KR20150009589A - Alkali-developable thermosetting resin composition, and printed wiring board - Google Patents

Abstract

An object of the present invention is to provide an alkali development type thermosetting resin composition and a printed wiring board capable of forming a pattern layer by development even when the inorganic filler is fully charged. It is also an object of the present invention to provide an alkali developing type thermosetting resin composition and a printed wiring board capable of forming a pattern layer having excellent cooling / heating cycle characteristics. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the positive photosensitive resin composition comprises an alkali developable resin, a thermally reactive compound, an inorganic filler, and a photobase generator, Which is an alkali developing type thermosetting resin composition.

Description

TECHNICAL FIELD [0001] The present invention relates to an alkaline developer type thermosetting resin composition, a 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 for solder resists for printed wiring boards and flexible printed wiring boards, an alkali developing type photocurable resin composition using an alkaline aqueous solution as a developer has become mainstream in consideration of environmental problems. As such an alkali developing type photocurable resin composition, an epoxy acrylate modified resin (hereinafter abbreviated as epoxy acrylate) derived by the modification of an epoxy resin is included as described in Patent Documents 1 and 2 Is generally used.

As a method of forming a solder resist using such a photo-curable resin composition, a photo-curable resin composition is applied to a base material and dried to form a resin layer, the photo-cured resin layer is irradiated with light in a pattern and then developed with an alkaline developer, There is a method of forming a predetermined pattern.

Further, the printed wiring board and the flexible printed wiring board are used by being mounted on various apparatuses. Therefore, it is required to have resistance against abrupt changes in the environment such as temperature. However, when the difference in coefficient of linear expansion (CTE) between the thermosetting resin and a substrate forming material such as a substrate, copper, underfill, etc. is large, There is a problem that a crack occurs.

On the other hand, recently, it has been widely practiced to match the CTE of the thermosetting resin with the CTE of the peripheral member material. For example, it is general that CTE is lowered by suppressing the hardening shrinkage by charging the thermosetting resin with an inorganic filler.

Japanese Patent Application Laid-Open No. 61-243869 (claims) Japanese Patent Application Laid-Open No. 250012/1995 (claims)

However, when the inorganic filler is highly charged in the thermosetting resin composition, the light is prevented from penetrating to the deep portion. In this case, there is a problem that resolution is not obtained and it is difficult to form a pattern layer.

Accordingly, an object of the present invention is to provide an alkaline developing type thermosetting resin composition and a printed wiring board capable of forming a pattern layer by development even when an inorganic filler is fully charged. It is also an object of the present invention to provide an alkali development type thermosetting resin composition and a printed wiring board capable of forming a pattern layer having excellent cooling / heating cycle characteristics.

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that the above problems can be solved by the following constitution, and have completed the present invention.

That is, the alkali developing type thermosetting resin composition of the present invention comprises an alkali developing resin, a heat reactive compound, an inorganic filler, and a photo base generating agent, wherein the alkali developing resin and the heat reactive compound This additional reaction enables formation of a negative pattern by alkali development.

In the alkali-developing type thermosetting resin composition of the present invention, it is preferable that the inorganic filler has an average particle diameter of 1 탆 or less.

In the alkali developing type thermosetting resin composition of the present invention, the difference in refractive index between the inorganic filler and the resin is preferably 0.3 or less.

In the alkali developing type thermosetting resin composition of the present invention, it is preferable that the inorganic filler has a refractive index of 1.45 or more and 1.65 or less.

Further, the alkali-developing type thermosetting resin composition of the present invention is characterized in that an exothermic peak is generated in DSC measurement by light irradiation or a heat generation starting temperature in DSC measurement of an alkali developing type thermosetting resin composition Of alkali-developing type thermosetting resin composition which is lower than the heat generation initiation temperature in DSC measurement of alkali-developable thermosetting resin composition of alkali developing type or in which the exothermic peak temperature in DSC measurement of alkali- Is preferably lower than the exothermic peak temperature in the DSC measurement.

According to the present invention, it is possible to provide an alkaline developing type thermosetting resin composition and a printed wiring board capable of forming a pattern layer by development. Further, according to the present invention, it is possible to provide an alkaline developing type thermosetting resin composition and a printed wiring board which can form a pattern layer having excellent curability and cold / heat cycle characteristics.

1 is a schematic diagram showing an example of a pattern forming method using the alkali developing type thermosetting resin composition of the present invention.
2 is a diagram showing a DSC chart of a resin layer containing an alkali developing type thermosetting resin composition of Example 1 of the present invention.
3 is a cross-sectional view of a double-sided printed wiring board for explaining evaluation of concave portions on a through hole.

The alkali-developing type thermosetting resin composition of the present invention (hereinafter occasionally referred to as " thermosetting resin composition ") comprises an alkali developing resin, a thermoreactive compound, an inorganic filler, The alkali developable resin and the thermally reactive compound are subjected to an addition reaction by light irradiation, whereby a negative pattern can be formed by the alkali development. Here, pattern formation means formation of a patterned cured product, that is, a pattern layer.

In the resin layer containing the thermosetting resin composition, a base is generated on the surface by light irradiation. It is considered that the base of the photobase is destabilized by the generated base, and the base further chemically proliferates to the deep part. Here, the base functions as a catalyst when the alkali developable resin and the heat-reactive compound undergo addition reaction, and the addition reaction proceeds to the core portion, so the resin layer hardens to the core portion in the light irradiation portion.

Therefore, even when the inorganic filler is filled in a high concentration, it is possible to easily form the pattern layer by irradiating the thermosetting resin composition in a pattern shape and then alkali developing to remove the unexposed portion.

Further, in the thermosetting resin composition of the present invention, since the alkali developable resin and the heat-reactive compound are cured by the addition reaction, a pattern layer having less deformation and less shrinkage than the photo-curable resin composition can be obtained.

The thermosetting resin composition may be a composition which does not cure even when heated in a state of not irradiated, and can be cured by heat in comparison with light irradiation.

The thermosetting resin composition of the present invention is a thermosetting resin composition which exhibits an exothermic peak in the DSC measurement by light irradiation or an exothermic peak in the DSC measurement of the thermosetting resin composition in which the exothermic onset temperature in the DSC measurement of the irradiated thermosetting resin composition is not irradiated It is preferable that the exothermic peak temperature in the DSC measurement of the thermosetting resin composition which is lower than the exothermic onset temperature or that is irradiated with light is lower than the exothermic peak temperature in the DSC measurement of the thermosetting resin composition not to be irradiated.

Further, the thermosetting resin composition of the present invention is a thermosetting resin composition of the present invention, wherein the temperature difference (referred to as? T start) of the exothermic onset temperature in the DSC measurement or the temperature difference (? T peak ) Is preferably 10 占 폚 or higher, more preferably 20 占 폚 or higher, and still more preferably 30 占 폚 or higher.

Here, the? T start is a method of preparing a thermosetting resin composition having the same composition, measuring the DSC (differential scanning calorimetry) without irradiating the other side after light irradiation, Refers to the temperature difference between the exothermic onset temperature that indicates the initiation of the curing reaction of the composition and the exothermic onset temperature of the resin composition that is not irradiated. ? T peak refers to the temperature difference of the exothermic peak temperature of the resin composition for light irradiation and non-irradiation at the time of DSC measurement.

Further, the irradiated amount in the DSC measurement of the irradiated thermosetting resin composition is an irradiation amount (saturation) in which the exothermic peak temperature shift due to light irradiation of the thermosetting resin composition does not occur while increasing the irradiation amount.

It is possible to suppress the occurrence of so-called overwriting, in which the unexposed portion remains due to the alkali development, or the so-called erosion, in which the light irradiated portion is removed by the alkali development due to ΔT start or ΔT peak of 10 ° C. or higher. Further, since the temperature difference ΔT start or ΔT peak is 10 ° C. or higher, it is possible to obtain a wider range of the heating temperature that can be obtained in the heating step (B1) described later.

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

[Alkali developing resin]

The alkali developable resin is a resin containing at least one functional group selected from the group consisting of a phenolic hydroxyl group, a thiol group and a carboxyl group and capable of being developed into an alkali solution, preferably a compound having two or more phenolic hydroxyl groups, a carboxyl group- A compound having a hydroxyl group and a carboxyl group, and a compound having two or more thiol groups.

