Organic solvent-releasable curable resin composition and coating film for etching resist derived therefrom

Abstract

An embodiment of the present invention relates to an organic solvent-releasable curable resin composition which comprises a (meth)acrylate-based monofunctional monomer and a photopolymerization initiator, does not comprise a polymer having a weight average molecular weight of 5000 or more, and does not have an acid value. The organic solvent-releasable curable resin composition according to the present invention can be easily cured even with a single-wavelength LED lamp installed in an inkjet printer, and can have acid resistance and alkali resistance.

Description

Organic solvent-released curable resin composition and etching resist coating film derived therefrom

[0001] The present invention relates to an organic solvent-released curable resin composition and an etching resist coating film derived therefrom.

[0002] With the ongoing development of inkjet printers, there have been attempts to replace the initial metal halide lamp as a light source for curing with LED lamps for environmental protection and cost reduction. However, while metal halide lamps emit light over a wide wavelength range, thus providing a smooth curing experience, LED lamps have been plagued by issues with ink under-curing. To address this issue and enhance the adhesion and durability of the cured film, conventional methods have involved additional UV curing with metal halide lamps or thermal curing after LED curing.

[0003] Meanwhile, most existing strippable ink compositions are acid-resistant and are typically stripped using alkaline solutions. However, these compositions are not suitable for selectively etching metals using acid and alkaline solutions, and are only resistant to one or the other. Therefore, an inkjet etching resist with both acid and alkaline resistance is needed.

[0004] Furthermore, from an environmental perspective, ink compositions that strip with alkaline solutions have the problem of reacting with metals and generating corrosive, toxic gases. Therefore, there is a need to develop a resist that can be stripped without generating toxic gases using a non-toxic organic solvent.

[0005] Patent document 1 uses a stripping solution containing 20 to 30% of an alkanolamine compound, but in this case, there are problems of harmfulness to the human body and environmental pollution when the stripping waste solution is disposed of. Patent document 2 describes providing an environmentally friendly aqueous stripping solution composition containing cyclodextrin or a derivative thereof to solve the problems of harmfulness to the human body and environmental pollution, but the stripping solution requires the addition of an additional substance to water.

[0006] Furthermore, while conventional etching resist inks can protect circuits by resisting stripping during the washing process, they have the disadvantage that exposed metal circuits in areas where the ink is not printed are easily corroded by large amounts of moisture. Therefore, to protect circuits during the washing process during industrial circuit manufacturing, an etching resist ink that exhibits selective stripping properties only when exposed to solvents and not water is required.

[0007] [Patent Document]

[0008] (Patent Document 1) Patent Publication No. 2017-0095661

[0009] (Patent Document 2) Patent Publication No. 2017-0123050

[0010] The present disclosure is intended to solve the above problems, and provides an organic solvent peelable curable resin composition that is well cured even with a single wavelength LED lamp mounted on an inkjet printer and has acid resistance and alkali resistance.

[0011] One embodiment of the present invention relates to an organic solvent peelable curable resin composition.

[0012] In one aspect, the organic solvent peelable curable resin composition comprises a (meth)acrylate-based monofunctional monomer; and a photopolymerization initiator, does not contain a polymer having a weight average molecular weight of 5000 or more, and may not have an acid value.

[0013] In one aspect, the (meth)acrylate-based monofunctional monomer may include a monomer containing at least one of a morpholino group and a hydroxyl group.

[0014] In one aspect, the (meth)acrylate-based monofunctional monomer may include at least one water-soluble monomer and at least one water-insoluble monomer.

[0015] In one aspect, the content of the water-soluble monomer may be 15 to 50 wt% based on the total weight of the composition.

[0016] In one aspect, the content of the (meth)acrylate-based monofunctional monomer may be 20 to 95 wt% based on the total weight of the composition.

[0017] In one aspect, the organic solvent peelable curable resin composition further includes a polyfunctional monomer, and the viscosity of the polyfunctional monomer when measured with a cone-plate viscometer at 25°C and 5 rpm may be 5 to 500 cps.

