiation of a negative pattern shape. It is thought that a process (B) destabilizes a photobase generator by the base which generate | occur | produced in the light irradiation part, and generate | occur | produces a base further. By chemically propagating the base in this manner, it can be sufficiently cured to the deep portion of the light irradiation part.

As a light irradiator used for light irradiation, the direct drawing apparatus which can irradiate a laser beam, lamp light, and LED light can be used, for example. The mask for light irradiation of pattern shape can use a negative mask.

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 making a maximum wavelength into this range, the thermal reactivity of a thermosetting resin composition can be improved efficiently. As long as the laser beam of this range is used, any of a gas laser and a solid state laser may be sufficient. The amount of light irradiation varies depending on the film thickness and the like, but can generally be in the range of 100 to 1500 mJ / cm 2, preferably 300 to 1500 mJ / cm 2.

As the direct drawing apparatus, for example, those manufactured by Nippon Orbotech Co., Ltd. and Pantax Co., Ltd. may be used, and any apparatus may be used as long as the apparatus emits laser light having a maximum wavelength of 350 to 410 nm.

[Step (B1)]

Process (B1) hardens a light irradiation part by heating. Process (B1) can be hardened to the core by the base which generate | occur | produced in process (B).

The heating temperature is preferably a temperature at which the light irradiation part is thermosetted in the thermosetting resin composition, but the non-irradiation part is not heat cured.

For example, the step (B1) is preferably lower than the exothermic onset temperature or exothermic peak temperature of the non-irradiated thermosetting resin composition, and is preferably heated at a temperature higher than the exothermic onset temperature or exothermic peak temperature of the irradiated thermosetting resin composition. By heating in this way, only light irradiation part can be selectively hardened.

Here, heating temperature is 80-140 degreeC, for example. By making heating temperature into 80 degreeC or more, a light irradiation part can fully harden | cure. On the other hand, only a light irradiation part can be selectively hardened by making heating temperature into 140 degrees C or less. Heating time is 10 to 100 minutes, for example. The heating method is the same as the above drying method.

In addition, in a non-irradiation part, since a base does not generate | occur | produce from a photobase generator, thermosetting is suppressed.

[Step (C)]

Process (C) is a process of forming a negative pattern layer by removing an unirradiated part by image development. As a developing method, it can be based on well-known methods, such as the dipping method, the shower method, the spray method, and the brush method. In addition, as a developing solution, aqueous alkali solution, such as amines, such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, ethanolamine, tetramethylammonium hydroxide aqueous solution (TMAH), or a mixture thereof can be used. .

[Process (D)]

It is preferable that the said pattern formation method further includes an ultraviolet irradiation process (D) after a process (C). By performing ultraviolet irradiation further after a process (C), the photobase generator remaining without activating at the time of light irradiation can be activated. The wavelength and the light irradiation amount (exposure amount) of the ultraviolet ray in the ultraviolet irradiation step (D) after the step (C) may be the same as or different from the step (B). Suitable light irradiation amount (exposure amount) is 150-2000 mJ / cm 2.

[Process (E)]

It is preferable that the said pattern formation method further includes a thermosetting (postcure) process (E) after a process (C).

In the case where both the step (D) and the step (E) are performed after the step (C), the step (E) is preferably performed after the step (D).

Step (E) sufficiently heat-cures the pattern layer with the base generated from the photobase generator by step (B) or step (B) and step (D). Since the unirradiated part is already removed at the time of a process (E), a process (E) can be performed at the temperature more than the hardening reaction start temperature of an unirradiated thermosetting resin composition. As a result, the pattern layer can be sufficiently thermally cured. Heating temperature is 160 degreeC or more, for example.

[Process (F)]

The pattern forming method may further include a laser processing step (F). Fine openings can be formed by laser processing. Lasers, it is possible to use a well-known laser such as YAG laser, CO ₂ laser, an excimer laser.

It is preferable to perform a process (F) after a process (C) or after a process (D) and (E), when including a process (D) and (E).

[Process (G)]

It is preferable that the pattern formation method of this invention further contains a desmear process (G) after a process (F).

