KR20130095683A - Photo-curable and thermo-curable resin composition and dry film solder resist - Google Patents

Abstract

PURPOSE: A resin composition which has photocurable and thermosetting property is provided to have dry film solder resist which has improved heat resisting reliability with a high glass transition temperature and a low coefficient of thermal expansion. CONSTITUTION: A resin composition which has photocurable and thermosetting property comprises: an acid-modified oligomer which includes iminocarbonate group compound which has carboxy radical and a photocurable unsaturated functional group; a photopolymer monomer which has more than 3 photocurable unsaturated functional groups; a thermosetting binder which has functional group capable of thermosetting; and photo initiator. The iminocarbonate group compound is formed by reacting a dicarboxylic acid compound and compound which has the photocurable unsaturated functional group and hydroxy group or carboxy radical in a cyanate ester group compound.

Description

Resin composition which has photocurability and thermosetting, and dry film soldering resist {PHOTO-CURABLE AND THERMO-CURABLE RESIN COMPOSITION AND DRY FILM SOLDER RESIST}

TECHNICAL FIELD The present invention relates to a resin composition having a photocurable and thermosetting property and a dry film solder resist (DFSR). More specifically, the present invention relates to resin compositions and DFSR having photocurable and thermosetting properties that enable the provision of DFSR with higher glass transition temperatures and improved heat resistance reliability.

BACKGROUND ART With the miniaturization and light weight of various electronic devices, photosensitive solder resists capable of forming fine opening patterns are used for printed circuit boards, semiconductor package substrates, and flexible circuit boards.

Semiconductor packaged products are composite materials consisting of epoxy molding, insulators such as solder resists, semiconductors such as chip dies, and conductors such as substrate circuit patterns, which require a number of processes involving severe thermal shock conditions. However, due to the difference in the coefficient of thermal expansion (CTE) of each of the insulators, semiconductors, and conductors, dimensional instability and warpage of the component appear as problems. This phenomenon causes a mismatch between the chip and the substrate when soldering the chip die and the semiconductor substrate with solder balls or gold wires, and also causes the product to crack and break due to shear stress, which may affect the life of the product. Can be. Recently, as the thickness of the substrate becomes thinner, such dimensional instability and warpage are becoming more problematic. In order to solve this problem, materials are being developed to minimize CTE mismatch between materials, and solder resists are continuously required to be developed as solder resists having a lower coefficient of thermal expansion.

The thermal expansion coefficient of the dry film type solder resist previously known is 45 to 70 ppm of α1 (coefficient of thermal expansion before Tg) and 140 to 170 ppm of α2 (coefficient of thermal expansion after Tg).

Recently, materials having a thermal expansion coefficient of 10 ppm or less or 5 ppm or less have been developed in the case of the core of the substrate material, but the development of a solder resist material that can be used with it has not been known until now.

In addition, there have been attempts to lower the coefficient of thermal expansion of the solder resist sheet by increasing the content of the filler, but if the content of the filler is raised above a certain level, poor coating may occur due to the aggregation of the filler. This decrease may cause problems such as poor workability.

The solder resist generally requires characteristics such as developability, high resolution, insulation, adhesion, soldering heat resistance, gold plating resistance, and the like. In particular, for solder resists for semiconductor package substrates, in addition to these characteristics, for example, the crack resistance for the temperature cycle test (TCT) of -65 ° C to 150 ° C or the HAST (Highly Accelerated Stress Test between fine wirings). ) Characteristics are required.

In recent years, as a soldering resist, the dry-film type soldering resist which has favorable film thickness uniformity, surface smoothness, and thin film formability attracts attention. Such a dry film type solder resist may have advantages such as simplification of the process for forming the resist and reduction of solvent emissions during the resist formation in addition to the above characteristics.

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, the solder resist formed from such a resin composition does not have a high glass transition temperature and is not sufficient in heat resistance reliability, so that the PCT resistance, TCT heat resistance, and HAST resistance between the fine wirings required for the package substrate material of the semiconductor device are adequate. There was a disadvantage that could not be met.

The present invention provides a resin composition having photocurability and thermosetting that can provide DFSR with improved heat resistance with higher glass transition temperature and low coefficient of thermal expansion (CTE).

The present invention also provides a DFSR that exhibits improved heat resistance reliability and the like.

The present invention provides an acid-modified oligomer comprising a carboxyl group (-COOH) and an iminocarbonate compound having a photocurable unsaturated functional group; Photopolymerizable monomers having three or more photocurable unsaturated functional groups; Thermosetting binders having thermosetting functional groups; And a photocurable and thermosetting resin composition comprising a photoinitiator.

The iminocarbonate-based compound may be formed by reacting a cyanate ester compound with a dicarboxylic acid compound, a compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group.

Examples of the dicarboxylic acid compound include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, norbornene dicarboxylic acid, cyclohexene dicarboxylic acid, It may include one or more compounds selected from the group consisting of cyclohexane dicarboxylic acid, imidazole dicarboxylic acid, pyridine dicarboxylic acid and acid anhydrides thereof.

The compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group is acrylic acid, methacrylic acid, butenoic acid, hexenoic acid, cinnamic acid, allylphenol, hydroxystyrene, hydroxycyclohexene or hydroxy It may include one or more compounds selected from the group consisting of oxynaphthoquinone.

The cyanate ester compound may include a bisphenol or novolac compound having a cyanide group (-OCN).

The dicarboxylic acid compound and the compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group may be used in a molar ratio of 2: 8 to 8: 2 to react with the cyanate ester compound.

The acid-modified oligomer may include an iminocarbonate-based compound of Formula 1 below.

[Formula 1]

In Formula 1, n is an integer of 1 to 100, R ₁ is a functional group derived from a compound having a photocurable unsaturated functional group and a hydroxy group or a carboxy group, R ₂ is a functional group derived from a dicarboxylic acid compound.