[0018] In one aspect, the content of the multifunctional monomer may be 15 wt% or less based on the total weight of the composition.

[0019] In one aspect, the photopolymerization initiator may be at least one of a phosphine oxide type or a hydrogen abstraction type.

[0020] In one aspect, the content of the photopolymerization initiator may be 1 to 10 wt% based on the total weight of the composition.

[0021] In one aspect, the organic solvent peelable curable resin composition may further include a colorant in an amount of 0.1 to 10 wt% based on the total weight of the composition.

[0022] In one aspect, the organic solvent peelable curable resin composition may have a viscosity of 1 to 50 cps at 25°C.

[0023] In one aspect, the organic solvent may not have metal corrosive properties.

[0024] In one aspect, the organic solvent peelable curable resin composition may be peelable at 20°C to 40°C with an organic solvent including a glycol solvent, an alcohol solvent, an acetate solvent, or a mixture thereof.

[0025] In one aspect, the organic solvent peelable curable resin composition may be capable of LED curing.

[0026] Another embodiment of the present invention relates to a coating film for etching resist formed by curing the organic solvent stripping type curable resin composition.

[0027] In one aspect, the curing can be performed using only a UV LED lamp.

[0028] In one aspect, the etching resist film may be peelable in an organic solvent.

[0029] The organic solvent-released curable resin composition of the present disclosure comprises a monofunctional monomer and does not contain a high molecular weight polymer, so it is resistant to acid or alkaline aqueous solutions, and because it has a low crosslinking density, it can be easily dissolved in organic solvents. Therefore, it has adhesion to various substrates (copper, stainless steel (SUS), glass, plastic, polyimide (PI), polyethylene terephthalate (PET), printed circuit boards (PCBs), etc.) and can be used for the purpose of protecting the substrate against contamination by foreign substances, physical scratches, and chemicals (acidic, alkaline).

[0030] In addition, the organic solvent peelable curable resin composition of the present disclosure can optionally form a peelable film using a multifunctional monomer. If a multifunctional group is contained, a peelable film can be formed, and if a multifunctional group is not contained, a soluble coating film can be formed.

[0031] In addition, the organic solvent peelable curable resin composition of the present disclosure can be easily peeled or dissolved at room temperature using an organic solvent with relatively low toxicity.

[0032] In addition, the organic solvent peelable curable resin composition of the present disclosure has a low viscosity at 25°C, enabling inkjet printing. This allows for non-contact printing with the substrate, thereby preventing scratches that may occur on the substrate during printing, and has the advantage of selectively allowing printing only on desired areas. In addition, the short working time allows for economical substrate manufacturing.

[0033] In this specification, “organic solvent peeling type” may mean both peeling by an organic solvent and dissolving by an organic solvent.

[0034] Various embodiments of the present invention are described below.

[0035] [Curable resin composition]

[0036] One embodiment of the present invention relates to an organic solvent-released curable resin composition comprising a (meth)acrylate-based monofunctional monomer and a photopolymerization initiator, and not including a polymer having a weight average molecular weight of 5000 or more and not having an acid value.

[0037] Here, the acid value can be measured by a method widely used in the art, for example, by using a KOH aqueous solution as a titrant.

[0038] Here, "having no acid value" means that the composition substantially does not contain a carboxyl group, or even if the composition does not contain a carboxyl group, a trace amount of acid value (e.g., about 1 KOH / mg or less) may inevitably be measured due to unreacted substances or the like during the manufacturing process of the composition. This "substantially containing no carboxyl group" means that the composition does not intentionally incorporate a carboxyl group, except in cases where a carboxyl group is unintentionally mixed into the composition.

[0039] Since the above organic solvent peeling curable composition does not have an acid value, it can have acid resistance and alkali resistance.