Step (G) includes a smear swelling step for swelling the smear and making it easier to remove, a step for removing smear, and a neutralization step for neutralizing sludge generated from the desmear liquid used in the step of removing.

A swelling process is performed using alkaline chemical liquids, such as sodium hydroxide, and makes smear removal by the desmear chemical liquid easy.

In the removal step, smear is removed using an acidic chemical solution containing an oxidizing agent such as dichromic acid or permanganic acid.

The neutralization step uses an alkaline chemical solution such as sodium hydroxide to reduce and remove the oxidant used in the removal step.

Example

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.

(Examples 1-18, Comparative Examples 1-4)

<Production of Alkali Developable Thermosetting Resin Composition>

According to the formulations shown in Tables 1 to 3 below, the materials described in Examples / Comparative Examples were each premixed with a blender and a stirrer, followed by kneading with three roll mills to prepare a thermosetting resin composition. The value in a table | surface is a mass part unless there is particular notice.

<Production of dry film>

As a carrier film, the thermosetting resin composition was apply | coated on the PET film of 38 micrometers thickness using the applicator, and it dried 90 degreeC / 30 minutes after that, and produced the dry film. After drying, the thickness of the thermosetting resin composition adjusted the coating amount so that it might be set to about 20 micrometers. Thereafter, the obtained dry film was subjected to slit processing at a predetermined size.

<Laminate>

A double film printed circuit board having a circuit formed with a copper thickness of 15 µm was prepared, and a dry film was applied to a printed circuit board using a Macy's vacuum laminator MVLP-500 on a substrate subjected to pretreatment using Mack's CZ-8100. Laminated. Lamination conditions were performed at the temperature of 80 degreeC, and the pressure of 5 kg / cm <2> / 60 second.

<Evaluation of B stage state (handling at the time of formation to base material)>

About Examples 1-18, the B stage state (semicured state) of DF was evaluated. The slit process was performed by the predetermined | prescribed size of DF in which the obtained thermosetting resin composition is formed, and the state of DF was confirmed by the following method.

(Assessment Methods)

(Double-circle): The crack of the resin layer and the powder fall of the resin were not confirmed after slit processing.

(Circle): After the slit process, the crack of the resin layer was confirmed a little. No powder drop of resin was identified

X: The crack of the resin layer and the powder fall of the resin were confirmed after the slit processing.

<Evaluation of Recesses on Through Hole>

As shown in Fig. 3, a 0.3 mm thick double-sided printed wiring substrate having a copper plated through hole formed at intervals of 300 mu m in diameter and 1 mm in pitch was prepared, and pretreatment was performed using Mack's CZ-8100. It was. Subsequently, a dry film having a thickness of 50 µm produced by the method described in the production paragraph of the dry film was laminated on both sides of the dry film on the printed wiring board on which the through holes were formed, using a vacuum laminator MVLP-500 manufactured by Meiki Corporation. It was. Lamination conditions were performed at the temperature of 80 degreeC, and the pressure of 5 kg / cm <2> / 60 second. Subsequently, the front and back of the substrate having the thermosetting resin layer were irradiated with light on both front and back by ORC's HMW680GW (metal halide lamp, scattered light). The light irradiation amount was set as described in Tables 1 to 3 with reference to the exothermic peak temperature by DSC. Subsequently, heat processing was performed by hanging a board | substrate vertically for 60 to 80 minutes in the temperature conditions of Table 1. In addition, UV irradiation was carried out at an energy amount of 1 J / cm 2 using an ORC ultraviolet irradiation device, followed by curing at 170 ° C./60 minutes in a hot air circulation drying furnace, followed by complete curing. Then, the amount of recessed parts on a through hole was confirmed using surface roughness measuring instrument SE-700 (made by Kosaka Corporation).

