KR101785706B1 - Photo-curable and thermo-curable resin composition, and dry film solder resist - Google Patents

Abstract

The present invention includes a reaction product between an alcohol compound and a diisocyanate compound containing a diol compound containing a carboxyl group, a diol compound containing an ethylenically unsaturated group, and an alkylene oxide additional aromatic diol compound in a molar ratio of 1: 0.5 to 2: 0.1 to 0.5 A urethane-based polymer; A photopolymerizable monomer having at least one photocurable unsaturated functional group; A (meth) acrylate-based polymer resin containing 3 mol% to 20 mol% of repeating units substituted with an epoxy-based functional group among all repeating units; A thermosetting binder having a thermosetting functional group; And a photoinitiator, and a dry film solder resist provided therefrom.

Description

PHOTO-CURABLE AND THERMO-CURABLE RESIN COMPOSITION, AND DRY FILM SOLDER RESIST BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having photo-

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having a photo-curable property and a thermosetting property, and a dry film solder resist (DFSR). More specifically, the present invention relates to a resin composition having photo-curability and thermosetting ability which enables to provide a DFSR having a higher adhesive force to a polymer base material or a metal base material while securing higher flexibility, heat resistance and low stiffness, and a DFSR .

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.

The coverlay film (insulation protective film) currently used to protect the circuit on the conductor surface of a flexible printed circuit (FPC), which is required to have flexibility and heat resistance, has problems such as deterioration in workability, Lt; / RTI > In addition, its use is limited due to its high modulus. In order to solve the above problems, a liquid developing solder resist is used. In this case, a plurality of processes are required and have various limited physical properties.

Recently, as the film of the photosensitive composition of the dry film type is presented, workability and circuit integration degree are improved, and FPCB (flexible print circuit board) production can proceed more quickly. The binder resin used in such a photosensitive composition mainly uses an acrylic resin or an epoxy resin, and a photosensitive composition which satisfies both high flexibility and low stiffness at the same time is not presented.

In addition, when the final cured film is not sufficiently adhered to the copper foil, there is a problem that the exposed copper foil portion does not exhibit sufficient plating resistance such as a plating solution penetrating the plating process such as gold plating.

The present invention is to provide a resin composition having photo-curability and thermosetting ability that can provide a DFSR having a higher adhesive force to a polymer base material or a metal base material while securing higher flexibility, heat resistance and low stiffness.

Further, the present invention is to provide a dry film solder resist having a higher adhesive force to a polymer base material or a metal base material while securing higher flexibility, heat resistance and low stiffness.

In the present specification, a reaction product between an alcohol compound containing a carboxyl group, a diol compound containing an ethylenic unsaturated group, and an alkylene oxide added aromatic diol compound in a molar ratio of 1: 0.5 to 2: 0.1 to 0.5, and a diisocyanate compound Containing urethane polymer; A photopolymerizable monomer having at least one photocurable unsaturated functional group; A (meth) acrylate-based polymer resin containing 3 mol% to 20 mol% of repeating units substituted with an epoxy-based functional group among all repeating units; A thermosetting binder having a thermosetting functional group; And a photoinitiator, wherein the photo-curable and thermosetting resin composition is provided.

Also, in this specification, a dry film solder resist including a cured product or a dried product of the resin composition having the photocurable and thermosetting properties is provided.

Further, in the present specification, a diol compound containing a carboxyl group, a diol compound containing an ethylenic unsaturated group, and an alkylene oxide additional aromatic diol compound in a molar ratio of 1: 0.5 to 2: 0.1 to 0.5 in combination with a diisocyanate compound A urethane-based polymer containing a reactant; A photopolymerizable monomer having at least one photocurable unsaturated functional group; A (meth) acrylate-based polymer resin containing 3 mol% to 20 mol% of repeating units substituted with an epoxy-based functional group among all repeating units; And a thermosetting binder having a thermosetting functional group, wherein the thermosetting binder has a cross-linking structure between two or more compounds selected from the group consisting of a thermosetting binder having a thermosetting functional group and a thermosetting binder having a thermosetting functional group.

BEST MODE FOR CARRYING OUT THE INVENTION A resin composition and a dry film solder resist having photo-curable properties and thermosetting properties according to specific embodiments of the present invention will be described in detail below.

In the present specification, (meth) acrylate is meant to include both acrylate and (meth) acrylate.

Also, in the present specification, alkylene means a divalent functional group derived from an alkane, and arylene means a divalent functional group derived from arene.

According to one embodiment of the present invention, an alcohol compound containing a diol compound containing a carboxyl group, a diol compound containing an ethylenically unsaturated group and an alkylene oxide additional aromatic diol compound in a molar ratio of 1: 0.5 to 2: 0.1 to 0.5, and a diisocyanate A urethane-based polymer containing a reactant between the compounds; A photopolymerizable monomer having at least one photocurable unsaturated functional group; A (meth) acrylate-based polymer resin containing 3 mol% to 20 mol% of repeating units substituted with an epoxy-based functional group among all repeating units; A thermosetting binder having a thermosetting functional group; And a photoinitiator, can be provided.

The inventors of the present invention have conducted studies on a dry film solder resist applicable to various printed circuit boards and a resin composition capable of providing the dry film solder resist. When using a resin composition having photo-curable and thermosetting properties, (DFSR) having a high adhesive force to a polymer substrate or a metal substrate can be provided while securing high flexibility, heat resistance and low stiffness, and has completed the invention.

