KR101799092B1 - Photo-curable and thermo-curable resin composition and dry film solder resist - Google Patents

Abstract

The present invention relates to an acid-modified oligomer comprising an iminocarbonate-based compound containing a carboxyl group and a photocurable unsaturated functional group; A photopolymerizable monomer having at least two photocurable unsaturated functional groups; A thermosetting binder having a thermosetting functional group; Photoinitiators; And a blue pigment, and a dry film solder resist prepared from the resin composition.

Description

[0001] PHOTO-CURABLE AND THERMO-CURABLE RESIN COMPOSITION AND DRY FILM SOLDER RESIST [0002]

The present invention relates to a resin composition and a dry film solder resist having photo-curable properties and thermosetting properties. More specifically, the present invention relates to a dry film type solder resist (hereinafter referred to as " dry film type solder resist ") having a low thermal expansion coefficient and an improved heat resistance reliability through high light curing efficiency and securing excellent workability based on high visibility and concealability (DFSR), and a dry film type solder resist.

BACKGROUND ART [0002] As electronic devices have become smaller and lighter in weight, photosensitive solder resists capable of forming fine opening patterns have been used in printed circuit boards, semiconductor package substrates, flexible circuit boards and the like.

Semiconductor package products are composite materials composed of epoxy molding, non-conductive materials such as solder resist, semiconductors such as chip die, and conductors such as substrate circuit patterns, which must undergo various processes with severe thermal shock conditions. However, dimensional instability and warpage of the components are caused by the difference of the coefficient of thermal expansion (CTE) of the insulator, the semiconductor and the conductor. This phenomenon can lead to position discrepancies between the chip and the substrate when the chip die and the semiconductor substrate are connected by solder balls or gold wires, and may cause cracking and breakage of the product due to shear stress, which may affect the life of the product. .

Recently, as the thickness of the substrate gradually becomes thinner, such dimensional instability and warping phenomena become more serious problems. In order to solve this problem, materials are being developed to minimize CTE mismatch between materials, and development of a solder resist having a lower thermal expansion coefficient is continuously required.

Previously known dry film solder resist (DFSR) has a thermal expansion coefficient of? 1 (a thermal expansion coefficient before Tg) of 45 to 70 ppm and? 2 (a thermal expansion coefficient after Tg) of 140 to 170 ppm.

Recently, it has been known that materials having a thermal expansion coefficient of 10 ppm or less or 5 ppm or less are being developed in the core material of the substrate, but the development of the material of the solder resist usable therefor has not yet been known.

There has been an attempt to lower the thermal expansion coefficient of the solder resist sheet by increasing the content of the filler used. However, when the content of the filler is increased to a certain level or more, coating failure may occur due to agglomeration of the filler. And the workability may be lowered.

The solder resist generally requires properties such as developability, high resolution, insulation, tackiness, solder heat resistance, and gold plating resistance. Particularly, the solder resist for the semiconductor package substrate may have a crack resistance against the temperature cycle test (TCT) of -65 DEG C to 150 DEG C, a high accelerated stress test (HAST) ) Characteristics are required.

In recent years, as a solder resist, a dry film type solder resist having good film thickness uniformity, surface smoothness and thin film forming property has been attracting attention. Such a dry film type solder resist may have advantages of simplifying the process for forming a resist and reducing the amount of the solvent discharged at the time of forming a resist in addition to the above characteristics.

Conventionally, resin compositions having photocurable and thermosetting properties including a photopolymerizable monomer such as a polyfunctional acrylate have been used in combination with an acid-modified oligomer, a photoinitiator and a thermosetting binder in order to form a solder resist. However, since the solder resist formed from such a resin composition is not so high in the glass transition temperature and thus has insufficient heat resistance reliability, it is required to properly prevent PCT resistance, TCT heat resistance and HAST resistance between fine wirings There was a disadvantage that it could not be met.

Meanwhile, in order to increase the workability in the manufacturing process or the manufacturing process of the semiconductor device, the previously known solder resist generally has a hue of green system. In order to give a green color to the solder resist, the yellow and blue series The pigments were added together or green pigments were used.

However, the yellow-based pigment added to the polymer solution for producing the solder resist absorbs ultraviolet rays during the curing process, thereby lowering the uniformity of curing of the finally prepared solder resist or preventing the opposite surface of the opposite direction of the ultraviolet ray from being hardened , There is a problem that the ultraviolet irradiation amount or the irradiation intensity is increased in order to secure sufficient curing degree.

The present invention provides a dry film type solder resist (DFSR) having low thermal expansion coefficient, improved heat resistance reliability and low chromaticity through high photocuring efficiency, which can secure excellent workability based on high visibility and concealability And a resin composition having photo-curability and thermosetting property.

The present invention also provides a dry film type solder resist (DFSR) having a low thermal expansion coefficient and an improved heat resistance reliability through a high photo-curing efficiency and a low color difference, which can secure excellent workability based on high visibility and concealability. .

The present invention relates to an acid-modified oligomer comprising an iminocarbonate-based compound containing a carboxyl group and a photocurable unsaturated functional group; A photopolymerizable monomer having at least two photocurable unsaturated functional groups; A thermosetting binder having a thermosetting functional group; Photoinitiators; And a blue pigment. The present invention also provides a resin composition having photo-curable and thermosetting properties.

The resin composition may have a thermal expansion coefficient (alpha 1) of 10 to 35 ppm before the glass transition temperature (Tg) when cured and a thermal expansion coefficient (alpha 2) of 150 ppm or less after the glass transition temperature (Tg) .

The blue pigment is one kind selected from the group consisting of Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6 and Pigment Blue 60 The above compounds may be included.

The resin composition having photo-curability and thermosetting property may contain 0.01 to 5% by weight, preferably 0.1 to 0.4% by weight of a blue pigment.

The iminocarbonate-based compound may be formed by reacting 1) a cyanate ester compound, 2) a dicarboxylic acid compound, and 3) a compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group.

The dicarboxylic acid compound may be an aliphatic dicarboxylic acid compound, an alicyclic dicarboxylic acid compound, or an aromatic dicarboxylic acid compound.

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 and reacted with the cyanate ester-based compound.

The dicarboxylic acid compound may be selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, server acid, azelaic acid, sebacic acid, norbornenedicarboxylic acid, cycloalkane of C5- CYCLOALKANE) dicarboxylic acid, an acid anhydride thereof, or a mixture of two or more of the above compounds.

Examples of the dicarboxylic acid compound include phthalic acid, norbornene dicarboxylic acid, tetrahydrophthalic acid, succinic acid, imidazole dicarboxylic acid ( imidazole dicarboxylic acid, pyridine dicarboxylic acid, acid anhydrides thereof, or a mixture of two or more of the foregoing compounds.

The photo-curable unsaturated functional group and the compound having a hydroxyl group or a carboxyl group are preferably selected from the group consisting of acrylic acid, methacrylic acid, cinnamic acid, butenoic acid, hexenoic acid, 2-allylphenol, Styrene, hydroxycyclohexene, 5-hydroxyl-p-naphthoquinone, or a mixture of two or more thereof.