Examples of the compound having two or more phenolic hydroxyl groups include phenol novolac resins, alkylphenol novolak resins, bisphenol A novolak resins, dicyclopentadiene type phenol resins, xylok type phenol resins, terpene modified phenol resins, Phenol resins such as polyvinyl phenols, bisphenol F, bisphenol S type phenol resins, poly-p-hydroxystyrene, condensates of naphthol and aldehydes, condensation products of dihydroxynaphthalene and aldehydes, and the like.

As the phenol resin, a compound having a biphenyl skeleton or a phenylene skeleton or both skeletons thereof and a compound having a phenolic hydroxyl group-containing compound such as phenol, orthocresol, paracresol, methacresol, 2,3-xylenol, 2 4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone , 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, fluoroglucinol, or the like may be used.

These may be used alone, or two or more of them may be used in combination.

As the carboxyl group-containing resin, a resin containing a known carboxyl group can be used. By the presence of a carboxyl group, the resin composition can be rendered alkali-developable. In addition to the carboxyl group, a compound having an ethylenically unsaturated bond in the molecule can be used. In the present invention, a carboxyl group-containing resin such as a carboxyl group-containing resin having no ethylenically unsaturated double bond But it is preferable to use.

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

(1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene,? -Methylstyrene, lower alkyl (meth) acrylate or isobutylene. Further, 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-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarbonate-based polyols, polyether Containing carboxyl groups in a diol compound such as polyol, polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A alkylene oxide adduct diol, phenolic hydroxyl group and alcoholic hydroxyl group. Urethane resin.

(3) A process for producing a polyisocyanate compound, which comprises reacting a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate with a polycarbonate-based polyol, a polyether- , A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride at the terminal of a urethane resin by a heavy-chain reaction of a diol compound such as a bisphenol A-based alkylene oxide adduct diol, a phenolic hydroxyl group and a compound having an alcoholic hydroxyl group .

(4) a bifunctional epoxy resin such as a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a beccylenol type epoxy resin and a biphenol type epoxy resin (Meth) acrylate or a partial acid anhydride thereof, a carboxyl group-containing dialcohol compound and a diol compound.

(5) In the synthesis of the resin of the above (2) or (4), a compound having one hydroxyl group and at least one (meth) acryloyl group in the molecule such as hydroxyalkyl (meth) Meth) acrylated carboxyl group-containing urethane resin.

(6) In the synthesis of the resin of the above (2) or (4), it is preferable to use a mixture of isophorone diisocyanate and pentaerythritol triacrylate, such as equimolar reactants, having one isocyanate group and at least one (meth) acryloyl group in the molecule (Meth) acrylate obtained by adding a compound to a carboxyl group-containing urethane resin.

(7) A method of reacting an unsaturated monocarboxylic acid such as (meth) acrylic acid with a polyfunctional (solid) epoxy resin as described above to react the hydroxyl groups present in the side chain with phthalic anhydride, tetrahydrophthalic anhydride, A carboxyl group-containing resin to which a dibasic acid anhydride is added.

(8) A method in which a saturated monocarboxylic acid is reacted with a polyfunctional (solid) epoxy resin as described above, and a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is added to the hydroxyl group present in the side chain Containing resin.

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

(10) A carboxyl group-containing polyester resin in which a dicarboxylic acid is reacted with a polyfunctional oxetane resin as described below, and dibasic acid anhydride is added to the resulting primary hydroxyl group.

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

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

(13) A process for producing a polyoxyalkylene compound, which comprises reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in a molecule with an alkylene oxide such as ethylene oxide or propylene oxide with a monocarboxylic acid containing an unsaturated group, A carboxylic group-containing resin obtained by reacting an anhydride.

(14) A method in which a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in a molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate is reacted with a saturated monocarboxylic acid, Is reacted with a polybasic acid anhydride.

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

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

(17) A process for producing an epoxy compound having a plurality of epoxy groups in one molecule by reacting a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol with a saturated monocarboxylic acid Containing carboxylic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride and adipic acid to the alcoholic hydroxyl group of the obtained reaction product.

(18) A process for producing an epoxy compound having a plurality of epoxy groups in one molecule by reacting a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in a molecule such as p-hydroxyphenethyl alcohol with an alcoholic Containing resin obtained by reacting a hydroxyl group with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic acid anhydride or adipic acid.

(19) A process for producing an epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, Containing monocarboxylic acid and reacting the alcoholic hydroxyl group of the obtained reaction product with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic acid anhydride, pyromellitic acid anhydride or adipic acid, Suzy.

(20) The resin composition according to any one of the above items (1) to (19), which contains one epoxy group in the molecule such as glycidyl (meth) acrylate and? -Methyl glycidyl (meth) ) A carboxyl group-containing resin obtained by further adding a compound having an acryloyl group.

Since the alkali developable resin has a large number of carboxyl groups and hydroxyl groups in the side chain of the backbone polymer, development with an aqueous alkaline solution becomes possible.

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 the equivalent of the hydroxyl group or the equivalent of the carboxyl group is more than 900 g / eq., Adhesion of the pattern layer may not be obtained or alkaline development may become difficult. On the other hand, when the hydroxyl group equivalent or the carboxyl group equivalent is 80 g / eq. , Dissolution of the light irradiation part by the developer proceeds, so that the line is thinned more than necessary, and in some cases, it is dissolved and peeled off as a developing solution without distinction between the light irradiation part and the non-irradiation part, It is not preferable because there is a case that When the carboxyl group equivalent or the phenol group equivalent is large, development is possible even when the content of the alkali developable resin is small, which is preferable.

The weight average molecular weight of the alkali developable resin used in the present invention varies depending on the resin skeleton, and is preferably from 2,000 to 150,000, more preferably from 5,000 to 100,000. If the weight average molecular weight is less than 2,000, the tack free performance may deteriorate, the moisture resistance of the resin layer after the light irradiation may be poor, the film may be reduced during development, and the resolution may be significantly lowered. On the other hand, if the weight average molecular weight exceeds 150,000, the developability may be markedly deteriorated and the storage stability may be deteriorated.

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

As the compound having a thiol group, for example, trimethylolpropane tristyropionate, pentaerythritol tetrakisthiopropionate, ethylene glycol bisthioglycolate, 1,4-butanediol bisthioglycolate, trimethylolpropane tristhio Glycolate, pentaerythritol tetrakisthioglycolate, di (2-mercaptoethyl) ether, 1,4-butanedithiol, 1,3,5-trimercaptomethylbenzene, 1,3,5-trimercaptomethyl -2,4,6-trimethylbenzene, a terminal thiol group-containing polyether, a terminal thiol group-containing polythioether, a thiol compound obtained by the reaction of an epoxy compound with hydrogen sulfide, a thiol compound obtained by reacting a polythiol compound with an epoxy compound A thiol compound having a terminal thiol group, and the like.

The alkali developable resin is preferably a compound having a carboxyl group-containing resin or a phenolic hydroxyl group. The alkali developable resin is preferably non-photosensitive, such as epoxy acrylate, having no photocurable structure. Such a non-photosensitive alkali developable resin has no ester bond derived from an epoxy acrylate and therefore has high resistance to a disperse liquid. Therefore, a pattern layer having excellent curing characteristics can be formed. Further, since it does not have a photo-curable structure, curing shrinkage can be suppressed.

When the alkali developable resin is a carboxyl group-containing resin, it can be developed into a weakly alkaline aqueous solution as compared with the case of the phenolic resin. Examples of the slightly alkaline aqueous solution include those in which sodium carbonate and the like are dissolved. By developing with a slightly alkaline aqueous solution, it is possible to suppress the development of the irradiated portion. Further, the light irradiation time in the step (B) and the heating time in the step (B1) can be shortened.

[Thermoreactive compound]

The thermally reactive compound is a resin having a functional group capable of a curing reaction by heat. Epoxy resins, and polyfunctional oxetane compounds.

The epoxy resin is a resin having an epoxy group, and any known epoxy resin can be used. A bifunctional epoxy resin having two epoxy groups in the molecule, and a polyfunctional epoxy resin having a large number of epoxy groups in the molecule. Further, it may be a hydrogenated bifunctional epoxy compound.