[0040] In particular, in the case of an acid resin having an acid value, the viscosity is relatively high and may not be suitable for use as an inkjet ink. However, in the present disclosure, since the composition is prepared through a combination of monomers without using an acid resin, the viscosity can be reduced.

[0041] Since the organic solvent strippable curable composition does not contain a polymer having a weight average molecular weight of 5,000 or more, it can have a viscosity suitable for inkjet printing and can be easily stripped with various solvents. For example, the organic solvent strippable curable composition can contain monomers having a weight average molecular weight of 5,000 or less, for example, 4,500 or less, 4,000 or less, 3,500 or less, or 3,000 or less.

[0042] Hereinafter, each component of the organic solvent peelable curable resin composition (hereinafter, curable resin composition) is described in detail.

[0043] [(meth)acrylate]

[0044] In this specification, “(meth)acrylate” is a general term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions. A (meth)acrylate-based monofunctional monomer means a (meth)acrylate having one (meth)acryloyl group, and a (meth)acrylate-based polyfunctional monomer means a (meth)acrylate having two or more (meth)acryloyl groups.

[0045] For example, (meth)acrylate monofunctional monomers include ethyl (meth)acrylate, trifluoroethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, Esters of monohydric alcohols and (meth)acrylic acid, such as tetrahydrofurfuryl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, 2-ethylhexyldiethylene glycol (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, phenol (EO) acrylate, and 3-phenoxybenzyl (meth)acrylate; 2-Hydroxyethyl (meth)acrylate, 2-Hydroxypropyl (meth)acrylate, 2-Hydroxybutyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate, 2-Hydroxy-3-phenoxypropyl (meth)acrylate, Octylacrylate, Nonylacrylate, Isononyl acrylate, 3,3,5-Trimethylcyclohexylacrylate, Cyclic trimethylolpropane formal acrylate, 1-Naphthalenemethyl (meth)acrylate, 1-Ethylcyclohexyl (meth)acrylate, 1-Methylcyclohexyl (meth)acrylate, 1-Ethylcyclopentyl (meth)acrylate, 1-Methylcyclopentyl (meth)acrylate, Dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate,Tetrahydrodicyclopentadienyl (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, isobornylcyclohexyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 1-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 2-methyl-2-adamantanyl (meth)acrylate, 2-ethyl-2-adamantanyl (meth)acrylate, 2-isopropyladamantan-2-yl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, (adamantan-1-yloxy)methyl (meth)acrylate, 2-Isopropyl-2-adamantyl (meth)acrylate, 1-methyl-1-ethyl-1-adamantyl methanol (meth)acrylate, 1,1-diethyl-1-adamantyl methanol (meth)acrylate, 2-cyclohexylpropan-2-yl (meth)acrylate, 1-isopropylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, tetrahydropyranyl (meth)acrylate, tetrahydro-2-furanyl (meth)acrylate, 2-oxotetrahydrofuran-3-yl (meth)acrylate, It may be at least one selected from the group consisting of mono(meth)acrylates of polyhydric alcohols such as (5-oxotetrahydrofuran-2-yl)methyl(meth)acrylate, (2-oxo-1,3-dioxolan-4-yl)methyl(meth)acrylate, 1-ethoxyethyl(meth)acrylate, succinic acid mono(2-acryloyloxyethyl) ester, acryloyl morpholine, N-vinylpyrrolidone, etc., but is not limited thereto. The (meth)acrylate-based monofunctional monomer may be one kind of compound or a mixture of two or more different compounds.

[0046] For example, (meth)acrylate-based multifunctional monomers include ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, Bifunctional (meth)acrylates such as hydroxypivalic neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, isocyanurate di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane Trifunctional (meth)acrylates such as tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, isocyanuric acid EO-modified tri(meth)acrylate, etc., tetrafunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate,It may be at least one selected from the group consisting of (meth)acrylates having five or more functional groups, such as propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate, but is not limited thereto. The (meth)acrylate-based multifunctional monomer may be one type of compound or a mixture of two or more different compounds.