In particular, the resin composition having photo-curable properties and thermosetting properties of the above-mentioned one embodiment is obtained by copolymerizing the above-mentioned urethane polymer, that is, a diol compound containing a carboxyl group, a diol compound containing an ethylenic unsaturated group and an alkylene oxide additional aromatic diol compound at a ratio of 1: 0.5 to 2: And a high molecular compound in which a diisocyanate compound is reacted with an alcohol compound contained in a molar ratio of 0.1 to 0.5, the heat resistance and developability of the dry film solder resist equal to or higher than that of the previously known dry film solder resist is ensured, Low stiffness can be realized.

Meanwhile, an example of a method for producing a dry film solder resist using the resin composition of one embodiment is as follows. However, such a dry film solder resist manufacturing method is merely an example of various manufacturing methods, and the details of the manufacturing method are not limited thereto.

After the resin composition of one embodiment is applied on a predetermined substrate, the resin composition in the portion where the pattern is to be formed is selectively exposed. When such exposure is carried out, the urethane-based polymer and the vinyl period contained in the photopolymerizable monomer are photocured, and as a result, a crosslinked 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.

When the resin composition remaining on the substrate is heat-treated and thermally cured, the carboxyl group and the ethylenic unsaturated group contained in the urethane polymer react with the thermosetting functional group (epoxy group) of the thermosetting binder. As a result, A cured film having excellent heat resistance and chemical resistance can be formed on a desired portion of the substrate.

The cured product of the resin composition of one embodiment has a basic crosslinking structure (i.e., a carboxyl group and an ethylenic unsaturated group of a urethane-based polymer, and (meth) acrylate containing 3 mol% to 20 mol% of repeating units in which epoxy- Based functional group of the thermosetting binder), the DFSR has high flexibility and low stiffness.

Particularly, as described above, as the urethane polymer is formed from a diol compound containing a carboxyl group, a diol compound containing an ethylenically unsaturated group, and an alkylene oxide containing an aromatic diol compound in a specific molar ratio as described above, The dry film solder resist formed from the resin composition has a high adhesive strength and a high adhesive strength because the alcohol compound further includes at least one diol compound selected from the group consisting of a polycarbonate diol compound and a polyester diol compound Together, they can have flexibility and improved flexibility (low stiffness).

As a result, the electroplating and heat resistance of the DFSR can be further improved, and excellent physical properties required for a flexible printed circuit board and the like can be satisfied. Therefore, by using the resin composition of one embodiment, it is possible to provide a DFSR that exhibits higher flexibility and lower stiffness and can be preferably used as a protective film of a flexible printed circuit board or the like.

Particularly, a (meth) acrylate-based polymer resin containing 3 mol% to 20 mol%, or 4 mol% to 12 mol% of recurring units substituted with epoxy-based functional groups in the entire repeating units is cured together with the urethane- The rigidity of the final cured product can be adjusted to an appropriate level according to the content of the epoxy mechanical functional group and the characteristics of the (meth) acrylate based polymer resin itself, and an improved flexibility (lower stiffness) can be secured I will.

The (meth) acrylate-based polymer resin includes a polymer or copolymer including an acrylate-based repeating unit and / or a (meth) acrylate-based repeating unit.

The epoxy-based functional group may include an epoxy group or a glycidyl group.

In the (meth) acrylate-based polymer resin containing 3 mol% to 20 mol%, or 4 mol% to 12 mol% of repeating units substituted with epoxy-based functional groups in the entire repeating units,

The epoxy-based functional group may be substituted with one or more repeating units constituting the main chain of the (meth) acrylate-based polymer resin.

 When the (meth) acrylate-based polymer resin contains a repeating unit in which the epoxy group is substituted in the entire repeating units in an amount that is too small, for example, less than 30 mol%, the coating film or film obtained from the resin composition of one embodiment has an improved crosslinking It is difficult to have a bond, or heat resistance or electrolytic resistance is lowered, so that it can be hardly applied to a circuit board. When the (meth) acrylate-based polymer resin contains a repeating unit in which the epoxy group is substituted in the entire repeating units in an excessively high content, for example, more than 20 mol%, the coating film or film obtained from the resin composition of one embodiment The elasticity is largely lowered or the rigidity is greatly increased, so that it is difficult to impart flexibility to the substrate and the corrosion resistance is remarkably lowered.

The (meth) acrylate-based polymer resin containing 3 mol% to 20 mol% of repeating units in which the epoxy functional group is substituted among the entire repeating units may have a weight average molecular weight of 40,000 to 200,000. If the weight-average molecular weight of the (meth) acrylate-based polymer resin containing 3 mol% to 20 mol% of repeating units substituted with epoxy-based functional groups in the entire repeating units is too low, the developability of the resin composition becomes excessively high, Can be reduced. If the weight-average molecular weight of the (meth) acrylate-based polymer resin containing 3 mol% to 20 mol% of repeating units substituted with epoxy-based functional groups in the total repeating units is too high, the developability of the resin composition may be significantly lowered, The compatibility between the components contained in the composition may be reduced.