The acid-modified oligomer may be included in 15 to 75% by weight based on the total weight of the resin composition.

The photopolymerizable monomer may include an acrylate compound having three or more photocurable unsaturated functional groups.

The photopolymerizable monomer is selected from the group consisting of a hydroxyl group-containing acrylate compound, a water-soluble acrylate compound, a polyester acrylate compound, a polyurethane acrylate compound, an epoxy acrylate compound, and a caprolactone-modified acrylate compound It may include one or more compounds.

The photopolymerizable monomer may be included in 5 to 30% by weight based on the total weight of the resin composition.

The photoinitiator is a group consisting of benzoin and its alkyl ethers, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, α-aminoacetophenones, acylphosphine oxides and oxime esters. It may include one or more selected from.

The photoinitiator may be included in 0.5 to 20% by weight based on the total weight of the resin composition.

The thermosetting functional group may be at least one selected from the group consisting of an epoxy group, an oxetanyl group, a cyclic ether group, and a cyclic thio ether group.

The thermosetting binder may be included in an amount corresponding to 0.8 to 2.0 equivalents based on 1 equivalent of the carboxyl group of the acid-modified oligomer.

The said resin composition is a solvent; And one or more selected from the group consisting of a thermosetting binder catalyst, a filler, a pigment, and an additive.

In addition, the present invention is an acid-modified oligomer comprising a carboxy group (-COOH) and an iminocarbonate compound having a photocurable unsaturated functional group; Photopolymerizable monomers having three or more photocurable unsaturated functional groups; And a cured product of a thermosetting binder having a thermosetting functional group.

In such DFSR, the cured product may include a crosslinked structure in which the carboxyl group of the iminocarbonate-based compound and the thermosetting functional group are crosslinked; A crosslinked structure in which the unsaturated functional groups of the iminocarbonate compound and the photopolymerizable monomer are crosslinked with each other; And a triazine crosslinked structure of Formula 2 derived from the iminocarbonate-based compound:

(2)

As the triazine crosslinked structure represented by Chemical Formula 2 and the like is included, the dry film solder resist (DFSR) provided from the resin composition may be used in a structure using an acid-modified epoxy acrylate based on an existing novolac structure. In comparison, it may have a higher glass transition temperature (Tg), and the DFSR may have a higher glass transition temperature (Tg) of about 120 to 200 ° C, or about 130 to 170 ° C, or about 140 ° C. Accordingly, it is possible to exhibit improved heat resistance reliability. Therefore, the DFSR can satisfy various physical properties such as PCT resistance, TCT heat resistance, and HAST resistance between fine interconnections required for the package substrate material of the semiconductor device.

The dry film solder resist may further include a photoinitiator dispersed in the cured product.

The dry film solder resist may be used to manufacture a package substrate of a semiconductor device.

Since the resin composition of this invention contains a specific acid-modified oligomer, it can form a predetermined triazine crosslinked structure in the hardened | cured material of the resin composition which comprises DFSR. Thus, the resin composition can be used to provide DFSR which exhibits higher glass transition temperature (Tg) and low coefficient of thermal expansion as well as improved heat resistance reliability.

Therefore, according to the present invention, it becomes possible to provide a DFSR exhibiting various physical properties such as excellent PCT resistance, TCT heat resistance, and HAST resistance between fine interconnects, and such DFSR can be preferably used for manufacturing a package substrate of a semiconductor device. have.

Hereinafter, a photocurable and thermosetting resin composition and an DFSR according to an embodiment of the present invention will be described in more detail.

According to one embodiment of the invention, an acid-modified oligomer comprising a carboxy group (-COOH) and an iminocarbonate compound having a photocurable unsaturated functional group; Photopolymerizable monomers having three or more photocurable unsaturated functional groups; Thermosetting binders having thermosetting functional groups; And a photocurable and thermosetting resin composition comprising a photoinitiator.

Such resin compositions include acid-modified oligomers, photopolymerizable monomers, photoinitiators and thermosetting binders, and particularly include iminocarbonate-based compounds having a carboxyl group and a photocurable unsaturated functional group as acid-modified oligomers.

DFSR can be formed by the following process using the resin composition of one embodiment. First, after forming a film with a resin composition and laminating such a film on a predetermined board | substrate, it selectively exposes to the resin composition of the part in which DFSR is to be formed. When such exposure is carried out, the acid-modified oligomer, for example, the unsaturated functional group contained in the iminocarbonate-based compound and the unsaturated functional group contained in the photopolymerizable monomer may cause photocuring to form crosslinks with each other. In the exposed portion, a crosslinked structure by photocuring may be formed.

Subsequently, when development is carried out using an alkali developer, the resin composition of the exposed part having the crosslinked structure is left on the substrate as it is, and the resin composition of the remaining non-exposed part may be dissolved in the developer and removed.

Then, when the resin composition remaining on the substrate is thermally cured by heat treatment, the acid-modified oligomer, for example, a carboxy group contained in the iminocarbonate-based compound reacts with a thermosetting functional group of the thermosetting binder to crosslink. Can be formed, and as a result, a DFSR can be formed in a desired portion on the substrate while forming a crosslinked structure by thermal curing.

At this time, as the resin composition of one embodiment includes the imino carbonate-based compound as an acid-modified oligomer, the secondary cross-linking structure in the thermosetting process, for example, triazine cross-link represented by the formula (2) of Scheme 1 A structure can be formed. It is formed by the nitrogens in the main chain of the iminocarbonate compound to form a triazine ring by bonding to each other by heat:

[Reaction Scheme 1]

또는 알릴페놀에서 유래한

등의 작용기로 될 수 있다. In Scheme 1, R ₁ is a functional group derived from a compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group, for example acrylic acid, methacrylic acid, butenoic acid, hexenoic acid, shin Functional groups derived from compounds of namsan, allylphenol, hydroxystyrene, hydroxycyclohexene or hydroxynaphthoquinone, specific examples derived from acrylic acid

Or derived from allylphenol

It may be a functional group such as.