[0047] In one embodiment of the present invention, the curable resin composition further includes a polyfunctional monomer, and the viscosity of the polyfunctional monomer may be 5 to 500 cps when measured with a cone-plate viscometer at 25°C and 5 rpm.

[0048] In one embodiment of the present invention, the curable resin composition contains a (meth)acrylate-based monofunctional monomer and a (meth)acrylate-based multifunctional monomer together, thereby having an effect of obtaining a viscosity and crosslinking density suitable for inkjet.

[0049] In one aspect, the (meth)acrylate-based monofunctional monomer and the (meth)acrylate-based multifunctional monomer may include a polar functional group capable of forming a cross-linking bond. The polar functional group may be at least one selected from the group consisting of a hydroxyl group, a morpholino group, a carboxyl group, an amino group, an amine group, a carbonyl group, an acrylic group, an acryloyl group, a nitrile group, a vinyl group, a halogen group, a urethane group, and an ester group, but is not limited thereto.

[0050] For example, the (meth)acrylate-based monofunctional monomer may include a (meth)acrylate having at least one of a morpholino group and a hydroxyl group. The content of the (meth)acrylate having the morpholino group or the hydroxyl group may be 5 to 50 wt% or 10 to 40 wt% based on the total weight of the curable resin composition. If it is less than the above range, the sensitivity of the composition to the LED lamp may be weakened, unreacted substances may exist, and this may reduce resistance to acids or alkalis. If it is more than the above range, over-curing may occur, which may increase the occurrence of cracks when folding or bending.

[0051] In one embodiment of the present invention, the content of the (meth)acrylate-based monofunctional monomer may be 20 to 95 wt%, 30 to 95 wt%, or 50 to 95 wt%, based on the total weight of the curable resin composition. The composition may include a solid content and a solvent. In one embodiment of the present invention, the (meth)acrylate-based monofunctional monomer may include at least one water-soluble monomer and at least one water-insoluble monomer. The water-soluble monomer may include a polar functional group.

[0052] In one embodiment of the present invention, the content of the water-soluble monomer may be 15 to 50 wt% based on the total weight of the composition.

[0053] In one embodiment of the present invention, the content of the (meth)acrylate-based multifunctional monomer may be 5 to 15 wt%, 6 to 15 wt%, or 7 to 15 wt% based on the total weight of the curable resin composition.

[0054] [Photopolymerization initiator]

[0055] There are no particular limitations on the photopolymerization initiator, as long as it can polymerize (meth)acrylate upon irradiation with energy rays. A radical polymerization initiator can be used. For example, there are no particular limitations on the photopolymerization initiator, as long as it absorbs light in the wavelength range of 300 nm to 450 nm. One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

[0056] In one embodiment of the present invention, the photopolymerization initiator may be at least one of a phosphine oxide type or a hydrogen-abstracting type.

[0057] Specific examples of the photopolymerization initiator include bisacylphosphine oxides such as bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, and bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; Monoacylphosphine oxides such as 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate; Hydroxyacetophenones such as 1-hydroxy-cyclohexylphenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ethers; Benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone;Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and N,N-dimethylaminoacetophenone; Thioxanthones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diethyl-9H-thioxanthen-9-one, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, and p-dimethylbenzoic acid ethyl ester; Oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); titanocenes such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyrrol-1-yl)ethyl)phenyl]titanium, and bis(2,6-difluoro-3-(1-hydropyrrol-1-yl)phenyl)titanocene; Examples include phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, and tetramethylthiuram disulfide.