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

The acid-modified oligomer may include an iminocarbonate-based compound represented by the following formula (1).

[Chemical 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 hydroxyl group or a carboxyl group, and R ₂ is a functional group derived from a dicarboxylic acid compound.

또는

일 수 있고, R₂는

,

또는

일 수 있다. 상기 '*'는 결합 지점을 의미한다. In Formula _1, R 1 is

or

And R < ₂ >

,

or

Lt; / RTI > The '*' means a joining point.

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

The photopolymerizable monomer may include an acrylate-based compound having at least two photocurable unsaturated functional groups.

The photopolymerizable monomer may be at least one 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, a caprolactone denatured acrylate compound, Or mixtures thereof.

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

The photoinitiator may be selected from the group consisting of benzoin and its alkyl ethers, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones,? -Aminoacetophenones, acylphosphine oxides and oxime esters And the like.

The photoinitiator may be contained in an amount of 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 thioether group.

The thermosetting binder may be 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.

The resin composition having photo-curable properties and thermosetting properties may be a solvent; And thermosetting binder catalysts, fillers, pigments, and additives.

The present invention also relates to an acid-modified oligomer comprising an iminocarbonate-based compound containing a carboxyl group and a photocurable unsaturated functional group; A photopolymerizable monomer having at least two photocurable unsaturated functional groups; And a cured product of a thermosetting binder having a thermosetting functional group and a blue pigment dispersed in the fused product.

The blue pigment is one kind selected from the group consisting of Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6 and Pigment Blue 60 The above compounds may be included.

The dry film solder resist may include 0.01 wt% to 5 wt%, preferably 0.1 wt% to 0.4 wt% of the blue pigment.

The color difference (? E) according to the CIE Lab shown by the dry film solder resist, specifically the color difference? E or? E * ab according to the CIE Lab (CIE 76) may be 0.5 or less.

In such a dry film solder resist (DFSR), the cured product has a crosslinked structure in which the carboxyl group of the iminocarbonate compound and the thermosetting functional group are crosslinked; A cross-linked structure in which the iminocarbonate-based compound and the photopolymerizable monomer have unsaturated functional groups crosslinked with each other; And a triazine bridged structure of the following formula 2 derived from the iminocarbonate-based compound:

(2)

The dry film solder resist (DFSR) provided from the resin composition includes a triazine bridged structure represented by the above formula (2) or the like, and the structure using an acid-modified epoxy acrylate based on the existing novolac structure Can have a higher glass transition temperature (Tg) and a lower coefficient of thermal expansion, and thus exhibit improved heat resistance reliability.

Therefore, the DFSR can satisfy various physical properties such as PCT resistance, TCT heat resistance and HAST resistance between micro wirings required for a package substrate material of a semiconductor device, and also reduces warpage phenomenon to reduce defects The life of the product can be increased.

The dry film solder resist may have a thermal expansion coefficient (alpha 1) of 10 to 35 ppm before the glass transition temperature (Tg) and a thermal expansion coefficient (alpha 2) of 150 ppm or less after the glass transition temperature (Tg).

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

The dry film solder resist may have a glass transition temperature (Tg) of 130 ° C to 180 ° C.

The dry film solder resist can be used for manufacturing a package substrate of a semiconductor device.

According to the present invention, a dry film type solder resist (DFSR) having a low thermal expansion coefficient and an improved heat resistance reliability through a high photo-curing efficiency and a low color difference can be obtained with high operability based on high visibility and concealability, Can be provided, and a dry film type solder resist having the above-mentioned characteristics can be provided.

When the resin composition having photo-curability and thermosetting property is used, a high degree of photo-curability can be ensured even at a relatively low light amount, and the color of the resin can be changed to green upon thermal curing, Thermal curing characteristics can be realized, and also, the DFSR finally produced can have a lower coefficient of thermal expansion and a lower color difference.

In addition, the dry film type solder resist prepared from the resin composition having photo-curability and heat curability of the embodiment can have a green-based color and can realize a lower color difference.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a resin composition having photo-curable properties and thermosetting properties according to embodiments of the present invention and DFSR will be described in more detail.

According to one embodiment of the invention, acid-modified oligomers comprising an iminocarbonate-based compound containing a carboxyl group and a photocurable unsaturated functional group; A photopolymerizable monomer having at least two photocurable unsaturated functional groups; A thermosetting binder having a thermosetting functional group; Photoinitiators; And a blue pigment are provided.

Such a resin composition includes an acid-modified oligomer, a photopolymerizable monomer, a photoinitiator, a blue pigment and a thermosetting binder, and in particular, an iminocarbonate-based compound having a carboxyl group and a photo-curable unsaturated functional group is included as an acid-modified oligomer.

The resin composition having photo-curable properties and thermosetting properties may contain a blue pigment. The components other than the acid-modified oligomer or the acid-modified oligomer contained in the resin composition having photo-curability and thermosetting property of the above-described embodiment have a yellowish color due to thermal curing and ultraviolet curing, and the blue pigment is used The final product obtained from the resin composition having the photo-curable property and the heat-curable property, for example, a dry film solder resist according to the present invention can have green color and can realize a lower color difference

Accordingly, the solder resist manufactured from the resin composition having photo-curability and thermosetting property of the embodiment can increase the visibility in the manufacturing process, the semiconductor device manufacturing process, etc., and can reduce the fatigue of the eyes of the operator. Can be further improved.

In addition, unlike the previously used yellow based pigments, the blue pigments can absorb ultraviolet rays during the curing process to prevent the curing uniformity or curing efficiency of the dry film solder resist from being deteriorated, Coefficient and improved heat resistance reliability.

Although specific examples of the usable blue pigment are not limited, in order to further improve the curing uniformity and curing degree of the solder resist prepared from the resin composition having the photo-curable and thermosetting properties of the embodiment, At least one compound selected from the group consisting of Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6 and Pigment Blue 60 .

The resin composition having photo-curability and thermosetting property of the one embodiment may include 0.01 to 5% by weight, preferably 0.1 to 0.4% by weight of the blue pigment.

If the content of the blue pigment is too small, it may be difficult to sufficiently secure the hue required for the DFSR manufacturing process or the semiconductor device manufacturing process, and the visibility and hiding power of the finally produced DFSR may be lowered. Also, if the content of the blue pigment is too high, miscibility with other components contained in the resin composition having photo-curability and thermosetting property of the embodiment may be deteriorated, or the patterning property may be rapidly deteriorated at the time of photo- And the uniformity of the properties, thickness, surface properties and the like of the dry film solder resist to be finally produced may be lowered.

In particular, as the resin composition having photo-curability and heat curability of the embodiment includes 0.1% by weight to 0.4% by weight of the blue pigment, a high degree of photo-curing can be secured even at a relatively low light amount, Can be changed to green so that excellent heat curing properties can be realized while ensuring easier workability and also the final produced DFSR can have a lower thermal expansion coefficient and a lower color difference.