Examples of the polyfunctional epoxy compound include bisphenol A epoxy resin, brominated epoxy resin, novolak epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, glycidylamine epoxy resin, hydantoin epoxy resin, Alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, biquileneol type or biphenol type epoxy resin or a mixture thereof, bisphenol S type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylol ethane type epoxy resin, Cyclic epoxy resins, cyclic epoxy resins, diglycidyl phthalate resins, tetraglycidyl silyloyl ethane resins, naphthalene group-containing epoxy resins, epoxy resins having dicyclopentadiene skeleton, glycidyl methacrylate copolymer epoxy resins, A copolymerized epoxy resin of mid and glycidyl methacrylate, a CTBN-modified epoxy resin And the like.

Examples of other liquid bifunctional epoxy resins include vinylcyclohexene diepoxide, (3 ', 4'-epoxycyclohexylmethyl) -3,4-epoxycyclohexanecarboxylate, (3', 4'- 6'-methylcyclohexylmethyl) -3,4-epoxy-6-methylcyclohexanecarboxylate, and the like. The naphthalene group-containing epoxy resin is preferable because thermal expansion of the cured product can be suppressed.

The above-mentioned epoxy resins may be used singly or in combination of two or more.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [ (3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [ (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, In addition to polyfunctional oxetanes such as oligomers and copolymers thereof, oxetane alcohol and novolak resins, poly (p-hydroxystyrene), cardo type bisphenols, calixarene, calix resorcinarene or And ether compounds with a resin having a hydroxyl group such as silsesquioxane. Other examples include copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

Here, when the thermally reactive compound has a benzene skeleton, heat resistance is improved, which is preferable. When the thermosetting resin composition contains a white pigment, the thermally reactive compound is preferably an alicyclic skeleton. Thereby, the photoreactivity can be improved.

The amount of the thermally reactive compound to be used is preferably 1: 0.1 to 1:10, more preferably 1: 0.2 to 1: 5 in terms of the equivalent ratio (thermal reactive group: alkali developing group) to the alkali developable resin. When the mixing ratio is within the range, the phenomenon is improved.

[Photobase generator]

The photobase generator is a compound capable of generating at least one basic substance capable of functioning as a catalyst for addition reaction of the above-mentioned thermoreactive compound by changing the molecular structure by irradiation of light such as ultraviolet rays or visible light, to be. As the basic substance, for example, secondary amine and tertiary amine can be mentioned.

As the photobase generator, for example, an? -Amino acetophenone compound, an oxime ester compound, an acyloxyimino group, an N-formylated aromatic amino group, a N-acylated aromatic amino group, a nitrobenzylcarbamate group, And a compound having a substituent such as a carboxylate group and a carboxylate group.

The? -aminoacetophenone compound has a benzoin ether bond in its molecule, and when exposed to light, cleavage takes place in the molecule to generate a basic substance (amine) which exerts a curing catalytic action. Specific examples of the? -amino acetophenone compound include 4- (methylthiobenzoyl) -1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, Methyl-1-morpholinoethane (Irgacure 907, trade name, manufactured by BASF Japan) and 2- (dimethylamino) -2 - [(4- methylphenyl) methyl] (Morpholinyl) phenyl] -1-butanone (IRGACURE 379, trade name, manufactured by BASF Japan), or a solution thereof can be used.

As the oxime ester compound, any compound capable of generating a basic substance by light irradiation can be used. Examples of oxime ester compounds include CGI-325, Irgacure-OXE01, Irgacure-OXE02, and N-1919 and NCI-831 manufactured by BASF Japan. Also, a compound having two oxime ester groups in the molecule can be suitably used, and specific examples thereof include oxime ester compounds having a carbazole structure represented by the following formula.

(Wherein X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino 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 having 1 to 8 carbon atoms), a naphthyl group 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, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 8 carbon atoms An alkoxy group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 8 carbon atoms An alkyl group having 1 to 8 carbon atoms, or an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group), an anthryl group, a pyridyl group, a benzofuryl group or a benzothienyl group, Ar represents a bond, To 10 carbon atoms, such as alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, thienylene, furylene, 2,5- -Diyl, 4,2'-styrene-diyl, and n is an integer of 0 or 1)

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

As preferable carbazole oxime ester compounds, there may be mentioned compounds which can be represented by the following formulas.

(Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group which may be substituted with a nitro group, a halogen atom or an alkyl group having 1 to 4 carbon atoms, R ² represents an alkyl group having 1 to 4 carbon atoms An alkyl group, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may be substituted with an alkyl group or an alkoxy group having 1 to 4 carbon atoms, R ³ may be connected by an oxygen atom or a sulfur atom, An alkyl group of 1 to 20 carbon atoms which may be substituted or a benzyl group which may be substituted by an alkoxy group of 1 to 4 carbon atoms, R ⁴ represents an acyl group represented by a nitro group or XC (= O) - , X represents an aryl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, a thienyl group, a morpholino group, a thiophenyl group, or a structure represented by the following formula:

Other examples include Japanese Patent Application Laid-Open Nos. 2004-359639, 2005-097141, 2005-220097, 2006-160634, 2008-094770 A carbazole oxime ester compound described in Japanese Patent Application Laid-Open No. 2008-509967, Japanese Patent Laid-Open Publication No. 2009-040762, and Japanese Patent Laid-Open No. 2011-80036.

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

Specific examples of the compound having an N-formylated aromatic amino group and an N-acylated aromatic amino group include di-N- (p-formylamino) diphenylmethane, di- , Di-N- (p-benzoamido) diphenylmethane, 4-formylaminotoluylenes, 4-acetylaminotoluylene, 2,4-diformylaminotoluylenes, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms, such as acetylaminonaphthalene, 5,3'-dimethyl-4,4'-diformylaminobiphenyl, 4,4'-diformylaminobenzophenone, and the like.

Specific examples of the compound having a nitrobenzylcarbamate group and an alkoxybenzylcarbamate group include, for example, bis {{(2-nitrobenzyl) oxy} carbonyl} diaminodiphenylmethane, 2,4- Nitrobenzyl) oxy} toluene, bis {{(2-nitrobenzyloxy) carbonyl} hexane-1,6-diamine, m- Amide} and the like.

As the photobase generator, oxime ester compounds and? -Amino acetophenone compounds are preferable. As the? -amino acetophenone compound, those having at least two nitrogen atoms are particularly preferred.

As other photobase generators,

(E) -1- [3- (2-hydroxyphenyl) -2-propylphenol (trade name: WPBG-018 (trade name: 9-anthrylmethyl N, N'- diethylcarbamate) (Anthraquinon-2-yl) ethyl imidazolecarboxylate (trade name: WPBG-081), WPBG-082 (trade name: guanidinium 2- (3- benzoylphenyl) propionate) Rate) may be used.

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

The photobase generator may be used alone or in combination of two or more. The blending amount of the photo-base generator in the thermosetting resin composition is preferably 1 to 50 parts by mass, more preferably 1 to 40 parts by mass, per 100 parts by mass of the heat-reactive compound. If the amount is less than 1 part by mass, development may be difficult, which is not preferable.

[Maleimide compound]

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

Examples of the maleimide compound include polyfunctional aliphatic / alicyclic maleimide and polyfunctional aromatic maleimide. A bifunctional or higher maleimide compound (polyfunctional maleimide compound) is preferable. Examples of the polyfunctional aliphatic / alicyclic maleimide include N, N'-methylenebismaleimide, N, N'-ethylenebismaleimide, tris (hydroxyethyl) isocyanurate and aliphatic / alicyclic maleimide A maleimide ester compound of an isocyanurate skeleton obtained by dehydrating esterification of a carboxylic acid; Isocyanurate skeleton polyamides such as maleimide urethane compounds of isocyanurate skeleton obtained by urethanating tris (carbamate hexyl) isocyanurate and aliphatic / alicyclic maleimide alcohol; (Maleimide ethyl carbonate), aliphatic / alicyclic maleimidic carboxylic acid and various aliphatic / cycloaliphatic polyols are dehydrated and esterified, or aliphatic / alicyclic polyhydric alcohols Aliphatic / alicyclic poly (maleimide) ester compounds obtained by transesterifying maleimide carboxylic acid esters with various aliphatic / cycloaliphatic polyols; Aliphatic / alicyclic poly (maleimide) ester compounds obtained by ether ring-opening reaction of aliphatic / alicyclic maleimide carboxylic acid and various aliphatic / cycloaliphatic polyepoxides; Aliphatic / alicyclic poly (maleimide) urethane compounds obtained by urethanizing aliphatic / alicyclic maleimide alcohols with various aliphatic / alicyclic polyisocyanates, and the like.