(Assessment Methods)

(Circle): The largest recessed part on a through hole is 5 micrometers or less

(Triangle | delta): The largest recessed part on a through hole exceeds 5 micrometers

<Formation evaluation of opening pattern>

The substrate provided with the resin layer obtained above was irradiated with ORC HMW680GW (metal halide lamp, scattered light) in negative pattern shape of 100 micrometers of opening design size. The light irradiation amount was set as described in Tables 1 to 3 below with reference to the exothermic peak temperature by DSC. Subsequently, heat processing were performed for 60 to 80 minutes on the temperature conditions of Tables 1-3. Then, the board | substrate was immersed in 3 degreeC TMAH / 5 wt% ethanolamine mixed aqueous solution of 35 degreeC, image development was performed for 3 minutes, and evaluation of developability and patterning was performed according to the following reference | standard. The obtained results are shown in Tables 1-3.

(Assessment Methods)

(Double-circle): Even if it is aqueous sodium carbonate instead of TMAH / 5 wt% ethanolamine mixed aqueous solution, image development is possible. No damage caused by the developer on the surface of the light irradiation part and no developing residue is visible on the unilluminated part

(Circle): No damage by a developing solution on the surface of a light irradiation part, and a developing residue is not seen in an unirradiated part.

X: The developing residue was confirmed by an unirradiated part. Or state which could not develop phenomenon of unirradiated part

××: state in which both the light irradiation part and the unirradiated part are completely dissolved

×××: Undercut is visible in the core of the opening

<Line pattern formation>

The board | substrate provided with the resin layer obtained above was irradiated with ORC HMW680GW (metal halide lamp, scattered light) by the negative pattern shape of the design value of line / space = 100/100 micrometer. The light irradiation amount was set as described in Tables 1 to 3 below with reference to the exothermic peak temperature by DSC. Subsequently, heat processing were performed for 60 to 80 minutes on the temperature conditions of Tables 1-3. Then, the board | substrate was immersed in 3 degreeC TMAH / 5 wt% ethanolamine mixed aqueous solution of 35 degreeC, image development was performed for 3 minutes, and the evaluation of the linear pattern of the obtained design value of 100 micrometers was performed according to the following reference | standard. The obtained results are shown in Tables 1-3.

(Assessment Methods)

(Circle): It became the line top length 100 micrometers, and bottom length 100 micrometers, and the pattern according to the design value was obtained.

(Triangle | delta): The top length of the line was 100 micrometers, and the bottom length became 60 micrometers or more and less than 100 micrometers, and the undercut was seen a little.

X: The top length of a line was 100 micrometers, and the bottom length became less than 60 micrometers, and the undercut was seen by the bottom large.

(Desmear tolerance)

About the base material produced by the method similar to the base material which evaluated formation of opening pattern, UV irradiation is performed by ORC company's ultraviolet irradiation device at 1 J / cm <2> of energy amount, and it follows to Tables 1-3 in a hot air circulation type drying furnace. It was hardened for 60 minutes at the post-cure temperature described (post-cure). Thereafter, laser processing was performed on the light irradiation surface. The light source was processed with a CO ₂ laser (Hitachi Via Mechanics Co., Ltd., light source 10.6 µm). Evaluation was made according to the following criteria. In order to cover the superiority of workability, laser processing was all performed on the same conditions.

The machining diameter target is a saw diameter of 65 mu m / bottom 50 mu m.

Conditions: Aperture (mask diameter): 3.1mm / pulse width 20μsec / output 2W / frequency 5kHz / shots: burst 3 shots

About the base material which performed this laser processing, the desmear process was further performed by the permanganic acid desmear aqueous solution (wet method). As evaluation of desmear tolerance, the surface roughness of the base material surface and the state around the laser opening were evaluated in accordance with the following criteria. As for the confirmation of surface roughness, each surface roughness Ra was measured with the laser microscope VK-8500 (keyens company, measurement magnification 2000 times, Z-axis direction measurement pitch 10 nm). Observation of the laser aperture was performed with an optical microscope.