Specifically, the dry film type solder resist prepared from the resin composition having photo-curability and thermosetting property according to one embodiment may have a green color, and may have a lower color difference (for example, color difference according to CIE Lab ? E), specifically, the color difference (? E or? E * ab) according to CIE Lab (CIE 76) is 0.5 or less

Meanwhile, DFSR can be formed by the following process using the resin composition of one embodiment. First, a film is formed from a resin composition, and after laminating the film on a predetermined substrate, the resin composition in the portion where the DFSR is to be formed is selectively exposed. When such exposure is carried out, the unsaturated functional group contained in the acid-modified oligomer, for example, the iminocarbonate compound, and the unsaturated functional group contained in the photopolymerizable monomer may cause photo-curing to form cross-linking with each other, A cross-linking structure due to photo-curing can be formed in the exposed portion.

Thereafter, when development is carried out using an alkali developing solution, the resin composition of the exposed portion where the crosslinked structure is formed is left on the substrate as it is, and the remaining resin composition of the unexposed portion is dissolved in the developer and can be removed.

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

At this time, as the resin composition contains the iminocarbonate-based compound as an acid-modified oligomer, a secondary crosslinking structure in the thermosetting process, for example, a triazine crosslinked structure represented by the following general formula (2) . This is because the nitrogen contained in the main chain of the iminocarbonate compound is bonded to each other by heat to form a triazine ring.

[Reaction Scheme 1]

In the above Reaction Scheme 1, n is an integer of 1 to 100.

또는 알릴페놀에서 유래한

등의 작용기로 될 수 있다. Wherein 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, cinnamic acid, , Hydroxystyrene, hydroxycyclohexene, or hydroxynaphthoquinone compounds. Specific examples of the R < ₁ > include those derived from acrylic acid

Or derived from allyl phenol

And the like.

R ₂ is a functional group derived from a dicarboxylic acid compound such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, server acid, azelaic acid, sebacic acid, norbornene dicar At least one compound selected from the group consisting of a carboxylic acid, a C5-C10 cycloalkane dicarboxylic acid, and an acid anhydride thereof; Or a phthalic acid, norbornene dicarboxylic acid, tetrahydrophthalic acid, succinic acid, imidazole dicarboxylic acid, pyridinedicarboxylic acid, Pyridine dicarboxylic acid, and acid anhydrides thereof. The term " functional group "

, 테트라하이드로프탈릭산에서 유래한

, 또는 시클로헥세인에서 유래한

등의 작용기 등을 들 수 있다.
Specific examples of the R < ₂ > include those derived from phthalic acid

, ≪ / RTI > derived from tetrahydrophthalic acid

, Or cyclohexane-derived

And the like.

In the case of forming the DFSR using the resin composition, in addition to the basic crosslinking structure (that is, the carboxyl group of the acid-modified oligomer and the thermosetting functional group of the thermosetting binder) derived from the cured product of the resin composition constituting the DFSR, The thermal expansion coefficient of the DFSR can be lowered to 30 ppm or less for alpha 1 and to 150 ppm or less for alpha 2. Accordingly, the heat resistance reliability of the DFSR can be further improved, and the difference in thermal expansion coefficient between the semiconductor substrate and the package substrate material is reduced, thereby minimizing the warpage problem.

Specifically, the resin composition may have a coefficient of thermal expansion (α1) of 10 to 35 ppm, preferably 20 ppm or less, before the glass transition temperature (Tg) when cured, and 150 ppm or less after the glass transition temperature (Tg) Or a thermal expansion coefficient (? 2) of 120 ppm or less, preferably 50 to 100 ppm.

Therefore, the use of the resin composition of one embodiment of the present invention can provide a DFSR which exhibits a lower thermal expansion coefficient and improved heat resistance reliability, and which can be preferably used as a package substrate material for a semiconductor device or the like.

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

Acid denaturation Oligomer

The resin composition of one embodiment includes an iminocarbonate-based compound containing a carboxyl group and a photocurable unsaturated functional group as an acid-modified oligomer. Such an acid-modified oligomer forms crosslinks with other components of the resin composition, that is, a photopolymerizable monomer and / or a thermosetting binder by photo-curing to enable the formation of DFSR, and the resin composition containing non- .

Particularly, the resin composition contains the iminocarbonate-based compound as an acid-modified oligomer, so that the triazine bridged structure represented by the above-mentioned general formula (2) can be formed in the cured product of the resin composition constituting the DFSR. Thus, the resin compositions of one embodiment enable the manufacture and delivery of DFSRs having higher glass transition temperatures and improved heat resistance reliability.

The iminocarbonate compound may be a compound formed by reacting a dicarboxylic acid compound with a cyanate ester compound and a compound having a photocurable unsaturated functional group and a hydroxy group or a carboxyl group. By using such an iminocarbonate-based compound, it is possible to form the triazine crosslinked structure in a thermosetting process, and to provide a DFSR exhibiting superior heat resistance reliability and the like.

The cyanate ester compound may be a bisphenol compound or a novolac compound having a cyanide group (-OCN), for example, a compound represented by the following formula (1a):

[Formula 1a]

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

The dicarboxylic acid compound to be reacted with the cyanate ester compound may be an aliphatic dicarboxylic acid compound, an alicyclic dicarboxylic acid compound or an aromatic dicarboxylic acid compound .

Specifically, the dicarboxylic acid compound may be selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, server acid, azelaic acid, sebacic acid, norbornenedicarboxylic acid, C5- CYCLOALKANE dicarboxylic acid, an acid anhydride thereof, or a mixture of two or more of the above compounds.

The dicarboxylic acid compound may be at least one selected from the group consisting of phthalic acid, norbornene dicarboxylic acid, tetrahydrophthalic acid, succinic acid, imidazole dicarboxylic acid imidazole dicarboxylic acid, pyridine dicarboxylic acid, acid anhydrides thereof, or a mixture of two or more of the above compounds.

The photo-curable unsaturated functional group and the compound having a hydroxyl group or a carboxyl group are preferably selected from the group consisting of acrylic acid, methacrylic acid, cinnamic acid, butenoic acid, hexenoic acid, 2-allylphenol, Styrene, hydroxycyclohexene, 5-hydroxyl-p-naphthoquinone, or a mixture of two or more thereof.

By reacting the above-mentioned dicarboxylic acid compound with a compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group in the cyanate ester compound, the carboxyl group and the photo-curable unsaturated functional group are appropriately introduced into the acid-modified oligomer An iminocarbonate-based compound can be preferably obtained. In addition, the iminocarbonate-based compound thus obtained appropriately forms a triazine cross-linking structure in the course of thermal curing, thereby enabling formation and provision of DFSR exhibiting improved heat resistance reliability.

The molar ratio of the carboxyl group and the unsaturated functional group introduced into the iminocarbonate compound described above is such that the molar ratio of the dicarboxylic acid compound reacting with the cyanate ester compound to the compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group Can be controlled and adjusted. In order for the iminocarbonate compound to function properly as an acid-modified oligomer, the molar ratio of the dicarboxylic acid compound which reacts with the cyanate ester compound to the compound having a photocurable unsaturated functional group and a hydroxyl group or a carboxyl group is From about 2: 8 to about 8: 2. As a result, the carboxyl group and the unsaturated functional group, which are properly introduced, are introduced into the iminocarbonate-based compound as the acid-modified oligomer, so that the resin composition of the non-visible portion exhibits excellent alkali developability and the acid-modified oligomer is crosslinked properly with the photopolymerizable monomer and the thermosetting binder Structure and DFSR can exhibit better heat resistance and mechanical properties.