Examples of the polyfunctional aromatic maleimide include aromatic polyimale ester compounds obtained by dehydrating esterification of maleimide carboxylic acid and various aromatic polyols, or transesterifying maleimide carboxylic acid esters with various aromatic polyols; Aromatic polymaleimide ester compounds obtained by ether ring-opening reaction of maleimide carboxylic acid with various aromatic polyepoxides; And aromatic polyfunctional maleimides such as aromatic poly (maleimide) urethane compounds obtained by urethanizing a maleimide alcohol with various aromatic polyisocyanates.

Specific examples of the polyfunctional aromatic maleimide include N, N '- (4,4'-diphenylmethane) bismaleimide, N, N'-2,4-tolylene bismaleimide, N, N' Methylene-2,4-bismaleimide benzene, N, N'-m-phenylene bismaleimide, N, N'-p-phenylene bismaleimide, N, N'-m-toluylene bismaleimide, N, N'-4,4'-biphenylene bismaleimide, N, N'- N, N'-4,4 '- [3,3'-dimethyldiphenylmethane] bismaleimide, N, N'- Phenylmethane] bismaleimide, N, N'-4,4'-diphenylmethane bismaleimide, N, N'-4,4'-diphenylpropanebismaleimide, N, N'- Diphenyl ether bismaleimide, N, N'-3,3'-diphenylsulfone bismaleimide, N, N'-4,4'-diphenylsulfone bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-t-butyl- Bis [4- (4-maleimidophenoxy) phenyl] decane, 1,1-bis [2 Methylphenyl) -2-methylpropane, 4,4'-cyclohexylidene-bis [1- (4-maleimidophenoxy) (1,1-dimethylethyl) benzene], 4,4'-methylene-bis [1- (4-maleimidophenoxy) , 4'-methylene-bis [1- (4-maleimidophenoxy) -2,6-di-s-butylbenzene], 4,4'- cyclohexylidene- 2-cyclohexylbenzene, 4,4'-methylenebis [1- (maleimidophenoxy) -2-nonylbenzene], 4,4 '- (1-methylethylidene) -bis [ - (maleimidophenoxy) -2,6-bis (1,1-dimethylethyl) benzene], 4,4 ' , 4,4'- (1-methylheptylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4'-cyclohexylidene-bis [1- (maleimidophenoxy) -3- Benzene], 2,2-bis [4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [ Bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2- Propane, 2,2-bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2- (4-maleimidophenoxy) phenyl] propane, bis [3-methyl- (4-maleimidophenoxy) phenyl] methane , Bis [3,5-dimethyl- (4-maleimidophenoxy) phenyl] methane, bis [3-ethyl- (4-maleimidophenoxy) phenyl] methane, Phenyl] -tricyclo [5.2.1.0 2,6] decane, 4,8-bis [4- (4-maleimidophenoxy) , 9-bis [4- (4-maleimide Phenoxy) phenyl] -tricyclo [5.2.1.02,6] decane, 4,9-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo [5.2.1.0 2,6] decane, 1,8 Bis [3-methyl-4- (4-maleimidophenoxy) phenyl] mentane, 1,8-bis [3,5 -Dimethyl-4- (4-maleimidophenoxy) phenyl] mentane.

The compounding amount of the maleimide compound is preferably 1: 0.1 to 1:10, and more preferably 1: 0.2 to 1: 5 in terms of the equivalent ratio (maleimide group: alkali developing group) to the alkali developable resin. Such blending ratio facilitates development.

[Polymer resin]

The thermosetting resin composition of the present invention can be blended with a publicly known polymer resin for the purpose of improving the flexibility and tackiness of the resulting cured product.

Examples of the polymer resin include cellulose type, polyester type, phenoxy resin type, polyvinyl acetal type, polyvinyl butyral type, polyamide type, polyamideimide type binder polymer, block copolymer, elastomer, rubber particle and the like. The binder polymer may be used alone or in combination of two or more.

By blending the polymer resin, the melt viscosity of the thermosetting resin composition is increased, and the resin fluidity of the through hole portion can be suppressed at the time of post-exposure heating. As a result, it is possible to manufacture a flat substrate on which the concave portion is not seen on the through hole.

The addition amount of the polymer resin is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, particularly preferably 5 to 30 parts by mass, based on 100 parts by mass of the heat-reactive compound. When the blending amount of the polymer resin exceeds 50 parts by mass, deterioration resistance of the thermosetting resin composition is undesirably deteriorated.

(Block copolymer)

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

As the block copolymer used in the present invention, an A-B-A or A-B-A 'type block copolymer is preferable. Among ABA or AB-A 'type block copolymers, it is preferable that B in the center is a soft block and the glass transition point Tg is low, preferably less than 0 ° C, and both A or A' are hard blocks and Tg is high , It is preferable that it is constituted by polymer units of 0 占 폚 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 comprising a polymer unit in which A or A' contains a polymer unit having a Tg of 50 ° C or higher and B has a Tg of -20 ° C or lower is more preferable .

It is preferable that A or A 'in the A-B-A or A-B-A' type block copolymer has high compatibility with the heat-reactive compound, and B has low compatibility with the heat-reactive compound. Thus, it is considered that a specific structure is easily exhibited in the matrix when the block at both ends is commonly used in a matrix and the central block is a block copolymer which is used as an emergency in a matrix.

A and A 'preferably include polymethyl (meth) acrylate (PMMA), polystyrene (PS), and the like as B and include poly n-butyl acrylate (PBA), polybutadiene . Further, a hydrophilic unit having excellent compatibility with the above-mentioned matrix represented by a styrene unit, a hydroxyl group-containing unit, a carboxyl group-containing unit, an epoxy-containing unit, an N-substituted acrylamide unit, It becomes possible to further improve the compatibility.

As the block copolymer to be used in the present invention, a block copolymer of three or more atoms is preferable, and a block copolymer in which the molecular structure synthesized by the living polymerization method is precisely controlled is more preferable for obtaining the effect of the present invention. This is presumably because the molecular weight distribution of the block copolymer synthesized by the living polymerization method was narrow and the characteristics of each unit became clear. The molecular weight distribution (Mw / Mn) of the block copolymer to be used is preferably 3 or less, more preferably 2.5 or less, and furthermore preferably 2.0 or less.

The block copolymer comprising such a (meth) acrylate polymer block can be obtained, for example, by the method described in Japanese Unexamined Patent Application Publication No. 2007-516326 or Japanese Unexamined Patent Publication No. 2005-515281, 4) as an initiator and then polymerizing the Y unit and then polymerizing the X unit.

(Wherein n represents 2, Z represents a divalent organic group, and preferably 1,2-ethanedioxy, 1,3-propanedioxy, 1,4-butane dioxy, (2-ethoxy) cyanuric acid, polyaminoamines such as polyethyleneamine, 1,3,5-tris (2-ethylamino) cyanuric acid, polythioxy , Phosphonate or polyphosphonate, and Ar represents a divalent aryl group)

The weight average molecular weight of the block copolymer is preferably in the range of 20,000 to 400,000, more preferably 50,000 to 300,000. When the weight-average molecular weight is less than 20,000, the desired toughness and flexibility are not obtained, and the adhesiveness of the thermosetting resin composition when the thermosetting resin composition is made into a dry film or when it is applied to a substrate and dried is also lowered. On the other hand, if the weight average molecular weight exceeds 400,000, the viscosity of the thermosetting resin composition becomes high, and the printability and processability may be significantly deteriorated. When the weight-average molecular weight is 50,000 or more, an excellent effect is obtained in terms of relaxation against impact from the outside.

As the polymer resin, a block copolymer is preferable because it is excellent in crack resistance at the time of a cooling / heating cycle and can suppress warpage after curing. The block copolymer is particularly preferable because the recesses on the through holes can be suppressed and a substrate having a flat surface can be produced. Further, by combining the inorganic filler, crack resistance during a cooling / heating cycle is excellent.

(Elastomer)

To the thermosetting resin composition of the present invention, an elastomer having a functional group may be added. By adding an elastomer having a functional group, it is expected that the coating property is improved and the strength of the coating film is also improved. Further, polyester elastomer, polyurethane elastomer, polyester urethane elastomer, polyamide elastomer, polyester amide elastomer, acrylic elastomer, olefin elastomer and the like can be used. Further, a resin obtained by modifying an epoxy group of part or all of the epoxy resin having various skeletons with both terminal carboxylic acid modified butadiene-acrylonitrile rubbers can also be used. Further, an epoxy-containing polybutadiene elastomer, an acrylic-containing polybutadiene elastomer, a hydroxyl group-containing polybutadiene elastomer, and a hydroxyl group-containing isoprene elastomer may be used. The elastomer may be used singly or in combination of two or more kinds.