About chemicals (Rom & Haas)

Swelling MLB-211 Temperature 80 ° C / hour 10 minutes

Permanganic Acid MLB-213 Temperature 80 ℃ / hr 15min

Reducing MLB-216 Temperature 50 ° C./hour 5 Minutes

About the evaluation method

(Double-circle): Surface roughness Ra after permanganic acid desmear is less than 0.1 micrometer, and the difference with the processing diameter after laser processing is 2 micrometers or less

(Circle): Surface roughness Ra after permanganic acid desmear is 0.1-0.3 micrometer or less, and the difference with the processing diameter after laser processing is 2-5 micrometers

X: Surface roughness Ra after permanganic acid desmear is more than 0.3 micrometer, and the difference with the processing diameter after laser processing is 5 micrometers or more

Flexural Evaluation after Curing

On the single side of the gloss side of 18-micrometer copper foil which the 20-micrometer-thick dry film produced by the method described in the production paragraph of the dry film was cut out into a square of 50 mm x 50 mm size using a vacuum laminator MVLP-500 manufactured by Meiki Corporation. Laminated. Lamination conditions were performed at the temperature of 80 degreeC, and the pressure of 5 kg / cm <2> / 60 second. Then, the copper foil provided with a thermosetting resin layer was irradiated with ORC's HMW680GW (metal halide lamp, scattered light) by the whole surface solid exposure. The light irradiation amount was set as described in Tables 1 to 3 with reference to the exothermic peak temperature by DSC. Subsequently, the board | substrate was heat-processed for 60 to 80 minutes at the temperature conditions of Tables 1-3. Furthermore, it irradiated with the amount of energy of 1 J / cm <2> by ORC company ultraviolet irradiation apparatus, and then it hardened | cured at 170 degreeC / 60 minutes in the hot air circulation type drying furnace, and obtained copper foil which has a thermosetting resin composition on one side. Then, as an evaluation of the curvature state of the obtained hardened | cured material, the curvature amount of four edge parts was measured by the vernier.

(Assessment Methods)

(Double-circle): A curvature is hardly seen. The bending amount of the largest bending part among four ends is less than 5 mm

(Double-circle): A little warpage was seen. The bending amount of the largest bending part among four ends is 5 mm or more and less than 20 mm

(Circle): The bending amount of the largest bending part among four edge parts is 20 mm or more

(Triangle | delta): Hardened | cured material shrink | contracted to cylindrical shape. The curvature amount of the edge part was not able to be measured by the calipers.

<CTE measurement>

According to the method described in the preparation item of a dry film, each dry film of thickness 40micrometer is produced. Then, the dry film was laminated on the gloss surface side of 18 micrometers copper foil using the vacuum laminator MVLP-500 of Meiki Corporation. Lamination conditions were performed at the temperature of 80 degreeC, and the pressure of 5 kg / cm <2> / 60 second. Then, the whole surface solid exposure was performed by ORMW HMW680GW (metal halide lamp, scattered light). The light irradiation amount was set as described in Tables 1 to 3 below with reference to the exothermic peak temperature by DSC. Subsequently, heat processing were performed for 60 to 80 minutes on the temperature conditions of Tables 1-3. Subsequently, ultraviolet irradiation was performed at an energy amount of 1 J / cm 2 with an ultraviolet irradiation device of ORC, followed by complete curing at 170 ° C./60 minutes in a hot air circulation drying furnace. Then, it peeled from copper foil and obtained the resin composition of an Example and a comparative example. Thereafter, the obtained resin composition was cut out into a rectangle having a width of 3 mm and a length of 10 mm, and the CTE measurement (thermal expansion coefficient) was evaluated by the TMA method (tensile method) described in JIS-C-6481. The temperature increase rate evaluated the thermal expansion coefficient below 5 degree-C / min and Tg. The thermal expansion coefficient was an average thermal expansion coefficient and unit of ppm in the temperature range 25 degreeC to 100 degreeC.

The numerical value of CTE obtained, respectively is shown in a table.

<Evaluation of cold cycle cycle characteristics>

The printed wiring board subjected to the permanganic acid desmear treatment as described above was further subjected to plating under conditions of 0.5 μm of nickel and 0.03 μm of gold plating using a commercially available electroless nickel plating bath and an electroless gold plating bath to form a pattern. The part was subjected to gold plating treatment. Cooling cycle characteristic evaluation was performed about the obtained printed wiring board. The treatment conditions were 30 minutes at -65 ° C and 30 minutes at 150 ° C as one cycle, and after 2000 cycles of applying a heat history, the condition of the surface and the periphery of the pattern layer was observed under an optical microscope, and cracked according to the following criteria. Was evaluated. The number of observation patterns was 100 holes. The results obtained are shown in Tables 1 to 3 below.