On the other hand, as a more specific example, the compound formed by reacting the acid-modified oligomer, particularly the cyanate ester compound, with a dicarboxylic acid compound and a compound having a photocurable unsaturated functional group and a hydroxy group or a carboxyl group, Of an iminocarbonate-based compound:

[Chemical Formula 1]

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

또는 알릴페놀에서 유래한

등의 작용기로 될 수 있다. Also, R ₁ represents 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, Phenol, hydroxystyrene, hydroxycyclohexene or hydroxynaphthoquinone compound, and specific examples thereof include those derived from acrylic acid

Or derived from allyl phenol

And the like.

, 테트라하이드로프탈릭산에서 유래한

또는 시클로헥세인에서 유래한

등의 작용기 등을 들 수 있다. R ₂ is a functional group derived from a dicarboxylic acid compound such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, server acid, azelaic acid, sebacic acid, norbornene dicar At least one compound selected from the group consisting of a carboxylic acid, a C5-C10 CYCLOALKANE dicarboxylic acid, and an acid anhydride thereof; Or a phthalic acid, norbornene dicarboxylic acid, tetrahydrophthalic acid, succinic acid, imidazole dicarboxylic acid, pyridinedicarboxylic acid, Pyridine dicarboxylic acid, and an acid anhydride thereof; a functional group derived from at least one compound selected from the group consisting of phthalic acid-derived

, ≪ / RTI > derived from tetrahydrophthalic acid

Or cyclohexane-derived

And the like.

The compound of the formula (1) can be produced, for example, by reacting the compound of the formula (1a) with a dicarboxylic acid compound such as phthalic acid, cyclohexanedicarboxylic acid or tetrahydrophthalic acid and an unsaturated carboxylic acid such as acrylic acid or 2- A functional group and a compound having a hydroxyl group or a carboxyl group and can be suitably used as an acid-modified oligomer, and also enables the formation and supply of a DFSR or the like having a superior heat-resistant reliability by effectively forming a triazine bridged structure.

Meanwhile, in addition to the above-mentioned iminocarbonate-based compound, the resin composition of one embodiment may additionally include an acid-modified oligomer that is conventionally known. However, the acid-modified oligomer of the iminocarbonate compound may be added in an amount of about 5 to 25% by weight, or about 7 to 20% by weight, based on the total weight of the resin composition, for the purpose of manifesting excellent developability and heat- %, Or about 9 to 15% by weight, and may include the remainder of the total content of the acid-modified oligomer, which will be described later, in addition to the acid-modified oligomer.

Such additional acid-modified oligomers include photo-curable functional groups having a carboxyl group and a photocurable functional group such as an acrylate group or an unsaturated double bond, and oligomers having a carboxyl group in the molecule, which can be used in a resin composition for forming a DFSR All ingredients known to the person skilled in the art may be used without limitation. For example, the main chain of the additional acid-modified oligomer may be novolac epoxy or polyurethane, and a component in which a carboxyl group and an acrylate group are introduced into the main chain may be used as an additional acid-modified oligomer. The photocurable functional group can be preferably an acrylate group, wherein the acid-modified oligomer can be obtained as an oligomer form by copolymerizing a monomer containing a carboxyl group-containing polymerizable monomer and an acrylate-based compound.

More specifically, specific examples of the additional acid-modified oligomer that can be used in the resin composition include the following components:

(1) a copolymer obtained by copolymerizing an unsaturated carboxylic acid (a) such as (meth) acrylic acid with a compound (b) having an unsaturated double bond such as styrene,? -Methylstyrene, lower alkyl (meth) acrylate or isobutylene A carboxyl group-containing resin;

(Meth) acryloyl group, an epoxy group, an acid chloride, and the like can be added to a part of the copolymer of the unsaturated carboxylic acid (a) and the unsaturated double bond-containing compound (b) A carboxyl group-containing photosensitive resin obtained by reacting a compound having a reactive group, for example, glycidyl (meth) acrylate, and an ethylenically unsaturated group as a pendant;

(3) To a copolymer of a compound (c) having an epoxy group and an unsaturated double bond such as glycidyl (meth) acrylate or? -Methyl glycidyl (meth) acrylate and a compound (b) having an unsaturated double bond A carboxyl group-containing photosensitive resin obtained by reacting an unsaturated carboxylic acid (a) with a saturated or unsaturated polybasic acid anhydride (d) such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride to the resulting secondary hydroxy group;

(4) To 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, one hydroxyl group such as hydroxyalkyl (meth) A carboxyl group-containing photosensitive resin obtained by reacting a compound (f) having at least one ethylenically unsaturated double bond;

(5) an epoxy group of a polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of a polyfunctional epoxy compound (g) or a polyfunctional epoxy compound having two or more epoxy groups in the molecule as described below with epichlorohydrin and ) The unsaturated monocarboxylic acid (h) such as acrylic acid or the like is subjected to an esterification reaction (entire esterification or partial esterification, preferably complete esterification), and a saturated or unsaturated polybasic acid anhydride (d) A carboxyl group-containing photosensitive compound;

(6) In the epoxy group of the copolymer of the compound (b) having an unsaturated double bond and glycidyl (meth) acrylate, 1 to 5 carbon atoms are contained in an alkylcarboxylic acid having 2 to 17 carbon atoms and an alkylcarboxylic acid having an aromatic group Containing resin obtained by reacting an organic acid (i) having a carboxyl group and no ethylenic unsaturated bond, and reacting the resulting secondary hydroxyl group with a saturated or unsaturated polybasic acid anhydride (d);

(7) Diisocyanates (j) such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, dialcohol compounds (k) containing carboxyl groups such as dimethylolpropionic acid and dimethylolbutanoic acid, A diol compound such as a polyol-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic-based polyol, a bisphenol A-based alkylene oxide adduct diol, a phenolic hydroxyl group and a compound having an alcoholic hydroxyl group m) is obtained by a reaction of a carboxyl group-containing urethane resin;

(8) A resin composition comprising a diisocyanate (j), a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a brominated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, (Meth) acrylate or its partial acid anhydride modification (n) of a bifunctional epoxy resin such as phenol type epoxy resin, carboxyl group-containing dialcohol compound (k), and diol compound (m) A urethane resin containing a carboxyl group;

(9) A compound (f) having one hydroxyl group such as hydroxyalkyl (meth) acrylate and at least one ethylenically unsaturated double bond in the synthesis of the resin of the above (7) or (8) A carboxyl group-containing urethane resin into which a double bond is introduced;

(10) A process for producing a compound represented by the above formula (7) or (8), wherein a compound having one isocyanate group and at least one (meth) acryloyl group in the molecule such as a molar reaction product of isophorone diisocyanate and pentaerythritol triacrylate (Meth) acrylated urethane resin containing a carboxyl group;

