KR102053322B1 - Photosensitive resin composition and photoimageable dielectric film - Google Patents

Abstract

The present invention is a novolac oligomer having a phenolic hydroxyl group and a photocurable unsaturated functional group; Acid-modified oligomers having a carboxyl group and a photocurable unsaturated functional group; Photopolymerizable monomers having photocurable unsaturated functional groups; Thermosetting binders having thermosetting functional groups; And it relates to a photosensitive resin composition having a photocurable and thermosetting comprising a photoinitiator and a photosensitive film prepared therefrom.

Description

Photosensitive resin composition and the photosensitive insulating film {PHOTOSENSITIVE RESIN COMPOSITION AND PHOTOIMAGEABLE DIELECTRIC FILM}

The present invention relates to a photosensitive resin composition and a photosensitive insulating film. More specifically, the present invention can be developed in a weak alkaline aqueous solution such as sodium carbonate solution, but has excellent adhesion with the plating layer, less deterioration in adhesion force at high temperature and high humidity, and discharges a small amount of outgas, thereby improving moisture absorption reliability. It relates to a photosensitive resin composition capable of providing a photosensitive insulating resin (PID, Photoimageable dielectics) or dry film solder resist (DFSR) having heat resistance and a photosensitive insulating film having the above-described characteristics.

BACKGROUND ART With the miniaturization and light weight of various electronic devices, a buildup film capable of forming a multilayer substrate is used for printed circuit boards and semiconductor package substrates.

The build-up film currently used generally is a non-photosensitive product, which uses a laser to form vias. However, since the cost of laser via formation is expensive and the limit of laser formation is known to be about 50 μm in diameter, it is difficult to form more fine vias.

Therefore, in order to solve this problem, a method of replacing the photosensitive resin has been proposed. When the photosensitive resin is used, a fine pitch is possible and the cost of using the laser can be reduced.

The photosensitive resin may be used not only as a buildup film but also as a redistriburion layer (RDL) or solder resist of a wafer level package.

Conventionally, in order to form a soldering resist, the resin composition which has photocurability and thermosetting, including photopolymerizable monomers, such as a polyfunctional acrylate, with an acid-modified oligomer, a photoinitiator, and a thermosetting binder, was used. However, when using such a resin composition, it is known that there is no big problem in the use of the solder resist, but when used as a build-up film, the adhesive strength with the plating layer is reduced after evaluating the hygroscopic reliability, or a blister occurs when reflowing. There was this.

Thus, the present invention can be developed in a weak alkaline aqueous solution, such as aqueous sodium carbonate solution, the process can proceed in the existing process line, excellent adhesion to the plating layer and less outgas (outgas) to discharge the build-up film, redistribution layer or It is providing the photosensitive resin composition which can be used as DFSR.

In addition, the present invention provides a photosensitive film such as an insulating film or DFSR by using the photosensitive resin composition.

In the present specification, a novolac oligomer having a phenolic hydroxyl group and a photocurable unsaturated functional group; Acid-modified oligomers having a carboxyl group and a photocurable unsaturated functional group; Photopolymerizable monomers having photocurable unsaturated functional groups; Thermosetting binders having thermosetting functional groups; And a photoinitiator is provided.

The novolak-based oligomer may be a photocurable unsaturated functional group is substituted directly or through a intermediate functional group to a portion of the phenolic hydroxyl group of the novolak resin, 5mol% to 50mol% of the phenolic hydroxyl group may include a photocurable unsaturated functional group In the formula, n1 to n3 are each independently an integer of 1 to 10.

The intermediate functional groups are -NH-, -O-, -CO-, -S-, -SO _2- , -NH-CO-O-, -NCO-, -C (CH ₃ ) _2- , -C (CF _{3) 2 -, -CO-NH-} , -CO-O-, - (CH 2) n1 -, -O (CH 2) n2 O-, and _{-CO-O- (CH 2) n3} -O-CO It may include one or more functional groups selected from the group consisting of-wherein n1 to n3 are each independently an integer of 1 to 10.

The photocurable unsaturated functional groups may include acrylates, methacrylates, alkyl acrylates having 1 to 5 carbon atoms, or alkyl methacrylates having 1 to 5 carbon atoms.

The novolac-based oligomer may include 5 wt% to 40 wt% based on the total weight of the photosensitive resin composition.

The acid-modified oligomer may be a photocurable functional group having an acrylate group or an unsaturated double bond, and an oligomer having a carboxyl group in a molecule.

The main chain of the acid-modified oligomer is novolak epoxy or polyurethane, and a carboxyl group and an acrylate group introduced into the main chain may be used.

The acid-modified oligomer is obtained by copolymerization of a polymerizable monomer having a carboxyl group and a monomer including an acrylate compound, and may have a weight average molecular weight of 1000 to 30000.

The acid-modified oligomer may include 10% by weight to 75% by weight based on the total weight of the photosensitive resin composition.

As the photopolymerizable monomer, an acrylate compound having an unsaturated functional group capable of photopolymerization may be used.

The photopolymerizable monomer may include 1 to 30% by weight based on the total weight of the photosensitive resin composition.

The thermosetting binder may include at least one functional group selected from an epoxy group, an oxetanyl group, a cyclic ether group, and a cyclic thio ether group.

The thermosetting binder may include 1 to 30% by weight based on the total weight of the photosensitive resin composition.

The photoinitiator may include a residue at 260 ° C. of 40% by weight or more based on the total weight of the photoinitiator when the weight loss is measured while heating at a temperature increase rate of 5 ° C./min using TGA. .

The photoinitiator may include 0.5 to 15% by weight based on the total weight of the photosensitive resin composition.

The photosensitive resin composition may further include a diaryliodine-based or trisulfonium-based cationic initiator based on the total weight of the photosensitive resin composition.

The photosensitive resin composition may further include at least one selected from the group consisting of a solvent, a thermosetting binder catalyst, a filler, a pigment, and an additive.

Moreover, in this specification, the novolak-type oligomer which has a phenolic hydroxyl group and photocurable unsaturated functional group; Acid-modified oligomers having a carboxyl group and a photocurable unsaturated functional group; Photopolymerizable monomers having photocurable unsaturated functional groups; And a cured product between the thermosetting binder having a thermosetting functional group, and a filler dispersed in the cured product.

The novolak-based oligomer may be a photocurable unsaturated functional group is substituted directly or through a intermediate functional group to a part of the phenolic hydroxyl group of the novolak resin, 5mol% to 50mol% of the phenolic hydroxyl group may include a photocurable unsaturated functional group have.

The intermediate functional groups are -NH-, -O-, -CO-, -S-, -SO _2- , -NH-CO-O-, -NCO-, -C (CH ₃ ) _2- , -C (CF _{3) 2 -, -CO-NH-} , -CO-O-, - (CH 2) n1 -, -O (CH 2) n2 O-, and _{-CO-O- (CH 2) n3} -O-CO It may include one or more functional groups selected from the group consisting of-wherein n1 to n3 are each independently an integer of 1 to 10.

The photocurable unsaturated functional groups may include acrylates, methacrylates, alkyl acrylates having 1 to 5 carbon atoms, or alkyl methacrylates having 1 to 5 carbon atoms.