(Rubber particles)

The rubber particles may be any particles as long as they are particles formed from organic materials such as polymers having a crosslinked structure. For example, crosslinked NBR particles obtained by copolymerizing acrylonitrile and butadiene as acrylonitrile butadiene copolymers; A copolymer of acrylonitrile, butadiene and a carboxylic acid such as acrylic acid; Crosslinked rubber particles (also referred to as " core-shell rubber particles ") having a so-called core shell structure comprising a crosslinked polybutadiene, a crosslinked silicone rubber, or NBR as a core layer and a crosslinked acrylic resin as a shell layer.

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

The crosslinked NBR particles are partially crosslinked in the step of copolymerizing acrylonitrile and butadiene and then copolymerized to form granules. It is also possible to obtain carboxylic acid-modified crosslinked NBR particles by copolymerizing a carboxylic acid such as acrylic acid or methacrylic acid.

The core-shell rubber particles of the crosslinked butadiene rubber-crosslinked acrylic resin can be obtained by a two-stage polymerization method of polymerizing the butadiene particles by emulsion polymerization and then continuing the polymerization by adding monomers such as acrylic acid ester and acrylic acid.

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

The size of the rubber particles is preferably 1 mu m or less in terms of the primary average particle diameter, and is preferably 50 nm to 1 mu m. If the primary average particle diameter exceeds 1 탆, the adhesive strength is lowered, but insulation reliability in the fine wiring is impaired. The term " primary average particle diameter " as used herein refers to the particle diameter in the aggregated particle diameter, that is, the particle diameter not in the secondary particle diameter but in the non-aggregated particle.

The primary average particle diameter can be measured by, for example, a laser diffraction particle size distribution meter.

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

The content of the rubber particles in the resin composition is preferably 50 mass% or less, and more preferably 1 to 30 mass%.

For example, as a commercially available product of carboxylic acid-modified acrylonitrile butadiene rubber particles, XER-91 manufactured by Nippon Gosei Rubber Co., Ltd. can be mentioned. The core shell particle of the butadiene rubber-acrylic resin is Paraloid EXL2655 manufactured by Rohm and Haas Co., Ltd. and AC-3832 manufactured by Gansu Kasei Kogyo Co., The core-shell rubber particle of the crosslinked silicone rubber-acrylic resin is GENIOPERLP52 manufactured by Asahi Chemical Industry Co., Ltd.

By using the rubber particles, the crack resistance during the cooling / heating cycle can be improved.

[Inorganic filler]

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

The average particle diameter (D50) of the inorganic filler is preferably 1 mu m or less, more preferably 0.7 mu m or less, and even more preferably 0.5 mu m. If the average particle diameter exceeds 1 탆, the pattern layer may become cloudy, which is not preferable. The lower limit value of the average particle diameter (D50) of the inorganic filler is not particularly limited, but is, for example, 0.01 m or more. Here, the average particle diameter (D50) means an average primary particle diameter.

The average particle diameter (D50) can be measured by a laser diffraction / scattering method. When the average particle diameter is within the above range, the refractive index is made closer to the resin component, and the permeability is improved, so that the efficiency of base generation from the photo-base generating agent by light irradiation is increased.

The difference in refractive index between the inorganic filler and the alkali developable resin is preferably 0.3 or less. By setting the refractive index difference to 0.3 or less, scattering of light can be suppressed and favorable deep curing characteristics can be obtained. Here, the refractive index of the inorganic filler is preferably 1.4 or more and 1.8 or less. The refractive index of the inorganic filler can be measured in accordance with JIS K7105.

The mixing ratio of the inorganic filler is preferably 20 mass% or more and 80 mass% or less, more preferably 30 mass% or more and 80 mass% or less, based on the total solid content of the thermosetting resin composition. When the compounding ratio of the inorganic filler exceeds 80 mass%, the viscosity of the composition becomes high, and the coating property may be lowered, or the cured product of the thermosetting resin composition may become brittle.

In the composition in which the curing is progressed by the radical reaction, the resolution is lowered when the content of the inorganic filler is increased. However, in the present invention, since the reaction is a curing reaction with the base generated, good resolution can be maintained even when the content of the inorganic filler is increased .

The specific gravity of the inorganic filler is preferably 3 or less, more preferably 2.8 or less, still more preferably 2.5 or less. When the specific gravity of the inorganic filler is 3 or less, thermal expansion can be suppressed. Examples of the inorganic filler of 3 or less include, for example, silica and aluminum hydroxide, and silica is particularly preferable.

Examples of the shape of the inorganic filler include indefinite shape, needle shape, disc shape, scaly shape, spherical shape, and hollow shape. Here, from the viewpoint that the composition can be blended at a high ratio, spherical shape is preferable. It is more preferable that the inorganic filler is treated with a surface treating agent such as a silane coupling agent in order to improve moisture resistance.

Further, by containing an inorganic filler, crack resistance during a cooling / heating cycle can be improved. By containing a large amount of an inorganic filler, warping after curing can be suppressed.

In the present invention, the coefficient of thermal expansion (CTE) of the cured product is preferably 40 ppm or less, more preferably 30 ppm or less, still more preferably 20 ppm or less.

[Organic solvents]

In the thermosetting resin composition of the present invention, an organic solvent may be used for the production of a resin composition or for viscosity adjustment for application to a substrate or a carrier film.

Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents and the like. These organic solvents may be used singly or as a mixture of two or more kinds.

[Photopolymerizable monomer]

The thermosetting resin composition of the present invention may contain a photopolymerizable monomer within a range that does not impair the effect of the present invention.

Examples of the photopolymerizable monomer include 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, trimethylol propane, pentaerythritol, ditrimethylol propane, dipentaerythritol, and trishydroxy ethylisocyanurate, or polyvalent (meth) acrylates of the ethylene oxide or propylene oxide adduct Ryu; (Meth) acrylates of ethylene oxide or propylene oxide adduct of phenols such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol A; (Meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; And melamine (meth) acrylate.

The blending amount of the photopolymerizable monomer is preferably 50 mass% or less, more preferably 30 mass% or less, still more preferably 15 mass% or less, based on the solid content excluding the solvent of the thermosetting resin composition. When the blending amount of the photopolymerizable monomer is more than 50% by mass, the shrinkage of the curing increases, and therefore the warpage may be increased. When the photopolymerizable monomer is derived from (meth) acrylate, it includes an ester bond. In this case, hydrolysis of the ester bond occurs due to the desmear treatment, so that there is a possibility that the electrical characteristics are lowered.

(Any other component)

In the thermosetting resin composition of the present invention, components such as a mercapto compound, an adhesion promoter, a colorant, an antioxidant, and an ultraviolet absorber may be further added, if necessary.

Particularly, in the present invention, even when the content of the coloring agent is increased, the undercut can be suppressed and good via holes and lines can be formed.

These materials may be those known in the field of electronic materials. The thermosetting resin composition may further contain a known thickener such as finely divided silica, hydrotalcite, organic bentonite or montmorillonite, a defoaming agent such as silicon, fluorine or high molecular weight and / or a leveling agent, a silane coupling agent, Additive additives can be blended.

As the thermosetting component, a known thermosetting resin such as a block isocyanate compound, an amino resin, a benzoxazine resin, a carbodiimide resin, a cyclocarbonate compound or an episulfide resin may be added.

In addition, a resin composition containing a phenol resin as an alkali developable resin and containing an epoxy resin as a heat-reactive compound can be used to obtain a cured product having a high Tg and excellent HAST resistance without depending on the softening point of the raw material have. When the photopolymerizable monomer (a low-molecular compound containing an ethylenic unsaturated group in its molecule and containing a carboxyl group-containing resin as a main component and being blended for promoting photo-curing) is not blended, It is possible to obtain a resin composition having excellent properties.

In the conventional photo-curable resin composition, since the photo-curing reaction is caused at room temperature, the Tg of the resin composition during curing is increased and the curing reaction is sometimes stopped, and it is necessary to design the resin composition to have a low Tg . In contrast, the alkali-developing type thermosetting resin composition of the present invention is not limited in Tg before the curing reaction, and can be expected to have a high Tg. The alkali-developable thermosetting resin composition of the present invention can be expected to be cured without being subjected to oxygen inhibition.