(Assessment Methods)

◎ ○: No cracks on the surface and periphery of the pattern layer

(Double-circle): Less than 10% of crack incidences of the peripheral part of a pattern layer

○: 10% or more and less than 30% crack occurrence rate at the periphery of the pattern layer

(Triangle | delta): The crack generation rate of 30% or more of the peripheral part of a pattern layer

<Method of Refractive Index Measurement of Thermally Reactive Compound, Maleimide Compound, and Alkaline Developable Resin>

Measuring Device: Abbe Refractometer

Measurement Condition: Wavelength 589.3nm, Temperature 25 ℃

Each component in Tables 1-3 is as follows.

(Thermally reactive compound)

※ 828: Bis-A type liquid epoxy (equivalent 190g / eq), Mitsubishi Chemical Corporation

※ HP-7200H60: A dicyclopentadiene type epoxy (equivalent to 265 g / eq) and DIC company are melt | dissolved in cyclohexanone. 60% solids

※ HF-1M H60: A phenol novolak (hydroxyl equivalent 105g / eq), Meiwa Kasei Inc. are melt | dissolved in cyclohexanone. 60% solids

(Alkali developable resin)

※ HF-1M H60: A phenol novolak (hydroxyl equivalent 105g / eq), Meiwa Kasei Inc. are melt | dissolved in cyclohexanone. 60% solids

* MEH-7851M H60: Biphenyl / phenol novolak (hydroxyl equivalent 210 g / eq), may, and Kasei Corporation are dissolved in cyclohexanone. 60% solids.

※ John creel 586 H60: Styrene acrylic acid copolymer resin, Mw = 3100, solid acid value = 108 mgKOH / g, Johnson polymer company melt | dissolve in cyclohexanone. 60% solids

※ John Creil 68 H60: Styrene acrylic acid copolymer resin, Mw = 10000, acid value 195 mgKOH / g, Johnson polymer company melt | dissolve in cyclohexanone. 60% solids

※ R-2000PG: It has 65% of solid content (DIC company make), epoxy acrylate structure

(Photobase generator)

※ Irg369: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, BASF Japan company

※ OXE-02: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), BASF Japan company

(Polymer resin)

* MAM M52 H30: MMA / nBA / MMA triblock copolymer, arcemasa is dissolved in cyclohexanone. 30% solids

※ PB3600: Epoxidized polybutadiene Mn = 5900, Daicel Chemical Industries

* KS-10 H30: Polyvinyl butyral and Sekisui Chemical Co., Ltd. dissolve in cyclohexanone. 30% solids

※ XER-91: particulate crosslinked rubber particles (NBR, functional group carboxylic acid), JSR company

* Paraloid EXL2655: core shell particles of butadiene-acrylic resin, rom and heart Japan

* YX8100 BH30: phenoxy resin. Mitsubishi Chemical Corporation. 30% solids

(Inorganic filler)

※ SO-C2: spherical silica D50 = 0.5㎛, refractive index = 1.45, admatex yarn, specific gravity: 2.2 g / cm3

※ B-30: Barium sulfate, D50 = 0.3 micrometer, refractive index = 1.64, sakai Kagaku company, specific gravity: 4.3 g / cm <3>.

(Other)

※ R-2000: Cresol novolac, acrylic acid, THPA modified resin (61% of solid content, solid acid value 87mgKOH / g, DIC company)

DPha: dipentaerythritol hexaacrylate _ Nippon Kayakusa

Irg-184: 1-hydroxycyclo hexyl-phenyl ketone _ shiva japan

As shown in Tables 1-3, in Examples 1-18, since alkali developing resin, a polymeric resin, and a photobase generator were made into essential components, it is excellent in hardening characteristic and stability of B-stage state, and alkali image development was carried out. It turned out that patterning by is possible.