The cured product may include a crosslinked structure between a photocurable unsaturated functional group of the novolac oligomer, a photocurable unsaturated functional group of an acid-modified oligomer, and a photopolymerizable monomer; A crosslinked structure in which a thermosetting functional group of the thermosetting binder and a carboxyl group of a phenolic hydroxyl group or an acid-modified oligomer of a novolac oligomer are crosslinked; And it may include a cross-linking structure between the thermosetting binder.

When the photosensitive film was formed with a total thickness of the entire copper plating on the film after curing to a predetermined thickness, the plating adhesion measured by using a universal testing machine (UTM) after 100 hours in 130 ℃, 85% RH HAST chamber, At least 70% of the plating adhesion prior to entering the HAST chamber can be maintained.

The photosensitive film may include PID (Photoimageable dielectics) or Dry Film Solder Resist (DFSR).

The photosensitive resin composition of the present invention uses a novolac-based oligomer having a predetermined amount of phenolic hydroxyl group and photocurable unsaturated functional group, and a specific photoinitiator having a high pyrolysis temperature, and the physical properties required in the photosensitive insulating film or dry film soldering resist. While satisfactory, excellent heat resistance at a high temperature, even after the moisture absorption under high conditions, the adhesive strength with the plating layer does not deteriorate, it can have excellent heat resistance reliability. Therefore, the present invention can easily provide a photosensitive film such as PID or DFSR having excellent physical properties using the photosensitive resin composition.

Hereinafter, the photosensitive resin composition and the insulating film using the same in embodiment of this invention are demonstrated in detail.

According to one embodiment of the invention, a novolak-based oligomer having a phenolic hydroxyl group and a photocurable unsaturated functional group; Acid-modified oligomers having a carboxyl group and a photocurable unsaturated functional group; Photopolymerizable monomers having photocurable unsaturated functional groups; Thermosetting binders having thermosetting functional groups; And a photoinitiator is provided.

Such a resin composition may further include a catalyst, an additive, a filler, and a solvent.

In addition, the photosensitive resin composition of this invention means the resin composition which has photocurability and thermosetting.

An insulating layer can be formed using the said photosensitive resin composition through the following processes.

First, after apply | coating a resin composition on a board | substrate, it exposes selectively to a part except a part to be via-formed using a mask. By performing such exposure, the unsaturated functional groups contained in the acid-modified oligomer and the novolak-based oligomer and the unsaturated functional groups contained in the photopolymerizable monomer may cause photocuring to form crosslinks with each other. Cross-linked structure can be formed.

Thereafter, when the development is performed using an alkaline developer, the resin composition of the exposed portion having the crosslinked structure is left on the substrate as it is, and the resin composition of the remaining non-exposed portion may be dissolved in the developer and removed.

Then, when the resin composition remaining on the substrate is thermally cured by heat treatment, the carboxyl groups included in the acid-modified oligomer and the hydroxyl groups included in the novolak-based oligomer react with the thermosetting functional groups of the thermosetting binder to crosslink. It can be formed, and as a result, an insulating layer can be formed on a desired portion on the substrate while forming a crosslinked structure by thermosetting.

After that, a pattern is formed using a semiadditive method, and the process is as follows.

According to a preferred embodiment, after forming the seed layer (sed layer) by sputtering or chemical copper plating method, to form a pattern using a DFR or the like, and to increase the thickness of the plating layer by electrolytic copper plating. Subsequently, the pattern of the wiring is formed by etching the seed layer of the portion where the wiring is not formed by peeling the DFR and performing flash etching.

Then, the second and third photosensitive insulating layers may be formed thereon or the substrate may be manufactured by forming DFSR on the pattern.

Unlike the solder resist, since the photosensitive insulating film is used as a buildup film of the inner layer, the adhesive force with copper plating used as the wiring layer must be expressed, and the discharge path at the outgas discharge is limited, thereby reflowing. It may cause a problem such as blister (blister), and because the plating layer is present, the adhesion to the plating layer should be maintained under high temperature and high humidity.

Accordingly, the present invention can be developed in a weak alkaline solution, such as sodium carbonate solution, the adhesive force with the plating layer is maintained even after high temperature and high moisture absorption, and the photosensitive resin composition and photosensitive insulation prepared using the same to prevent the occurrence of blister during reflow There is a feature to provide a film.

Hereinafter, the photosensitive resin composition according to one embodiment will be described in more detail for each component.

Novolac-based oligomers

The photosensitive resin composition of this invention contains the novolak-type oligomer which has a phenolic hydroxyl group and the photocurable unsaturated functional group.

Such novolac-based oligomers can be reacted by photocuring to form a crosslinked structure to form a pattern, and to form a hard film by combining with a thermosetting binder.

In addition, the present invention can obtain an insulating film that does not deteriorate the adhesive force with the plating layer even after the moisture absorption by containing a certain amount of novolac-based oligomer.

The novolak-based oligomer is a part of the phenolic hydroxyl group of the novolak resin is a photocurable unsaturated functional group is substituted directly or through an intermediate functional group, 5mol% to 50mol% of the phenolic hydroxyl group comprises a photocurable unsaturated functional group desirable.

The intermediate functional groups are -NH-, -O-, -CO-, -S-, -SO _2- , -NH-CO-O-, -NCO-, -C (CH ₃ ) _2- , -C (CF _{3) 2 -, -CO-NH-} , -CO-O-, - (CH 2) n1 -, -O (CH 2) n2 O-, and _{-CO-O- (CH 2) n3} -O-CO It may include one or more functional groups selected from the group consisting of-wherein n1 to n3 are each independently an integer of 1 to 10.

The photocurable unsaturated functional groups may include acrylates, methacrylates, alkyl acrylates having 1 to 5 carbon atoms, or alkyl methacrylates having 1 to 5 carbon atoms.

The novolac oligomer may be formed by copolymerizing 0.05 to 0.5 equivalents of a compound having a photocurable unsaturated functional group and a carboxyl or isocyanate group with respect to 1 equivalent of the phenolic hydroxyl group of the novolac oligomer.

At this time, if the equivalent weight of the compound having a photocurable unsaturated functional group and a carboxyl group or an isocyanate group is 0.05 equivalent or less, there may be a problem in that the photocuring is insufficient and the solution is dissolved to the exposed portion. There is a problem that falls, developability is deteriorated and the adhesion of the plating layer deteriorates after moisture absorption.

In addition, the novolac oligomer may use a generally known material, but the type thereof is not particularly limited, but is preferably a group consisting of phenol novolac, cresol novolac, bisphenol-A novolac and phenol aralkyl novolac One or more selected from can be used.

Examples of the compound having an acrylate-based functional group or an intermediate functional group include acrylic acid, methacrylic acid, butanoic acid, hexanoic acid, and cinnamic acid. acid), 2-isocyanatoethyl methacrylate (2-isocyanatoethyl methacylate), 2-isocyanatoethyl acrylate (2-isocyanatoethyl acylate) and the like can be obtained by reacting at least one monomer selected from the group consisting of.