[0058] Commercially available products of α-aminoacetophenone-based photopolymerization initiators include Omnirad 907, 369, 369E, 379, and Esacure ONE manufactured by IGM Resins. In addition, commercially available products of acylphosphine oxide-based photopolymerization initiators include Omnirad TPO, TPO-L, and 819 manufactured by IGM Resins, and Mosaphoto 348 manufactured by UFC Corporation. Commercially available products of oxime ester photopolymerization initiators include Irgacure OXE01 and OXE02 manufactured by BASF Japan Co., Ltd., N-1919 and ADEKA Acruze NCI-831 and NCI-831E manufactured by ADEKA Co., Ltd., and TR-PBG-304 manufactured by Changzou Tronly New Electronic Materials Co., Ltd. Commercial products of thioxanthone photopolymerization initiators include ITX manufactured by Zhejiang Shou & Fu Chemtrade Co., Ltd. and SPEEDCURE DETX manufactured by LAMBSON FINE CHEMICALS LTD. Commercial products of titanocene photopolymerization initiators include Mosaphoto 533 manufactured by UFC Corporation.

[0059] For example, the photopolymerization initiator may be at least one selected from the group consisting of a phosphine oxide compound, a thioxanthone compound, and a benzoate compound. For example, if the photopolymerization initiator is an acylphosphine oxide compound or a thioxanthone compound, curing of the resin composition is possible with LED light of 300 to 395 nm.

[0060] In the resin composition of the present invention, the content of the photopolymerization initiator may be 1 to 10 wt%, or 1 to 8 wt%, based on the total composition.

[0061] If the photopolymerization initiator content is less than 1 wt%, unreacted materials may be present due to insufficient photocuring, and film properties such as chemical resistance may deteriorate. On the other hand, if it exceeds 10 wt%, the film surface may become over-cured, and differences in the degree of curing may occur in the deeper portions, resulting in poor adhesion.

[0062] In combination with the above-mentioned photopolymerization initiator, a photoinitiation aid or sensitizer may be used. Examples of the photoinitiation aid or sensitizer include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. In particular, thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone can be used. By including a thioxanthone compound, deep curing property can be improved. These compounds can be used as photopolymerization initiators, but can also be used in combination with a photopolymerization initiator. In addition, the photoinitiation aid or sensitizer may be used alone or in combination of two or more types.

[0063] Furthermore, since these photopolymerization initiators, photoinitiation aids, and sensitizers absorb specific wavelengths, in some cases, sensitivity is lowered and they function as ultraviolet absorbers. However, they are not used solely for the purpose of improving the sensitivity of the resin composition. If necessary, they can increase the photoreactivity of the surface by absorbing light of a specific wavelength, change the line shape and aperture of the resist pattern to a vertical, tapered, or reverse taper shape, and also improve the precision of the line width or aperture diameter.

[0064] [coloring agent]

[0065] The resin composition of the present invention may contain a colorant.

[0066] The colorant may include one or more types of red colorant, green colorant, blue colorant, yellow colorant, white colorant, black colorant, and other colorants in appropriate combinations. Any pigment, dye, or pigment may be used. Specifically, a colorant with a Color Index (CI; published by The Society of Dyers and Colorists) number may be used. However, from the perspective of reducing environmental impact and human health, it may be a colorant that does not contain halogen.

[0067] Examples of red colorants include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone.

[0068] As green colorants, there are also metal-substituted or unsubstituted phthalocyanine, anthraquinone, and perylene compounds.

[0069] The blue colorant may be any pigment, dye, or pigment, but may preferably be one that does not contain a halogen atom. Examples of blue colorants include phthalocyanine and anthraquinone compounds, and pigment compounds include compounds classified as pigments, specifically, the following: Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60. Examples of dye compounds include Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds may also be used. The blue colorant may be used alone or in combination of two or more.

[0070] Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone.

[0071] Examples of white colorants include titanium oxides of rutile and anatase types.

[0072] Examples of black colorants include titanium black, carbon black, graphite, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, aniline pigments, molybdenum sulfide, and bismuth sulfide.

[0073] Other than that, you can also add colorants such as purple, orange, and brown to adjust the color tone.

[0074] [Other optional ingredients]

[0075] The resin composition of the present invention may contain, as necessary, one or more of the following materials as optional components.