The photocurable and thermosetting resin composition may contain 1 to 40% by weight of a (meth) acrylate-based polymer resin containing 3 mol% to 20 mol% of repeating units substituted with epoxy-based functional groups in the entire repeating units. If the content of the (meth) acrylate-based polymer resin containing 3 mol% to 20 mol% of repeating units in which the epoxy functional group is substituted among the above total repeating units in the resin composition having photo-curable properties and thermosetting properties is too small, And the formation of fine patterns may be deteriorated. On the contrary, if the content of the (meth) acrylate polymer resin containing 3 mol% to 20 mol% of the repeating units in which the epoxy functional group is substituted in the above total repeating units in the resin composition having the photocurable property and the thermosetting property is increased, It is not only excessively developed but also may be uneven in coating.

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

Urethane-based  Polymer

The urethane polymer includes a reaction product between an alcohol compound containing a carboxyl group, a diol compound containing an ethylenic unsaturated group, and an alkylene oxide additional aromatic diol compound in a molar ratio of 1: 0.5 to 2: 0.1 to 0.5, and a diisocyanate compound .

As described above, as the alcohol compound includes the above-mentioned diol compound in the above ratio, a dry film solder resist (DFSR) having a higher adhesive force to a polymer base material or a metal base material, while ensuring higher flexibility, heat resistance and low stiffness, May be provided.

The diol compound containing a carboxyl group may be an aliphatic diol compound having 2 to 20 carbon atoms in which a carboxyl group is substituted, an alicyclic diol compound having 4 to 20 carbon atoms in which at least one carboxyl group is substituted and an aromatic aliphatic compound having 6 to 20 carbon atoms in which at least one carboxyl group is substituted. Diol compounds, and the like.

Specifically, the diol compound containing a carboxyl group may include a straight chain or branched aliphatic diol compound having 3 to 8 carbon atoms in which one to three carboxyl groups are substituted.

The diol compound containing an ethylenically unsaturated group is preferably a compound having at least one functional group selected from the group consisting of a vinyl group, a (meth) acryloyl group and a (meth) acryloyloxy group. An aliphatic diol compound having 2 to 20 carbon atoms in which at least one is substituted; ii) at least one functional group selected from the group consisting of a vinyl group, a (meth) acryloyl group and a (meth) acryloyloxy group; Alicyclic diol compounds; And iii) at least one functional group selected from the group consisting of a vinyl group, a (meth) acryloyl group and a (meth) acryloyloxy group. An aromatic diol compound; and at least one diol compound selected from the group consisting of aromatic diol compounds.

Specifically, the diol compound containing the ethylenic unsaturated group may include a diol compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, A is a direct bond or alkylene group of a straight-chain or branched-chain having 1 to 20, X is oxygen, sulfur, or N (R ₁₄₎ - a, and wherein R ₁₄ is hydrogen or C 1 -C 10 Alkyl group, and R ₁₁ , R ₁₂ and R ₁₃ are each hydrogen or an alkyl group having 1 to 3 carbon atoms.

The alkylene oxide added aromatic diol compound means a diol compound containing an alkylene oxide repeating unit having 2 to 5 carbon atoms and at least one aromatic group.

Specifically, the alkylene oxide-added aromatic diol compound may include a compound represented by the following formula (2).

(2)

Wherein Ar ₁ and Ar ₂ are each an arylene group having 6 to 20 carbon atoms, Z is oxygen, sulfur, or a straight or branched alkylene group having 1 to 10 carbon atoms, Ak ₁ and Ak ₂ are And m1, m2, and m3 are integers of 1 to 5, respectively.

The alcohol compound may further include at least one diol compound selected from the group consisting of a polycarbonate-based diol compound and a polyester-based diol compound.

The polycarbonate diol compound may include i) a linear or branched alkylene diol having 2 to 12 carbon atoms and ii) a reaction product between a phosgene carbonate or a dialkyl carbonate.

The polyester-based diol compound means a compound having two or more repeating units containing an ester functional group and having hydroxy groups substituted at both ends thereof.

Specific examples of the polyester-based diol compound may include at least one diol compound selected from the group consisting of compounds represented by the following formulas (3) to (5).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

Wherein L 1, L 2, L 3, L 4, L 5 and L 6 each represent a straight or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkenylene group having 2 to 20 carbon atoms, A straight or branched alkylene group having 1 to 20 carbon atoms, ^a linear or branched alkenylene group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms or a branched Or an arylene group having 6 to 20 carbon atoms, and n1, n2 and n3 are each an integer of 2 to 100,

The molar ratio of the diol compound containing a carboxyl group to the diol compound selected from the group consisting of the polycarbonate diol compound and the polyester diol compound may be 0.1 to 0.5 or 0.2 to 0.4.

As described above, when the alcohol compound contains the polycarbonate-based diol compound or the polyester-based diol compound in a molar ratio of 0.1 to 0.5 relative to the diol compound containing the carboxyl group, The prepared dry film solder resist (DFSR) can have a higher adhesive force to a polymer base material or a metal base material while securing higher flexibility, heat resistance and low stiffness.

On the other hand, the diol compound included in the alcohol compound may have a weight average molecular weight of 200 to 10,000, or 500 to 5,000. If the weight average molecular weight of the diol compound is too small, the flexibility of the finally produced DFSR may not be sufficiently secured. In addition, if the weight average molecular weight of the diol compound is too large, the surface or appearance characteristics of the DFSR formed from the resin composition of one embodiment may be deteriorated, and physical properties such as developability and crosslinkability may also be lowered.

Meanwhile, in the process of forming the urethane polymer, the alcohol compound and the diisocyanate compound may be reacted at a molar ratio of 1: 0.5 to 2.0.