In addition, according to one embodiment of the present invention, the novolak-based oligomer may include a novolak-based oligomer of formula (1) prepared by copolymerization of phenol novolak structure of the formula (2) and acrylic acid.

[Formula 1]

[Formula 2]

In addition, in the novolac-based oligomer, the content of the photocurable unsaturated functional group is preferably 5 mol% to 50 mol% with respect to the molar equivalent of hydroxyl groups. When the photocurable unsaturated functional group is present in less than 5mol%, there may be a problem that the photocuring is insufficient to dissolve to the exposed portion, if the content is more than 50mol%, uniformity during coating falls and developability is lowered. The problem that the adhesive force of the plating layer deteriorates after the moisture absorption occurs.

The novolak-based oligomer preferably contains 10 mol% to 60 mol% of the molar equivalent of the hydroxyl group to the molar equivalent of the carboxyl group of the acid-modified oligomer.

The novolac-based oligomer may be included in 5% by weight to 40% by weight, or 7% by weight to 35% by weight based on the total weight of the photosensitive resin composition. If the content of the novolac-based oligomer is less than 5% by weight, there is a problem in that the adhesion to the plating layer is lowered after moisture absorption, and when the content of the novolac-based oligomer is more than 40% by weight, the developer does not develop in a dilute alkali solution such as 1% by weight of sodium carbonate.

Acidity  Oligomer

The acid-modified oligomer may be a photocurable functional group having an unsaturated double bond such as a carboxyl group and a photocurable functional group, for example, an acrylate group, and an oligomer having a carboxyl group in a molecule.

For example, the main chain of the acid-modified oligomer may be a novolac epoxy or polyurethane, and the main chain may be one having a carboxyl group and an acrylate group introduced therein.

The photocurable functional group may be preferably an acrylate group, wherein the acid-modified oligomer may be obtained in an oligomer form by copolymerizing a monomer including a polymerizable monomer having a carboxyl group and an acrylate-based compound. In addition, the acid-modified oligomer may have a weight average molecular weight of 1000 to 30000.

More specifically, specific examples of acid-modified oligomers usable in the resin composition include the following components:

(1) Obtained by copolymerizing unsaturated carboxylic acids (a) such as (meth) acrylic acid and compounds (b) having unsaturated double bonds such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene Carboxyl group-containing resins;

(2) ethylenically unsaturated groups such as vinyl groups, allyl groups, (meth) acryloyl groups, epoxy groups, acid chlorides, and the like, as part of the copolymer of the unsaturated carboxylic acid (a) and the compound (b) having an unsaturated double bond Carboxyl group-containing photosensitive resin obtained by making a compound which has a reactive group, for example, glycidyl (meth) acrylate react, and adding an ethylenically unsaturated group as a pendant;

(3) to a copolymer of a compound (c) having an unsaturated double bond with an epoxy group such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate and a compound (b) having an unsaturated double bond; Carboxyl group-containing photosensitive resin obtained by making unsaturated carboxylic acid (a) react, and making saturated or unsaturated polybasic acid anhydride (d), such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride, react with the produced | generated secondary hydroxy group;

(4) One hydroxy group such as hydroxyalkyl (meth) acrylate in a copolymer of an acid anhydride (e) having an unsaturated double bond such as maleic anhydride and itaconic anhydride and a compound (b) having an unsaturated double bond Carboxyl group-containing photosensitive resin obtained by making compound (f) which has 1 or more ethylenically unsaturated double bond react;

(5) The epoxy group of the polyfunctional epoxy compound (g) which has two or more epoxy groups in the molecule mentioned later, or the polyfunctional epoxy resin in which the hydroxy group of the polyfunctional epoxy compound was further epoxidized with epichlorohydrin, (meth The carboxyl group of unsaturated monocarboxylic acid (h) such as acrylic acid is subjected to esterification reaction (full esterification or partial esterification, preferably total esterification) and further saturated or unsaturated polybasic acid anhydride (d) Carboxyl group-containing photosensitive compound obtained by making it react;

(6) 1 in 1 molecule of an alkyl group having 2 to 17 carbon atoms, an aromatic group-containing alkyl carboxylic acid, etc., in the epoxy group of the copolymer of the compound (b) having an unsaturated double bond and glycidyl (meth) acrylate A carboxyl group-containing resin obtained by reacting an organic acid (i) having two carboxyl groups and not having an ethylenically unsaturated bond and reacting a saturated or unsaturated polybasic acid anhydride (d) with the resulting secondary hydroxy group;

(7) diisocyanates (j) such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates; carboxyl group-containing dialcohol compounds (k) such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarboxes Diol compounds such as carbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adducts, diols, phenolic hydroxyl groups and compounds having alcoholic hydroxyl groups ( carboxyl group-containing urethane resin obtained by the polyaddition reaction of m);

(8) diisocyanate (j), bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, non Photosensitive properties obtained by polyaddition reaction of (meth) acrylate or partial acid anhydride modified product (n) of bifunctional epoxy resins, such as a phenol type epoxy resin, its carboxyl group-containing dialcohol compound (k), and a diol compound (m) Carboxyl group-containing urethane resin;

(9) Compound (f) having one hydroxy group such as hydroxyalkyl (meth) acrylate and one or more ethylenically unsaturated double bonds is added during the synthesis of the resin of the above (7) or (8) and unsaturated at the terminal. Carboxyl group-containing urethane resin which introduce | transduced the double bond;

(10) A compound having one isocyanate group and one or more (meth) acryloyl groups in a molecule such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate during the synthesis of the resin (7) or (8). Carboxyl group-containing urethane resin which was added and terminal (meth) acrylated;

(11) Saturated or unsaturated polybasic anhydrides with respect to the primary hydroxy group in the modified oxetane compound obtained by reacting unsaturated monocarboxylic acid (h) with a polyfunctional oxetane compound having two or more oxetane rings in a molecule as described later. carboxyl group-containing photosensitive resin obtained by making (d) react;

(12) Carboxyl group-containing photosensitive resin obtained by introducing an unsaturated double bond into the reaction product of a bisepoxy compound and bisphenols, and then making a saturated or unsaturated polybasic acid anhydride (d) react;

(13) Novolak-type phenol resins, alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran and / or ethylene carbonate, propylene carbon Unsaturated monocarboxylic acid (h) is reacted with a reaction product with cyclic carbonates such as carbonate, butylene carbonate, 2,3-carbonate propyl methacrylate, and saturated or unsaturated polybasic acid. Carboxyl group-containing photosensitive resin obtained by making anhydride (d) react;

Among the above-mentioned components, in the said (7)-(10), when the isocyanate group containing compound used for resin synthesis becomes diisocyanate which does not contain a benzene ring, and in said (5) and (8), When the polyfunctional and bifunctional epoxy resins used in the synthesis are linear compounds having bisphenol A skeleton, bisphenol F skeleton, biphenyl skeleton or bixylenol skeleton, or hydrogenated compounds thereof, the flexibility and the like of DFSR The component which can be preferably used as an acid-modified oligomer can be obtained. In addition, in another aspect, the modified product of the resins of the above (7) to (10) is preferable for the bending including the urethane bond in the main chain.