또는 시클로헥센 디카르복실산(Cyclohexene dicarboxylic acid)에서 유래한

등의 작용기로 될 수 있다. 상기‘*'은 결합 지점을 의미한다.R ₂ is a functional group derived from a dicarboxylic acid compound, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, norbornene dicarboxylic acid, cyclohexene Dicarboxylic acid compounds selected from the group consisting of dicycloacid (Cyclohexene dicarboxylic acid), cyclohexane dicarboxylic acid, imidazole dicarboxylic acid, pyridine dicarboxylic acid and acid anhydrides thereof Functional groups derived from, specific examples derived from phthalic acid

Or derived from cyclohexene dicarboxylic acid

It may be a functional group such as. '*' Means a point of attachment.

That is, when DFSR is formed using the resin composition of one embodiment, the crosslinked structure (that is, derived from the carboxyl group of the acid-modified oligomer and the thermosetting functional group of the thermosetting binder) in the cured product of the resin composition constituting the DFSR. In addition, as the secondary triazine crosslinked structure is included, the glass transition temperature of the DFSR can be higher as about 120-200 ° C, or about 130-170 ° C, or about 140 ° C. As a result, the heat resistance reliability of the DFSR can be further improved, and various physical properties such as excellent PCT resistance, TCT heat resistance, and HAST resistance between fine wirings required for a package substrate material of a semiconductor device can be satisfied.

Therefore, using the resin composition of one embodiment, a DFSR which exhibits a higher glass transition temperature and improved heat resistance reliability, and which can be preferably used as a package substrate material of a semiconductor element, can be provided.

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

Acid denaturation Oligomer

The resin composition of the embodiment includes a carboxyl group (-COOH) and an iminocarbonate-based compound having a photocurable unsaturated functional group as an acid-modified oligomer. Such acid-modified oligomers form crosslinks with other components of the resin composition by photocuring, that is, photopolymerizable monomers and / or thermosetting binders, thereby enabling the formation of DFSR, and the resin composition of the non-exposed portion, including the carboxyl group, is alkali developable. To indicate.

In particular, the resin composition of one embodiment may form a triazine crosslinked structure represented by Chemical Formula 2 in the cured product of the resin composition forming DFSR, as the iminocarbonate-based compound is included as an acid-modified oligomer. Thus, the resin composition of one embodiment enables the preparation and provision of DFSR with higher glass transition temperature and improved heat resistance reliability.

The imino carbonate compound may be a compound formed by reacting a cyanate ester compound with a dicarboxylic acid compound, a compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group. By using such an imino carbonate-based compound, it is possible to form the triazine crosslinked structure preferably in the heat curing process, it is possible to provide a DFSR showing more excellent heat resistance reliability and the like.

In this case, as the cyanate ester compound, a bisphenol-based or novolak-based compound having a cyanide group (-OCN), for example, a compound of Formula 1a may be used:

[Formula 1a]

In Formula 1a, n is an integer of 1 to 100.

In addition, the dicarboxylic acid compound that reacts with the cyanate ester compound, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, norbornene dicarboxylic acid, cyclo Compounds selected from the group consisting of hexene dicarboxylic acid, cyclohexane dicarboxylic acid, imidazole dicarboxylic acid, pyridine dicarboxylic acid and acid anhydrides thereof may be used. Possible compounds having unsaturated functional groups and hydroxyl or carboxyl groups include acrylic acid, methacrylic acid, butenoic acid, hexenoic acid, cinnamic acid, allylphenol, hydroxystyrene, hydroxycyclohexene and hydroxynaph It may include one or more compounds selected from the group consisting of toquinones.

By reacting the dicarboxylic acid compound with a compound having a photocurable unsaturated functional group and a hydroxy group or a carboxyl group to the cyanate ester compound described above, an acid-modified oligomer to which a carboxyl group and a photocurable unsaturated functional group are appropriately introduced. Iminocarbonate type compounds can be obtained preferably. In addition, the iminocarbonate-based compound thus obtained properly forms a triazine crosslinked structure during the thermosetting process, thereby enabling the formation and provision of DFSR exhibiting improved heat resistance reliability.

The molar ratio of the carboxyl group introduced into the iminocarbonate-based compound and the unsaturated functional group is a molar ratio of the dicarboxylic acid compound reacting with the cyanate ester compound and the compound having a photocurable unsaturated functional group and a hydroxyl group or carboxyl group. It can be controlled and adjusted. In order for the imino carbonate-based compound to function properly as an acid-modified oligomer, the molar ratio of the dicarboxylic acid compound reacted with the cyanate ester-based compound and the compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group is About 2: 8 to 8: 2. The carboxyl group and the unsaturated functional group introduced therein are introduced into the iminocarbonate-based compound as the acid-modified oligomer, and the acid-modified oligomer is appropriately crosslinked with the photopolymerizable monomer and the thermosetting binder, while the resin composition of the non-exposed part exhibits excellent alkali developability. By forming the structure, the DFSR may exhibit more excellent heat resistance and mechanical properties.

