TWI595015B - Photo-curable and thermo-curable resin composition and dry film solder resist - Google Patents

Description

Photohardening and thermosetting resin composition and dry film solder resist

The present invention relates to a photohardening and thermosetting resin composition and a dry film solder resist. More particularly, the present invention relates to a dry film type for providing properties having high developability, which can more easily achieve fine pitch and having low alpha particle emissivity, low dielectric constant, low thermal expansion coefficient, and excellent heat resistance reliability. A photocurable and thermosetting resin composition of a solder resist and a dry film solder resist having the above characteristics.

With the trend toward miniaturization and weight reduction of various electronic devices, photosensitive solder resists which can form fine opening patterns are used for printed circuit boards, semiconductor package boards, flexible circuit boards, and the like.

The semiconductor package product is a complex material combination composed of a non-conductor such as an epoxy mold or solder resist, a semiconductor such as a wafer, and a conductor such as a board circuit pattern, and in order to prepare a semiconductor package product, There should be a number of procedures that are accompanied by severe thermal shock conditions. However, due to the difference in coefficient of thermal expansion (CTE) of non-conductors, semiconductors, and conductors, dimensional instability and warpage are caused. This phenomenon may cause the wafer and the board between the wafer and the semiconductor board via solder balls or gold wires. Mismatched positional alignment; and cracking or cracking of the product due to shear stress, which in turn affects product life.

In recent years, as the plate body becomes thinner, problems such as dimensional instability and warpage become more serious. In order to solve the above problems, the development of materials is directed to minimizing CTE mismatch between materials. At the same time, it is necessary to develop a solder resist having a low coefficient of thermal expansion.

The thermal expansion coefficient of the dry film type solder resist currently known is a thermal expansion coefficient (α1) of 45 to 70 ppm at a temperature lower than the glass transition temperature (Tg); and thermal expansion at a temperature higher than the glass transition temperature (Tg). The coefficient (α2) is 140 to 170 ppm.

As a core for use between today's plate materials, materials having a thermal expansion coefficient of 10 ppm or less and even 5 ppm or less have been studied. However, there has not been research to develop materials for solder resists that can be used with cores.

Attempts have been made to reduce the coefficient of thermal expansion of the solder resist by increasing the amount of filler used. However, if the filler is increased beyond a certain level, it may be difficult to apply due to the cohesive force of the filler, and the ductility after coating and before hardening may be lowered, resulting in deterioration of workability.

Generally, the characteristics required for the solder resist are: developability, high resolution, insulation, adhesion, heat resistance at the time of soldering, resistance to gold coating, and the like. Specifically, in addition to the above properties, such as resistance to cracking from a temperature cycle test (TCT) from -65 ° C to 150 ° C; or a highly accelerated stress test (for a highly accelerated stress test, HAST) properties are all requirements for solder resists for semiconductor package boards.

Recently, in the case of solder resists, dry film solder resists which contribute to uniformity of film thickness, surface smoothness, and film formability have been paid attention to. In addition to the above characteristics, such a dry film solder resist can have the advantages of simplifying the formation of a photoresist process and reducing solvent replacement in forming a photoresist process.

In the early stage, a photohardenable and thermosetting resin composition containing a photopolymerizable monomer (e.g., a polyfunctional acrylate) together with an acid-modified oligomer, a photoinitiator, and a thermosetting binder was used to form a solder resist. However, the solder resist formed of such a resin composition cannot exhibit a high glass transition temperature or sufficient heat resistance reliability. Therefore, the composition has a drawback that it cannot satisfy the PCT tolerance, the TCT heat resistance, the HAST resistance to fine wire bonding, and the like for the material of the package material of the semiconductor device.

The present invention provides a photohardenable and thermosetting resin composition for providing high developability, which can more easily achieve fine pitch and has low alpha particle emissivity, low dielectric constant, low thermal expansion coefficient, and excellent Dry film solder resist with properties such as heat resistance reliability.

Furthermore, the present invention provides a dry film solder resist having high developability and which can more easily realize fine pitch and has low α particle emissivity, low dielectric constant, low thermal expansion coefficient, and excellent heat resistance reliability (dry film solder resist) , DFSR).

The photohardening and thermosetting resin composition provided by the present invention comprises: a first acidic modified oligomer comprising a carboxyl group and having an acid value of 100 to 180 mgKOH/g An iminocarbonate-based compound; a photopolymerizable monomer having two or more photocurable unsaturated functional groups; a thermosetting binder having a thermosetting functional group; and an inorganic filler comprising 50 to 90 Percent by weight of cerium oxide; and a photoinitiator.

The photohardenable and thermosetting resin composition may further comprise a second acidic modified oligomer having a carboxyl group and a photocurable unsaturated functional group. The above "second" is a term used to distinguish between two acidic modified oligomers, and should not be construed as limiting the order or importance or the like.

The inorganic filler may comprise 50 to 90% by weight of cerium oxide and 10 to 50% by weight of one or more selected from the group consisting of barium sulfate, barium titanate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, and hydroxide. a compound of the group consisting of aluminum and mica.

The photohardenable and thermosetting resin composition may contain 5 to 50% by weight of the inorganic filler.

The imino carbonate-based compound may be a compound formed by reacting a cyanate-based compound and a dicarboxylic acid compound.

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

The aliphatic dicarboxylic acid compound may comprise oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid (pimelic acid), suberic acid, azelaic acid, sebacic acid, norbornene dicarboxylic acid (norbornene dicarboxylic acid), C5-C10 cycloalkane dicarboxylic acid, acid anhydrides, or a mixture of two or more thereof.

The aromatic dicarboxylic acid compound may include phthalic acid, norbornene dicarboxylic acid, tetrahydrophthalic acid, succinic acid, imidazole dicarboxylic acid, A pyridine dicarboxylic acid, an acid anhydride thereof, or a mixture of two or more thereof.

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

The iminocarbonate-based compound having a carboxyl group and having an acid value of from 100 to 180 mgKOH/g may comprise an iminocarbonate-based compound of the following formula 1:

In the above formula 1, n is an integer of 0 to 100, and R ₁ is a functional group derived from the dicarboxylic acid compound.

Specifically, in the above formula 1, the R ₁ may be selected from the group consisting of a C6-C20 aromatic ring, a C4-C20 cycloalkylene ring, and a C4-C20 cycloalkenylene ring. The functional groups of the thiol group and the carboxyl group are bonded to the core group of the group formed.

In the above formula 1, R ₁ may be , or The above "*" indicates the point of integration.

The content of the first acidic modified oligomer contained may be 5 to 75 weight percent or 10 to 50 weight percent based on the total weight of the resin composition. Further, the first acidic modified oligomer and the carboxyl group and the photocurable unsaturated functional group may be optionally contained in an amount of 5 to 75 weight percent or 10 to 50 weight percent based on the total amount of the resin composition. The second acidic modified oligomer.

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

The photopolymerizable monomer may include an acrylate-based compound having a hydroxyl group, a water-soluble acrylate-based compound, a polyester acrylate-based compound, a urethane acrylate-based compound, an epoxy acrylate-based compound, or the like. Caprolactone modified acrylate a compound, or a mixture of two or more thereof.

The photopolymerizable monomer may be included in an amount of 1 to 30% by weight or 2 to 20% by weight based on the total mass of the resin composition.

The photoinitiator may comprise one or more selected from the group consisting of: benzoins and their alkylethers, acetophenones, anthraquinones, thioxanthones, condensed A compound of the group consisting of ketals, benzophenones, alpha-aminoacetophenones, acylphosphine oxides, and oxime esters.

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

The thermosetting functional group may be one or more selected from the group consisting of: an epoxy group, an oxetanyl group, a cyclic ether group, and a cyclic thioether group. The functional groups of the group formed.

The content of the thermosetting binder contained may be equivalent to 0.5 to 2.0 equivalents with respect to 1 equivalent of the carboxyl group of the first acid-modified oligomer. For example, the photohardenable and thermosetting resin composition may contain 1 to 30% by weight or 2 to 25% by weight of the thermosetting adhesive.

The photohardenable and thermosetting resin composition may further comprise: a solvent; and one or more substances selected from the group consisting of thermosetting binder catalysts, fillers, pigments, and additives. The photohardenable and thermosetting resin composition may, for example, contain 1 to 50% by weight of a solvent.

In addition, the present invention can provide a dry film solder resist comprising: a first acid modified oligomer, a photopolymerizable monomer, and a hardening product of a thermosetting binder, and an inorganic filler, wherein The first acidic modified oligomer comprises an imino carbonate-based compound having a carboxyl group and having an acid value of from 100 to 180 mgKOH/g, wherein the photopolymerizable monomer has two or more photocurable unsaturated functional groups. The thermosetting bonding agent has a thermosetting functional group dispersed in the hardened product and containing 50 to 90% by weight of cerium oxide.