Commercially available components may be used as the acid-modified oligomer, and specific examples of such components include the Japanese chemical powder company's CCR series, ZAR series, ZFR series, and DIC's UE series. More specific examples of acid-modified oligomers include ZAR-2000, CCR-1235, ZFR-1122 or CCR-1291H from Nippon Chemical Co., Ltd.

On the other hand, the acid-modified oligomer described above can calculate the molar equivalent of the carboxyl group according to the acid value, and the ratio of the molar equivalent of the hydroxyl group present in the novolak-based oligomer described above is in the range of 40:60 to 90:10. desirable. If the content of the carboxyl group in the acid-modified oligomer is too small, the developability of the resin composition is lowered. If the content is too high, the resin composition is excessively developed as well as a problem that the adhesion of the plating layer deteriorates after moisture absorption.

In addition, the acid value of the acid-modified oligomer may be about 40 to 150 mgKOH / g or about 50 to 130 mgKOH / g. If the acid value of the acid-modified oligomer is too low, alkali developability may be lowered. On the contrary, if the acid value of the acid-modified oligomer is too high, the photocurable part, for example, the exposed part may be dissolved by the developer, and thus, normal pattern formation of PID or DFSR may occur. It can be difficult.

The acid-modified oligomer may be included in 10% by weight to 75% by weight or 10% by weight to 50% by weight based on the total weight of the photosensitive resin composition.

When the content of the acid-modified oligomer is too small, the developability of the resin composition may be lowered and the strength of the DFSR may be lowered. On the contrary, when the content of the acid-modified oligomer is too high, not only the resin composition may be excessively developed, but also the decrease in adhesion to the plating layer after moisture absorption may increase.

Photopolymerizable  Monomer

Meanwhile, the resin composition of one embodiment includes a photopolymerizable monomer. Such a photopolymerizable monomer may be, for example, a compound having a photocurable unsaturated functional group such as two or more polyfunctional vinyl groups, and may form a crosslink with the unsaturated functional group of the acid-modified oligomer described above to provide photocuring during exposure. Crosslinked structure can be formed. Thereby, the resin composition of the exposure part corresponding to the part where DFSR is to be formed can be left on the substrate without alkali development.

As the photopolymerizable monomer, a liquid phase may be used at room temperature, and accordingly, the viscosity of the resin composition of one embodiment may be adjusted according to the coating method, or the role of improving the alkali developability of the non-exposed part may also be combined.

As the photopolymerizable monomer, an acrylate compound having two or more photocurable unsaturated functional groups can be used.

As a more specific example, acrylate type compound containing hydroxyl groups, such as pentaerythritol triacrylate or dipentaerythritol pentaacrylate; Water-soluble acrylate compounds such as polyethylene glycol diacrylate or polypropylene glycol diacrylate; Polyfunctional polyester acrylate compounds of polyhydric alcohols such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol hexaacrylate; Acrylate compounds of ethylene oxide adducts and / or propylene oxide adducts of polyfunctional alcohols such as trimethylolpropane or hydrogenated bisphenol A or polyhydric phenols such as bisphenol A and biphenol; Polyfunctional or monofunctional polyurethane acrylate compounds which are isocyanate modified products of the hydroxyl group-containing acrylate; Epoxy acrylate compounds that are (meth) acrylic acid adducts of bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, or phenol novolac epoxy resins; Caprolactone modified acrylate compounds such as caprolactone modified ditrimethylolpropane tetraacrylate, acrylate of ε-caprolactone modified dipentaerythritol, or caprolactone modified hydroxy pivalate neopentyl glycol ester diacrylate, And one or more compounds selected from the group consisting of photosensitive (meth) acrylate compounds such as methacrylate compounds corresponding to the acrylate compounds described above, and these may be used alone or in combination of two or more thereof. .

Among these, as said photopolymerizable monomer, the polyfunctional (meth) acrylate type compound which has two or more (meth) acryloyl groups in 1 molecule can be used preferably, Especially pentaerythritol triacrylate and a trimethylol propane Triacrylate, dipentaerythritol hexaacrylate, caprolactone modified ditrimethylol propane tetraacrylate, etc. can be used suitably. As an example of a commercially available photopolymerizable monomer, Kaylarad DPEA-12 etc. are mentioned.

The photopolymerizable monomer may be included in 1 to 30% by weight or 2 to 20% by weight based on the total weight of the photosensitive resin composition. If the content of the photopolymerizable monomer is too small, the photocuring may not be sufficient, and if the content of the photopolymerizable monomer is too large, the drying property of the DFSR may deteriorate and the physical properties may be degraded.

Photoinitiator

The resin composition of one embodiment includes a photoinitiator. Such photoinitiator may be, for example, a radical photoinitiator, and serves to initiate radical photocuring between the acid-modified oligomer and the photopolymerizable monomer in the exposed portion of the photosensitive resin composition. In addition, since the photoinitiator used in the present invention has a high pyrolysis temperature, less decomposition of the unreacted photoinitiator occurs during reflow and less outgas is generated, so that blistering between the plating layer and the photosensitive composition layer can be suppressed.

In addition, the photosensitive resin composition of this invention may further use a cationic photoinitiator together with a radical photoinitiator. Cationic initiators can mainly cause photocuring of cycloaliphatic epoxy or aliphatic epoxy, so that crosslinking of the exposed part can be more robust during photocuring.

The photoinitiator, when the weight loss was measured while heating at a temperature increase rate of 5 ℃ / min using an TGA, the residue at 260 ℃ 40 to the weight of the total photo initiator It is preferable to use what is more than weight%. The 260 ° C. is known as the general reflow temperature.

Therefore, as the photoinitiator, if the residue at 260 ° C. is 40% by weight or more, the type thereof is not limited and may be used, and commercially available ones may be used.

As a photoinitiator, a well-known thing can be used and benzoin, its alkyl esters, acetophenones, anthraquinones, thioxanthones, ketals, amino ketones containing benzophenones, amino acetophenones, and acylphosphine oxides are mentioned. Phosphines, oxime esters containing oxime esters, phenylglyoxylates, keto sulfones and the like.

Of these, examples of the residue having a residue at 260 ° C of 40% by weight or more include phosphines such as TPO and Irgacure 819, oximes include Oxe01 and Oxe02, and amino ketones include Irgacure 379 and phenyl Examples of glyoxylates include Irgacure 754, thioxanthones include DETX, and keto sulfones include Lamberti's Esacure 1001M.

The content of the photoinitiator may be about 0.5 to 15% by weight, or about 1 to 10% by weight, or about 1 to 5% by weight based on the total weight of the photosensitive resin composition. If the content of the photoinitiator is too small, the photocuring may not occur properly, on the contrary, if the content of the photoinitiator is too large, the resolution of the resin composition may be lowered or the reliability of PID or DFSR may not be sufficient.

In addition, the cationic photoinitiator may be a diaryl iodine-based, trisulfonium-based and the like. When the cationic photoinitiator is further included, it may further include 0.5 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition.