The diisocyanate compound may be an aliphatic, alicyclic, fat-alicyclic or aromatic diisocyanate containing 2 to 20 carbon atoms. The isocyanate may be unsubstituted or substituted, for example, with C1-C4 alkyl or C1-C4 alkoxy, such as methyl, ethyl, methoxy and ethoxy.

Specific examples of the diisocyanate compound include di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, deca-, undeca- and dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate Propylene diisocyanate, 2,3-dimethyl-1,4-butylene diisocyanate, 2,5-dimethyl Hexylene diisocyanate, 1,2- or 1,3-cyclobutylene or -cyclopentylene diisocyanate, mono-, di- or trimethyl-1,2- or 1,3-cyclobutylene Or cyclopentylene diisocyanate, 1,2-, 1,3- or 1,4-cyclohexylene diisocyanate, mono-, di- or trimethyl-1,2-, 1,3- or 1,4- Cyclohexylene diisocyanate, 1,3- or 1,4-cyclooctylene diisocyanate, 1-isocyanatomethyl-3-isocyanatocyclohexyl , 1-isocyanatomethyl-3-isocyanato-2-methylcyclohexane, 1-isocyanatomethyl-3-isocyanato-1,3-dimethylcyclohexane, 1- 3,3-trimethylcyclohexane (isophorone diisocyanate), 1,3- or 1,4-diisocyanatomethylcyclohexane, 4,4'-diisocyanate Bis (4-isocyanatocyclohexyl) methane or -ethane, 2,3- or 2,4-diisocyanatobenzene, 2,4- or 2,6-diisocyanatotoluene , 2,5- or 2,6-diisocyanato-xylene, 1,5- or 2,7-diisocyanatonaphthalene, 1-isocyanatomethyl-3- or 4- Diisocyanatomethylbenzene, 4,4'-diisocyanatobiphenyl, 4,4'-diisocyanatomethylbenzene, 4,4'-diisocyanatobiphenyl, 4,4'- - diisocyanatobiphenyl ether, 4,4'-diisocyanatobiphenyl Diisocyanatobiphenylsulfone and bis (4-isocyanatophenyl) methane, bis (4-isocyanatophenyl) ethane, norbornenedisocyanate, isophorone diisocyanate, 3, 3'-methylbiphenyl-4,4'-diisocyanate, 4,4'-methylenebis (cyclohexyldiisocyanate), or lysine diisocyanate.

The urethane polymer may have a weight average molecular weight of 1,000 to 80,000, or 2,000 to 60,000. If the weight average molecular weight of the urethane polymer is too small, the mechanical properties and heat resistance of the DFSR formed from the resin composition of one embodiment may not be sufficiently secured. If the weight average molecular weight of the urethane polymer is too high, compatibility between the components of the resin composition of the embodiment may be deteriorated, and the surface or appearance characteristics of the finally produced DFSR may be deteriorated. And physical properties such as crosslinkability may also be lowered.

The urethane-based polymer may have an acid value of 20 mgKOH / g to 120 mgKOH / g. If the acid value of the urethane polymer is too low, alkali developability may be lowered. On the other hand, if the acid value is too high, the photo-curing unit, for example, the exposure unit may be dissolved by the developing solution, so that normal pattern formation of DFSR may become difficult.

In addition, the urethane polymer may have an ethylenic unsaturated group equivalent of 0.05 mmol / g to 3.0 mmol / g. The ethylenic unsaturated group equivalent can be obtained by measuring the equivalent of an ethylenic unsaturated group such as a vinyl group contained in the compound.

The urethane polymer 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. If the content of the urethane-based polymer is too small, the developability of the resin composition may deteriorate and the formation of fine patterns may be deteriorated. On the other hand, if the content of the urethane polymer is too high, the resin composition may be excessively developed and the uniformity of the coating may be deteriorated.

Meanwhile, the resin composition according to one embodiment may further include an acid-modified oligomer conventionally known together with the urethane polymer.

Photopolymerization Monomer

On the other hand, the resin composition of one embodiment includes a photopolymerizable monomer having at least one photocurable unsaturated functional group. Such a photopolymerizable monomer can be, for example, a compound having a photocurable unsaturated functional group such as at least one polyfunctional vinyl group. The photopolymerizable monomer can be crosslinked with an unsaturated functional group of the above-mentioned urethane polymer by photocuring A crosslinked structure can be formed. 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 one photocurable unsaturated functional group can be used. As specific examples, 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. These compounds may be used singly or in combination of two or more thereof .

Specific examples of the acrylate compound having at least one photocurable unsaturated functional group include products such as EB-3700, EB-3703, EB3708, EB-210, EB-270 and EB-150 manufactured by SK cytec However, the usable compounds are not limited thereto.

As the photopolymerizable monomer, a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in one molecule can be preferably used. In particular, pentaerythritol triacrylate, trimethylolpropane tri Acrylate, 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 1 to 40% by weight, about 5 to 30% by weight, about 7 to 20% by weight, or about 7 to 15% by weight based on the total weight of the photocurable and thermosetting resin composition . If the content of the photopolymerizable monomer is too small, photocuring may become insufficient. If the content of the photopolymerizable monomer is excessively large, dryness of the DFSR may be deteriorated and physical properties may be deteriorated.

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 0.1 to 20% by weight, or 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 this embodiment also includes a thermosetting binder having at least one selected from among thermosetting functional groups, 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 urethane-modified epoxy resin. 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 unsaturated monomers having an oxetane ring and alkyl (meth) acrylates.