The dry film type solder resist may have an alpha particle emissivity of 0.010 alphas/cm ² /hr or less (or 0.010 c/hr/cm ² ).

The hardened product may include: a crosslinked structure in which a carboxyl group of the imino carbonate-based compound is crosslinked with the thermosetting functional group; and the second acidic modified group having a carboxyl group and a photocurable unsaturated functional group a crosslinked structure in which a carboxyl group of the oligomer is crosslinked with the thermosetting functional group; a crosslinked triazine structure derived from the imino carbonate compound; and a group having a carboxyl group and a photocurable unsaturated functional group A crosslinked structure in which the unsaturated functional groups of the second acidic modified oligomer and the photopolymerizable monomer are crosslinked with each other.

The dry film solder resist may have a coefficient of thermal expansion of less than 40 ppm/K.

The dry film solder resist may have a glass transition temperature (Tg) of 120 to 180 °C.

The inorganic filler comprises 50 to 90% by weight of cerium oxide and 10 to 50% by weight of one or more selected from the group consisting of barium sulfate, barium titanate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, and aluminum hydroxide. And a group of compounds composed of mica.

The dry film solder resist may contain 5 to 50% by weight of the inorganic filler.

Since the crosslinked triazine structure represented by Formula 2 or the like, the dry film type solder resist (DFSR) provided by the resin composition and the conventional structure using an acid modified epoxy acrylate based on a novolac structure Compared with a higher glass transition temperature (Tg) and a lower coefficient of thermal expansion, it can have improved heat resistance reliability.

Further, a dry film type solder resist prepared by using an acid-modified oligomer having a compound formed by reacting a cyanate-based compound and a dicarboxylic acid compound is greatly improved in developability, so that fine pitch can be more easily realized. (fine pitch).

Therefore, the DFSR can satisfy all the requirements of the packaging material of the semiconductor device: for example, PCT resistance, TCT heat resistance, HAST resistance to fine wire bonding, and reduction of warpage, thereby reducing defects and prolonging The life of the product.

The dry film solder resist may further comprise a photoinitiator dispersed in the hardened product.

The dry film solder resist can be used to manufacture a package board for a semiconductor device.

According to the present invention, it is possible to provide a dry film solder resist which has high developability and can more easily realize fine pitch and has properties such as low α particle emissivity, low dielectric constant, low thermal expansion coefficient, and excellent heat resistance reliability.

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

In an embodiment of the invention, the photohardenable and thermosetting resin composition comprises: an acid-modified oligomer comprising an imino carbonate-based compound having a carboxyl group and having an acid value of from 100 to 180 mgKOH/g; a polymerizable monomer having two or more photocurable unsaturated functional groups; a thermosetting binder having a thermosetting functional group; an inorganic filler comprising 50 to 90% by weight of cerium oxide; and light Starting agent.

The photohardenable and thermosetting resin composition comprises the above specific acid-modified oligomer, photopolymerization a conjugate monomer, a photoinitiator, an inorganic filler containing 50 to 90% by weight of cerium oxide, and a thermosetting binder, and particularly an iminocarbonate compound having a carboxyl group as an acidic modified oligomer .

The DFSR can be formed by the following steps using the resin composition of the above embodiment. First, a film is formed using a resin composition, and a film is laminated on a supplied plate; and then a portion of the resin composition where DFSR is expected to be formed is selectively exposed. Next, development with an alkali solution leaves the exposed portion of the resin composition only on the plate body (the portion where the crosslinked structure is formed), and the unexposed portion of the other resin composition is dissolved in the developer to be Remove.

Next, the resin composition remaining on the plate body is thermally hardened by heat treatment, and further, the carboxyl group contained in the acid-modified oligomer (for example, an imino carbonate-based compound) is contained in the heat-curing adhesive. The thermosetting functional group reacts to form a crosslink. Therefore, a crosslinked structure can be formed by thermal hardening, and a DFSR can be formed in a desired portion on the plate.

Since the resin composition contains an imino carbonate-based compound as an acidic modified oligomer, a crosslinked structure can be formed during thermal hardening, for example, an iminocarbonate-based compound of the following formula 1 is formed by the following formula 2 Cross-linking triazine structure. This is because a nitrogen atom contained in the main chain of the imino carbonate-based compound is bonded to each other by heat treatment to obtain a triazine ring.

[Formula 1]

In the above formula 1, n is an integer of 0 to 100, and R ₁ is a functional group derived from a dicarboxylic acid compound.

The above R ₁ may be a functional group derived from a dicarboxylic acid compound, for example, derived from one or more selected from the group consisting of: oxalic acid, malonic acid, succinic acid, glutaric acid ( Glutaric acid), adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, norbornene dicarboxylic acid a compound of the group consisting of: norbornene dicarboxylic acid, cycloalkane dicarboxylic acid, and acid anhydrides; or one or more selected from the group consisting of: phthalic acid, a compound of the group consisting of borneol dicarboxylic acid, tetrahydrophthalic acid, succinic acid, imidazole dicarboxylic acid, pyridine dicarboxylic acid, and anhydride thereof .

Specifically, the above R ₁ may be a thiol group bonded to a core group selected from the group consisting of a C6-C20 aromatic ring, a C4-C20 cycloalkylene ring, and a C4-C20 cycloalkenyl ring. a functional group of a carboxyl group.

The above specific example of R ₁ may be a functional group derived from phthalic acid a functional group derived from tetrahydrophthalic acid Or a functional group derived from cyclohexane .

In other words, when the DFSR is formed using the resin composition, the hardened product of the resin composition forming the DFSR contains a crosslinked triazine structure, and as the amount of other residual compounds is minimized, higher developability can be ensured, and thus it is easier Achieve fine pitch. Moreover, using light hard The chemically and thermally hardened resin composition can provide a dry film solder resist having low alpha particle emissivity, low dielectric constant, low thermal expansion coefficient, and excellent heat resistance reliability.

The photohardenable and thermosetting resin composition may comprise an inorganic filler comprising 50 to 90% by weight of cerium oxide. By controlling the cerium oxide contained in the inorganic filler of the photohardenable and thermosetting resin composition to 50 to 90% by weight, the α-particle emissivity and dielectric constant of the DFSR formed by the resin composition can be greatly reduced. It is also ensured that the formed DFSR has sufficient hardness and maintains high adhesion to a common substrate.

The inorganic filler may contain from 50 to 90% by weight of cerium oxide and other inorganic fillers. If the content of cerium oxide in the inorganic filler is less than 50% by weight, the hardness of the hardened product of the resin composition of the above embodiment or the dry film solder resist formed therefrom may be lowered or the dielectric constant may be greatly increased Rising, and the alpha particle emissivity of the dry film solder resist may increase greatly.

In addition, when the content of cerium oxide in the inorganic filler exceeds 90% by weight, the photocuring of the above-described embodiment and the developability of the thermosetting resin composition may be lowered due to the high refractive index of the cerium oxide. Further, the adhesion of the resin composition to the substrate after development may be lowered.

The cerium oxide may have an average diameter of 50 nm to 500 nm.

Specifically, the inorganic filler may comprise 50 to 90% by weight of cerium oxide and 10 to 50% by weight of one or more selected from the group consisting of barium sulfate, barium titanate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, hydrogen a compound of the group consisting of alumina and mica.

The photohardenable and thermosetting resin composition of the above embodiment may contain 5 to 50% by weight of an inorganic filler. If the content of the inorganic filler is too low, it may not be possible to ensure the final The formed DFSR has sufficient hardness and stiffness to cause a decrease in operability, and does not sufficiently exhibit the effect caused by the addition of the inorganic filler. Further, if the content of the inorganic filler is too high, the inorganic filler is not easily dispersed in the photohardenable and thermosetting resin composition of the above embodiment, and the viscosity of the resin composition is greatly enhanced to cause coating on the substrate. Therefore, it may be difficult to form a dry film solder resist, and the ductility of the finally formed dry film solder resist may be lowered.

Hereinafter, the components of the resin composition will be described more carefully according to an embodiment of the present invention.

Acid modified oligomer

According to an embodiment of the present invention, the resin composition contains an iminocarbonate-based compound having a carboxyl group and having an acid value of from 100 to 180 mgKOH/g as an acidic modified oligomer. The acid-modified oligomer has a higher alkali developability due to the carboxyl group so that the unexposed portion of the resin composition.

In detail, when the resin composition contains an imino carbonate-based compound as an acidic modified oligomer, a crosslinked triazine structure of Formula 2 can be formed in the hardened product of the resin composition forming DFSR. Therefore, an embodiment of the resin composition is capable of preparing and providing a DFSR having a high glass transition temperature and improved heat resistance reliability.