Thermosetting binder

The resin composition of one embodiment also includes a thermosetting binder having at least one member selected from thermosetting functional groups such as epoxy groups, oxetanyl groups, cyclic ether groups and cyclic thio ether groups. The thermosetting binder may form a crosslinking bond with an acid-modified oligomer and the like by thermosetting to secure heat resistance or mechanical properties of the photosensitive insulating film or DFSR.

As the thermosetting binder, a resin having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in a molecule can be used, and a bifunctional epoxy resin can be used. have. Other diisocyanate, its bifunctional block isocyanate, melamine, etc. can also be used.

The thermosetting binder having two or more cyclic (thio) ether groups in the molecule may be a compound having one, two or more groups of 3, 4 or 5 membered cyclic ether groups, or cyclic thioether groups in the molecule. have. The thermosetting binder may be a polyfunctional epoxy compound having at least two epoxy groups in a molecule, a polyfunctional oxetane compound having at least two oxetanyl groups in a molecule, or an episulfide resin having two or more thioether groups in a molecule And so on.

Examples of the polyfunctional epoxy compound include bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, novolac type epoxy resins, and phenols. Novolac type epoxy resin, Cresol novolac type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolac type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, chelate type epoxy resin, glyoxal type Epoxy resin, amino group-containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenolic epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoylethane resin, silicone modified epoxy resin, ε -A caprolactone modified epoxy resin, etc. are mentioned. In addition, in order to impart flame retardancy, those in which atoms such as phosphorus are introduced into the structure may be used. By thermosetting these epoxy resins, characteristics, such as adhesiveness of a cured film, solder heat resistance, and electroless plating resistance, are improved.

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) methylacrylic Latex, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or these In addition to polyfunctional oxetanes such as oligomers and copolymers, oxetane alcohols and novolac resins, poly (p-hydroxystyrenes), cardo-type bisphenols, charixarenes, carlixresolecinarenes, or silses And etherates with resins having hydroxy groups such as quoxane. In addition, the copolymer etc. of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate are mentioned.

As a compound which has a 2 or more cyclic thioether group in the said molecule, bisphenol-A episulfide resin YL7000 by the Japan epoxy resin company, etc. are mentioned, for example. Moreover, episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom can also be used.

In addition, the thermosetting binder is commercially available, and the YDCN-500 series of Kukdo Chemical Co., Ltd., the EOCN series of Nippon Kayaku Chemical, etc. can be used.

The thermosetting binder may be included in an amount corresponding to about 0.3 to 2.0 equivalents based on 1 equivalent of the carboxyl group of the acid-modified oligomer. In addition, it is preferable to use 30% or more of the thermosetting binder as a liquid from the viewpoint of developability and vacuum lamination.

The thermosetting binder may include 1 to 30% by weight, or 2 to 25% by weight based on the total weight of the photosensitive resin composition. When the content of the thermosetting binder is too small, a carboxyl group or a hydroxyl group remains in the insulating layer after curing, and thus the heat resistance, alkali resistance, electrical insulation, etc. are lowered, and the moisture absorption rate is increased, thereby decreasing reliability. On the contrary, when the content is too large, it is not preferable because the low molecular weight cyclic (thio) ether group remains in the dry coating film because the strength and the like of the coating film decrease.

menstruum

The present invention can be used in combination of one or more solvents to dissolve the resin composition or to impart the appropriate viscosity.

The solvent may be one or more selected from the group consisting of an aromatic hydrocarbon solvent, an acetate ester solvent, an alcohol solvent, a petroleum solvent, and an amide solvent.

More preferably, as a solvent, ketones, such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; Ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether Glycol ethers (cellosolve) such as dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate Acetate esters, such as these; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol and carbitol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; Amides such as dimethylacetamide and dimethylformamide (DMF). These solvents can be used alone or as a mixture of two or more thereof.

The content of the solvent may be about 10 to 50% by weight based on the total weight of the photosensitive resin composition. When the content of the solvent is less than 10% by weight, the viscosity is high, the coating property is inferior, and when it exceeds 50% by weight, the drying is not good, the stickiness increases.

In addition to each component described above, the resin composition of one embodiment may further include at least one member selected from the group consisting of a thermosetting binder catalyst, a filler, a pigment, and an additive.

Thermosetting binder catalyst

The thermosetting binder catalyst serves to promote thermosetting of the thermosetting binder.

As such a thermosetting binder catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine compound; Hydrazine compounds such as adipic dihydrazide and sebacic acid dihydrazide; Phosphorus compounds, such as a triphenylphosphine, etc. are mentioned. Moreover, as what is marketed, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are brand names of an imidazole type compound) by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N and UCAT3502T by San Apro Corporation (All are brand names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATS A102, U-CAT5002 (both bicyclic amidine compounds and salts thereof), and the like. It is not specifically limited to these, It may be the thing which accelerates reaction of the thermosetting catalyst of an epoxy resin or an oxetane compound, or an epoxy group and / or an oxetanyl group, and a carboxyl group, It can also be used individually or in mixture of 2 or more types. . Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine-isosaururic acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isosaanuric acid S-triazine derivatives, such as an adduct, can also be used, Preferably, the compound which also functions as these adhesive imparting agents can be used together with the said thermosetting binder catalyst.

The use amount of the thermosetting binder catalyst may be about 0.3 to 2% by weight based on the total weight of the resin composition in terms of suitable thermosetting.

filler

The filler can be used without limitation as long as it is an inorganic filler well known in the art. For example, the inorganic filler may be one or more compounds selected from the group consisting of silica, barium sulfate, barium titanate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide and mica.

In addition, the filler may be used in an amount of 5 wt% to 40 wt% based on the total weight of the photosensitive resin composition.

Pigment

Pigments exhibit visibility and hiding power to hide defects such as scratches on circuit lines.

As the pigment, red, blue, green, yellow, black pigments and the like can be used. As the blue pigment, phthalocyanine blue, pigment blue 15: 1, pigment blue 15: 2, pigment blue 15: 3, pigment blue 15: 4, pigment blue 15: 6, pigment blue 60, and the like can be used. have. Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. may be used as the green pigment. Examples of the yellow pigments include anthraquinones, isoindolinones, condensed azos, and benzimidazolones. For example, Pigment Yellow 108, Pigment Yellow 147, Pigment Yellow 151, Pigment Yellow 166, Pigment. Pigment yellow 181, pigment yellow 193 and the like can be used.

The content of the pigment is preferably used at about 0.5 to 3% by weight based on the total weight of the resin composition. When used in less than 0.5% by weight, visibility and hiding power is lowered, and when used in excess of 3% by weight is less heat resistance.

additive

The additive may be added to remove bubbles in the resin composition or remove popping or craters from the surface of the film, impart flame retardancy, adjust viscosity, and catalyze the film.

Specifically, known conventional thickeners such as finely divided silica, organic bentonite and montmorillonite; Antifoaming agents and / or leveling agents such as silicone, fluorine, and polymers; Silane coupling agents such as imidazole series, thiazole series, and triazole series; Known and common additives such as flame retardants such as phosphorus flame retardants and antimony flame retardants can be blended.

Among them, the leveling agent serves to remove the popping or craters of the surface when the film is coated, for example, BYK-380N, BYK-307, BYK-307, BYK-378, BYK-350, etc. of BYK-Chemie GmbH.