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

[Pattern formation method]

A pattern forming method capable of suitably using the thermosetting resin composition of the present invention includes a step (A) of forming a resin layer containing a thermosetting resin composition on a substrate, a step of irradiating light in a negative pattern shape, (B) a step of activating the photo-base generator to cure the light-irradiated portion, and (C) a step of forming a negative-type pattern layer by removing the non-irradiated portion by alkali development.

By irradiating light in a pattern shape to generate a base in the light irradiation portion of the thermosetting resin composition, the light irradiation portion can be cured. Thereafter, by developing with an aqueous alkali solution, the unexposed portions can be removed to form a negative pattern layer.

Here, in the present invention, it is preferable to have the step (B1) of heating the resin layer after the step (B). Thereby, the resin layer is sufficiently cured, and a pattern layer having further excellent curing characteristics can be obtained.

[Step (A)]

The pattern forming method will be described with reference to Fig. Step (A) is a step of forming a resin layer containing a thermosetting resin composition on a substrate. The resin layer can be formed by applying and drying a liquid thermosetting resin composition on a substrate or by laminating a thermosetting resin composition with a dry film on a substrate.

As a method of applying the thermosetting resin composition to the substrate, known methods such as a blade coater, a lip coater, a comma coater, and a film coater can be suitably employed. The drying method includes a method in which warm air in a dryer is countercurrently contacted by using a hot air circulation type drying furnace, IR, a hot plate, a convection oven, or the like, And a method of spraying the solution onto the substrate.

As the base material, a base material such as a paper-phenol resin, a paper-epoxy resin, a glass cloth-epoxy resin, a glass-polyimide, a glass cloth / nonwoven- A polyimide film, a PET film, a glass substrate, a ceramic substrate, a wafer, and the like, of all grades (FR-4 and the like) using a composite material such as epoxy resin, synthetic fiber-epoxy resin, fluororesin, polyethylene, PPO, cyanate ester, And the like can be used.

[Process (B)]

Step (B) is a step of irradiating light in a negative pattern shape to activate the photo-base generating agent contained in the thermosetting resin composition to cure the light irradiated portion. In the step (B), it is considered that the base of the photobase generator is destabilized by the base generated in the light irradiating part, and more base is generated. By chemically propagating the base in this manner, it is possible to sufficiently cure the deep portion of the light irradiation portion.

As the light irradiator used for light irradiation, for example, a direct drawing apparatus capable of irradiating laser light, lamp light, or LED light can be used. As the mask for photo-shaping of the pattern shape, a negative type mask can be used.

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

As the direct writing apparatus, for example, those manufactured by Nippon Orbotech Co., Ltd. and manufactured by FANUC Corporation may be used, and any apparatus may be used as long as it is an apparatus for emitting laser light having a maximum wavelength of 350 to 410 nm.

[Step (B1)]

Step (B1) cures the irradiated portion by heating. Step (B1) can be cured to the core by the base generated in step (B).

It is preferable that the heating temperature is a temperature at which the light-irradiated portion of the thermosetting resin composition is thermally cured, but the non-irradiated portion is not thermally cured.

For example, it is preferable that the step (B1) is lower than the heat generation starting temperature or the exothermic peak temperature of the uncured thermosetting resin composition and is heated at a temperature higher than the heat generation initiation temperature or exothermic peak temperature of the light irradiated thermosetting resin composition. By heating in this way, only the irradiated portion can be selectively cured.

Here, the heating temperature is, for example, 80 to 140 占 폚. By setting the heating temperature at 80 占 폚 or higher, the irradiated portion can be sufficiently cured. On the other hand, by setting the heating temperature at 140 占 폚 or lower, only the irradiated portion can be selectively cured. The heating time is, for example, 10 to 100 minutes. The heating method is the same as the above-mentioned drying method.

In the non-irradiated portion, since no base is generated from the photobase generator, thermal curing is suppressed.

[Step (C)]

Step (C) is a step of forming a negative pattern layer by removing the unexposed portion by development. As the developing method, a known method such as a dipping method, a shower method, a spray method, and a brush method can be used. As the developer, an aqueous solution of an alkali such as an aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia or ethanolamine or aqueous solution of tetramethylammonium hydroxide (TMAH) .

[Process (D)]

It is preferable that the pattern forming method further includes an ultraviolet irradiation step (D) after the step (C). By further performing ultraviolet irradiation after the step (C), the remaining photobase generator can be activated without being activated at the time of light irradiation. The wavelength of the ultraviolet rays and the irradiation amount (irradiation amount) in the ultraviolet irradiation step (D) after the step (C) may be the same as or different from the step (B). A suitable dose (irradiation dose) is 150 to 2000 mJ / cm 2.

[Step (E)]

It is preferable that the pattern forming method further includes a thermosetting (postcuring) step (E) after the step (C).

When both step (D) and step (E) are performed after step (C), step (E) is preferably performed after step (D).

Step (E) sufficiently thermally cures the pattern layer by the step (B), or the base generated from the photo-base generator by steps (B) and (D). At the time of the step (E), since the non-irradiated portion has already been removed, the step (E) can be performed at a temperature not lower than the curing reaction initiation temperature of the uncured thermosetting resin composition. Thereby, the pattern layer can be sufficiently thermally cured. The heating temperature is, for example, 160 DEG C or more.

[Step (F)]

The pattern forming method may further include a laser processing step (F). A fine opening can be formed by laser machining. As the laser, a known laser such as a YAG laser, a CO ₂ laser, or an excimer laser can be used.

It is preferable that the step (F) is performed after the step (C), or after the step (D) or (E) when the step (D) or (E) is included.

[Process (G)]

The pattern forming method of the present invention may further include a desmearing step (G) after the step (F).

Step (G) includes a smear swelling process to make the smear swell and to be easily removed, a removal process to remove smear, and a neutralization process to neutralize the sludge generated from the distillate liquid used in the removal process.

The swelling process is performed using an alkaline chemical solution such as sodium hydroxide, and facilitates the removal of smear by the chemical liquid.

In the removing step, the acidic chemical liquid containing an oxidizing agent such as dichromic acid or permanganic acid is used to remove the smear.

In the neutralization step, an alkali chemical such as sodium hydroxide is used to reduce and remove the oxidizing agent used in the removing step.

Example

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited by these examples and comparative examples.

(Examples 1 to 19 and Comparative Examples 1 to 4)

≪ Preparation of alkali developing type thermosetting resin composition >

According to the formulations described in Tables 1 to 3, the materials described in Examples / Comparative Examples were each compounded, preliminarily mixed with an agitator, and kneaded with a three roll mill to prepare a thermosetting resin composition. The values in the tables are parts by mass unless otherwise specified.

≪ Preparation of dry film &

A thermosetting resin composition was applied onto a PET film having a thickness of 38 mu m as a carrier film using an applicator, and then dried at 90 DEG C for 30 minutes to produce a dry film. The thickness of the thermosetting resin composition was adjusted so that the thickness of the thermosetting resin composition became about 20 占 퐉 after drying. Thereafter, the obtained dry film was slit-processed to a predetermined size.

<Laminate>

A double-sided printed wiring board having a circuit with a copper thickness of 15 mu m was prepared and a substrate prepared by using CZ-8100 manufactured by Mack Co., Ltd. was pretreated with a vacuum laminator MVLP-500, Lt; / RTI &gt; Lamination was carried out at a temperature of 80 캜 and a pressure of 5 kg / cm 2/60 seconds.

&Lt; Evaluation of B-stage state (handling at the time of formation on substrate) >

For Examples 1 to 19, the B-stage state (semi-cured state) of the dry film was evaluated. The slit processing was performed to a predetermined size of the dry film on which the obtained thermosetting resin composition was formed, and the state of the dry film was confirmed by the following method.