On the other hand, as a more specific example, the compound formed by reacting the acid-modified oligomer, in particular, the cyanate ester-based compound with a dicarboxylic acid compound, a compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group is represented by the formula It may be an iminocarbonate-based compound of:

[Formula 1]

또는 알릴페놀에서 유래한

등의 작용기로 될 수 있고, R₂는 디카르복실산 화합물에서 유래한 작용기, 예를 들어, 옥살산, 말론산, 석신산, 글루타르산, 아디프산, 프탈산, 이소프탈산, 테레프탈산, 노보넨 디카르복실산, 시클로헥센 디카르복실산(Cyclohexene dicarboxylic acid), 시클로헥세인 디카르복실산(Cyclohexane dicarboxylic acid), 이미다졸 디카르복실산, 피리딘 디카르복실산 및 이들의 산 무수물로 이루어진 군에서 선택된 디카르복실산 화합물에서 유래한 작용기, 구체적인 예로서, 프탈산에서 유래한

또는 시클로헥센 디카르복실산(Cyclohexene dicarboxylic acid)에서 유래한

등의 작용기로 될 수 있다.In Formula 1, n is an integer of 1 to 100, R ₁ is a functional group derived from a compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group, for example acrylic acid, methacrylic acid, butenoic acid , Functional groups derived from compounds of hexenoic acid, cinnamic acid, allylphenol, hydroxystyrene, hydroxycyclohexene or hydroxynaphthoquinone, specific examples derived from acrylic acid

Or derived from allylphenol

It may be a functional group such as, R ₂ is a dicarboxylic one functional group, for example, oxalic acid, horses derived from acid compound acid, succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, norbornene Group consisting of dicarboxylic acid, cyclohexene dicarboxylic acid, cyclohexane dicarboxylic acid, imidazole dicarboxylic acid, pyridine dicarboxylic acid and acid anhydrides thereof Functional groups derived from dicarboxylic acid compounds selected from, specific examples, derived from phthalic acid

Or derived from cyclohexene dicarboxylic acid

It may be a functional group such as.

Such a compound of Formula 1 may be, for example, a compound of Formula 1a, a dicarboxylic acid compound such as phthalic acid or cyclohexene dicarboxylic acid, an unsaturated functional group such as acrylic acid or 2-allylphenol, and It can be obtained by reacting a compound having a hydroxyl group or a carboxyl group, and can be suitably used as an acid-modified oligomer, while effectively forming a triazine crosslinked structure, thereby enabling the formation and provision of DFSR and the like having better heat resistance reliability.

On the other hand, the resin composition of one embodiment may further include a conventionally known acid-modified oligomer, in addition to the above-described iminocarbonate-based compound. However, in order to express excellent developability and heat resistance according to one embodiment, the acid-modified oligomer of the iminocarbonate-based compound is about 5 to 25% by weight, or about 7 to 20% by weight based on the total weight of the resin composition %, Or about 9 to 15% by weight, and may include additional acid-modified oligomer of the remaining content of the total content of the acid-modified oligomer described below.

Such additional acid-modified oligomers include carboxyl groups and photocurable functional groups, such as photocurable functional groups having acrylate groups or unsaturated double bonds, and oligomers having carboxyl groups in a molecule, which can be used in resin compositions for forming DFSR. All known ingredients can be used without limitation. For example, the main chain of such additional acid-modified oligomer may be a novolak epoxy or polyurethane, or the like. A component having a carboxyl group and an acrylate group introduced therein may be used as an additional acid-modified oligomer. The photocurable functional group may preferably be an acrylate group, wherein the acid-modified oligomer may be obtained as an oligomer form by copolymerizing a polymerizable monomer having a carboxyl group and a monomer including an acrylate compound.

More specifically, specific examples of additional 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; and 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.

In addition, commercially available components may be used as the above-mentioned additional acid-modified oligomer, and specific examples of such components include ZAR-2000, CCR-1235, ZFR-1122 or CCR-1291H, etc.

On the other hand, the acid-modified oligomer described above may be included in an amount of about 15 to 75% by weight, or about 20 to 50% by weight, or about 25 to 45% by weight relative to the total weight of the resin composition of one embodiment. 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 uniformity may be decreased during coating.

In addition, the acid value of the acid-modified oligomer may be about 40 to 120 mgKOH / g, or about 50 to 110 mgKOH / g, or about 60 to 90 mgKOH / g. When the acid value is too low, alkali developability may be lowered. On the contrary, when the acid value is too high, it may be possible to dissolve the photocurable portion, for example, the exposed portion, by the developing solution, which makes it difficult to form a normal pattern of the DFSR.

Photopolymerization 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 three 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 three or more photocurable unsaturated functional groups can be used. More specifically, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol Hydroxyl group-containing acrylate compounds such as 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 content of the photopolymerizable monomer described above may be about 5 to 30% by weight, about 7 to 20% by weight, or about 7 to 15% by weight based on the total weight of the 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 a photoinitiator, for example, serves to initiate radical photocuring between the acid-modified oligomer and the photopolymerizable monomer in the exposed portion of the resin composition.

As a photoinitiator, a well-known thing can be used and benzoin, such as benzoin, benzoin methyl ether, and benzoin ethyl ether, and its alkyl ether; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone and 4- (1-t-butyldioxy-1-methylethyl) acetophenone; Anthraquinones such as 2-methyl anthraquinone, 2-amylanthraquinone, 2-t-butyl anthraquinone and 1-chloro anthraquinone; Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone Materials such as these can be used.

In addition, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropaneone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1 -One, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone ( As commercially available products, α-aminoacetophenones such as Irugacure (registered trademark) 907, Irugacure 369, Irugacure 379, etc. of Chiba Specialty Chemical Co., Ltd. (currently Chiba Japan Co., Ltd.), 2,4,6- Trimethylbenzoyldiphenylhospinoxite, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide ( As a commercial item, acyl phosphine oxides, such as Rucillin (trademark) TPO by BASF Corporation and Irgacure 819 by Chivas Specialty Chemical Co., Ltd.), etc. can be mentioned as a preferable photoinitiator.

Moreover, oxime ester is mentioned as a preferable photoinitiator. Specific examples of oxime esters include 2- (acetyloxyiminomethyl) thioxanthene-9-one, (1,2-octanedione, 1- [4- (phenylthio) phenyl]-, and 2- (O-benzoyloxime ), (Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)), and the like. Commercially available products include GGI-325 from Chiba Specialty Chemical, Irugacure OXE01, Irugacure OXE02, ADEKA N-1919, Chiba Specialty Chemical's Darocur TPO, and the like.