As described above, the iminocarbonate-based compound may have an acid value of from 100 to 180 mgKOH/g or from 120 to 160 mgKOH/g, and that the iminoaminocarbonate compound having a carboxyl group has an acid value in the above range, photohardening and thermosetting resin The composition can have higher developability, and the fine pitch can be more easily realized on the dry film solder resist thus manufactured.

Further, when the acid value of the iminocarbonate-based compound is less than 100 mgKOH/g, it is difficult to control the thickness of the pattern or the difficulty on the dry film formed of the photocurable and thermosetting resin composition. Achieve a higher aspect ratio. Further, when the acid value of the iminocarbonate-based compound exceeds 180 mgKOH/g, there is a possibility that the developability of the photohardenable and thermosetting resin composition becomes too high, and the exposed portions are also developed together after development after exposure.

The iminocarbonate-based compound can be formed by reacting a monocyanate compound with a monocarboxylic acid compound. According to the use of such an imino carbonate-based compound, the crosslinked triazine structure is preferably formed during the thermosetting process, and provides a DFSR exhibiting better heat resistance reliability.

As the cyanate ester compound, a bisphenol-based or noyolak-based compound having a cyanide group (-OCN), for example, a compound of the following formula 1a can be used.

In the above formula 1a, n is an integer of from 1 to 100.

Further, the dicarboxylic acid compound which is 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 include: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Pimelic acid, suberic acid, azelaic acid, sebacic acid, norbornene dicarboxylic acid, C5-C10 cycloalkane Carboxylic acid (C5-C10 cycloalkane dicarboxylic acid), its acid anhydride (acid Anhydrides), or a mixture of two or more thereof.

Also, the dicarboxylic acid compound may include: phthalic acid, norbornene dicarboxylic acid, tetrahydrophthalic acid, succinic acid, imidazole dicarboxylic acid And a pyridine dicarboxylic acid, an acid anhydride thereof, or a mixture of two or more thereof.

By reacting the cyanate-based compound with the dicarboxylic acid compound, an iminocarbonate-based compound in which a carboxyl group is appropriately introduced can be obtained as an acid-modified oligomer. Further, the obtained imino carbonate-based compound can be appropriately formed into a crosslinked triazine structure during the heat hardening process, so that a DFSR having improved heat resistance reliability can be formed and provided.

As a more specific example, an imino carbonate-based compound having a carboxyl group and having an acid value of 100 to 180 mg KOH/g or 120 to 160 mg KOH/g, particularly reacting the cyanate-based compound with a dicarboxylic acid compound The compound formed may be an imino carbonate-based compound of the following formula 1.

In the above formula 1, n is an integer of 0 to 100, and R ₁ is a functional group derived from a dicarboxylic acid compound.

The above R ₁ may be a functional group derived from a dicarboxylic acid compound, for example, derived from one or more selected from the group consisting of: oxalic acid, malonic acid, succinic acid, glutaric acid ( Glutaric acid), adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, norbornene dicarboxylic acid a compound of the group consisting of: norbornene dicarboxylic acid, cycloalkane dicarboxylic acid, and acid anhydrides; or one or more selected from the group consisting of: phthalic acid, a compound of the group consisting of borneol dicarboxylic acid, tetrahydrophthalic acid, succinic acid, imidazole dicarboxylic acid, pyridine dicarboxylic acid, and anhydride thereof .

Specifically, the above R ₁ may be a thiol group bonded to a core group selected from the group consisting of a C6-C20 aromatic ring, a C4-C20 cycloalkylene ring, and a C4-C20 cycloalkenyl ring. a functional group of a carboxyl group.

The above specific example of R ₁ may be a functional group derived from phthalic acid a functional group derived from tetrahydrophthalic acid Or a functional group derived from cyclohexane .

For example, a compound of Formula 1 can be obtained by reacting a compound of Formula 1a with a dicarboxylic acid compound such as phthalic acid, cyclohexanedicarboxylic acid, tetrahydrophthalic acid, and the like. The compound can be suitably used as an acidic modified oligomer, and can effectively form a crosslinked triazine structure, thereby forming a DFSR exhibiting more improved heat resistance reliability.

Meanwhile, according to an embodiment, in addition to the above iminocarbonate-based compound, the resin composition may further include a known second acid-modified oligomer.

The additional second acidic modified oligomer is an oligomer having a carboxyl group and a photocurable functional group, for example, a photocurable functional group having an unsaturated double bond in one molecule or an acrylate group and a carboxyl group, and any The known components of the resin composition forming the DFSR can be used without limitation. For example, the main chain of the additional second acidic modified oligomer may be a novolac epoxy, a polyurethane or the like, and a component having a carboxyl group, an acrylate group or the like introduced into the main chain may be used as an additional second acidic modified oligomer. Polymer. The photocurable functional group may preferably be an acrylate group, and the second acidic modified oligomer may be an oligomer formed by copolymerizing a polymerizable monomer having a carboxyl group and a monomer containing an acrylate compound.

More specifically, an additional second acidic modified oligomer which can be used in the resin composition is, for example, the following: (1) a carboxyl group-containing resin which is copolymerized by an unsaturated carboxylic acid such as (meth)acrylic acid or the like. (a); and have, for example, styrene, α-methylstyrene, lower alkyl (meth)acrylate, or isobutylene (iso-butylene) a compound of the unsaturated double bond (b); (2) a carboxyl group-containing photosensitive resin which has a reaction such as a vinyl group, an allyl group, or a (meth) acrylonitrile group. (meth) acryloyl group), such as an ethylenically unsaturated group, and a compound such as an epoxy group, an acid chloride or the like; and an unsaturated carboxylic acid (a) and having an unsaturated double bond a part of the copolymer of the compound (b), and further an ethylenically unsaturated group as a pendant; (3) a photosensitive resin containing a carboxyl group, which is a reaction of the unsaturated carboxylic acid (a), And a compound (c) having an epoxy group and an unsaturated double bond (for example, glycidyl (meth) acrylate, α-methyl glycidyl (meth) acrylate, etc.) and a compound having an unsaturated double bond a copolymer of (b), and a second hydroxyl group formed with a saturated or unsaturated polybasic acid anhydride (d) (for example, phthalic anhydride, tetrahydroortylene) a reaction product obtained by reacting formic acid anhydride, hexahydrophthalic anhydride or the like; (4) a photosensitive resin containing a carboxyl group, which is a compound (f) having a monohydroxy group and one or more ethylenically unsaturated double bonds (for example, hydroxy group) a copolymer of an alkyl (meth) acrylate or the like, an acid anhydride (e) having an unsaturated double bond (maleic acid anhydride, itaconic acid anhydride), and a compound (b) having an unsaturated double bond (5) a photosensitive compound containing a carboxyl group which is subjected to an esterification reaction between epoxy groups of a polyfunctional epoxy group (g) having two or more epoxy groups in one molecule (all esters) Or partially esterified, preferably fully esterified), as described below; or a polyfunctional epoxy resin which is further epoxidized with a hydroxyl group of a polyfunctional epoxy compound and epichlorohydrin, And after the carboxyl group of the unsaturated monocarboxylic acid (h) (for example, (meth)acrylic acid, etc.), Further reacting the obtained hydroxyl group with a saturated or unsaturated polybasic acid anhydride (d); (6) a carboxyl group-containing resin which is an organic acid (i) having a carboxyl group in one molecule and having no ethylenic unsaturated bond ( For example, after the epoxy group of a copolymer of a C2-C17 alkyl carboxylic acid, an aromatic alkyl group-containing carboxylic acid, or the like, and a compound having an unsaturated double bond (b) and a glycidyl (meth) acrylate, Further, the obtained second hydroxyl group is reacted with a saturated or unsaturated polybasic acid anhydride (d); (7) a carboxyl group-containing urethane resin which is composed of a diisocyanate (j) (for example, an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate or the like, a carboxyl group-containing diol (dialcohol) compound (k) (for example, dimethylolpropionic acid, dimethylolbutanoic acid, etc.) And a diol compound (m) (for example, a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, and a bisphenol A-type oxidation) a bisphenol A type alkylene oxide adduct diol, having a phenolic hydroxyl group and (8) a carboxyl group-containing photosensitive urethane resin which is composed of an isocyanate (j), a difunctional epoxy resin (such as a bisphenol A type epoxy resin, a hydrogenated bisphenol) A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixyienol type epoxy resin, biphenol type (9) epoxy resin or the like (meth) acrylate or partial acid anhydride modified compound (n), carboxyl group-containing diol compound (k), and diol compound (m) addition reaction; (9 a carboxyl group-containing urethane resin which is obtained by adding a compound (f) having a hydroxyl group and one or more ethylenically unsaturated double bonds during the reaction of (7) or (8) (for example, a hydroxyalkyl group (A) a acrylate or the like to give an unsaturated double bond at the terminal; (10) a carboxyl group-containing urethane resin which is added during the reaction of the (7) or (8) a compound containing one isocyanate group and one or more (meth) acrylonitrile groups in one molecule (for example, isophorone diisocyanate and pentaerythritol triacrylate), etc. And (meth) acrylated terminal; (11) a carboxyl group-containing photosensitive resin obtained by reacting a saturated or unsaturated polybasic acid anhydride (d) with a main hydroxy group of a modified oxetane Wherein the modified propylene oxide is obtained by reacting an unsaturated monocarboxylic acid (h) with a polyfunctional propylene oxide compound having two or more oxetane rings in one molecule; (12) a photosensitive resin of a carboxyl group obtained by introducing an unsaturated double bond to a reaction product of a diepoxy compound and a bisphenol compound, followed by reacting it with a saturated or unsaturated polybasic acid anhydride (d); (13) a photosensitive resin of a carboxyl group which is a reaction-saturated or unsaturated polybasic acid anhydride (d), a reactive monocarboxylic acid (h) and a novolak phenol resin, an alkylene oxide (for example, an ethylene oxide) ), propylene oxide (propylene) Oxide), butylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, etc., and/or cyclic carbonates (eg ethylene carbonate, propylene) A reaction product obtained from a reaction product of a carbonate, a butylene carbonate, a 2,3-carbonate propylmethacrylate, or the like.