The content of the additive is preferably about 0.01 to 10% by weight based on the total weight of the resin composition.

[Photosensitive film]

On the other hand, according to another embodiment of the invention, a novolak-based oligomer having a phenolic hydroxyl group and a photocurable unsaturated functional group; Acid-modified oligomers having a carboxyl group and a photocurable unsaturated functional group; Photopolymerizable monomers having photocurable unsaturated functional groups; And a cured product between a thermosetting binder having a thermosetting functional group, and a filler dispersed in the cured product.

The cured product may include a crosslinked structure between a photocurable unsaturated functional group of the novolac oligomer, a photocurable unsaturated functional group of an acid-modified oligomer, and a photopolymerizable monomer; A crosslinked structure in which a thermosetting functional group of the thermosetting binder and a carboxyl group of a phenolic hydroxyl group or an acid-modified oligomer of a novolac oligomer are crosslinked; And it may include a cross-linking structure between the thermosetting binder.

As described above, the photosensitive film may mean an insulating film including PID (photoimageable dielectics) or a dry film solder resist.

Referring to the process of manufacturing an insulating film and a dry film solder resist (DFSR) using the photosensitive resin composition of the embodiment as follows.

First, the resin composition of the embodiment as a photosensitive coating material on a carrier film is used as a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater or After coating with a spray coater or the like, the oven is dried for 1 to 30 minutes through a temperature of 50 to 130 minutes, and then a release film is laminated to the carrier film, the photosensitive film, and the release film from below. The dry film comprised can be manufactured.

The photosensitive film may have a thickness of about 5 to 100 μm. In this case, a plastic film such as polyethylene terephthalate (PET), a polyester film, a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film may be used as the carrier film, and polyethylene (PE), A polytetrafluoroethylene film, a polypropylene film, a surface treated paper, or the like can be used, and when the release film is peeled off, it is preferable that the adhesive force of the photosensitive film and the release film is lower than that of the photosensitive film and the carrier film.

Next, after peeling off a release film, the photosensitive film layer is bonded together on the board | substrate with a circuit using a vacuum laminator, a hot roll laminator, a vacuum press, etc.

Next, the substrate is exposed to light (UV, etc.) having a constant wavelength band. The exposure may be selectively exposed with a photo mask or may be directly pattern exposed with a laser direct exposure machine. The carrier film peels off after exposure. Although exposure amount changes with coating film thickness, 0-1,000 mJ / cm <2> is preferable. When the exposure is performed, for example, in the exposed portion, photocuring may occur to form crosslinks between unsaturated functional groups included in novolak-based oligomers, acid-modified oligomers, and photopolymerizable monomers, and as a result, Can be left unremoved. On the contrary, the non-exposed portion may not be formed with the crosslink and the crosslinked structure thereof, and thus the carboxyl group and the hydroxyl group may be maintained to be in an alkali developable state.

After exposure, an additional post exposure baking (PEB) may be performed. PEB may be performed at a temperature of 50 to 100 ° C. for 1 to 20 minutes to harden the exposed portion.

Next, development is carried out using an alkaline solution or the like. The alkaline solution may be an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like. According to one embodiment of the present invention, it is possible to develop with an aqueous solution of 1% by weight of sodium carbonate, so that existing lines used for developing existing PSR or DFSR can be used as they are.

Finally, the alkali-developed film is heated and cured (Post Cure) to form an insulating layer formed from the photosensitive film, a seed layer is formed on the insulating layer through sputtering or chemical copper plating, and patterned using a plating resistor. After forming the wiring through the electroplating, additional multilayer formation is possible, and finally the printed circuit board is completed by covering the DFSR. At this time, the heat curing temperature is preferably 130 or more.

Through the above-described method, a photosensitive film and a printed circuit board including the same may be provided. The photosensitive film may include a novolac oligomer having a phenolic hydroxyl group and a photocurable unsaturated functional group through photocuring and thermosetting; Acid-modified oligomers having a carboxyl group and a photocurable unsaturated functional group; Photopolymerizable monomers having photocurable unsaturated functional groups; And a cured product between thermosetting binders having thermosetting functional groups. In addition, the photosensitive film may include a filler dispersed in the cured product and having the above-described specific physical properties.

Accordingly, the photosensitive film of the embodiment is not only excellent in developability, but also does not generate a blister upon refrlow of PCT heat resistance and excellent plating adhesion even under high temperature and high humidity.

For example, the photosensitive film was measured by using a universal testing machine (UTM) after 100 hours in a HAST chamber of 130 ° C. and 85% RH when the entire copper plating was formed to a predetermined thickness after curing. The plating adhesion can maintain 70% or more of the plating adhesion before entering the HAST chamber. The temperature at the time of measuring the plating adhesion before being put into the HAST chamber may be room temperature.

According to a preferred embodiment, the photosensitive insulating film of the present invention, when copper plating is formed to a thickness of 25um to the front of the film after curing, put into a HAST chamber of 130 ℃, 85% RH after 100 hours using a universal testing machine (UTM) The plating adhesion measured as described above can maintain 70% or more of the normal temperature adhesion.

In addition, the insulating film and the dry film solder resist may include basic physical properties and may exhibit low coefficient of thermal expansion. For example, the insulation pitch may have a thermal expansion coefficient of 20 to 80 ppk / K.

The filler represents a conventional filler as described above. In addition, specific details regarding components that may be included in the photosensitive insulating film include the above-described content with respect to the photosensitive resin composition of the embodiment.

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

[ Example  And Comparative example : Manufacture of Resin Composition, Dry Film and Printed Circuit Board]

Synthesis Example 1

300 g of bisphenol A novolac resin VH4170 of DIC Corporation was put in 300 g of MEK and stirred until completely dissolved. 71.76 g of 2-isocyanatoethyl methacrylate and 0.36 g of dibutyltin dilaurate as a catalyst were added to the completely dissolved solution, and the reaction mixture was heated to 50 ° C. for 3 hours. The mixture was cooled to room temperature to obtain a novolac oligomer 1 in which 20 mol% of the phenolic hydroxyl group was substituted with a photocurable unsaturated functional group. FT-IR confirmed that all isocyanate groups were lost.

Synthesis Example 2

Synthesis example except that 300 g of MIPHOTO NOVOL 5505S (30wt% PGEMA), a misol Corporation's cresol novolak resin, 31.75 g of 2-isocyanatoethyl methacrylate and 0.16 g of dibutyltin dilaurate were used. Proceed in the same manner as 1 to obtain a novolac oligomer 2 in which 30 mol% of the phenolic hydroxyl group was substituted with a photocurable unsaturated functional group.

Phenolic hydroxyl group (- OH )Wow Photocuring  Synthesis of Novolac Oligomers with Possible Unsaturated Functional Groups

Example 1

As a acid-modified oligomer having 24 g of phenolic hydroxyl group (-OH) and the photocurable unsaturated functional group of Synthesis Example 1, carboxyl group (-COOH) and the photocurable unsaturated functional group, ZAR-1035 (Bisphenol A- novolac-type epoxy acrylate) 60 g, a photopolymerizable monomer having a photocurable unsaturated functional group, 14 g of TMPTA (trimethylolpropane triacrylate) from Entis Co., Ltd., a thermosetting binder having a curable functional group A photosensitive resin composition was obtained with 24 g of RE-305 which is a phenol novolving epoxy, 4 g of Darocur TPO of BASF Corporation as a photoinitiator, 40 g of BaSO 4 as a filler, and 15 g of PGMEA as a solvent.