The content of the photoinitiator may be about 0.5 to 20% by weight, or about 1 to 10% by weight, or about 1 to 5% by weight based on the total weight of the resin composition. If the content of the photoinitiator is too small, 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 the DFSR may not be sufficient.

Thermosetting binder

The resin composition of one embodiment also includes a thermosetting binder having at least one selected from among thermosetting functional groups such as epoxy groups, oxetanyl groups, cyclic ether groups and cyclic thio ether groups. Such a 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 DFSR.

Such a thermosetting binder may have a softening point of about 70 to 100 ° C., thereby reducing unevenness during lamination. Low softening points increase the tackiness of the DFSR, and high flow rates may deteriorate.

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 diisocyanates or their difunctional block isocyanates can also be used.

The thermosetting binder having two or more cyclic (thio) ether groups in the molecule may be a compound having any one or two or more of three, four or five 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.

As a specific example of the said polyfunctional epoxy compound, bisphenol-A epoxy resin, hydrogenated bisphenol-A epoxy resin, brominated bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, novolak-type epoxy resin, for example , Phenol novolak type epoxy resin, cresol novolak type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolak type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, chelate type epoxy resin, glyc Oxal type epoxy resin, amino group containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenolic epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoyl ethane resin, silicone modified epoxy resin and (epsilon) -caprolactone modified epoxy resins. In addition, in order to impart flame retardancy, those in which atoms such as phosphorus are introduced into the structure may be used. These epoxy resins improve the properties such as adhesiveness of the cured film, solder heat resistance, and electroless plating resistance by thermosetting.

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.

Examples of the compound having two or more cyclic thioether groups in the molecule include a bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resin Co., An episulfide resin in which the oxygen atom of the epoxy group of the novolac epoxy resin is replaced with a sulfur atom can also be used.

Moreover, as marketed, YDCN-500-80P etc. of Kukdo Chemical Co., Ltd. can be used.

The thermosetting binder may be included in an amount corresponding to about 0.8 to 2.0 equivalents based on 1 equivalent of the carboxyl group of the acid-modified oligomer. When the content of the thermosetting binder is too small, carboxyl groups may remain in the DFSR after curing, thereby deteriorating heat resistance, alkali resistance, electrical insulation, and the like. 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.

In addition to the above-mentioned components, the resin composition of one embodiment includes a solvent; And at least one selected from the group consisting of a thermosetting binder catalyst, a filler, a pigment, and an additive to be described later.

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; And phosphorus compounds such as triphenylphosphine. 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd., U-CAT 3503N and UCAT3502T DBU, DBN, U-CATSA102, and U-CAT5002 (all of 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 isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric 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 content of the thermosetting binder catalyst may be about 0.3 to 15% by weight based on the total weight of the resin composition in terms of suitable thermosetting.

filler

The filler plays a role of improving heat stability, dimensional stability by heat, and resin adhesion. In addition, it also serves as a constitution pigment by reinforcing the color.

As the filler, inorganic or organic fillers can be used, for example barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide (alumina), Aluminum hydroxide, mica and the like can be used.

The content of the filler is preferably about 5 to 50% by weight based on the total weight of the composition. In the case of using more than 50% by weight, the viscosity of the composition is increased, so that the coating property is lowered or the degree of curing is lowered.

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.

solvent

One or more solvents may be used in combination to dissolve the resin composition or impart an appropriate viscosity.

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; But are not limited to, 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 And the like; 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 resin composition. If it is less than 10% by weight, the viscosity is high, the coating is inferior, and if it exceeds 50% by weight, the drying is not good, the stickiness increases.

Meanwhile, according to another embodiment of the present invention, an acid-modified oligomer including a carboxy group (-COOH) and an iminocarbonate-based compound having a photocurable unsaturated functional group; Photopolymerizable monomers having three or more photocurable unsaturated functional groups; And a cured product of a thermosetting binder having a thermosetting functional group, a dry film solder resist (DFSR) can be provided.

Dry film Solder Resist

First, the process of manufacturing the DFSR using the resin composition having the photocurable and thermosetting of the embodiment is as follows.

First, the resin composition of the above embodiment is used as a photosensitive coating material on a carrier film. After coating with a spray coater or the like, the oven was dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes and dried, and then a release film was laminated to form a carrier film, a photosensitive film, and a release film from below. The dry film comprised by this 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 exposure unit, photocuring occurs to form a crosslink between the acid-modified oligomer (for example, the iminocarbonate-based compound described above) and the unsaturated functional groups included in the photopolymerizable monomer. And as a result can be left unremoved by subsequent development. On the contrary, the non-exposed part may not be formed with the crosslinked structure and thus the crosslinked structure, and thus the carboxyl group may be maintained to be in an alkali developable state.

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. By this phenomenon, only the film of the exposed portion may remain.

Finally, by heat curing (Post Cure), a printed circuit board including a solder resist formed from the photosensitive film is completed. The heat curing temperature is preferably at least 100 ° C.

Through the above-described method, a DFSR and a printed circuit board including the same may be provided. The DFSR is an acid-modified oligomer comprising an iminocarbonate-based compound having a carboxyl group (-COOH) and a photocurable unsaturated functional group through photocuring and thermosetting; Photopolymerizable monomers having three or more photocurable unsaturated functional groups; And a cured product of a thermosetting binder having a thermosetting functional group.