Among the components, in the case where the compound having an isocyanate group for synthesizing (7) to (10) resin does not contain a benzene ring, and the polyfunctional group for synthesizing (5) to (8) resin and When the bifunctional epoxy resin is a linear compound having a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol skeleton, or a bisxylenol skeleton, or a hydrogenated compound thereof, the acidic modified oligomer is preferably Got To the flexible point of the DFSR. Further, on the other hand, the modified resin (7) to (10) having a urethane bond in its main chain is preferably a point of bending.

Further, commercially available ingredients may also be used as the additional second acidic modified oligomer, and specific examples thereof may be ZAR-2000, CCR-1235, ZFR-1122, CCR-1291H, etc. (Nippon Kayaku Co. , Ltd.).

The acid-modified oligomer may be included in an amount of from about 5 to 75 weight percent, or from about 10 to 50 weight percent, based on the total weight of the resin composition. Moreover, the photohardenable and thermosetting resin composition may optionally comprise an acid modified and a second acidic modified oligomer having a carboxyl group and a photocurable unsaturated functional group in an amount of from 5 to 75 weight percent based on the total amount. , or 10 to 50 weight percent.

When the content of the acid-modified oligomer is too low, the developability of the resin composition may decrease and the strength of the DFSR may be deteriorated. Conversely, when the content of the acid-modified oligomer is too high, the resin composition is excessively developed and the uniformity at the time of coating may be lowered.

Further, the acid-modified oligomer may have an acid value of about 40 to 200 mgKOH/g, or about 50 to 150 mgKOH/g, or about 60 to 120 mgKOH/g. When the acid value is too low, alkali developability may be deteriorated; and when it is too high, it may be difficult to form a normal DFSR pattern because even a photohardenable portion (for example, an exposed portion) may be dissolved by the developer.

Photopolymerizable monomer

According to an embodiment, the resin composition contains a photopolymerizable monomer. The photopolymerizable monomer may be a compound having a photocurable unsaturated functional group (for example, two or more polyfunctional vinyl groups, etc.), and which may be exposed upon photohardening and unsaturated with the above-described acidic modified oligomer. The functional groups are crosslinked to form a crosslinked structure. Therefore, the composition of the resin corresponding to the exposed portion where the DFSR portion is formed The material may not have alkali developability and will remain on the board.

A photopolymerizable monomer which is liquid at room temperature can be used, and therefore the viscosity of the resin composition of an embodiment can be controlled according to the application method, or the alkali developability of the unexposed portion can be further enhanced.

As the photopolymerizable monomer, an acrylate-based compound having two or more photocurable unsaturated functional groups can be used, for example, one or more selected from the group consisting of: an acrylate compound having a hydroxyl group (for example, pentaerythritol triacrylate, dipentaerythritol Acrylates, etc.; water-soluble acrylate compounds (eg, polyethylene glycol diacrylate, polypropylene glycol diacrylate, etc.); polyhydric alcohol polyfunctional polyester acrylate compounds (eg, trimethylolpropane) Ethylene oxidation of triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc.; polyfunctional alcohols (such as trimethylolpropane, hydrogenated bisphenol A, etc.) or polyphenols (such as bisphenol A, bisphenol, etc.) An acrylate compound of an adduct and/or a propylene oxide adduct; a polyfunctional or monofunctional acrylate compound which is an isocyanate-modified compound of the hydroxy group-containing acrylate; an epoxy acrylate compound, It is a bisphenol A diglycidyl ether, a hydrogenated bisphenol A diglycidyl ether, or a (meth)acrylic acid addition of a novolac epoxy resin. And a caprolactone-modified acrylate compound (for example, caprolactone-modified ditrimethylolpropane tetraacrylate, ε-caprolactone-modified dipentaerythritol acrylate, or caprolactone modified a hydroxypivalic acid neopentylglycol ester diacrylate or the like; and a compound corresponding to the group consisting of photosensitive (meth) acrylate compounds of the acrylate compound, and the compound They may be used singly or in combination of two or more.

Among these compounds, a polyfunctional (meth) acrylate compound having two or more (meth) acryl fluorenyl groups in one molecule is preferably used as the photopolymerizable monomer, and it is particularly suitable for use in the season. Pentaerythritol triacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, or caprolactone-modified ditrimethylolpropane tetraacrylate. Further, commercially available DPEA-12 (Kayarad Co., Ltd.) or the like can also be used as the photopolymerizable monomer.

The content of the photopolymerizable monomer may be from 1 to 30% by weight, or from 2 to 20% by weight, based on the total mass of the resin composition. When the content of the photopolymerizable monomer is too low, photohardening may be insufficient, and when the content is too high, the drying property of DFSR may be deteriorated and properties may be impaired.

Photoinitiator

In one embodiment of the resin composition, a photoinitiator is included. The role of the photoinitiator is, for example, photohardening of a radical between the acid-modified oligomer and the photopolymerizable monomer in the exposed portion of the resin composition.

As the photoinitiator, a conventional compound can be used, and benzoin and an alkyl ether compound thereof such as benzoin methyl ether, benzoin ethyl ether and the like; acetophenone compound such as acetophenone, 2, can be used. 2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-tert-butyldioxy-1-methylethyl)acetophenone, etc.; a hydrazine compound, such as 2-methyl hydrazine, 2-pentyl hydrazine, 2-tert-butyl fluorene, 1-chloroindole, etc.; a thioxanthone compound, such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.; ketal compounds, such as acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.; benzophenone compounds, For example, benzophenone, 4-(1-tert-butyldioxy-1-methylethyl)benzophenone, 3,3',4,4'-tetrakis(tert-butyldioxycarbonyl) Benzophenone (3,3',4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone) and the like.

Further, α-aminoacetophenone such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylacetone-1,2-benzyl-2 is preferably used. -Dimethylamine-1-(4-morpholinylphenyl)-butan-1-one, 2-(two Methylamine)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylamine benzene Ethyl ketone (Irgacure® 907, Irgacure® 369, Irgacure® 379, etc. sold by Chiba Speciality Chemical Co., Ltd. (now Chiba Japan Co., Ltd.); or fluorenylphosphine oxide, such as 2,4,6-trimethyl Benzobenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2 4,4-Trimethyl-pentylphosphine oxide (commercially available from Lucirin® TPO of BASF Co., Ltd., Irgacure® 819 of Chiba Speciality Chemical Co., Ltd.) as a photoinitiator.

Further, it is preferred to use an oxime ester as a photoinitiator. An example of an oxime ester as a photoinitiator may be 2-(ethylideneoxyiminomethyl)thioxan-9-one, (1,2-octanedione, 1-[4-(phenylthio) Phenyl]-, 2-(O-benzylidene fluorenyl)), (ethanone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole-3 -Based on -, 1-(O-ethylindenyl)) and the like. In terms of commercially available products, it may be GGI-325, Irgacure® OXE01 and Irgacure® OXE02 of Chiba Speciality Chemical Co., Ltd., N-1919 of ADEKA Co., Ltd., and Darocur TPO of Chemical Co., Ltd.

The photoinitiator content may be from about 0.5 to 20 weight percent, or from about 1 to 10 weight percent, or from about 1 to 5 weight percent, based on the total weight of the resin composition. When the content of the photoinitiator is too low, photohardening may not be appropriately caused, and when the content is too high, the resolution of the resin composition or the reliability of the DFSR may be insufficient.