(11) A process for producing a modified oxetane compound, which comprises reacting an unsaturated monocarboxylic acid (h) with a multifunctional oxetane compound having two or more oxetane rings in a molecule as described below to give a saturated or unsaturated polybasic acid anhydride (d);

(12) a photosensitive resin containing a carboxyl group obtained by introducing an unsaturated double bond into a reaction product of a bis-epoxy compound and a bisphenol and subsequently reacting a saturated or unsaturated polybasic acid anhydride (d);

(13) A process for producing a novolac-type phenol resin, which comprises reacting a novolak-type phenol resin with an alkylene oxide and / or an ethylene carbonate such as ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyrane, Unsaturated monocarboxylic acid (h) is reacted with a cyclic carbonate such as ethylene carbonate, propylene carbonate, propylene carbonate, propylene carbonate, propylene carbonate, propylene carbonate, A carboxyl group-containing photosensitive resin obtained by reacting an anhydride (d);

Among the above-mentioned components, the case where the isocyanate group-containing compound used in the resin synthesis in (7) to (10) is a diisocyanate not containing a benzene ring and the case where in the above (5) When the polyfunctional and bifunctional epoxy resin used in the synthesis is a compound having a linear structure with a bisphenol A skeleton, a bisphenol F skeleton, a biphenyl skeleton, or a bicyclensol skeleton or a hydrogenated compound thereof, the flexibility and the like of the DFSR A component which can be preferably used as an acid-modified oligomer can be obtained. In addition, in another aspect, the modified products of the resins (7) to (10) include a urethane bond in the main chain and are preferable for bending.

Commercially available components may also be used as the above-mentioned additional acid-modified oligomers. Specific examples of such components include ZAR-2000, CCR-1235, ZFR-1122 and CCR-1291H manufactured by Nippon Yakushi Kasei.

On the other hand, the above-mentioned acid-modified oligomer may be contained in an amount of about 15 to 75% by weight, or about 20 to 50% by weight, or about 25 to 45% by weight based on 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 is deteriorated and the strength of the DFSR may be lowered. On the other hand, if the content of the acid-modified oligomer is excessively high, the resin composition may not only be excessively developed, but also may be uneven in coating.

Also, 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, the alkali developability may be lowered. On the other hand, if the acid value is excessively high, the photo-curing portion, for example, the exposure portion may be dissolved by the developer, so that the normal pattern formation of the DFSR may become difficult.

Photopolymerization Monomer

On the other hand, the resin composition of one embodiment includes a photopolymerizable monomer. Such a photopolymerizable monomer may be a compound having a photocurable unsaturated functional group such as, for example, two or more polyfunctional vinyl groups, and may form a crosslinked bond with an unsaturated functional group of the above-mentioned acid-modified oligomer, Can form a crosslinked structure. Thereby, the resin composition of the exposed portion corresponding to the portion where the DFSR is to be formed can be left on the substrate without alkali development.

Such a photopolymerizable monomer may be a liquid at room temperature, and accordingly, the viscosity of the resin composition of one embodiment may be adjusted according to the application method, and the alkali developability of the unexposed portion may be further improved.

As the photopolymerizable monomer, an acrylate compound having at least two photocurable unsaturated functional groups can be used. As specific examples thereof, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol Triacrylate, dipentaerythritol pentaacrylate and the like; Water-soluble acrylate-based compounds such as polyethylene glycol diacrylate, and polypropylene glycol diacrylate; Polyfunctional polyester acrylate-based compounds of polyhydric alcohols such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate; Acrylate compounds of ethylene oxide adducts and / or propylene oxide adducts of polyhydric alcohols such as trimethylol propane or hydrogenated bisphenol A or polyhydric phenols such as bisphenol A and biphenol; A polyfunctional or monofunctional polyurethane acrylate-based compound which is an isocyanate-modified product of the hydroxyl group-containing acrylate; An epoxy acrylate-based compound which is a (meth) acrylic acid adduct of bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or phenol novolac epoxy resin; Caprolactone-modified acrylate compounds such as caprolactone-modified ditrimethylolpropane tetraacrylate, acrylate of? -Caprolactone-modified dipentaerythritol, or caprolactone-modified hydroxypivalic acid neopentyl glycol ester diacrylate, And a photosensitive (meth) acrylate compound such as a methacrylate compound corresponding to the above-mentioned acrylate compound may be used alone, or a combination of two or more thereof may be used .

Among these, as the photopolymerizable monomer, a polyfunctional (meth) acrylate compound having at least two (meth) acryloyl groups in one molecule can be preferably used. In particular, pentaerythritol triacrylate, trimethylol propane Triacrylate, dipentaerythritol hexaacrylate, caprolactone-modified ditrimethylol propane tetraacrylate, and the like can be suitably used. Examples of commercially available photopolymerizable monomers include DPEA-12 of Kayarad and the like.

The content of the photopolymerizable monomer may be about 5 to 30% by weight, or 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 become insufficient. If the content of the photopolymerizable monomer is excessively large, the dryness of the DFSR may deteriorate and the physical properties may deteriorate.

Photoinitiator

The resin composition of one embodiment includes a photoinitiator. Such a photoinitiator serves to initiate radical photocuring between the acid-modified oligomer and the photopolymerizable monomer in the exposed portion of the resin composition, for example.

As the photoinitiator, known ones can be used, and benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and the like; 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 and 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone Can be used.

Further, it is also possible to use 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone- -One, 2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone Examples of commercially available products include α-amino acetophenones such as Irugacure (registered trademark) 907, Irugacure 369, Irugacure 379, etc., manufactured by Chiba Specialty Chemicals (now Ciba Japan) Trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide As commercially available products, mention may be made of acylphosphine oxides such as Lucinyl (registered trademark) TPO manufactured by BASF, and IRGACURE 819 manufactured by Ciba Specialty Chemicals, Inc. as a preferred photoinitiator.

Examples of preferred photoinitiators include oxime esters. Specific examples of oxime esters include 2- (acetyloxyiminomethyl) thioxanthien-9-one, (1,2-octanedione, 1- [4- (phenylthio) phenyl] ), (Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] - and 1- (O-acetyloxime). Examples of commercially available products include GGI-325, Irgacure OXE01, Irugacure OXE02, ADEKA N-1919, and Ciba Specialty Chemicals Darocur TPO, all of which are commercially available products.

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, the photo-curing may not occur properly. On the other hand, if the content is excessively large, the resolution of the resin composition may be lowered and 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 thermosetting functional group selected from, for example, an epoxy group, an oxetanyl group, a cyclic ether group, and a cyclic thioether group. These thermosetting binders can form cross-links with acid-modified oligomers and the like by thermal curing to ensure the heat resistance or mechanical properties of DFSR.

The thermosetting binder may have a softening point of about 70 to 100 캜, thereby reducing irregularities during lamination. If the softening point is low, the tackiness of the DFSR increases, and if it is high, the flowability may deteriorate.