[0076] Epoxy resin

[0077] The epoxy resin of the present invention may be a known, commonly used compound having one or more epoxy groups. For example, it may be a compound having two or more epoxy groups. For example, it may be a compound having two or more epoxy groups in one molecule, such as a monoepoxy compound such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl (meth)acrylate, bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic ring epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4'-diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris(2,3-epoxypropyl)isocyanurate, triglycidyltris(2-hydroxyethyl)isocyanurate. These can be used alone or in combination of two or more types to suit the required characteristics.

[0078] Antioxidant

[0079] The resin composition of the present invention may also contain an antioxidant. By including an antioxidant, not only can the curable resin and other components be prevented from oxidative degradation, thereby suppressing discoloration, but also improved heat resistance and improved resolution (line width reproducibility) can be achieved. Specifically, while some colorants can deteriorate resolution by reflecting and absorbing light, the inclusion of an antioxidant ensures good resolution regardless of the colorant type.

[0080] Weapon Refill

[0081] A curable resin composition according to one embodiment of the present invention is used to improve properties such as adhesion and hardness by including an inorganic filler. In addition, the inorganic filler can be used as a colorant.

[0082] The inorganic filler may be, for example, one or more selected from the group consisting of titanium oxide, zinc oxide, carbon black, basic carbonates, basic sulfates, sulfates, zinc sulfide, antimony oxide, aluminum hydroxide, silica, and barium sulfate.

[0083] For example, the manufacturing method of titanium oxide can be either the sulfuric acid method or the chlorine method, and for example, the chlorine method may be used. For example, the manufacturing process may not use sulfuric acid. Furthermore, the surface treatment of titanium oxide is not particularly limited, but may be titanium oxide treated with an acid other than sulfuric acid, such as hydrochloric acid, nitric acid, phosphoric acid, or acetic acid, during neutralization.

[0084] The titanium oxide may be of any structure, including rutile, anatase, and Ramsdelight types, and may be used alone or in combination of two or more types. Among these, Ramsdelight type titanium oxide is Ramsdelight type Li. 0.5 TiO2 can be obtained by performing chemical lithium oxide removal treatment.

[0085] Among the above, the use of rutile-type titanium oxide can further improve heat resistance, make it difficult for discoloration due to light irradiation to occur, and make it difficult for quality to deteriorate even in a strict usage environment. In particular, the heat resistance can be improved by using rutile-type titanium oxide surface-treated with aluminum oxide such as alumina. The content of rutile-type titanium oxide surface-treated with aluminum oxide in the total titanium oxide is, for example, 35 mass% or more, for example, 55 mass% or more, and the upper limit is 100 mass% or less, that is, the entire amount of titanium oxide may be rutile-type titanium oxide surface-treated with the above aluminum oxide. In addition, since anatase-type titanium oxide has a lower hardness than rutile-type titanium oxide, the formability of the composition is further improved when anatase-type titanium oxide is used.

[0086] Among the inorganic fillers, titanium oxide may have a sulfur concentration of 100 ppm or less, or 50 ppm or less. Commercially available titanium oxide with a sulfur concentration of 100 ppm or less may be used, or commercially available titanium oxide with a sulfur concentration of 100 ppm or more may be mixed with the sulfur concentration reduced by heat treatment, chemical treatment, washing, or calcination. Here, the sulfur contained in the titanium oxide refers to all sulfur detected through analysis. It includes sulfur adsorbed on the titanium oxide and sulfur coated as an impurity on the titanium oxide. The titanium oxide may also have a sodium concentration of 100 ppm or less, or 50 ppm or less. A lower sodium concentration is preferable. If the sodium concentration is too high, the copper substrate may accelerate corrosion or oxidation when exposed to moisture due to sodium ions. For this reason, the concentration of sodium ions may be less than 100 ppm.

[0087] In addition, the curable resin composition of the present invention may contain titanium oxide having a sulfur concentration of 100 ppm or more, as long as the effects of the present invention are not impaired. Titanium oxide having a sulfur concentration of 100 ppm or more includes CR-58, CR-90, and R-630 from Isahara Sangyo Co., Ltd., and R-21 from Sakai-chem Co., Ltd.