(Assessment Methods)

○: After slit processing, breakage of the resin layer and powder falling of the resin were confirmed

?: After the slit processing, breakage of the resin layer and powder falling of the resin were confirmed

&Lt; Evaluation of concave portion on through hole &

As shown in Fig. 3, a double-sided printed wiring board having a thickness of 0.3 mm and copper-plated-through holes formed at intervals of 300 mu m in diameter and 1 mm in pitch was prepared and preprocessed using CZ- Respectively. Thereafter, a dry film having a thickness of 50 占 퐉 produced by the method described in the production section of the dry film was laminated on a printed wiring board on which a through hole was formed using a vacuum laminator MVLP-500 made by Meiki Co., Respectively. Lamination was carried out at a temperature of 80 캜 and a pressure of 5 kg / cm 2/60 seconds. Subsequently, the base material provided with the thermosetting resin layer was irradiated with light by full-surface solid exposure using HMW680GW (metal halide lamp, scattered light) of ORC Co., both front and back. With regard to the light irradiation amount, the exothermic peak temperature by DSC was set as described in Tables 1 to 3 with reference to the reference. Subsequently, the substrate was heated vertically by heating for 60 to 80 minutes at the temperature conditions shown in Tables 1 to 3. Further, ultraviolet ray irradiation was performed at an energy amount of 1 J / cm 2 with an ultraviolet ray irradiation apparatus of ORC Co., and subsequently, the resultant was longitudinally cured at 170 ° C for 60 minutes in a hot air circulation type drying furnace to be completely cured. Thereafter, the surface roughness meter SE-700 (manufactured by Kosaka Kagaku Co., Ltd.) was used to check the amount of recesses on the through holes.

(Assessment Methods)

?: The maximum concave portion on the through hole is 5 占 퐉 or less

DELTA: maximum concave portion on the through hole exceeds 5 mu m

<Formation evaluation of opening pattern>

The substrate having the resin layer obtained above was irradiated with light in a negative pattern shape having an opening design size of 100 mu m with HMW680GW (metal halide lamp, scattered light) of ORC Co., Ltd. With respect to the light irradiation amount, the exothermic peak temperature by DSC was set as described in Tables 1 to 3 below. Subsequently, heat treatment was performed for 60 to 80 minutes under the temperature conditions shown in Tables 1 to 3. Subsequently, the substrate was immersed in a mixed aqueous solution of 3 wt% TMAH / 5 wt% ethanolamine at 35 캜 for 3 minutes to evaluate developability and patterning according to the following criteria. The obtained results are shown in Tables 1 to 3.

(Assessment Methods)

◎: It is possible to develop even an aqueous solution of sodium carbonate instead of TMAH / 5 wt% ethanolamine mixed aqueous solution. A state in which there is no damage due to the developing solution on the surface of the light irradiation portion and no development residue is visible on the non-

?: No damage due to the developing solution on the surface of the light irradiation part, and no development residue on the non-irradiation part

X: No residue was confirmed on the non-irradiated area. Or a state in which the phenomenon of the non-irradiation part can not be performed

XX: Both the light-irradiated portion and the non-irradiated portion are completely dissolved

×××: Undercut is seen in the deep part of the opening

&Lt; Line pattern formation &

The substrate having the resin layer thus obtained was light-irradiated with a negative pattern of a design value of line / space = 100/100 占 퐉 with HMW680GW (metal halide lamp, scattered light) from ORC. With respect to the light irradiation amount, the exothermic peak temperature by DSC was set as described in Tables 1 to 3 below. Subsequently, heat treatment was performed for 60 to 80 minutes under the temperature conditions shown in Tables 1 to 3. Subsequently, the substrate was immersed in a mixed aqueous solution of 3 wt% TMAH / 5 wt% ethanolamine at 35 ° C for 3 minutes to perform development, and the obtained line-shaped pattern having the designed value of 100 μm was evaluated according to the following criteria. The obtained results are shown in Tables 1 to 3.

(Assessment Methods)

?: The top length of the line was 100 占 퐉 and the bottom length was 100 占 퐉, and a pattern according to the designed value was obtained.

DELTA: The top length of the line was 100 mu m and the bottom length was 60 mu m or more and less than 100 mu m, and a slight undercut was observed.

X: The top length of the line was 100 占 퐉 and the bottom length was less than 60 占 퐉, and undercuts were found in the bottoms.

(Resistant to desmear)

The base material prepared in the same manner as in the evaluation of the formation of the opening pattern was further irradiated with ultraviolet rays at an energy amount of 1 J / cm 2 with an ultraviolet ray irradiation apparatus of ORC Co., And cured at the post-curing temperature described (post-curing) for 60 minutes. Thereafter, the light irradiation surface was subjected to laser processing. The light source was processed with CO ₂ laser (Hitachi Biomechanics, light source 10.6 탆). And evaluated according to the following criteria. Laser processing was carried out under the same conditions in order to determine the superiority of the workability.

The working diameter target is a top diameter of 65 占 퐉 / bottom 50 占 퐉.

Condition: Aperture (mask diameter): 3.1 mm / pulse width 20 μs / output 2 W / frequency 5 kHz / number of shots: burst 3 shots

The base material subjected to this laser processing was further subjected to a desmear treatment by an aqueous solution of permanganic acid dismear (wet method). As evaluation of the demister resistance, confirmation of the surface roughness of the substrate surface and the state around the laser aperture were evaluated according to the following criteria. The surface roughness of each sample was measured with a laser microscope VK-8500 (a measurement magnification of 2000 times by KEENS Co., and a measurement pitch of 10 nm in the Z-axis direction). The observation of the laser aperture was performed by an optical microscope.

About chemical solution (Rohm & Haas)

Swelling MLB-211 Temperature 80 캜 / hour 10 min

Permanganate MLB-213 Temperature 80 캜 / hour 15 min

Reduction MLB-216 Temperature 50 캜 / hour 5 min

About evaluation method

?: The surface roughness Ra after the permanganate dissemme is less than 0.1 占 퐉 and the difference from the processing diameter after laser processing is 2 占 퐉 or less

?: The difference in surface roughness Ra after permanganate dissemination from 0.1 to 0.3 占 퐉 or less and the working diameter after laser processing was 2 to 5 占 퐉

X: The surface roughness Ra after permanganate desmear exceeds 0.3 占 퐉 and the difference from the working diameter after laser processing is 5 占 퐉 or more

&Lt; Evaluation of flexural strength after curing &

A dry film having a thickness of 20 占 퐉 produced by the method described in the production section of the dry film was applied to one side of a glossy surface of an 18 占 퐉 copper foil cut into a square of 50 mm 占 50 mm using a vacuum laminator MVLP- Lt; / RTI &gt; Lamination was carried out at a temperature of 80 캜 and a pressure of 5 kg / cm 2/60 seconds. Thereafter, the copper foil having the thermosetting resin layer was irradiated with light by full surface solid exposure with HMW680GW (metal halide lamp, scattered light) manufactured by ORC. With regard to the light irradiation amount, the exothermic peak temperature by DSC was set as described in Tables 1 to 3 with reference to the reference. Subsequently, the substrate was heat-treated for 60 to 80 minutes under the temperature conditions shown in Tables 1 to 3. Further, ultraviolet rays were irradiated with an energy amount of 1 J / cm 2 by ORC's ultraviolet ray irradiation apparatus, and then cured at 170 ° C for 60 minutes in a hot air circulation type drying furnace to obtain a copper foil having a thermosetting resin composition on one side. Thereafter, as the evaluation of the warpage state of the obtained cured product, the amount of warpage at the four end portions was measured with a nogris.

(Assessment Methods)

?: Almost no warpage is observed. The warpage of the maximum bending portion among the four ends is less than 5 mm

○: A slight warpage was observed. The warpage of the maximum bending portion among the four ends is 5 mm or more and less than 20 mm

?: The warpage of the maximum bending portion among the four ends is not less than 20 mm

X: The cured product shrank in a cylindrical shape. The amount of deflection of the end portion could not be measured by the nog- gis

<CTE measurement>

A dry film having a thickness of 40 占 퐉 was prepared according to the method described in the production items of the dry film. Thereafter, a dry film was laminated using a vacuum laminator MVLP-500 made by Meikyu Co., Ltd. on the glossy surface side of a copper foil of 18 mu m. Lamination was carried out at a temperature of 80 캜 and a pressure of 5 kg / cm 2/60 seconds. Thereafter, full surface solid exposure was performed with HMW680GW (metal halide lamp, scattered light) manufactured by ORC. With respect to the light irradiation amount, the exothermic peak temperature by DSC was set as described in Tables 1 to 3 below. Subsequently, heat treatment was performed for 60 to 80 minutes under the temperature conditions shown in Tables 1 to 3. Thereafter, ultraviolet ray irradiation was performed at an energy amount of 1 J / cm 2 by an ultraviolet ray irradiation apparatus of ORC Co., and then completely cured at 170 ° C for 60 minutes in a hot air circulation type drying furnace. Thereafter, the copper foil was peeled off to obtain a resin composition described in Examples and Comparative Examples. Thereafter, the obtained resin composition was cut into a rectangle having a width of 3 mm and a length of 10 mm, and CTE measurement (thermal expansion coefficient) was evaluated by the TMA method (tensile method) described in JIS-C-6481. The rate of temperature rise was 5 占 폚 / min and the coefficient of thermal expansion was evaluated to be Tg or less. The coefficient of thermal expansion is an average coefficient of thermal expansion in the temperature range of 25 ° C to 100 ° C, in units of ppm.