Heat hardening adhesive

One embodiment of the resin composition is a thermosetting binder comprising a thermosetting functional group, for example, one or more selected from the group consisting of: an epoxy group, an oxetanyl group, a cyclic ether group, And a functional group of a thioether group. The heat-curing adhesive is crosslinked by an acid-modified oligomer or the like during thermal hardening to ensure heat resistance and mechanical properties of the DFSR.

As the thermosetting binder, a resin containing two or more kinds of cyclic ether groups and/or cyclic sulfide groups (hereinafter referred to as "cyclo(thio)ether groups") in one molecule can be used, and a difunctional epoxy group can also be used. Resin. In addition to this, diisocyanates or their bifunctional block isocyanates can also be used.

The thermosetting adhesive containing two or more cyclic (thio)ether groups in one molecule may be a compound having two or more groups in one molecule, and the group may be selected from a 3-membered ring, a 4-membered ring or The 5-membered ring has one or both of an ether group and a cyclosulfide group. Further, the thermosetting binder may be a polyfunctional epoxy compound containing two or more epoxy groups in one molecule, and a polyfunctional propylene oxide compound containing two or more oxetanyl groups in one molecule. An episulfide resin containing two or more thioether groups in one molecule.

Specific examples of the polyfunctional epoxy compound may be: 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 novolac type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolak type epoxy resin, Bis-xylenol type epoxy resin, bisphenol type epoxy resin, chelating type epoxy resin, glyoxal type epoxy resin, amine group-containing epoxy resin, rubber-modified epoxy resin , dicyclopentadiene phenol type epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoyl ethane, decane modification Epoxy resin and epoxy resin modified with ε-caprolactone. Further, a phosphorus atom or the like may be introduced into the structure to obtain flame retardancy. The epoxy resin improves adhesion of the cured film after heat curing, solder heat resistance, resistance to electroless plating, and the like.

As the polyfunctional propylene oxide compound, it may be an etherified product of a propylene oxide alcohol and a resin having a hydroxyl group (such as a novolak resin, a poly(p-hydroxystyrene), a bismuth bisphenol, a calixarene) (calixarenes), resorcinol calixarenes, silsesquioxanes, and the like. In addition to the polyfunctional propylene oxide, it may be bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxa) Cyclobutane methoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3) -ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl-3-oxo Heterocyclobutane)methacrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methacrylic acid Methyl ester, and oligomers or copolymers thereof. Further, it may be a copolymer of an unsaturated monomer having a four-membered oxygen ring and an alkyl (meth) acrylate.

The compound having two or more episulfide groups in one molecule may, for example, be a bisphenol A type episulfide resin YL7000 manufactured by Nippon Epoxy Resin Co., Ltd. Further, an episulfide resin obtained by replacing an oxygen atom in an epoxy group of a novolac type epoxy resin with a sulfur atom can also be used.

Further, YDCN-500-80P available from Kukdo Chemical Co., Ltd. on the market can be used.

The content of the thermosetting binder contained may be equivalent to 0.5 to 2.0 equivalents per 1 equivalent of the carboxyl group in the acid-modified oligomer. For example, the photohardenable and thermosetting resin composition may contain 1 to 30% by weight or 2 to 25% by weight of a heat-curing adhesive. When the content of the thermosetting binder is too low, the carboxyl group remains in the DFSR even after hardening, which may deteriorate heat resistance, alkali resistance, electrical insulation, and the like. On the other hand, if the content is too high, the strength of the low molecular weight cyclic (thio)ether group-degrading film remaining in the dry film is not suitable.

In addition to the above components, one embodiment of the resin composition may further comprise a solvent, and one or more selected from the group consisting of a thermosetting binder catalyst, a filler, a pigment, and an additive. Group of substances.

Thermal hardening binder catalyst

The heat hardening binder catalyst plays a role in accelerating the hardening of the heat hardening adhesive.

As the thermosetting binder catalyst, for example, it may be an imidazole derivative such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenyl group. Imidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.; amine compounds such as dicyandiamide, benzyl di Methylamine, 4-(dimethylamine)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N- Dimethylbenzylamine or the like; a hydrazine compound such as adipic acid dihydrazide, sebacic acid dihydrazide or the like; and a phosphorus compound such as triphenylphosphine. Further, in view of a commercially available catalyst, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (product name of imidazole compound) manufactured by Sikoku Kasei Kogyo Co., Ltd. can be used; manufactured by San Apro Co., Ltd. U-CAT3503N and UCAT3502T (product names of block isocyanate compounds of dimethylamine), and DBU, DBN, U-CATSA102 and U-CAT5002 (bicyclic guanidine compounds and salts thereof). However, the catalyst is not limited thereto, and may be a thermosetting catalyst for an epoxy resin or a propylene oxide compound, or may accelerate the reaction of an epoxy group and/or an oxetane group with a carboxyl group. Compound. The catalyst may be used singly or in combination of two or more. Further, S-triazine derivatives such as guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamine-6- can be used. Methyl propylene oxiranyl ethyl-S-triazine, 2-vinyl-4,6-diamine-S-triazine, 1-vinyl-4,6-diamine-S-triazine and different An adduct of cyanuric acid, an adduct of 2,4-diamine-6-methylpropenyloxyethyl-S-triazine and iso-cyanuric acid. Preferably, the compound having the tackifier function is combined with the heat hardening adhesive catalyst use.

In terms of appropriate thermosetting property, the content of the heat-curing adhesive catalyst may be from about 0.3 to 15% by weight based on the total weight of the resin composition.

pigment

By providing visibility and hiding power, the pigment acts as a circuit line that masks scratches.

As the pigment, red, blue, green, yellow, and black pigments can be used. As the blue pigment, phthalocyanine blue, blue pigment 15:1, blue pigment 15:2, blue pigment 15:3, blue pigment 15:4, blue pigment 15:6, blue pigment 60 can be used. Wait. As the green pigment, green pigment 7, green pigment 36, green solvent 3, green solvent 5, green solvent 20, green solvent 28, or the like can be used. As the yellow pigment, an anthraquinone, an isoporphyrin-based, a condensed azo-based, a benzimidazolone-based or the like, for example, a yellow pigment 108, a yellow pigment 147, a yellow pigment 151, a yellow pigment 166, a yellow pigment 181, and a yellow color can be used. Pigment 193 and the like.

The pigment content is preferably from about 0.5 to 3% by weight based on the total weight of the resin composition, and when the pigment content is less than 0.5% by weight, the visibility and hiding power are attenuated, and when the pigment content is exceeded, At 3 weight percent, its heat resistance will decrease.

additive

The inclusion of an additive can be used to eliminate bubbles in the resin composition, to eliminate popping or crater on the surface of the film, impart flame retardancy and control viscosity, and can also be included as a catalyst.

In detail, conventional conventional additives may be used in combination, for example, conventional thickeners such as micro cerium oxide powder, organic bentonite, montmorillonite, etc.; antifoaming agent and/or homogenizing agent (leveling) An agent), for example, an oxime compound, a fluorine compound, a polymer compound, etc.; a decane coupling agent such as an imidazole compound, a thiazole compound, a triazole compound, etc.; and a flame retardant such as a phosphorus flame retardant or a lanthanum resistance Burning agent, etc.

Among them, the homogenizer plays the role of eliminating the crack generated in the coating process or the pit on the surface of the film. The example of the homogenizer can be BYK-380N, BYK-307, BYK-378, BYK-350 manufactured by BYK-Chemie GmbH. Wait.

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

Solvent

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

As the solvent, it may be a ketone such as methyl ethyl ketone or cyclohexanone; an aromatic hydrocarbon such as toluene, xylene, tetramethylbenzene or the like; a glycol ether (cellosolve) such as an ethylene glycol single Ethyl 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, dipropylene glycol dimethyl ether, triethylene glycol monoethyl ether, etc.; acetates such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl Ethyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, etc.; alcohol Such as ethanol, propanol, ethylene glycol, propylene glycol, carbitol, etc.; aliphatic hydrocarbons such as octane, decane, etc.; petroleum solvents such as petroleum ether, petroleum naphtha, Hydrogenated naphtha, solvent naphtha, etc.; and guanamines such as dimethylacetamide, dimethylformamide (DMF), and the like. The solvent may be used singly or in combination of two or more.

The solvent may be included in an amount of from about 1 to 50% by weight based on the total mass of the resin composition. When the content of the solvent is less than 11% by weight, the viscosity is too high and the coatability is attenuated, and when the content exceeds 50% by weight, the drying property is deteriorated and the viscosity is increased.