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 resin composition having photo-curability and thermosetting property of the one embodiment may contain 1 to 40% by weight or 5 to 30% by weight of the thermosetting binder having the thermosetting functional group.

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 above-mentioned respective components, the resin composition of one embodiment may further include at least one additive selected from the group consisting of a solvent, a thermosetting catalyst, a filler, and a pigment.

Heat curing  catalyst

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

Such thermosetting binder catalysts include, for example, 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-CATSA102, and U-CAT5002 (all of bicyclic amidine compounds and salts thereof), and the like. But is not limited to these, and may be a thermosetting catalyst of an epoxy resin, or may be one which promotes the reaction between an epoxy group and a carboxyl group, or 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 Triazine derivatives such as adducts may be used, and preferably compounds that also function as adhesion promoters may 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 of the embodiment in terms 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.

Pigment

The pigment exhibits visibility and hiding power, and serves to hide defects such as scratches on circuit lines. As the pigment, red, blue, green, yellow, black pigment and the like can be used. As blue pigments, phthalocyanine blue, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 60, have. Green pigments include Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like. Examples of the yellow pigment include anthraquinone type, isoindolinone type, condensed azo type, and benzimidazolone type. Examples thereof include Pigment Yellow 108, Pigment Yellow 147, Pigment Yellow 151, Pigment Yellow 166, Mention Yellow 181, Pigment Yellow 193, and the like.

The content of the pigment is preferably about 0.5 to 3% by weight based on the total weight of the resin composition. If it is used in an amount less than 0.5% by weight, visibility and hiding power will be lowered, and if it is used in an amount exceeding 3% by weight, heat resistance will be deteriorated.

Other additives

The resin composition of one embodiment may further include other additives. Such other additives may be added to remove bubbles of the resin composition, to remove popping or craters on the surface 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 of one embodiment or to impart 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.

Dry film Solder Resist

First, the process of preparing the DFSR using the photosensitive resin composition of the embodiment will be described briefly.

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 performed, for example, light curing occurs in the exposed portion and cross-linking can be formed between the urethane polymer and unsaturated functional groups contained in the photopolymerizable monomer or the like, and as a result, State. 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. As the DFSR is subjected to photo-curing and thermosetting, the urethane-based polymer; A photopolymerizable monomer having at least one vinyl group in the molecule; And a thermosetting binder having a thermosetting functional group.

More specifically, the cured product is a crosslinked structure in which a carboxyl group and an ethylenic unsaturated group of the urethane polymer and the thermosetting functional group are crosslinked by thermosetting; The vinyl group of the acid-modified urethane polymer and the photopolymerizable monomer may include a cross-linked structure in which they are cross-linked by photocuring.

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

On the other hand, according to another embodiment of the present invention, a dry film solder resist including a cured product or a dried product of the resin composition having photo-curable and thermosetting properties of the above-described embodiment can be provided.

According to another embodiment of the present invention, an alcohol compound containing a carboxyl group-containing diol compound, an ethylenically unsaturated group-containing diol compound and an alkylene oxide additional aromatic diol compound in a molar ratio of 1: 0.5 to 2: 0.1 to 0.5 And a diisocyanate compound; A photopolymerizable monomer having at least one photocurable unsaturated functional group; A (meth) acrylate-based polymer resin containing 3 mol% to 20 mol% of repeating units substituted with an epoxy-based functional group among all repeating units; A thermosetting binder having a thermosetting functional group, and a cross-linking structure between two or more compounds selected from the group consisting of a thermosetting binder having a thermosetting functional group.

The alcohol compound may further include at least one diol compound selected from the group consisting of a polycarbonate-based diol compound and a polyester-based diol compound.

The molar ratio of the diol compound containing a carboxyl group to the diol compound selected from the group consisting of the polycarbonate diol compound and the polyester diol compound may be 0.1 to 0.5.

The dry film solder resist can have a higher adhesive force to a polymer substrate, a metal substrate or the like while ensuring higher flexibility, heat resistance and low stiffness.

According to the present invention, it is possible to provide a resin composition having photo-curability and thermosetting property which enables to provide a DFSR having a higher adhesive force to a polymer base material, a metal base material or the like while ensuring higher flexibility, heat resistance and low stiffness.

Further, according to the present invention, it is possible to provide a semiconductor device having the above-described physical properties, suitably protecting the circuit, excellent adhesion after curing, and excellent resistance to electrolytic plating and excellent in physical properties such as soldering heat resistance, bending resistance (brittleness and bending resistance), chemical resistance, A dry film solder resist may be provided.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Synthetic example : Photopolymerization  contain Urethane-based  Synthesis of Polymer]

Synthesis Example 1

(0.121 mol) of 2,2-bis (hydroxymethyl) propionic acid, 20.23 g (0.126 mol) of glycerol monomethacrylate (GLM) and 20.23 g (0.126 mol) of bisphenol A propylate were added to a 500 mL 3-neck round bottom flask equipped with a stirrer, 16.68 g (0.0242 mol) of [BPA (PO) ₈ (OH) ₂ ] was dissolved in 100 mL of methyl ethyl ketone to prepare a reaction solution.

46.8 g (0.28 mol) of hexamethylene diisocyanate (HMDI) and 0.8 g of dibutyllaurate were added to the reaction solution, and the mixture was heated and stirred at 75 DEG C for 5 hours to obtain a urethane polymer containing a photopolymerizable group (LGSN-9 solution, Solid content: 50% by weight).