The obtained CTE values are shown in Tables 1 to 3.

&Lt; Evaluation of cooling /

The printed wiring board subjected to the permanganate desmear treatment as described above was further plated using a commercially available electroless nickel plating bath and electroless gold plating bath under the conditions of nickel 0.5 탆 and gold plating 0.03 탆, Was subjected to a gold plating treatment. The obtained printed wiring board was evaluated for its cooling / heating cycle characteristics. The conditions of the treatment were set to -65 占 폚 for 30 minutes and 150 占 폚 for 30 minutes to 1 cycle. After 2000 cycles after applying a thermal history, the state of the surface and periphery of the pattern layer was observed with an optical microscope, Were evaluated. The number of observation patterns was 100 holes. The obtained results are shown in Tables 1 to 3 below.

(Assessment Methods)

?: No cracks on the surface and peripheral portion of the pattern layer

?: Percentage of cracks in the periphery of the pattern layer less than 10%

?: Percentage of cracks in the periphery of the pattern layer 10% or more and less than 30%

DELTA: Crack generation rate at the periphery of the pattern layer: 30% or more

<Method of Measuring the Refractive Index of Thermally Reactive Compound, Maleimide Compound, and Alkali Developable Resin>

Measuring device: Abbe refractometer

Measurement conditions: a wavelength of 589.3 nm, a temperature of 25 DEG C

(Thermosetting compound + alkali developable resin + photo-base generator + filler)

(+ Polymer resin)

(Comparative Example)

The components in Tables 1 to 3 are as follows.

(Thermoreactive compound)

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

※ HP-4032: naphthol type epoxy (equivalent 150g / eq), DIC company

※ HP-7200 H60: Dicyclopentadiene epoxy (equivalent 265 g / eq), DIC is dissolved in cyclohexanone. Solid content 60%

(Maleimide compound)

※ UVT-302: Acrylic polymer (equivalent 320 g / eq) having a maleimide group on its side chain,

(Alkali developable resin)

※ HF-1M H60: Phenol novolac (hydroxyl equivalent 105g / eq), Meiwa Kasei Co., Ltd. dissolved in cyclohexanone. Solid content 60%

MEH-7851M H60: Biphenyl / phenol novolac (hydroxyl equivalent: 210 g / eq), dissolved in MeOHwagassei with cyclohexanone. Solids 60%.

* John Krill 586 H60: styrene acrylic acid copolymer resin, Mw = 3100, solid acid value = 108 mgKOH / g, and Johnson Polymer Co. dissolved in cyclohexanone. Solid content 60%

※ John Krill 68 H60: Styrene acrylic acid copolymer resin, Mw = 10000, acid value 195 mgKOH / g,

(Photobase generator)

* Irg369: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,

* WPBG-140: 1- (Anthraquinon-2-yl) ethylimidazole carboxylate, Wako Pure Chemical Industries, Ltd.

(Polymer resin)

※ YX8100 BH30: Phenoxy resin. Mitsubishi Corporation Solid content 30%

(Inorganic filler)

* SO-C2: spherical silica D50 = 0.5 占 퐉, refractive index = 1.4 to 1.5, Admatech Co., specific gravity: 2.2 g / cm3

* AO-502: spherical alumina D50 = 0.7 탆, refractive index = 1.76, Admatex, specific gravity: 3.9 g / ㎤

※ Higilite H-42M: aluminum hydroxide D50 = 1.0 탆, refractive index = 1.65, Showa Denko K., specific gravity: 2.4 g / ㎤

* B-30: barium sulfate, D50 = 0.3 탆, refractive index = 1.64, Sakaikagaku, specific gravity: 4.3 g / ㎤

(Etc)

※ R-2000: cresol novolak, acrylic acid, THPA modified resin (solid content 61%, solid acid value 87 mgKOH / g, DIC)

※ DPHA: dipentaerythritol hexaacrylate _ Nippon Kayakaji

* IRG-184: 1-hydroxycyclohexyl-phenyl ketone

As shown in Tables 1 to 3, in Examples 1 to 19, it was possible to form a pattern by alkali development, and it was confirmed that the obtained pattern was excellent in curing characteristics and cold / heat cycle characteristics.

Further, in Examples 15 and 16, by blending the polymer resin, the melt viscosity of the thermosetting resin composition is increased, and the resin fluidity of the through hole portion can be suppressed during heating after exposure. As a result, it is possible to manufacture a flat substrate on which the concave portion is not seen on the through hole.

In Examples 18 and 19, even when the content of the inorganic filler was considerably large, good curability was obtained during the cooling / heating cycle.

On the other hand, in the photo-radical composition of Comparative Example 4, pattern formation due to alkali development became difficult. The line shape was also poor. Further, the degree of warpage after curing was high and the curability during the cooling / heating cycle was also deteriorated.

&Lt; Measurement of DSC immediately after light irradiation >

The substrate having the resin layer obtained in Example 1 was irradiated with light in a negative pattern with HMW680GW (metal halide lamp, scattered light) manufactured by ORC. Each substrate was subjected to light irradiation with a pattern at a dose of 1000 mJ / cm 2. After the light irradiation, the resin layer was cut off from the substrate and immediately heated to 30 to 300 DEG C at a temperature raising rate of 5 DEG C / min in a DSC-6200 manufactured by Seiko Instruments Inc., DSC measurement was performed on each of the light irradiated portion and non- Respectively. DSC measurement was similarly performed on the cured layer including the thermosetting resin composition immediately after the ultraviolet ray irradiation and before the post-curing.

2 is a DSC chart of a non-irradiated portion, a light irradiated portion with an irradiation dose of 1000 mJ / cm 2, and a light irradiated portion irradiated with light with an irradiation dose of 1000 mJ / cm 2 and further with 1000 mJ / cm 2. In the light irradiation portion 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 and a circuit formed of copper having a thickness of 15 mu m was prepared and subjected to a pre-treatment using CZ-8100 manufactured by Mack. Thereafter, a PSR-4000G23K (trade name, a photo-curable resin composition containing an alkali developable resin having an epoxy acrylate structure) was applied by screen printing to a thickness of 20 mu m after drying . Subsequently, the resultant was dried in a hot air circulating type drying furnace at 80 DEG C for 30 minutes, and then irradiated with light of a negative pattern at an irradiation dose of 300 mJ / cm2 using HMW680GW (metal halide lamp, scattered light) manufactured by ORC. Thereafter, the resist film was developed with a 1 wt% sodium carbonate aqueous solution for 60 seconds, and then heat-treated at 150 DEG C for 60 minutes using a hot-air circulation type drying furnace to obtain a patterned cured coating film.

Thereafter, as in the case of the second embodiment, evaluation of the dummies resistance was carried out. As a result, the desmear resistance was "x".

Claims (4)

Alkali developable resin,
Thermally reactive compounds,
Inorganic filler, and
A photoacid generator,
Wherein the alkali developable resin and the thermally reactive compound are subjected to an addition reaction by selective light irradiation so that a negative pattern can be formed by an alkali development. The alkali-developable thermosetting resin composition according to claim 1, wherein the inorganic filler has an average particle diameter of 1 占 퐉 or less. 3. The method according to claim 1 or 2, wherein an exothermic peak is generated in the DSC measurement by light irradiation, or a heat generation initiation temperature in the DSC measurement of the alkali developing type thermosetting resin composition which is irradiated with light is in an alkali developing type The DSC measurement of the alkali developing type thermosetting resin composition in which the exothermic peak temperature in the DSC measurement of the alkali developing type thermosetting resin composition which is lower than the heat generation starting temperature in the DSC measurement of the thermosetting resin composition of the alkali- Wherein the heat generation peak temperature of the alkali-developing type thermosetting resin composition is lower than the exothermic peak temperature of the alkali-developing type thermosetting resin composition. A printed wiring board characterized by having a pattern layer comprising the alkali developing type thermosetting resin composition according to any one of claims 1 to 3.

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