As the thermosetting binder, a resin having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as a cyclic (thio) ether group) in the molecule can be used, and a bifunctional epoxy resin can be used have. Other diisocyanates or their bifunctional block isocyanates may also be used.

The thermosetting binder having at least two cyclic (thio) ether groups in the molecule may be a compound having at least two, three or 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 the molecule, a polyfunctional oxetane compound having at least two oxetanyl groups in the molecule, or an episulfide resin having two or more thioether groups in the molecule Or the like.

Specific examples of the polyfunctional epoxy compound include 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, novolak type epoxy resin , Phenol novolak type epoxy resin, cresol novolak type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolak type epoxy resin, biquilene type epoxy resin, biphenol type epoxy resin, chelate type epoxy resin, Epoxy-containing epoxy resins, epoxy-modified epoxy resins, dicyclopentadiene-phenolic epoxy resins, diglycidyl phthalate resins, heterocyclic epoxy resins, tetraglycidylsilaneoyl ethane resins, silicone modified epoxy resins ,? -caprolactone-modified epoxy resin, and the like. Further, in order to impart flame retardancy, a phosphorus or other atom 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 [ Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (P-hydroxystyrene), cardo-type bisphenols, caries alenes, caries-threzine isomers, or silsesquioxanes such as novolac resins, poly And ether of a resin having a hydroxy group such as quinoxane. Other examples include copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

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.

As a commercially available product, YDCN-500-80P manufactured by Kukdo Chemical Co., Ltd. can be used.

The thermosetting binder may be contained 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. If the content of the thermosetting binder becomes too small, a carboxyl group may remain in the DFSR after curing, resulting in deterioration of heat resistance, alkali resistance, electrical insulation and the like. On the other hand, when the content is excessively large, a cyclic (thio) ether group having a low molecular weight remains in the dried coating film, and the strength or the like of the coating film is lowered.

In addition to the components described above, the resin composition of one embodiment includes a solvent; And at least one selected from the group consisting of thermosetting binder catalysts, fillers, pigments, and additives described below.

Thermosetting binder catalyst

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

Examples of such thermosetting binder catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- 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 and 4- compound; Hydrazine compounds such as adipic acid 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-CATS A102, and U-CAT5002 (all of bicyclic amidine compounds and salts thereof), and the like. The present invention is not limited thereto and may be a thermal curing catalyst for an epoxy resin or an oxetane compound or a catalyst for accelerating a reaction between an epoxy group and / or an oxetanyl group and a carboxyl group, or they may be used alone or in combination of two or more . Further, it is also possible to use one or more compounds selected from the group consisting of guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid Or an S-triazine derivative such as an adduct, and preferably, a compound functioning as such an adhesion-imparting agent can also be used in combination with the 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 view of adequate thermosetting property.

filler

The filler improves thermal stability, dimensional stability by heat, and resin adhesion. It also acts as an extender pigment by enhancing the color.

As the filler, an inorganic or organic filler 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 Aluminum hydroxide, mica, or 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. When it is used in an amount of more than 50% by weight, the viscosity of the composition is increased and the coating property is lowered or the curing degree is lowered.

additive

The additive may be added to remove the bubbles of the resin composition, to remove popping or craters on the surface of the resin composition during film coating, to impart flame retardant properties, to control viscosity, and to provide a catalyst.

Specifically, known thickeners such as fine silica, organic bentonite, and montmorillonite; Defoaming agents and / or leveling agents such as silicone, fluorine, and high molecular weight; Silane coupling agents such as imidazole, thiazole and triazole; Flame retardants such as phosphorus flame retardants and antimony flame retardants, and the like.

For example, BYK-380N, BYK-307, BYK-378, and BYK-350 of BYK-Chemie GmbH can be used as the leveling agent in removing the popping or craters on the surface during film coating.

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 to impart an appropriate viscosity.

Examples of the solvent include 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), and the like. These solvents may 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. When the content is less than 10% by weight, the coating property is low due to the high viscosity, and when the content is more than 50% by weight, the coating is not dried well and the stickiness is increased.

On the other hand, according to another embodiment of the present invention, acid-modified oligomers comprising an iminocarbonate-based compound containing a carboxyl group and a photocurable unsaturated functional group; A photopolymerizable monomer having at least two photocurable unsaturated functional groups; And a dry film solder resist including a cured product between a thermosetting binder having a thermosetting functional group and a blue pigment dispersed in the fused product may be provided.

A process for producing a dry film solder resist (DFSR) using a resin composition having photo-curability and thermosetting properties according to one embodiment will be described as follows.

First, a resin composition of the above embodiment is applied to a carrier film as a photosensitive coating material by a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, A spray coater or the like, and then the oven is passed through the oven at a temperature of 50 to 130 캜 for 1 to 30 minutes to dry the laminate. Then, a release film is laminated thereon to form a carrier film, a photosensitive film, Can be produced.

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

Next, the release film is peeled off, and then the photosensitive film layer is bonded to the substrate on which the circuit is formed by using a vacuum laminator, a hot roll laminator, a vacuum press, or the like.

Next, the substrate is exposed by a light beam (UV or the like) having a certain wavelength band. The exposure may be selectively exposed by a photomask, or may be directly pattern-exposed by a laser direct exposure apparatus. The carrier film peels off after exposure. The exposure dose varies depending on the thickness of the coating film, but is preferably 0 to 1,000 mJ / cm 2. When the above-described exposure is carried out, for example, photocuring occurs in the exposed portion and crosslinking is formed between the acid-modified oligomer (for example, iminocarbonate-based compound described above) and the unsaturated functional groups contained in the photopolymerizable monomer or the like And as a result, can not be removed by the subsequent phenomenon. On the other hand, the unexposed portion can be in a state in which the crosslinking and thus the crosslinking structure are not formed, and the carboxyl group is retained and can be alkali-developed.

Next, development is performed using an alkali solution or the like. The alkali 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 can remain.

Finally, a printed circuit board including the solder resist formed from the photosensitive film is completed by heat curing (Post Cure). A heat curing temperature of 100 ° C or higher is suitable.

Through the above-described method or the like, a DFSR and a printed circuit board including the DFSR can be provided. The DFSR is an acid-modified oligomer comprising an iminocarbonate-based compound containing a carboxyl group and a photo-curable unsaturated functional group through photocuring and thermosetting; A photopolymerizable monomer having at least two photocurable unsaturated functional groups; And a thermosetting binder having a thermosetting functional group. The dry film solder resist may include a blue pigment dispersed in the fired product.

The cured product included in the dry film solder resist may have a yellowish color. The dry film solder resist may have a hue of green based on the blue pigment.

Accordingly, the dry film solder resist of the embodiment can improve visibility of the manufacturing process or the manufacturing process of the semiconductor device, and workability can be further improved because the fatigue of the eyes of the operator can be reduced. In addition, unlike the previously used yellow based pigments, the blue pigments can absorb ultraviolet rays during the curing process to prevent the curing uniformity or curing efficiency of the dry film solder resist from being deteriorated, Coefficient and improved heat resistance reliability.