[0088] In addition, rutile type chlorinated titanium dioxide such as T-550, T-580, R-630, R-820, CR-50, CR-60, R-90, CR-97 manufactured by Ishihara Sangyo Co., Ltd., Ti PURE R-706, R-902+, R931 manufactured by DuPont, TR-600, TR-700, TR-840 manufactured by Fuji Titanium Industry Co., Ltd., and KR-270, KR-310, KR-380 manufactured by Titanium Industry Co., Ltd. can be used.

[0089] If the particle size of titanium oxide is too small, its fluidity may be poor, and conversely, if it is too large, its insertability into small diameter substrates may be poor. Considering these factors, the median particle size of the titanium oxide is in the range of 0.1 to 5 ㎛, for example, in the range of 0.1 to 1 ㎛, for example, in the range of 0.1 to 0.5 ㎛, and may be 0.36 ㎛. When the particle size of the titanium oxide is within the above range, it can exhibit high reflectivity. The above particle size was measured using a laser diffraction method.

[0090] Among inorganic fillers, barium sulfate includes precipitated barium sulfate #100, precipitated barium sulfate #300, precipitated barium sulfate SS-50, BARIACE B-30, BARIACE B-31, BARIACE B-32, BARIACE B-33, BARIACE B-34, BARIFINE BF-1, BARIFINE BF-10, BARIFINE BF-20, BARIFINE BF-40 (manufactured by Sakai Kagaku Kogyo Co., Ltd.), W-1, W-6, W-10, C300 (manufactured by Takehara Kagaku Kogyo Co., Ltd.), etc.

[0091] Among inorganic fillers, silica particles are not particularly limited and can be obtained by methods known to those skilled in the art. For example, they can be manufactured by burning silicon powder using the VMC (Vaporized Metal Combustion) method. The VMC method is a method in which a chemical flame is formed by a burner in an atmosphere containing oxygen, and a metal powder constituting a portion of the target oxide particles is injected into the chemical flame in an amount that forms a dust cloud, thereby causing knocking to obtain oxide particles. Examples of commercially available silica include the SO series manufactured by Admatex Co., Ltd. and the HPS series manufactured by Toagosei Co., Ltd. (HPS-0500, HPS-1000, HPS3500, etc.).

[0092] Among inorganic fillers, carbon black can be used as a black-based colorant. Specifically, the carbon black may have a particle diameter of greater than about 0 nm and less than or equal to about 30 nm, for example, from about 10 nm to about 30 nm. The particle diameter of the carbon black can be derived by measuring the diameter of the projected image when the carbon black is projected with parallel light in a certain direction. When the particle diameter of the carbon black satisfies the above range, the dispersibility within the curable resin composition is improved. Examples of the carbon black include Carbon Black, M-40, M-45, M-50, MA-8, and MA-100 manufactured by Mitsubishi Chemical Corporation, and Carbon Black 1255 manufactured by Columbia Chemical Company.

[0093] For example, there is no particular limitation on the inorganic filler, but when titanium oxide is used, it can be used in combination with a photopolymerization initiator that absorbs light at 350 nm to 450 nm, and from the viewpoint of coloring, it can be used in combination with a photopolymerization initiator of an acylphosphine oxide compound.

[0094] Other additives

[0095] In addition, the resin composition of the present invention may contain other commonly known additives in the field of electronic materials. Examples of such additives include thermal polymerization inhibitors, ultraviolet absorbers, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial and antifungal agents, antifoaming agents, leveling agents, thickeners, fluidity additives, adhesion-imparting agents, thixotropic agents, photoinitiation aids, sensitizers, curing accelerators, release agents, surface treatment agents, dispersants, dispersing aids, surface modifiers, stabilizers, and the like.

[0096] The curable resin composition of the present invention may not be stripped by water. The curable resin composition of the present invention may not be stripped by an acidic solution or an alkaline solution.