The molar equivalent of the carboxyl group and the molar equivalent of the hydroxyl group were obtained by the following equations (1) and (2).

[Equation 1]

Molar equivalent of carboxyl group = (input of acid-modified oligomer) * (solid content) * (acid value of acid-modified oligomer) / 56 (KOH molecular weight) / 1000

[Equation 2]

Molar equivalent of hydroxyl group = (novolak-based oligomer input) * (solid content) / (hydroxyl equivalent of novolak-based oligomer)

EXAMPLES 2-3, COMPARATIVE EXAMPLES 1-2

As shown in the following table | surface, the photosensitive composition of Examples 2-3 and Comparative Examples 1-2 was obtained by the method similar to Example 1. (Unit: g)

Example Comparative example One 2 3 One 2 Carboxylic molar equivalent 0.068 0.068 0.068 0.138 0.068 Hydroxyl molar equivalent 0.072 0.064 0.064 0.000 0.076 Component A Synthesis Example 1 24.00 Synthesis Example 2 40.00 40.00 VH4170_50 18.00 Component B ZAR-1035 60.00 60.00 60.00 120.00 60.00 Component C TMPTA 14.00 14.00 14.00 14.00 14.00 Component D RE-305 24.00 24.00 24.00 24.00 24.00 Photoinitiator Darocur TPO 4.00 4.00 4.00 Irgacure 907 OXE02 0.60 0.60 catalyst 2-PI 0.70 0.70 0.70 0.70 0.70 additive BYK-333 0.60 0.60 0.60 0.60 0.60 filler BaSO ₄ 40.00 40.00 40.00 40.00 40.00 menstruum PGMEA 15.00 15.00 15.00 15.00 15.00

week)

Component A: Novolac oligomer having phenolic hydroxyl group (-OH) and photocurable unsaturated functional group

Component B: acid-modified oligomer having a carboxyl group (-COOH) and a photocurable unsaturated functional group

Component C: photopolymerizable monomer having a photocurable unsaturated functional group;

Component D: thermosetting binder having a thermosetting functional group

ZAR-1035: Nippon Kayaku Co., Ltd. product name, bisphenol A- novolac-type acid-modified epoxy acrylate

VH4170_50: 50 wt% solution of DIC Corporation Bisphenol A novolac MEK

TMPTA: Entis, trimethylolpropane triacylate

RE-305: Nippon Kayaku Co., Ltd. product name, phenol novolac type epoxy

Darocur TPO: BASF Corporation brand name, diphenyl- (2,4,6-trimethylbenzoyl) -phosphine oxide

Irgacure 907: BASF Corporation brand name, 2-methyl-4 '-(methylthio) -2-morpholino-propiophenone

OXE02: BASF Corporation brand name, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone-1- (O-acetyloxime)

2-PI: 2-phenyl imidazole

BYK-333: BYK Chemi Co., Ltd.

PGMEA: Propylene Glycol Monomethyl Ether Acetate

< Test Example  >

The photosensitive resin compositions prepared in Examples and Comparative Examples were applied on a PET film as a carrier film using a baker applicator after drying to a thickness of 20 μm, and dried at 90 ° C. for 5 minutes to form a film, followed by PE as a cover film. A dry film was prepared by covering the film.

( Developability )

Fine roughness was formed on the copper foil surface by CZ treatment of MEC on 0.15 mm thick copper foil laminated sheets. After peeling off the cover film of the produced film, the photosensitive film was laminated at 60 degreeC using the vacuum laminator on the copper foil laminated board. A negative type mask having a hole shape of 50 μm is closely attached to the mask, exposed to an exposure dose of 500 mJ / cm ² under UV of 365 nm wavelength, and then the PET film is removed and sprayed in a 1 wt% aqueous solution of Na ₂ CO ₃ at 30 ° C. It developed for 100 second and formed the pattern. Scanning electron microscopy (SEM) was used to observe the shape of the pattern thus formed. The residue was not found at the bottom and the via size was 35 μm.

( PCT  Heat resistance)

Fine roughness was formed on the copper foil surface by CZ treatment of MEC on 0.15 mm thick copper foil laminated sheets. After removing the cover film of the film, the photosensitive film was laminated at 60 ° C. using a vacuum laminator on a copper foil laminate having a width of 5 cm and a length of 5 cm. After exposing at an exposure dose of 500mJ / cm ^{2 with} UV in 365nm wavelength band, PET film was removed, developed for 30 seconds by spraying method in a 1 wt% aqueous solution of Na ₂ CO ₃ at 30 ° C, and then heated and cured at 170 ° C for 1 hour. Specimen was produced.

This specimen was treated with a PCT apparatus (ESPEX, HAST system TPC-412MD) for 100 hours at 121 ° C., 100% humidity, 2 atm, and the state of the coating film was observed and evaluated according to the following criteria. . After PCT evaluation, it was OK that there was no peeling of a dry film soldering resist, and there was no blister and discoloration, and it evaluated NG that there was peeling, blister and discoloration.

(Adhesion and reflow  Test Specimen Preparation)

Fine roughness was formed on the copper foil surface by CZ treatment of MEC on 0.15 mm thick copper foil laminated sheets. After peeling off the cover film of the produced film, the photosensitive film was laminated at 60 degreeC using the vacuum laminator on the copper foil laminated board. After exposing at an exposure dose of 500mJ / cm ^{2 with} UV in 365nm wavelength band, PET film was removed, developed for 30 seconds by spraying method in a 1 wt% aqueous solution of Na ₂ CO ₃ at 30 ° C, and then heated and cured at 170 ° C for 1 hour. Specimen was produced.

After pre-treatment using the Ar / O ₂ plasma on the cured substrate, as a seed layer was sputtered to a thickness of Ti / Cu = 100nm / 500nm.

After the sputtering, the copper foil was plated by electrolytic copper plating until the thickness of the copper foil was 25 μm. After plating, drying was performed at 100 ° C. for 1 hour to complete the specimen.

( after reflow blister  Occurrence evaluation)

The finished specimens were cut into 5 cm and 5 cm lengths and allowed to stay for 60 seconds in a reflow oven having a maximum temperature of 260 ° C.

After passing through the reflow oven, the blister between the plating layer and the photosensitive composition layer was observed, and it was confirmed that blister did not occur, and it was determined as NG that blister occurred.

( After moisture absorption  Plating adhesion evaluation)

After the prepared adhesive evaluation specimens were cut to a size of 10 mm * 100 nm, the adhesion was measured using a universal testing machine (UTM).

The same sample was placed in a HAST chamber of 130 ° C. and 85% RH, and after 100 hours, adhesion was measured again using UTM.

After 100 hours, the plating adhesion was evaluated by determining that 2, which was maintained at 70% or more of the initial adhesive strength between 1 and 30 to 70%, and 3 or less which was less than 30% of the initial adhesive strength.