More specifically, the cured product includes a crosslinked structure in which the carboxyl group of the iminocarbonate-based compound and the thermosetting functional group are crosslinked by thermosetting; A crosslinked structure in which the unsaturated functional groups of the iminocarbonate compound and the photopolymerizable monomer are crosslinked by photocuring with each other; And it may include a triazine cross-linked structure of the formula (2) derived from the imino carbonate-based compound. In particular, as the cured product comprises a triazine crosslinked structure derived from an iminocarbonate-based compound, the DFSR is higher glass of about 130 to 180 ° C., for example about 140 to 170 ° C., or about 150 ° C. It can have a transition temperature and can exhibit improved heat resistance reliability. Accordingly, the DFSR satisfies various physical properties such as excellent PCT resistance, TCT heat resistance, and HAST resistance between fine wirings required for the package substrate material of the semiconductor device, and can be preferably used as the package substrate material of the semiconductor device.

In addition, the DFSR may further include a small amount of photoinitiator remaining in the cured product after participating in photocuring.

Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through specific examples of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

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

Example 1

The iminocarbonate compound of the acid-modified oligomer is composed of acrylic acid and 1,2,3,6-tetrahydrophthalic acid (4-Cyclohexene-1,2-dicarboxylic acid). And an iminocarbonate compound, which is an acid-modified oligomer, by reacting with a molar ratio of 1: 1.

10 wt% of this iminocarbonate compound is used, and as an additional acid-modifying oligomer, 25 wt% of ZAR-2000 of Nippon Gunpowder, 5 wt% of DPHA of SK Cytec, photopolymerizable monomoro, 2 wt% of TPO as a photoinitiator, and a thermosetting binder 15% by weight of Japanese powder YDCN-500-80P, 2-PI 0.4% by weight as thermosetting binder catalyst, 23% by weight of filler BaSO ₄ , 0.3% by weight of phthalocyanine blue as pigment, 0.3% by weight of additive BYK-110, 19% by weight of solvent DMF The resin composition was prepared by mixing%.

The resin composition prepared above was applied to PET as a carrier film, and then dried by passing through an oven at 75 ° C., and then laminated with PE as a release film to form a carrier film, a photosensitive film (thickness 20 μm), and a release film from below. The dry film which consists of was manufactured.

After removing the cover film of the manufactured dry film, the photosensitive film layer was vacuum-laminated on the board | substrate with a circuit, the photomask corresponding to the circuit pattern was put on the photosensitive film layer, and it exposed by UV. Exposure progressed UV of 365 nm wavelength band by the exposure amount of 350mJ / cm <^2> . Thereafter, the PET film was removed, and developed with a Na ₂ CO ₃ 1 wt% alkaline solution at 31 ° C. for a predetermined time to remove unnecessary portions, thereby forming a desired pattern. Subsequently, photocuring was performed at an exposure amount of 1000 mJ / cm ² , and finally heat curing was performed at 160 to 170 ° C. for 1 hour to complete a printed circuit board including a protective film (solder resist) formed from the photosensitive film. .

Example  2 to 3

5 wt% (Example 2) or 15 wt% (Example 3) of the imino carbonate-based compound, except that the solvent content is increased or decreased according to the increase or decrease of the content of the imino-carbonate-based compound. A dry film and a printed circuit board were manufactured in the same manner as in Example 1.

Example  4 to 6

As a photopolymerizable monomer, T-1420 (Example 4) from Japan Gunpowder, DPCA-60 (Example 5) from Japan Gunpowder, and R-684 (Example 6) from Japan Gunpowder were used instead of 5% by weight of DPHA from SK Cytec. A dry film and a printed circuit board were manufactured in the same manner as in Example 1, except that 5 wt% was used.

Specific compositions of the resin compositions of Examples 1 to 6 are as summarized in Table 1 below.

ingredient
Ingredients
(Or product name) Example
One Example
2 Example
3 Example
4 Example
5 Example
6 Acid-modified oligomer Imino carbonate 10 5 15 10 10 10 ZAR-2000 25 25 25 25 25 25 Photopolymerizable monomer DPHA 5 5 5 T-1420 5 DPCA-60 5 R-684 5 Thermosetting binder YDCN-500-80P 15 15 15 15 15 15 Photoinitiator TPO 2 2 2 2 2 2 catalyst 2-PI 0.4 0.4 0.4 0.4 0.4 0.4 filler BaSO ₄ 23 23 23 23 23 23 Pigment Phthalocyanine blue 0.3 0.3 0.3 0.3 0.3 0.3 additive BYK-110 0.3 0.3 0.3 0.3 0.3 0.3 menstruum DMF 19 24 14 19 19 19 Sum Unit: wt% 100 100 100 100 100 100

Comparative Example  1 to 3

ZAR-2000 (Comparative Example 1), CCR-1235 (Comparative Example 2), and ZFR-1122 (Comparative Example 3) from Nippon Gunpowder were used as acid-modifying oligomers in an amount of 35% by weight without using an iminocarbonate compound. A dry film and a printed circuit board were manufactured in the same manner as in Example 1 except for the use.

Comparative Example 4

A dry film and a printed circuit board were manufactured in the same manner as in Example 1, except that DPHA of SK Cytec was not used as the photopolymerizable monomer.

Comparative Example 5

A dry film and a printed circuit board were manufactured in the same manner as in Example 1, except that no thermosetting binder was used.