On the other hand, according to another embodiment of the present invention, a dry film solder resist may be provided, comprising: an acid modified oligomer, a photopolymerizable monomer, and a hardening product of a thermosetting binder, and an inorganic filler, wherein The acidic modified oligomer comprises an imino carbonate-based compound having a carboxyl group and having an acid value of from 100 to 180 mgKOH/g, the photopolymerizable monomer having two or more photocurable unsaturated functional groups, The heat-curing adhesive has a thermosetting functional group dispersed in the hardened product and containing 50 to 90% by weight of cerium oxide.

The preparation of a dry film solder resist (DFSR) is a photohardening and thermosetting resin composition according to an embodiment, which is briefly described as follows: First, a comma coater, a knife coater, and a lip coater are used. A cloth coating machine, a bar coater, an extrusion coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, etc., coating a resin composition according to an embodiment Applying to the carrier film as a photosensitive coating material, then passing the film through an oven at 50 to 130 ° C for 1 to 30 minutes to dry, and then laminating the release film thereon to prepare a dry film (from the bottom to the bottom) The order is a carrier film, a photosensitive film, and a release film).

The thickness of the photosensitive film may be about 5 to 100 μm. In this case, a plastic film may be used as a carrier film, such as a polyethylene terephthalate (PET) film, a polyester film, a polyimide film, and a polyamide. A film, a polypropylene film, a polystyrene film; and a polyethylene (PE) film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used as the release film. When the release film is peeled off, it is preferred that the adhesion between the photosensitive film and the release film is lower than the adhesion between the photosensitive film and the carrier film.

Next, after the release film is peeled off, the photosensitive film is attached to the board on which the circuit is formed by a vacuum laminator, a hot roll laminator, a vacuum machine or the like.

The substrate is then exposed to light (UV or the like) having a specific wavelength range, the substrate can be selectively exposed by a photomask, or the pattern can be directly exposed using a laser direct exposure device. The carrier film was peeled off after exposure. The exposure intensity may vary depending on the film thickness, and is preferably from 0 to 1000 mJ/cm ² . At the time of exposure, for example, photohardening occurs in the exposed portion to form a crosslink between the acidic modified oligomer (such as the above imino carbonate-based compound), the photopolymerizable monomer, and the like, and the unsaturated functional group is contained. The exposed portion is then removed after the development process. On the other hand, the above-mentioned cross-linking and subsequent cross-linking structure is not formed in the unexposed portion, and the carboxyl group remains as it is, so that it may be developed by alkali.

Thereafter, the substrate is developed using an alkali solution. An alkaline aqueous solution can be used as the alkali solution, including potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia, amine, and the like. According to the development procedure, only the exposed portion of the film can be retained.

Finally, a printed circuit board containing a solder resist is formed by thermal hardening (post hardening) in which a solder resist is formed of a photosensitive film. Thereby, a preferable heat hardening temperature is 100 ° C or more.

According to the above method, a DFSR and a printed circuit board containing the same can be provided. Since the DFSR is prepared from a photohardenable and thermosetting resin composition, the DFSR may comprise a hardened product which is a hardened product of an acidic modified oligomer comprising a carboxyl group and an acid value 100 to 180 mg KOH/g or 120 to 160 mg KOH/g of an imino carbonate-based compound; a photopolymerizable monomer having two or more photocurable unsaturated functional groups; and a thermosetting adhesive having thermosetting property Functional group. Further, the dry film solder resist may further contain an inorganic filler dispersed in the hardened product and containing 50 to 90% by weight of cerium oxide.

More specifically, the hardened product may include: a crosslinked structure in which a carboxyl group of the imino carbonate-based compound is crosslinked with the thermosetting functional group; and a cross derived from the iminocarbonate-based compound Bis-triazine structure.

Furthermore, since the photohardenable and thermosetting resin composition for preparing a dry film solder resist of the above embodiment further comprises a second acidic modified oligomer having a carboxyl group and a photocurable unsaturated functional group, The hardened product of DFSR may comprise a hardened product of an acidic modified oligomer comprising an imino carbonate-based compound having a carboxyl group and having an acid value of from 100 to 180 mgKOH/g or from 120 to 160 mgKOH/g; a modified oligomer having a carboxyl group and a photocurable unsaturated functional group; a photopolymerizable monomer having two or more photocurable unsaturated functional groups; and a thermosetting binder having thermosetting functionality base.

The dry film type solder resist of the above embodiment contains a crosslinked product having a crosslinked triazine structure and the amount of other residual compounds is minimized, so that higher developability can be ensured, and fine pitch can be more easily realized.

In particular, since the hardened product contains a crosslinked product having a crosslinked triazine structure derived from an imino carbonate compound and the above inorganic filler, the dry film solder resist may have a relatively low α particle emissivity, e.g. 0.010alphas / cm ² / hr or less of α particle radiation, and having a low dielectric constant, for example, a dielectric constant of 3.5 or less in the region of 10GHz or less 3.4.

In addition, the DFSR can exhibit a higher glass transition temperature, i.e., about 120 to 180 ° C or about 140 to 170 ° C, and can improve heat resistance reliability. Therefore, the DFSR can satisfy various physical properties, such as requirements for packaging board materials of semiconductor devices: PCT resistance, TCT heat resistance, HAST resistance to fine wire bonding, etc., so that it can be used as a package for a semiconductor device. Board material.

The dry film solder resist may have a coefficient of thermal expansion of less than 40 ppm/K.

In addition, the DFSR may further comprise a small amount of a photoinitiator which remains after the photohardening process and is dispersed in the hardened product.

As described above, the dry film solder resist contains an inorganic filler dispersed in the hardened product, and the inorganic filler contains 50 to 90% by weight of cerium oxide, so that the α particles of the DFSR can be greatly reduced. The emissivity and dielectric constant also ensure that the formed DFSR has sufficient hardness and maintains high adhesion to common substrates.

The inorganic filler may contain 50 to 90% by weight of cerium oxide and other inorganic fillers. If the content of the cerium oxide in the inorganic filler is less than 50% by weight, the hardness of the dry film solder resist may be lowered or the dielectric constant may be greatly increased, and the dry film solder resist may be α. The rate of particle emissivity may increase significantly. In addition, if the content of cerium oxide in the inorganic filler exceeds 90% by weight, there is a possibility that the developability of the DFSR is lowered due to the high refractive index of the cerium oxide, and the pair of the DFSR is The adhesion of the substrate may be reduced.

The cerium oxide may have an average diameter of 50 nm to 500 nm.

Specifically, the inorganic filler may comprise 50 to 90% by weight of cerium oxide and 10 to 50% by weight of one or more selected from the group consisting of barium sulfate, barium titanate, talc, clay, magnesium carbonate, calcium carbonate, and aluminum oxide. a compound of the group consisting of aluminum hydroxide and mica.

The dry film solder resist of the above embodiment may contain 5 to 50% by weight of the inorganic filler. If the content of the inorganic filler is too low, there is a possibility that the DFSR cannot have sufficient hardness and rigidity to cause operability to be lowered, and the operability cannot be sufficiently exhibited. The effect caused by the addition of the inorganic filler is added. Further, if the content of the inorganic filler is too high, the inorganic filler is not uniformly dispersed in the DFSR, and the ductility of the dry film solder resist may be lowered.

The details of the components contained in the dry film solder resist include the above description of the photohardenable and thermosetting resin compositions of the embodiment.

Hereinafter, the present invention will be described in detail by the following examples. However, the following examples are only intended to illustrate the invention, and the scope of the invention is not limited by the examples.

[Examples and Comparative Examples: Preparation of Resin Composition, Dry Film, and Printed Circuit Board]

Example 1

By the cyanate group of the bisphenol cyanate compound BA-230 (Lonza Co., Ltd.) and 1,2,5,6-tetrahydrophthalic acid (4-cyclohexene-1,2- The dicarboxylic acid) was reacted at a molar ratio of 1:1 to prepare an imino carbonate-based compound 1 as an acidic modified oligomer.

The acid value of the produced imino carbonate-based compound 1 was 145 mgKOH/g. At this time, the acid value of the prepared imino carbonate-based compound 1 was determined by dissolving about 0.1 g of the sample in a 1:1 mixture of xylene and isopropyl alcohol, specifically according to ASTM D1639. method.

10% by weight of the above iminocarbonate-based compound 1 was used, together with 15% by weight of ZAR-2000 as an additional acidic modified oligomer and 85% by weight of CCR-1171H (Nippon Kayaku Co., Ltd.), 55% by weight of DPHA (SK Cytec Co., Ltd.) as photopolymerizable monomer, 2.5% by weight of TPO as photoinitiator, and 10% by weight of YDCN-500-80P (Nippon Kayaku as thermosetting binder) Co., Ltd.), 0.95 weight percent 2-PI as a thermosetting binder catalyst, 20 weight percent molten cerium oxide (Denka Corporation, SFP-120MC) having an average diameter of 300 nm as a filler, and 8 weight percent BaSO ₄ , 0.25 weight percent of phthalocyanine blue as a pigment, 0.3 weight percent of BYK-110 as an additive, and 20 weight percent of DMF as a solvent were mixed to prepare a resin composition.