The results evaluated in the above experiments are shown in Tables 2 and 3 below.

Example 1 Example 2 Example 3 Developability OK OK OK PCT heat resistance OK OK OK Blister after reflow OK OK OK Plating adhesion after moisture absorption One One One

Comparative Example 1 Comparative Example 2 Developability OK NG PCT heat resistance OK - Blister after reflow NG - Plating adhesion after moisture absorption 3 -

As shown in Table 2, Examples 1 to 3 were not only excellent in developability, but also did not generate PCT heat resistance and blister after refrlow, and also showed excellent plating adhesion test results after moisture absorption.

On the other hand, through the results of Table 3, Comparative Examples 1 and 2 were generally poorer than Examples 1 to 3. Although Comparative Example 1 had good developability and PCT heat resistance, a blister occurred between the plating layer and the photosensitive composition layer after passing through the reflow oven, and the plating adhesion was also poor. In addition, in the case of Comparative Example 2, a problem that melted to the exposed portion during development occurred, and no other test was performed.

Claims (24)

Novolac oligomers having a phenolic hydroxyl group and a photocurable unsaturated functional group;
Acid-modified oligomers having a carboxyl group and a photocurable unsaturated functional group;
Photopolymerizable monomers having photocurable unsaturated functional groups;
Thermosetting binders having thermosetting functional groups; And
A photoinitiator;
The novolak-based oligomer is a part of the phenolic hydroxyl group of the novolak resin, a photocurable unsaturated functional group is substituted directly or through a mediating functional group, 5mol% to 50mol% of the phenolic hydroxyl group comprises a photocurable unsaturated functional group,
The intermediate functional groups are -NH-, -O-, -CO-, -S-, -SO _2- , -NH-CO-O-, -NCO-, -C (CH ₃ ) _2- , -C (CF _{3) 2 -, -CO-NH-} , -CO-O-, - (CH 2) n1 -, -O (CH 2) n2 O-, and _{-CO-O- (CH 2) n3} -O-CO Photosensitive resin composition comprising at least one functional group selected from the group consisting of: n1 to n3 each independently represent an integer of 1 to 10.
delete delete The photosensitive resin composition of claim 1, wherein the photocurable unsaturated functional group comprises acrylate, methacrylate, alkyl acrylate having 1 to 5 carbon atoms, or alkyl methacrylate having 1 to 5 carbon atoms.
The photosensitive resin composition of claim 1, wherein the novolac-based oligomer comprises 5 wt% to 40 wt% based on the total weight of the photosensitive resin composition.
The photosensitive resin composition according to claim 1, wherein the acid-modified oligomer is an oligomer having a photocurable functional group having an acrylate group or an unsaturated double bond and a carboxyl group in a molecule.
The photosensitive resin composition according to claim 1, wherein a main chain of the acid-modified oligomer is a novolac epoxy or polyurethane, and a carboxyl group and an acrylate group are introduced into the main chain.
The photosensitive resin composition of claim 1, wherein the acid-modified oligomer is obtained by copolymerization of a polymerizable monomer having a carboxyl group and a monomer including an acrylate compound, and has a weight average molecular weight of 1000 to 30000.
The photosensitive resin composition of claim 1, wherein the acid-modified oligomer comprises 10 wt% to 75 wt% based on the total weight of the photosensitive resin composition.
The photosensitive resin composition according to claim 1, wherein the photopolymerizable monomer has photocurability and thermosetting properties using an acrylate compound having an unsaturated functional group capable of photopolymerization.
The photosensitive resin composition of claim 1, wherein the photopolymerizable monomer comprises 1 to 30 wt% based on the total weight of the photosensitive resin composition.
The photosensitive resin composition of claim 1, wherein the thermosetting binder comprises at least one functional group selected from an epoxy group, an oxetanyl group, a cyclic ether group, and a cyclic thio ether group.
The photosensitive resin composition of claim 1, wherein the thermosetting binder comprises 1 to 30 wt% based on the total weight of the photosensitive resin composition.
According to claim 1, wherein the photoinitiator, when the weight loss was measured while heating at a temperature increase rate of 5 ℃ / min using TGA, the residue at 260 ℃ 40% by weight relative to the total weight of the photo initiator The photosensitive resin composition containing the above thing.
The photosensitive resin composition of claim 1, wherein the photoinitiator comprises 0.5 to 15 wt% based on the total weight of the photosensitive resin composition.
The photosensitive resin composition of claim 1, further comprising a diaryliodine-based or trisulfonium-based cationic initiator based on the total weight of the photosensitive resin composition.
The photosensitive resin composition of claim 1, further comprising at least one member selected from the group consisting of a solvent, a thermosetting binder catalyst, a filler, a pigment, and an additive.
Novolac oligomers having a phenolic hydroxyl group and a photocurable unsaturated functional group; Acid-modified oligomers having a carboxyl group and a photocurable unsaturated functional group; Photopolymerizable monomers having photocurable unsaturated functional groups; And a cured product between a thermosetting binder having a thermosetting functional group, and a filler dispersed in the cured product.
19. The method of claim 18, wherein the novolak-based oligomer is a part of the phenolic hydroxyl group of the novolak resin, a photocurable unsaturated functional group is substituted directly or through a mediated functional group, 5mol% to 50mol% of the phenolic hydroxyl group is photocurable The photosensitive film containing an unsaturated functional group.
The method of claim 19, wherein the intermediate functional group is -NH-, -O-, -CO-, -S-, -SO _2- , -NH-CO-O-, -NCO-, -C (CH ₃ ) ₂ -, -C (CF ₃ ) _2- , -CO-NH-, -CO-O-,-(CH ₂ ) _{n 1-} , -O (CH ₂ ) _{n 2} O-, and -CO-O- (CH ₂ ) _n3 -O-CO-, at least one functional group selected from the group consisting of, wherein n1 to n3 are each independently an integer of 1 to 10, the photosensitive film.
The photosensitive film of claim 19, wherein the photocurable unsaturated functional group comprises acrylate, methacrylate, alkyl acrylate of 1 to 5 carbon atoms, or alkyl methacrylate of 1 to 5 carbon atoms.
The method of claim 18, wherein the cured product
A crosslinked structure between the photocurable unsaturated functional group of the novolac oligomer and the photocurable unsaturated functional group of the acid-modified oligomer, and the photopolymerizable monomer; A crosslinked structure in which a thermosetting functional group of the thermosetting binder and a carboxyl group of a phenolic hydroxyl group or an acid-modified oligomer of a novolac oligomer are crosslinked; And crosslinking structure between thermosetting binder
Photosensitive film comprising a.
19. The method according to claim 18, wherein when the entire copper plating is formed on the film after curing to a predetermined thickness, the plating adhesion measured using a universal testing machine (UTM) after 100 hours in a HAST chamber at 85 ° C and 130% at 130 ° C. The photosensitive film which keeps 70% or more of the plating adhesive force before entering this HAST chamber.
19. The photosensitive film of claim 18 comprising photoimageable dielectics (PID) or dry film solder resist (DFSR).