The resultant urethane-based polymer LGSN-9 solution containing the photopolymerizable group had a solid acid value of 69 mgKOH / g, a weight average molecular weight (polystyrene standard) of 24,000 as measured by gel permeation chromatography (GPC), a photopolymerizable group equivalent (vinyl group equivalent) Was 750 mmol / g.

Synthetic example  2

(0.136 mol) of 2,2-bis (hydroxymethyl) propionic acid, 21.12 g (0.132 mol) of glycerol monomethacrylate (GLM), and 20.5 g (0.132 mol) of bisphenol A propylate were added to a 500 mL 3-neck round bottom flask equipped with a stirrer, 12.14 g (0.026 mol) of [BPA (PO) ₄ (OH) ₂ ] was dissolved in 100 mL of methyl ethyl ketone to prepare a reaction solution.

46.8 g (0.28 mol) of hexamethylene diisocyanate (HMD) and 0.8 g of dibutyllaurate were added to the reaction solution, and the mixture was heated and stirred at 75 DEG C for 5 hours to obtain a urethane polymer containing a photopolymerizable group (LGSN-10 solution, Solid content: 50% by weight).

The resultant urethane-based polymer LGSN-10 solution containing the photopolymerizable group had a solid acid value of 77.5 mgKOH / g, a weight average molecular weight (polystyrene standard) of 28,000 as measured by gel permeation chromatography (GPC), a photopolymerizable group equivalent (vinyl group equivalent) Was 750 mmol / g.

[ Example  1 to 3: Photocurable  And production of a resin composition having a thermosetting property and a dry film]

Example  One

100 g of the urethane-based polymer solution containing the photopolymerizable group obtained in Synthesis Example 1, 16 g of trifunctional epoxy resin (VG-3101L) and 5 g of a methacrylate resin (weight average molecular weight: 26 g of glass transition temperature: 5 ° C), 1 g of a photopolymerizable monomer (EB-3708, SK cytec), 1 g of a thermal crosslinking catalyst CXC-1756, 2 g of a light stabilizer ITX and 5.0 g of a photo initiator DAROCURE TPO And a thermosetting resin composition were prepared.

The resin composition thus prepared was coated on a PET film with a comma coater at 80 占 퐉 and then dried in an oven at 80 占 폚 for 10 minutes to prepare a dry film having a thickness of 38 占 퐉.

Example 2

Except that the urethane polymer solution containing the photopolymerizable group obtained in Synthesis Example 2 was used in place of the urethane polymer solution containing the photopolymerizable group obtained in Synthesis Example 1 and 2.5 g of DAROCURE TPO as a photoinitiator was used. A dry film having a thickness of 38 mu m was prepared in the same manner.

Example 3

Except that 33 g of a methacrylate resin (weight average molecular weight: 27,000, glass transition temperature: 5 캜) containing 5 mol% of the glycidyl methacrylate repeating unit and 2.5 g of DAROCURE TPO as a photoinitiator were used. A dry film having a thickness of 38 탆 was prepared.

[ Comparative Example  1 and 2: Preparation of Photosensitive Resin Composition and Dry Film]

Comparative Example 1

200 g of an acid-modified BPF novolak resin ZFR-266H (solid content 50% by weight) containing a photopolymerizable group, 55 g of a urethane-modified epoxy UME-330 (National Kagaku Co., Ltd.), 13 g of an epoxy-modified polybutadiene PB3600 (DAICEL) EB-150, SK cytec), 2.2 g of a thermal crosslinking catalyst CXC-1756, and 7 g of DAROCURE TPO as a photoinitiator were mixed to prepare a photosensitive resin composition.

The above photosensitive resin composition was coated on a PET film with a doctor blade at 80 占 퐉 and then dried in an oven at 80 占 폚 for 10 minutes to prepare a dry film having a thickness of 38 占 퐉

Comparative Example  2

200 g of a urethane-modified epoxyacrylate resin (UXE-3024, solid content 50% by weight, manufactured by Nippon Kayaku Co., Ltd.), 39 g of a urethane-modified epoxy UME-330 (National Kagaku Co., Ltd.), an epoxy-modified polybutadiene PB3600 ), 40 g of a photopolymerizable monomer (EB-150, polyester methacrylate oligomer, SK cytec), 2.2 g of a thermal crosslinking catalyst CXC-1756 and 7 g of DAROCURE TPO as a photoinitiator were mixed and mixed to prepare a photosensitive resin composition.

The above photosensitive resin composition was coated on a PET film with a doctor blade at 80 占 퐉 and then dried in an oven at 80 占 폚 for 10 minutes to prepare a dry film having a thickness of 38 占 퐉

< Test Example : Evaluation of dry film properties>

The dry film prepared in the above Examples and Comparative Examples was put on a copper foil of a patterned 2CCL product, vacuum laminated at 70 ° C for 30 seconds, and then cured in an oven under a nitrogen atmosphere at 150 ° C for 1 hour. The properties of the obtained cured product were evaluated in the following manner. The results are shown in Table 2 below.

Experimental Example 1 : Developability

The prepared photosensitive film was subjected to vacuum lamination on a copper foil, exposed at 350 mJ / cm ² , spray-developed with a 1 wt% aqueous solution of sodium carbonate at 35 ° C and then confirmed to be developable at a pitch of 50 μm / 50 μm .