By coating a resin composition on a PET film (carrier film), drying it through an oven at 75 ° C, and laminating a PE film (release film) thereon, to prepare a carrier film from bottom to top. , a photosensitive film (thickness 20 μm) and a dry film composed of a release film.

After the prepared cover film of the dry film is peeled off, the photosensitive film layer is vacuum-laminated onto the board on which the circuit is formed, and the photomask corresponding to the circuit pattern is placed on the photosensitive film layer, followed by exposure under UV light. . The exposure was carried out at a UV light having a wavelength of 365 nm and a light intensity of 400 mJ/cm ² . Next, the PET film was removed, and development was also carried out at 31 ° C for a period of time in a 1 wt% Na ₂ CO ₃ alkali solution to remove unnecessary portions to form a desired pattern. Then, photohardening was carried out at a light intensity of 1500 mJ/cm ² , and finally heat hardening was performed at 160 to 170 ° C for 1 hour to obtain a printed circuit board comprising a protective film (solder resist) formed of a photosensitive film.

Example 2

The dry film and the printed circuit board were prepared according to the same procedure as in Example 1 except that 15% by weight of the iminocarbonate-based compound 1 was used, and the content of the solvent was increased or decreased depending on the content of the iminocarbonate-based compound.

Example 3

As shown in the following Table 1, except that 25 wt% of the above CCR-117H was used, 5 wt% of TMPA (SK Cytec Co., Ltd.) was used as the photopolymerizable monomer, and 8 wt% of YDCN was used as the above thermosetting binder. -500-8P (Nippon Kayaku shares) In addition to the company, it was prepared according to the same procedure as in Example 1 to prepare a dry film and a printed circuit board.

Example 4

As shown in the following Table 1, except that 5 wt% of YDCN-500-8P (Nippon Kayaku Co., Ltd.) and 5 wt% of NC-3000H (Nippon Kayaku Co., Ltd.) were used as the above-mentioned thermosetting binder, it was based on The dry film and printed circuit board were prepared in the same manner as in Example 1.

The specific components of the resin compositions of Examples 1 to 4 were summarized in Table 1 below.

Comparative example 1

As shown in Table 2, except that 20% by weight of ZAR-2000 and 13% by weight of CCR-1171H (Nippon Kayaku Co., Ltd.) were used without using an imino carbonate-based compound, it was the same procedure as in Example 1. Dry film and printed circuit boards are prepared.

Comparative example 2

By using a cyanate group of a bisphenol cyanate compound BA-230 (Lonza Co., Ltd.) with acrylic acid and 1,2,5,6-tetrahydrophthalic acid (4-cyclohexene-1, 2-Dicarboxylic acid) was reacted at a molar ratio of 1:1 to prepare an imino carbonate-based compound 2 as an acidic modified oligomer.

The acid value of the produced imino carbonate-based compound 2 was 76 mgKOH/g. At this time, the acid value of the prepared imino carbonate-based compound 2 was determined by dissolving about 0.1 g of the sample in a 1:1 mixture of xylene and isopropyl alcohol, specifically according to ASTM D1639. method.

A dry film and a printed circuit board were prepared in the same manner as in Example 1 except that the iminocarbonate-based compound 2 was used as the acidic modified oligomer.

Comparative example 3

A dry film and a printed circuit board were prepared in accordance with the same procedure as in Example 1 except that the components shown in Table 2 below (in particular, iminocarbonate-based compound 2 and 28% barium sulfate) were used.

Comparative example 4

As shown in the following Table 2, in addition to the use of the iminocarbonate-based compound 2 as the acid-modified oligomer, and the solvent content was increased without using a thermosetting binder, it was prepared by the same procedure as in Example 1 to prepare a dry film and printing. Circuit board.

The specific components of the resin compositions of Comparative Examples 1 to 4 were as shown in Table 2 below.

[Test example]

The dry film and the printed circuit board prepared in the examples and the comparative examples were subjected to the following tests.

Test Example 1: Hygroscopic heat resistance test

Take LG-T-500GA of LG Chemical Co., Ltd., a copper foil laminate with a thickness of 0.1 mm and a copper thickness of 12 μm, cut into a length and width of 5 cm × 5 cm, and formed on the copper surface by chemical etching. Micro-roughness. The release film of the dry film prepared in the examples and the comparative examples was peeled off to prepare a sample, and the film layer was vacuum-compressed by a vacuum press machine (MV LP-500, Meiki Seisakusho Co., Ltd.) to form copper of roughness. The foil laminate (plate) was then exposed to 400 mJ/cm ² of 365 nm wavelength UV light. Then, the PET film was removed, and immersed in a 1 wt% Na ₂ CO ₃ alkali solution, developed at 31 ° C for a specific period of time, and then photohardened at an exposure intensity of about 1000 mJ/cm ² . Finally, heat hardening was performed at about 170 ° C for 1 hour to prepare a sample.

The sample was treated with a PCT apparatus (HAST System TPC-412MD, ESPEC) at a temperature of 121 ° C, 100% saturated humidity, and a pressure of 2 atm for 24 hours, and then the state of the coating film was observed, with the substrate facing downward. The film was floated in a lead bath at 288 ° C for 1 minute, and the state of the coating film was observed. The observations are judged according to the following criteria.

1: After floating, the DFSR has no peeling, bursting or color change.

2: After moisture absorption, the DFSR may be peeled, bursted, or changed in color, but there is a case of peeling, bursting, or color change after floating.

3: After moisture absorption, the DFSR has a peeling, bursting or color change.

Test Example 2: Glass transition temperature (Tg) test

The film was laminated on a 12 μm bright copper surface of 3EC-M3-VLP (Mitsui Mining & Smelting Co., Ltd.) as prepared for the sample for measuring PCT heat resistance; preparation of DFSR sample, except that 5 mm would be obtained A negative reticle with a stripe pattern of 5 mm spacing and 5 mm spacing is placed on the surface of the sample, and the sample is exposed to light other than the same steps as the preparation of the sample for measuring PCT heat resistance to the thermal hardening step. Finally, the copper-clad layer was peeled off from the sample to obtain a sample having a 5 mm stripe shape for evaluation of TMA (thermal Mechanical analysis, thermomechanical analyzer, METTLER TOLEDO, TMA/SDTA 840).

The glass transition temperature (Tg) was measured as follows. First, the sample was mounted on a stent and had a length of 10 mm. When 0.05 N stress was applied to both ends of the sample and the temperature was raised from 50 ° C to 250 ° C at 10 ° C per minute, the length of the sample extension was measured. How many. The inflection point displayed in the temperature rise is indicative of Tg and is evaluated according to the following criteria.

1: Tg is 150 ° C or higher; 2: Tg is 120 ° C or higher and lower than 150 ° C; 3: Tg is lower than 120 ° C.

The coefficient of thermal expansion (CTE) was simultaneously obtained during the measurement of Tg and compared. First, the coefficient of thermal expansion is calculated from the slope of the extended sample from 50 ° C to 80 ° C. The calculation results are evaluated according to the following criteria.

(Thermal expansion coefficient)

1: less than 25 ppm/K; 2: 25 ppm/K or more and less than 40 ppm/K; 3: 40 ppm/K or more and less than 50 ppm/K; 4: 50 ppm/K or more.

Test Example 3: Evaluation of developability

Take 3EC-M3-VLP of Mitsui Mining & Smelting Co., Ltd., a copper foil laminate with a thickness of 12 μm, cut it into a length and width of 5 cm × 5 cm, and chemically etch it. A microroughness is formed on the copper surface. The release film of the dry film prepared in the examples and the comparative examples was peeled off to prepare a sample; the film layer was vacuum-bonded to a copper foil laminate using a vacuum press machine (MV LP-500, Meiki Seisakusho Co., Ltd.) (plate body) on which the copper foil stack A roughness is formed on the surface of the laminate.

Then, a negative mask having a hole shape having a diameter of 100 μm to 10 μm (10 μm per unit diameter) was closely adhered, and then exposed to 400 mJ/cm ² of 365 nm wavelength UV light. Next, the PET film was removed and developed in a 1 wt% Na ₂ CO ₃ alkali solution at 31 ° C for a specific period of time to form a pattern. Then, the shape of the formed pattern was observed by SEM and evaluated according to the following criteria.

1: Developable with a hole diameter of 30 μm or less

2: The hole diameter is 40 to 50 μm and can be developed

3: Only the hole diameter of 60μm or more can be developed or not developed

Test Example 4: Dielectric constant test

Except that the dry film solder resist having a length and width of 15 cm × 15 cm obtained in the examples and the comparative examples was laminated on a copper foil having a size of 16 cm × 16 cm, the entire mask was not used at a exposure intensity of 400 mJ/cm ^{2 .} In addition to the area exposure, it was thermally hardened according to the same procedure as that for preparing a sample for testing moisture absorption heat resistance of Test Example 1, and only a copper foil was etched to prepare a DFSR sample (cured film).