Although specific examples of the usable blue pigment are not limited, in order to further improve the curing uniformity and curing degree of the solder resist prepared from the resin composition having the photo-curable and thermosetting properties of the embodiment, : 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6 and Pigment Blue 60 can be used.

Specifically, the dry film solder resist may include 0.01 wt% to 5 wt%, preferably 0.1 wt% to 0.4 wt% of the blue pigment.

If the content of the blue pigment is too small, the visibility and hiding power of the finally produced DFSR may be lowered. If the content of the blue pigment is too high, compatibility with other components of the dry film solder resist may be deteriorated or the patternability of the finally produced DFSR may be rapidly lowered, The uniformity of the physical properties, thickness, surface properties, etc. of the solder resist may be lowered.

Particularly, as the dry film solder resist contains 0.1 wt.% To 0.4 wt.% Of the blue pigment, it can have a green color and a lower color difference (for example, a color difference ΔE ), Specifically, the color difference (? E or? E * ab) according to CIE Lab (CIE 76) is 0.5 or less.

On the other hand, the cured product is a crosslinked structure in which the carboxyl group of the iminocarbonate compound and the thermosetting functional group are crosslinked by thermosetting; A crosslinking structure in which the iminocarbonate compound and the unsaturated functional group of the photopolymerizable monomer are cross-linked by photocuring; And the triazine bridged structure of Formula 2 derived from the iminocarbonate-based compound.

In particular, as the cured product comprises a triazine bridged structure derived from an iminocarbonate-based compound, the DFSR may have a higher glass transition temperature of about 130 to 180 ° C, for example about 140 to 170 ° 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 package substrate materials of semiconductor devices, and can be suitably used as a package substrate material for semiconductor devices.

In addition, the DFSR may further include a small amount of a photoinitiator remaining in the cured state to participate in the photo-curing.

The details of the components that can be included in the dry film solder resist include the above-described contents of the resin composition having photo-curable and thermosetting properties of the one embodiment.

The dry film solder resist may have a coefficient of thermal expansion (α1) of 10 to 35 ppm, preferably 20 ppm or less, before the glass transition temperature (Tg), preferably 150 ppm or less, or 120 ppm or less after the glass transition temperature May have a coefficient of thermal expansion (? 2) of 50 to 100 ppm.

Specific embodiments of the invention are described in more detail in the following examples. It should be noted, however, that the following examples are illustrative of specific embodiments of the invention only and are not intended to limit the scope of the invention.

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

Example 1

The iminocarbonate-based compound of the acid-modified oligomer is obtained by reacting the cyanate group of the bisphenol-based cyanate ester compound BA-230 of Lonza with acrylic acid and 1,2-dicarboxylic acid (1,2,3,6-tetrahydrophthalic acid) At a molar ratio of 1: 1 to prepare an iminocarbonate compound as an acid-modified oligomer.

10% by weight of this iminocarbonate-based compound was used, and 25% by weight of ZAR-2000 of Japanese explosive, 5% by weight of DPHA of photopolymerizable monomolo SKcotech, 2% by weight of TPO as a photoinitiator, YDCN-500-80P 15% by weight of the Japan Explosives, PI-2 0.4% by weight of a thermosetting binder, a catalyst, filler, BaSO ₄ 23% by weight, a copper phthalocyanine pigment blue 15: 3 0.3 wt.%, additive BYK-110 0.3% by weight, And 19 wt% of solvent DMF were mixed to prepare a resin composition.

The resin composition thus prepared was applied to PET as a carrier film, passed through an oven at 75 deg. C to be dried, and then PE was laminated as a release film to form a carrier film, a photosensitive film (thickness 20 mu m) To prepare a dry film.

After peeling off the cover film of the prepared dry film, the photosensitive film layer was vacuum laminated on the circuit-formed substrate, and the photomask corresponding to the circuit pattern was placed on the photosensitive film layer and exposed by UV. The exposure was carried out at an exposure amount of 350 mJ / cm ^{2 at} a wavelength of 365 nm. Thereafter, the PET film was removed, and the film was developed with a 1 wt% alkali solution of N 留₂ CO ₃ at 31 캜 for a predetermined time to remove unnecessary portions to form a desired pattern. Subsequently, photo-curing was carried out at an exposure amount of 1000 mJ / cm ² , and finally, curing was conducted at 160 to 170 ° C for 1 hour to complete a printed circuit board comprising a protective film (solder resist) formed from a photosensitive film .

Example 2  To 3

Except that 5% by weight of the iminocarbonate compound (Example 2) or 15% by weight (Example 3) was used, and the content of the solvent was increased or decreased according to the content of the iminocarbonate compound A dry film and a printed circuit board were prepared in the same manner as in Example 1.

Example  4 to 6

A dry film and a printed circuit board were prepared in the same manner as in Example 1, except that the pigment shown in the following Table 1 was used in place of the copper phthalocyanine blue 15: 3.

The specific compositions of the resin compositions of Examples 1 to 6 are 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 Iminocarbonate system 10 5 15 10 10 10 ZAR-2000 25 25 25 25 25 25 Photopolymerizable monomer DPHA 5 5 5 5 5 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 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

* Pigment

Examples 1 to 3: copper phthalocyanine blue 15: 3

- Example 4: copper phthalocyanine blue 15: 4

- Example 5: copper phthalocyanine blue 15: 6

Example 6: Pigment Blue 60

Comparative Example 1

Except that the iminocarbonate compound was not used and ZAR-2000 (Comparative Example 1), which is a Japanese explosive, was used in an amount of 35% by weight as an acid-modified oligomer and 0.3% by weight of Pigment Yellow 147 was used. A dry film and a printed circuit board were prepared in the same manner.

Comparative Example  2 to 4

A dry film and a printed circuit board were prepared in the same manner as in Example 1, except that the acid-modified oligomer and the yellow 147 pigment were used in the compositions and contents shown in Table 2 below.

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

ingredient
Ingredients
(Or product name) Comparative Example
One Comparative Example
2 Comparative Example
3 Comparative Example
4 Acid-modified oligomer Iminocarbonate system 10 ZAR-2000 35 25 35 35 Photopolymerizable monomer DPHA 5 5 5 5 Thermosetting binder YDCN-500-80P 15 15 15 15 Photoinitiator TPO 2 2 2 2 catalyst 2-PI 0.4 0.4 0.4 0.4 filler BaSO ₄ 23 23 23 23 Pigment Copper phthalocyanine blue 15: 3 0.3 0.3 0.3 0.3 Yellow 147 0.3 0.3 0 0.1 additive BYK-110 0.3 0.3 0.3 0.3 menstruum DMF 18.7 18.7 19 18.9 Sum Unit: wt% 100 100 100 100

< Test Example  >

The properties of dry films and printed circuit boards prepared in Examples and Comparative Examples were measured by the following methods:

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 into 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 on a light-emitting copper clad laminate (substrate) with a vacuum laminator (MV LP-500, manufactured by Meiki Seisakusho Co., Ltd.) , And UV at a wavelength of 365 nm was exposed at an exposure dose of 350 mJ / cm ² . Then, remove the PET film, which was in progress the photocurable at a predetermined time, and the developing, exposure dose of about 1000mJ / cm ² during the Nα2CO ₃ 1% by weight of the alkaline solution 31 ℃. 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 according to the following criteria:

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

2: DFSR peeling, blistering or discoloration occurs, but not less severe than in Example 3;

3: DFSR peeling, blistering and discoloration occur severely.