Specific compositions of the resin compositions of Comparative Examples 1 to 5 are as summarized in Table 2 below.

ingredient
Ingredients
(Or product name) Comparative Example
One Comparative Example
2 Comparative Example
3 Comparative Example
4 Comparative Example
5 Acid-modified oligomer Imino carbonate 10 10 ZAR-2000 35 25 25 CCR-1235 35 ZFR-1122 35 Photopolymerizable monomer DPHA 5 5 5 - 5 Thermosetting binder YDCN-500-80P 15 15 15 15 - Photoinitiator TPO 2 2 2 2 2 catalyst 2-PI 0.4 0.4 0.4 0.4 0.4 filler BaSO ₄ 23 23 23 23 23 Pigment Phthalocyanine blue 0.3 0.3 0.3 0.3 0.3 additive BYK-110 0.3 0.3 0.3 0.3 0.3 menstruum DMF 19 19 19 24 34 Sum Unit: wt% 100 100 100 100 100

< Test Example  >

The physical properties of the dry film and the printed circuit board prepared in Examples and Comparative Examples were measured by the following method:

Test Example 1 : PCT  Heat resistance and Electroless  Nickel Plating Resistance

A copper clad laminate of LG-T-500GA manufactured by LG Chemical Co., Ltd., having a thickness of 0.1 mm and a thickness of copper foil of 12 mm, was cut to a size of 5 cm x 5 cm in width X and a micro-roughness was formed on the surface of the copper foil by chemical etching. After the release films of the dry films prepared in Examples and Comparative Examples were removed, the film layers were vacuum laminated with a vacuum laminator (MV LP-500, manufactured by Meiki Seisakusho Co., Ltd.) on the illuminated copper clad laminate , And UV at a wavelength of 365 nm was exposed at an exposure dose of 350 mJ / cm ² . Thereafter, the PET film was removed, developed with Nα ₂ CO ₃ 1 wt% alkali solution at 31 ° C. for a predetermined time, and photocuring was performed at an exposure amount of about 1000 mJ / cm ² . Finally, the specimen was heated and cured at about 170 ° C for 1 hour.

This specimen was treated for 192 hours under conditions of a temperature of 121 캜, a humidity of 100% saturation and a pressure of 2 atm using a PCT apparatus (Espec Co., Ltd., HAST system TPC-412MD). The observations were evaluated based on the following criteria:

1: No exfoliation of DFSR, no blisters and no discoloration;

2: delamination, blistering or discoloration of the DFSR occurs, but not worse than 3;

3: Severe peeling, blistering and discoloration of DFSR occur.

Next, the electroless nickel plating resistance is treated with an electroless nickel plating solution (Pungwon Chemical, ELN-M, ELN-A) for 30 minutes at a temperature of 85 ℃, and then observed the state of the coating film as follows. Criteria evaluated:

1: no whitening of DFSR;

2: whitening of DFSR occurs, but not more severe than 3;

3: Whitening of DFSR occurs badly.

Test Example 2 : Tg  And thermal expansion coefficient

On the Shiny surface of 3EC-M3-VLP 12 micrometer copper foil of Mitsui Metals, the film layer was laminated | stacked similarly to the preparation of the measurement specimens, such as PCT heat resistance. DFSR specimens were prepared by proceeding to the heat curing in the same manner as in the preparation of the test specimens such as PCT heat resistance, except that a negative type mask having a width of 5 mm and a spacing of 5 mm was placed on the specimen and exposed. Finally, the copper foil was peeled from the specimen to prepare a 5 mm striped test piece for evaluation of TMA (thermal mechanical analysis, METTLER TOLEDO, TMA / SDTA 840).

The glass transition temperature (Tg) was measured by the following method. First, the specimen was mounted on a holder to have a length of 10 mm, a force was applied to both ends with 0.05 N, and the length of the specimen was measured at a heating rate of 10 ° C./min from 50 ° C. to 250 ° C. The inflection point seen in the temperature increase section was Tg, and Tg was evaluated by the following method:

1: Tg 150 ° C. or higher;

2: Tg 140 degreeC or more and less than 150 degreeC;

3: Tg 120 degreeC or more and less than 140 degreeC;

4: Tg 100 degreeC or more and less than 120 degreeC;

5: Tg less than 100 ° C.

And the coefficient of thermal expansion (CTE) simultaneously required by the Tg measurement was measured and compared at the same time. First, the coefficient of thermal expansion α1 at a temperature lower than Tg was calculated as the slope of the specimen increased from 50 ° C. to 80 ° C., and the coefficient of thermal expansion α2 at the temperature higher than Tg was calculated as the slope of the specimen increased from 170 ° C. to 210 ° C. The results of these calculations were evaluated under the following criteria:

(Coefficient of Thermal Expansion α1)

1: less than α1 20 ppm;

2: α1 20 ppm or more but less than 30 ppm;

3: α1 30 ppm or more but less than 50 ppm;

4: at least 50 ppm α1.

(Coefficient of Thermal Expansion α2)

1: less than α2 100 ppm;

2: α2 100 ppm or more but less than 120 ppm;

3: 120 ppm or more but less than 150 ppm of (alpha) 2;

3: α2 150 ppm or more but less than 200 ppm;

4: at least 200 ppm of a2.

Experimental Example 3 : Developability  evaluation

The 3EC-M3-VLP 12 micrometer copper foil laminated board of Mitsui Metals was cut into the horizontal X length = 5 cm X 5 cm size, and fine roughness was formed in the copper foil surface by chemical etching. After removing the release film of the dry film manufactured by the said Example and the comparative example, the said film layer was vacuum laminated on the copper foil laminated board (board | substrate) in which roughness was formed by the vacuum laminator (MV LP-500 by Meisei Seisakusho Co., Ltd.). .

And the negative type photo mask which has a hole shape of 80 micrometers in diameter was made to adhere, and UV of 365 nm wavelength band was exposed by the exposure amount of 350mJ / cm <^2> . Thereafter, the PET film was removed, and developed with a Na ₂ CO ₃ 1 wt% alkaline solution at 31 ° C. for a period of time to form a pattern.

The shape of the formed pattern was observed by SEM, and evaluated under the following criteria.

1: cross section is straight, no film residue on the bottom

2: The cross section is not straight and there is an under cut or overhang in the hole shape

3: Observe Undeveloped

4: pattern cannot be formed due to overdevelopment

PCT heat resistance, electroless nickel plating resistance, Tg, coefficient of thermal expansion, and developability measured and evaluated in Experimental Examples 1 to 3 are summarized in Table 3 below.