For the cured film, a Vector Network Analyzer, (Agilent Technologies, Agilent Technologies) was used as a test instrument and a separate dielectric resonator (Split Post Dieletrci Resonator, QWED) was used as a test fixture. Dielectric constant at 10 GHz.

Test Example 5: Alpha particle emissivity test

The α-particle emissivity of the dry film obtained in the examples and the comparative examples was tested using a Large Area Propotional Counter (model: 8600A-LB) of ORDELA.

Specifically, after placing each dry film (900 cm ² , 30 cm × 30 cm) into the tester, high-purity P-10 gas (10 volume percent) was introduced at a temperature of 25 ± 2 ° C and a relative humidity of 60 ± 20 RH %. Methane and 90 volume percent argon) and measured the amount of alpha particles emitted within 48 hours.

The results of the tests and evaluations of Test Examples 1 to 5 are summarized in Table 3 below.

As shown in the measurement and evaluation results of Table 3 above, the DFSR developability of the examples was greatly improved, so that fine pitches were more easily realized, and various heat resistance, glass transition temperature, thermal expansion coefficient, dielectric constant, and alpha particle emissivity were various. In nature, it exhibits excellent properties compared to the DFSR of the comparative example. Therefore, the embodiment is suitable for forming a DFSR having high temperature heat resistance reliability.

no

Claims (29)

A photohardenable and thermosetting resin composition comprising: a first acid-modified oligomer comprising an iminocarbonate compound of the following formula 1 having a carboxyl group and having an acid value of from 100 to 180 mgKOH/g; photopolymerizability a monomer having two or more photocurable unsaturated functional groups; a thermosetting binder having a thermosetting functional group; an inorganic filler comprising 50 to 90% by weight of cerium oxide; and a light initiation Agent In the above formula 1, n is an integer of 0 to 100, and R ₁ is a functional group derived from a dicarboxylic acid compound. The photocuring and thermosetting resin composition according to claim 1, further comprising a second acidic modified oligomer having a carboxyl group and a photocurable unsaturated functional group. The photohardening and thermosetting resin composition according to claim 1, wherein the inorganic filler comprises 50 to 90% by weight of cerium oxide and 10 to 50% by weight of one or more selected from the group consisting of barium sulfate a compound of the group consisting of barium titanate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica. The photohardening and thermosetting resin composition according to claim 1, wherein the inorganic filler is contained in an amount of from 5 to 50% by weight. The photocuring and thermosetting resin composition according to claim 1, wherein the iminocarbonate-based compound is a compound formed by reacting a cyanate-based compound and a dicarboxylic acid compound. The photocuring and thermosetting resin composition according to claim 5, wherein the dicarboxylic acid compound is an aliphatic dicarboxylic acid compound, an alicyclic dicarboxylic acid compound or an aromatic dicarboxylic acid compound. The photohardening and thermosetting resin composition according to claim 6, wherein the aliphatic dicarboxylic acid compound comprises one or more selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, and hexanic acid. A compound of the group consisting of acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, norbornene dicarboxylic acid, C5-C10 cycloalkane dicarboxylic acid and anhydride thereof. The photohardening and thermosetting resin composition according to claim 6, wherein the aromatic dicarboxylic acid compound comprises one or more selected from the group consisting of phthalic acid, norbornene dicarboxylic acid, and tetrahydrogen A compound of the group consisting of phthalic acid, succinic acid, imidazole dicarboxylic acid, dipicolinic acid, and anhydride thereof. The photocuring and thermosetting resin composition according to claim 5, wherein the cyanate-based compound comprises a bisphenol-based or novolak-based compound having a cyanide group. The photohardening and thermosetting resin composition according to claim ₁ , wherein in Formula 1, R ₁ is in a ring selected from a C6-C20 aromatic ring, a C4-C20 cycloalkylene ring, and A functional group of a thiol group and a carboxyl group is bonded to a core group of the group consisting of a C4-C20 cycloalkenyl ring. The photohardening and thermosetting resin composition according to claim ₁ , wherein in Formula 1, the R ₁ is , or And "*" indicates a joint point. The photohardening and thermosetting resin composition according to claim 1, wherein the content of the first acidic modified oligomer is included based on the total weight of the photohardening and thermosetting resin composition. It is 5 to 75 weight percent. The photocurable and thermosetting resin composition according to the above aspect of the invention, wherein the photopolymerizable monomer comprises an acrylate-based compound having two or more photocurable unsaturated functional groups. The photocurable and thermosetting resin composition according to claim 1, wherein the photopolymerizable monomer comprises one or more selected from the group consisting of: an acrylate compound having a hydroxyl group, a water-soluble acrylate compound, A compound composed of a polyester acrylate compound, a urethane acrylate compound, an epoxy acrylate compound, and a caprolactone-modified acrylate compound. The photohardenable and thermosetting resin composition according to claim 1, wherein the content of the photopolymerizable monomer is 1 to 1 based on the total weight of the photocuring and thermosetting resin composition. 30 weight percent. The photohardening and thermosetting resin composition according to claim 1, wherein the photoinitiator comprises one or more selected from the group consisting of: benzoin and its alkyl ether, acetophenone, anthracene, A compound of the group consisting of thioxanthone, ketal, benzophenone, alpha-aminoacetophenone, decylphosphine oxide and decyl ester. The photohardening and thermosetting resin composition according to claim 1, wherein the photoinitiator is contained in an amount of 0.5 to 20 based on the total weight of the photohardenable and thermosetting resin composition. Weight percentage. The photohardenable and thermosetting resin composition according to claim 1, wherein the thermosetting functional group is one or more selected from the group consisting of epoxy groups, oxetane groups, and cyclic ether groups. A functional group of a group consisting of cyclic thioether groups. The photohardenable and thermosetting resin composition according to claim 1, wherein the thermosetting binder is contained in an amount of one equivalent of the carboxyl group in the first acid-modified oligomer. The content is equivalent to 0.5 to 2.0 equivalents. The photohardening and thermosetting resin composition according to claim 1, further comprising: a solvent and one or more substances selected from the group consisting of thermosetting binder catalysts, fillers, pigments and additives. A dry film solder resist comprising: a first acid-modified oligomer, a photopolymerizable monomer, and a hardening product of a thermosetting binder, and an inorganic filler, wherein the first acid-modified oligomer comprises a carboxyl group And an iminocarbonate-based compound of the following formula 1 having an acid value of from 100 to 180 mgKOH/g, the photopolymerizable monomer having two or more photocurable unsaturated functional groups, the thermosetting bonding agent having heat a hardening functional group, the inorganic filler being dispersed in the hardened product and comprising 50 to 90% by weight of cerium oxide; In the above formula 1, n is an integer of 0 to 100, and R ₁ is a functional group derived from a dicarboxylic acid compound. The dry film solder resist according to claim 21, wherein the hardened product comprises: a crosslinked structure in which a carboxyl group of the imino carbonate-based compound is crosslinked with the thermosetting functional group; A crosslinked triazine structure derived from the iminocarbonate-based compound. The dry film solder resist according to claim 21, wherein the hardened product further comprises a second acidic modified oligomer, wherein the second acidic modified oligomer has a carboxyl group and photocurability Saturated functional group. The dry film solder resist according to claim 23, wherein the hardened product comprises: a crosslinked structure in which a carboxyl group of the imino carbonate compound is crosslinked with the thermosetting functional group; a crosslinked structure in which a carboxyl group of the second acidic modified oligomer of the carboxyl group and the photocurable unsaturated functional group is crosslinked with the thermosetting functional group; cross-linking derived from the imino carbonate-based compound a triazine structure; and a crosslinked structure in which the second acidic modified oligomer having a carboxyl group and a photocurable unsaturated functional group and each of the unsaturated functional groups of the photopolymerizable monomer are crosslinked with each other. The dry film solder resist according to claim 21, wherein the α particle emissivity is 0.010 alphas/cm ² /hr or less. The dry film solder resist of claim 21, which has a thermal expansion coefficient of less than 40 ppm/K. The dry film solder resist according to claim 21, which has a glass transition temperature (Tg) of from 120 ° C to 180 ° C. The dry film solder resist according to claim 21, wherein the inorganic filler contains 50 to 90% by weight of cerium oxide and 10 to 50% by weight or A plurality of compounds selected from the group consisting of barium sulfate, barium titanate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica. The dry film solder resist according to claim 21, wherein the inorganic filler is contained in an amount of 5 to 50% by weight.