Next, the electroless nickel plating resistance was evaluated by treating the above sample with an electroless nickel plating solution (PUWON CHEMICAL, ELN-M, ELN-A) at a temperature of 85 캜 for 30 minutes, &Lt; / RTI &gt;

1: No occurrence of whitening of DFSR;

2: some whitening of the DFSR occurred but not less severe than the following 3;

3: DFSR whitening occurs severely.

Test Example 2 : Tg  And thermal expansion coefficient

On the Shiny side of the 3EC-M3-VLP 12 占 퐉 copper foil of Mitsui Metal Co., film layers were laminated in the same manner as in the preparation of the measurement specimen 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 shown in the temperature rising section was taken as Tg, and Tg was evaluated by the following method:

1: Tg 150 DEG C or higher;

2: Tg 140 DEG C or more and less than 150 DEG C;

3: Tg 120 DEG C or more and less than 140 DEG C;

4: Tg 100 DEG C or more and less than 120 DEG C;

5: Tg &lt; 100 ° C.

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

(Thermal expansion coefficient? 1)

1:? 1 less than 20 ppm;

2:? 1 20 ppm or more and less than 30 ppm;

3: alpha 1 30 ppm or more and less than 50 ppm;

4: α1 50 ppm or more.

(Thermal expansion coefficient? 2)

1:? 2 less than 100 ppm;

2:? 2 100 ppm or more and less than 120 ppm;

3: alpha 2 120 ppm or more and less than 150 ppm;

3:? 2 150 ppm or more and less than 200 ppm;

4: α2 200 ppm or more.

Experimental Example 3 : Developability  evaluation

3EC-M3-VLP 12 mu m copper clad laminate of Mitsui Metal Co., Ltd. was cut into a size of 5 cm x 5 cm in width X length, and micro-roughness was formed on the surface of the copper foil by chemical etching. After the release films of the dry films prepared in the above Examples and Comparative Examples were removed, the film layers were vacuum-laminated on a light-emitting copper clad laminate (substrate) with a vacuum laminator (MV LP-500, manufactured by Meiki Seisakusho Co., Ltd.) .

Then, a negative type photomask having a hole shape of 80 mu m in diameter was closely contacted, and UV of 365 nm wavelength was exposed at an exposure amount of 350 mJ / cm &lt; ^{2 &} gt ;. Thereafter, the PET film was removed, and developed with a 1 wt% alkali solution of N 留₂ CO ₃ at 31 캜 for a predetermined time to form a pattern.

Then, the shape of the formed pattern was observed with an SEM and evaluated under the following criteria.

1: The cross section is straight shape, no film residue on the floor

2: The cross section is not a straight shape, and undercut or overhang exists in the hole shape

3: Observation in unfinished state

4: Pattern can not be formed by phenomenon

Experimental Example  4: Color difference  evaluation

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 on a light-emitting copper clad laminate (substrate) with a vacuum laminator (MV LP-500, manufactured by Meiki Seisakusho Co., Ltd.) , And UV at a wavelength of 365 nm was exposed at an exposure dose of 350 mJ / cm ² . Then, remove the PET film, which was in progress the photocurable at a predetermined time, and the developing, exposure dose of about 1000mJ / cm ² during the Nα2CO ₃ 1% by weight of the alkaline solution 31 ℃. Finally, the specimen was heated and cured at about 170 ° C for 1 hour.

The color difference (ΔE or ΔE * ab) according to CIE Lab (CIE 76) was measured using a Spectrophotometer CM-5 instrument (Transmittance mode) manufactured by Konica Minolta. As a reference sample for comparing the color difference, 0.3 wt% of copper phthalocyanine blue 15: 3 and yellow 147 were added in an amount of 0.3 wt%, respectively, and the sample of Comparative Example 1 in which the iminocarbonate compound was not used was used.

The measured color difference values were evaluated under the following criteria.

1:? E * ab is not more than 0.5

2:? E * ab is more than 0.5 and not more than 1

3: DELTA E * ab exceeds 1

The results of evaluation of PCT heat resistance, electroless nickel plating resistance, Tg, thermal expansion coefficient, developability and color difference measured and evaluated in Experimental Examples 1 to 4 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 Tg One 2 One One One One 4 2 4 4 alpha 1 One 2 One One One 2 3 2 3 3 α2 One 2 One One One 2 4 2 4 4 Developability One One One One One One 2 2 One 2 PCT heat resistance One One One One One One One One One One Plating resistance One One One One One One One One One One ΔE One One One One One One One 2 3 2 color G G G G G G G Y-G B B-G

-color: G: green, YG: yellow green, B: blue, BG: blue

As shown in the results of the measurement and evaluation in Table 3, it was confirmed that the DFSR of the examples exhibited excellent physical properties as compared with the DFSR of the comparative example in terms of not only developability but also various physical properties such as PCT heat resistance, glass transition temperature and thermal expansion coefficient .

In particular, when the resin composition having photo-curability and thermosetting property of the embodiment is used, a high degree of photo-curability can be ensured even at a relatively low light amount, and the color of the resin can be changed to green upon thermal curing, It is possible to realize excellent thermal curing properties while ensuring that the final produced DFSR can have a lower thermal expansion coefficient and a lower color difference. The dry film type solder resist of the above example can have a hue of green system and a lower color difference of 0.5 or less could be realized.

Claims (30)

delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete An acid-modified oligomer comprising an iminocarbonate-based compound containing a carboxyl group and a photocurable unsaturated functional group; A photopolymerizable monomer having at least two photocurable unsaturated functional groups; And a thermosetting binder having a thermosetting functional group
And a blue pigment dispersed in the cured product,
The blue pigment is copper phthalocyanine blue 15: 3, copper phthalocyanine blue 15: 4, copper phthalocyanine blue 15: 6, or pigment blue 60,
Wherein a color difference (? E) according to CIE Lab is 0.5 or less.
delete 24. The method of claim 23,
And 0.01% to 5% by weight of the blue pigment.
24. The method of claim 23,
And 0.1% to 0.4% by weight of the blue pigment.
delete 24. The method of claim 23,
Wherein the cured product has a crosslinked structure in which the carboxyl group of the iminocarbonate compound and the thermosetting functional group are crosslinked;
A cross-linked structure in which the iminocarbonate-based compound and the photopolymerizable monomer have unsaturated functional groups crosslinked with each other; And
A dry film solder resist comprising a triazine bridged structure of the following formula (2) derived from the iminocarbonate-based compound:
(2)

.
24. The method of claim 23,
A dry film solder resist having a glass transition temperature (Tg) of 130 to 180 占 폚.
24. The method of claim 23,
A dry film solder resist used for manufacturing a package substrate of a semiconductor element.