Experimental Example 2 : Adhesion

The cross-cut film of the cured dry film was measured in accordance with JIS K5404. Specifically, a 10 X 10 grid-shaped sheath was formed on the cured dry film (the size of each grid was 100 μm), and then a NICHIBANG tape was bonded. After peeling the adhered tape, the number of lattice of the photosensitive resin film peeled off with the tape was counted to evaluate the adhesiveness.

Experimental Example  3: Lead heat resistance

The film was floated at 288 ± 5 ° C for one minute with the dry film side facing up. Then, the film was inspected for abnormalities of the dry film.

Experimental Example  4: Flexibility

The dry film was subjected to vacuum lamination on an FCCL pattern having L / S = 100 mu m / 100 mu m, followed by exposure, development, and curing. Flexibility was measured by the MIT method (0.38R, 500 g load). (JIS C6471)

Experimental Example  5: Chemical resistance

The specimens were immersed in a sulfuric acid solution of 10 (v / v)%, a sodium hydroxide solution of 10 (v / v)% and isopropyl alcohol at room temperature for 10 minutes, and then peeling or discoloration was confirmed. And evaluated under the following criteria.

Experimental Example  6: Venus also

The substrate with the patterned final cured film was immersed in an electroless nickel plating solution at 85 캜 for 30 minutes to perform plating. After the plating was formed, whether the cured film was lifted or immersed in the plating liquid was visually confirmed.

Experimental Example  7: Stiffness ( Stiffness )

The dry films obtained in the above-mentioned Examples and Comparative Examples were each vacuum-laminated on a polyimide base film having a thickness of 25 mu m, and then exposed and cured. A specimen having a width of 3 cm and a length of 7 cm was prepared from the cured product thus obtained, and the specimen was pressed with a force of 5 g / min and a force of 1 cm / min while the loop height reached 10 mm. The stiffness of the specimen was determined.

The stiffness of the polyimide base film was 2 g when the loop height was 10 mm.

The results obtained in Experimental Examples 1 to 7 are shown in Table 1 below.

Developability Adhesion Lead heat resistance Flexibility Chemical resistance Venus also Stiffness
[Unit: g] Example 1 50/50
possible 100/100 no problem 370 OK OK 4 Example 2 50/50
possible 100/100 no problem 350 OK OK 4.5 Example 3 50/50
possible 100/100 no problem 410 OK OK 3.5 Comparative Example 1 50/50
possible 100/100 no problem 250 OK OK 18 Comparative Example 2 50/50
possible 0/100 no problem 270 OK OK 15

As shown in Table 1, the dry film solder resists formed using the resin compositions of Examples 1 to 3 had excellent dry property, lead heat resistance, chemical resistance, and resistance to water, It has been confirmed that it has higher adhesion and flexibility and lower stiffness than the film solder resist. That is, the dry film solder resists obtained in Examples 1 to 3 have flexibility and flexibility (low stiffness) with high adhesive strength.

Claims (25)

A urethane-based polymer comprising a reactant between an alcohol compound containing a diol compound containing a carboxyl group, a diol compound containing an ethylenic unsaturated group, and an alkylene oxide additional aromatic diol compound in a molar ratio of 1: 0.5 to 2: 0.1 to 0.5, and a diisocyanate compound ;
A photopolymerizable monomer having at least one photocurable unsaturated functional group;
A (meth) acrylate-based polymer resin containing 3 mol% to 20 mol% of repeating units substituted with an epoxy-based functional group among all repeating units;
A thermosetting binder having a thermosetting functional group; And
A photoinitiator, and a photoinitiator.
The method according to claim 1,
The urethane-based polymer has a weight average molecular weight of 1,000 to 80,000.
The method according to claim 1,
Wherein the urethane-based polymer has an acid value of 20 mgKOH / g to 120 mgKOH / g.
The method according to claim 1,
Wherein the urethane-based polymer has an ethylenic unsaturated group equivalent of 0.05 mmol / g to 3.0 mmol / g.
The method according to claim 1,
The diol compound containing a carboxyl group may be an aliphatic diol compound having 2 to 20 carbon atoms in which a carboxyl group is substituted, an alicyclic diol compound having 4 to 20 carbon atoms in which at least one carboxyl group is substituted and an aromatic aliphatic compound having 6 to 20 carbon atoms in which at least one carboxyl group is substituted. Wherein the photo-curable and thermosetting resin composition comprises at least one member selected from the group consisting of diol compounds.
The method according to claim 1,
Wherein the diol compound containing a carboxyl group comprises a straight chain or branched aliphatic diol compound having 3 to 8 carbon atoms substituted with a carboxyl group.
The method according to claim 1,
The diol compound containing the ethylenic unsaturated group
An aliphatic diol having 2 to 20 carbon atoms in which at least one functional group selected from the group consisting of a (meth) acryloyl group and a (meth) acryloyloxy group is substituted by at least one functional group selected from the group consisting of compound;
An alicyclic group having 4 to 20 carbon atoms substituted with at least one functional group selected from the group consisting of a (meth) acryloyl group, a (meth) acryloyl group and a (meth) acryloyloxy group, Diol compounds; And
An aromatic diol having 6 to 20 carbon atoms in which at least one functional group selected from the group consisting of a (meth) acryloyl group and a (meth) acryloyloxy group is substituted by at least one functional group selected from the group consisting of And at least one diol compound selected from the group consisting of compounds represented by the following general formulas (I) and (II).
The method according to claim 1,
Wherein the diol compound comprising an ethylenically unsaturated group comprises a diol compound represented by the following formula (1).
[Chemical Formula 1]