Moreover, in Examples 14-18 containing an inorganic filler, it turned out that it is excellent in cold-heat cycle characteristics.

Moreover, by mix | blending a polymeric resin, the melt viscosity of a thermosetting resin composition rises and the resin flow of a through-hole part can be suppressed at the time of the heating after exposure. As a result, the flat board | substrate with which a recessed part is not seen can be manufactured on a through hole.

On the other hand, in the photoradical composition of Comparative Example 4, pattern formation by alkali development became difficult. Moreover, the line shape was also bad. Moreover, the curability at the time of a cold heat cycle was also inferior.

<DSC measurement immediately after light irradiation>

The board | substrate provided with the resin layer obtained in Example 1 was irradiated with negative pattern shape with HMW680GW (metal halide lamp, scattered light) of ORC company. Each substrate was irradiated with a pattern with a light irradiation amount of 1000 mJ / cm 2. After light irradiation, the resin layer was scraped off from the board | substrate, immediately heated up to 30-300 degreeC by the temperature increase rate of 5 degree-C / min in the DSC-6200 of Seiko Instruments, and DSC measurement was performed with respect to each of the light irradiation part and the unirradiated part. It was. In addition, DSC measurement was similarly performed about the cured layer containing the thermosetting resin composition before post-curing immediately after ultraviolet irradiation.

FIG. 2 is a DSC chart of the unilluminated portion, the light irradiation portion having a light irradiation amount of 1000mJ / cm 2, and the light irradiation portion which was irradiated with UV at 1000mJ / cm 2 after light irradiation with a light irradiation amount of 1000mJ / cm 2. In the light irradiation part of Example 1, the peak shifted to the low temperature side by light irradiation.

(Comparative Example 5)

A double-sided printed wiring board having a thickness of 0.4 mm having a circuit formed with a copper thickness of 15 µm was prepared, and pretreatment was performed using CZ-8100 manufactured by Mack. Then, the brand name PSR-4000G23K (Photocurable resin composition containing the alkali developable resin which has an epoxy acrylate structure) by Daiyo Inky Seijo Co., Ltd. was apply | coated so that it might become 20 micrometers after drying by screen printing. . Subsequently, after drying at 80 degreeC / 30 minutes in a hot-air circulation type drying furnace, light irradiation was carried out by ORC's HMW680GW (metal halide lamp, scattered light) in a negative pattern at an irradiation dose of 300 mJ / cm 2. Then, it developed for 60 second with the 1 wt% sodium carbonate aqueous solution, and then heat-processed 150 degreeC / 60 minutes using the hot-air circulation type drying furnace, and obtained the patterned cured coating film.

Thereafter, desmear resistance was evaluated in the same manner as in Example 2. As a result, the desmear tolerance was "x".

Claims (4)

Alkali developable resin,
Thermally reactive compounds,
Polymer resin, and
A composition comprising a photobase generator, wherein the alkali-developable resin and the thermally reactive compound are added and reacted by heating after selective light irradiation, whereby a negative pattern can be formed by alkali development.
The polymer resin is a block copolymer represented by ABA or ABA '(wherein A or A' is a polymer unit having a glass transition point Tg of 0 ° C. or higher, and B is a polymer unit of glass transition point Tg of less than 0 ° C.). An alkali developing type thermosetting resin composition characterized by the above-mentioned. delete The exothermic peak is generated in DSC measurement of the alkali-developing thermosetting resin composition by light irradiation, or
The exothermic onset temperature in the DSC measurement of the alkali-developed thermosetting resin composition irradiated with light is lower than the exothermic onset temperature in the DSC measurement of the non-irradiated alkali-developed thermosetting resin composition, or the alkali-developed thermosetting resin irradiated with light The exothermic peak temperature in the DSC measurement of a composition is lower than the exothermic peak temperature in the DSC measurement of the unexplored alkali-developed thermosetting resin composition, The alkali-developed thermosetting resin composition characterized by the above-mentioned. It has a pattern layer containing the alkali developing type thermosetting resin composition of Claim 1 or 3, The printed wiring board characterized by the above-mentioned.

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