Results of Test Examples 1 to 3 Example
One Example
2 Example
3 Example
4 Example
5 Example
6 Comparative Example
One Comparative Example
2 Comparative Example
3 Comparative Example
4 Comparative Example
5 Tg One 3 2 One One One 4 4 5 5 5 alpha 1 One 2 2 One 2 2 3 4 3 3 4 α2 One 3 2 One 3 2 4 3 4 5 5 Developability One One 3 2 One One 2 2 One 4 One PCT heat resistance One 2 One One One One One One One 3 3 Plating resistance One One One One One One One One One 3 3

As shown in the measurement and evaluation results of Table 3, it was confirmed that the DFSR of the example exhibited superior physical properties in comparison with the DFSR of the comparative example in not only developability but also various physical properties such as PCT heat resistance, glass transition temperature and thermal expansion coefficient. . Therefore, it was confirmed that the example is suitable for the formation of DFSR showing high temperature heat resistance reliability.

Claims (21)

Acid-modified oligomers containing an carboxyl group (-COOH) and an iminocarbonate compound having a photocurable unsaturated functional group;
Photopolymerizable monomers having three or more photocurable unsaturated functional groups;
Thermosetting binders having thermosetting functional groups; And
Resin composition which has photocurability and thermosetting containing photoinitiator.
According to claim 1, wherein the imino carbonate-based compound having a photocurable and thermosetting is formed by reacting a cyanate ester compound with a dicarboxylic acid compound, a compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group Resin composition.
The dicarboxylic acid compound according to claim 2, wherein the dicarboxylic acid compound is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, norbornene dicarboxylic acid, cyclohexene dicarboxylic acid. (Cyclohexene dicarboxylic acid), cyclohexane dicarboxylic acid (Cyclohexane dicarboxylic acid), a sight containing at least one compound selected from the group consisting of imidazole dicarboxylic acid, pyridine dicarboxylic acid and acid anhydrides thereof Resin composition which has chemical property and thermosetting property.
According to claim 2, wherein the compound having a photocurable unsaturated functional group and a hydroxyl group or carboxyl group is acrylic acid, methacrylic acid, butenoic acid (hexenoic acid), cinnamic acid, allylphenol, hydroxy styrene, A resin composition having a photocurable and thermoset comprising at least one compound selected from the group consisting of hydroxycyclohexene or hydroxynaphthoquinone.
3. The resin composition according to claim 2, wherein the cyanate ester compound comprises a bisphenol or novolac compound having a cyanide group (-OCN).
The photocurable according to claim 2, wherein the dicarboxylic acid compound and the compound having a photocurable unsaturated functional group and a hydroxy group or a carboxyl group are used in a molar ratio of 2: 8 to 8: 2 to react with the cyanate ester compound. A resin composition having thermosetting properties.
The resin composition of claim 2, wherein the acid-modified oligomer has a photocurable and thermosetting composition comprising an iminocarbonate-based compound of Formula 1 below:
[Formula 1]

In Formula 1, n is an integer of 1 to 100, R ₁ is a functional group derived from a compound having a photocurable unsaturated functional group and a hydroxy group or a carboxy group, R ₂ is a functional group derived from a dicarboxylic acid compound.
The resin composition of claim 1, wherein the acid-modified oligomer is included in an amount of 15 to 75% by weight based on the total weight of the resin composition.
The resin composition of claim 1, wherein the photopolymerizable monomer comprises an acrylate compound having three or more photocurable unsaturated functional groups.
The method of claim 9, wherein the photopolymerizable monomer is a hydroxyl group-containing acrylate compound, a water-soluble acrylate compound, a polyester acrylate compound, a polyurethane acrylate compound, an epoxy acrylate compound and a caprolactone modified acrylate A photocurable and thermosetting resin composition comprising at least one compound selected from the group consisting of compounds.
The resin composition of claim 1, wherein the photopolymerizable monomer is included in an amount of 5 to 30 wt% based on the total weight of the resin composition.
The photoinitiator of claim 1, wherein the photoinitiator is selected from benzoin, alkyl ethers, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, α-aminoacetophenones, acylphosphine oxides, and the like. Resin composition which has photocurability and thermosetting containing 1 or more types chosen from the group which consists of oxime esters.
The resin composition of claim 1, wherein the photoinitiator is included in an amount of 0.5 to 20 wt% based on the total weight of the resin composition.
The resin composition of claim 1, wherein the thermosetting functional group is at least one selected from the group consisting of an epoxy group, an oxetanyl group, a cyclic ether group, and a cyclic thio ether group.
The resin composition according to claim 1, wherein the thermosetting binder is contained in an amount corresponding to 0.8 to 2.0 equivalents based on 1 equivalent of the carboxyl group of the acid-modified oligomer.
A solvent according to claim 1; And at least one selected from the group consisting of a thermosetting binder catalyst, a filler, a pigment, and an additive.
Acid-modified oligomers containing an carboxyl group (-COOH) and an iminocarbonate compound having a photocurable unsaturated functional group;
Photopolymerizable monomers having three or more photocurable unsaturated functional groups; And
A dry film solder resist comprising a cured product of a thermosetting binder having a thermosetting functional group.
18. The method of claim 17, wherein the cured product comprises: a crosslinked structure in which the carboxyl group of the iminocarbonate-based compound and the thermosetting functional group are crosslinked;
A crosslinked structure in which the unsaturated functional groups of the iminocarbonate compound and the photopolymerizable monomer are crosslinked with each other; And
A dry film solder resist comprising a triazine crosslinked structure of Formula 2 derived from the iminocarbonate-based compound:
(2)

.
18. The dry film solder resist of claim 17, further comprising a photoinitiator dispersed in said cured product.
18. The dry film solder resist according to claim 17, having a glass transition temperature (Tg) of 120 to 200 ° C.
18. The dry film solder resist according to claim 17, which is used for the manufacture of a package substrate of a semiconductor device.