In Formula 1,
A is a direct bond or a linear or branched alkylene group having 1 to 20 carbon atoms,
X is oxygen, sulfur, or N (R &lt; ₁₄ &gt;) -
R &lt; ₁₄ &gt; is hydrogen or an alkyl group having 1 to 10 carbon atoms,
R ₁₁ , R ₁₂ and R ₁₃ are each hydrogen or an alkyl group having 1 to 3 carbon atoms.
The method according to claim 1,
Wherein the alkylene oxide-added aromatic diol compound comprises a compound represented by the following formula (2): &lt; EMI ID =
(2)

Wherein Ar ₁ and Ar ₂ are each an arylene group having 6 to 20 carbon atoms, Z is oxygen, sulfur, or a straight or branched alkylene group having 1 to 10 carbon atoms, Ak ₁ and Ak ₂ are And m1, m2, and m3 are integers of 1 to 5, respectively.
The method according to claim 1,
Wherein the alcohol compound further comprises at least one diol compound selected from the group consisting of a polycarbonate-based diol compound and a polyester-based diol compound.
11. The method of claim 10,
Wherein the polycarbonate diol compound comprises i) a linear or branched alkylene diol having 2 to 12 carbon atoms and ii) a reaction product between a phosgene carbonate or a dialkyl carbonate.
11. The method of claim 10,
Wherein the polyester diol compound comprises at least one diol compound selected from the group consisting of compounds represented by the following Chemical Formulas 3 to 5:
(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above Chemical Formulas 3 to 5,
Each of L1, L2, L3, L4, L5 and L6 is a linear or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkenylene group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms,
X ^a represents a linear or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkenylene group having 2 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms or an alkenylene group having a branched chain, An arylene group having 6 to 20 carbon atoms,
n1, n2 and n3 are integers of 2 to 100, respectively.
11. The method of claim 10,
Wherein the molar ratio of the diol compound containing a carboxyl group to the diol compound selected from the group consisting of the polycarbonate-based diol compound and the polyester-based diol compound is 0.1 to 0.5.
The method according to claim 1,
Wherein the epoxy-based functional group comprises an epoxy group or a glycidyl group.
The method according to claim 1,
Wherein the (meth) acrylate-based polymer resin containing 3 mol% to 20 mol% of repeating units substituted with an epoxy functional group in the total repeating units has a weight average molecular weight of 40,000 to 200,000.
The method according to claim 1,
15 to 75% by weight of the urethane polymer;
1 to 40% by weight of a photopolymerizable monomer having at least one photocurable unsaturated functional group;
1 to 40% by weight of a (meth) acrylate-based polymer resin containing 3 mol% to 20 mol% of repeating units substituted with epoxy-based functional groups in all repeating units;
1 to 40% by weight of a thermosetting binder having a thermosetting functional group; And
0.1 to 20% by weight of a photoinitiator; and a photocurable and thermosetting resin composition.
17. The method of claim 16,
Wherein the thermosetting binder is contained in an amount corresponding to 0.8 to 2.0 equivalents based on 1 equivalent of the carboxyl group of the urethane polymer.
The method according to claim 1,
Wherein the photopolymerizable monomer having at least one photocurable unsaturated functional group is selected from the group consisting of a hydroxyl group-containing acrylate compound, a water-soluble acrylate compound, a polyester acrylate compound, a polyurethane acrylate compound, an epoxy acrylate compound and caprolactone Modified acrylate compound, and a modified acrylate compound. The photocurable and thermosetting resin composition according to claim 1,
The method according to claim 1,
Wherein the thermosetting binder having a thermosetting functional group is a polyfunctional epoxy compound having at least two epoxy groups in the molecule; A multifunctional oxetane compound having at least two oxetanyl groups in the molecule; And an episulfide resin having at least two thioether groups in the molecule. The photocurable and thermosetting resin composition according to claim 1,
The method according to claim 1,
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 at least one selected from the group consisting of a photo-curable resin and a thermosetting resin.
The method according to claim 1,
Wherein the resin composition further comprises at least one additive selected from the group consisting of a solvent, a thermosetting catalyst, a filler, and a pigment.
A dry film solder resist comprising a cured product or a dried product of the resin composition having the photocurable and thermosetting properties of claim 1.
A urethane-based polymer comprising a reactant between an alcohol compound containing a diol compound containing a carboxyl group, a diol compound containing an ethylenic unsaturated group, and an alkylene oxide additional aromatic diol compound in a molar ratio of 1: 0.5 to 2: 0.1 to 0.5, and a diisocyanate compound ; A photopolymerizable monomer having at least one photocurable unsaturated functional group; A (meth) acrylate-based polymer resin containing 3 mol% to 20 mol% of repeating units substituted with an epoxy-based functional group among all repeating units; And a thermosetting binder having a thermosetting functional group.
24. The method of claim 23,
Wherein the alcohol compound further comprises at least one diol compound selected from the group consisting of a polycarbonate-based diol compound and a polyester-based diol compound.
25. The method of claim 24,
Wherein the molar ratio of the diol compound containing a carboxyl group to the diol compound selected from the group consisting of the polycarbonate-based diol compound and the polyester-based diol compound is 0.1 to 0.5.