[0097] The curable resin composition of the present invention is peeled off by an organic solvent, and the organic solvent may have metal corrosive properties.

[0098] The above organic solvent may be an organic solvent including a glycol solvent, an alcohol solvent, an acetate solvent, or a mixture thereof, and may be capable of being peeled at 20°C to 40°C.

[0099] The curable resin composition of the present invention is capable of LED curing, and thus curing can be performed by a UV LED lamp.

[0100] The curable resin composition of the present invention can be used as an etching resist, and a coating film formed by curing it can be used as an etching resist. The coating film can be peeled off using an organic solvent.

[0101] [Etching resist film and its manufacturing method]

[0102] The etching resist film of the present invention can be formed by curing the curable resin composition of the present invention.

[0103] The etching resist film of the present invention can be suitably used for printed circuit boards, electronic components, etc.

[0104] In addition, by simply irradiating the etching resist film with an active energy ray, it is possible to form a cured film for etching resist with excellent properties such as acid resistance and alkali resistance by finally curing it.

[0105] The exposure device used for the above active energy ray irradiation may be a device equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc., and may irradiate ultraviolet (UV) rays in the range of 300 to 450 nm, and may also be a direct drawing device (e.g., a laser direct imaging device that directly draws an image with a laser based on CAD data of a computer). The laser light source of the direct drawing device may have a maximum wavelength in the range of 300 to 450 nm. The exposure for image formation varies depending on the thickness, etc., but is generally 5 to 1000 mJ / cm. 2 It can be 10 to 800 mJ / cm 2 It could be.

[0106] <Example>

[0107] Hereinafter, the present invention will be described in detail using examples. The present invention is not limited to the following examples.

[0108] Preparation of curable resin composition

[0109] The raw materials were placed in a container and stirred to prepare a composition. The contents of each component are as shown in Table 1 below.

[0110] Table 1. Content and properties of each component of the composition (unit: calculated as 100 parts by weight of the total of monomers and oligomers of Example 1)

[0111]

[0112] The details of each component shown in Table 1 above are as follows.

[0113]

[0114] LED curability evaluation

[0115] The ink compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were inkjet printed on a glass substrate to form a film, and then 300 mJ / cm was used using an LED (FJ100 (8W) from Phoseon) with a wavelength of 365 nm. 2 It was photocured. The hardening properties were evaluated based on the following criteria and are shown in Table 2.

[0116] ◎: Complete curing of the coating

[0117] ○: Tacky

[0118] △: Ink is smeared on the surface

[0119] ×: Not hardened

[0120] Evaluation of water resistance, acid resistance, and alkali resistance

[0121] The coating films of Examples 1 to 4 and Comparative Examples 1 to 4, which were photocured as described above, were each immersed in water at 80°C for 10 minutes, immersed in a 10 wt% HNO3 aqueous solution at 50°C for 3 minutes, or immersed in a 10 wt% NaOH solution at 50°C. After immersion in an aqueous solution for 3 minutes, water resistance, acid resistance, and alkali resistance were evaluated based on the following criteria, and are shown in Table 2.

[0122] ◎: No deformation of the film

[0123] ○: The coating has not peeled off, but the gloss has decreased.

[0124] △: The coating did not peel off, but dissolution occurred on the surface.

[0125] ×: Occurrence of peeling of the coating

[0126] Pencil hardness test

[0127] As described above, a pencil from B to 9H, polished to make the tip flat, was pressed at an angle of about 45° on the coating films of Examples 1 to 4 and Comparative Examples 1 to 4 that had undergone photocuring, and the hardness of the pencil at which peeling of the coating film did not occur was recorded, and is shown in Table 2.

[0128] Adhesion evaluation

[0129] After forming the coating films of Examples 1 to 4 and Comparative Examples 1 to 4 through photocuring as described above, adhesion was evaluated using 3M tape.

[0130] ◎: There will be no peeling of the film and no ink residue on the tape.

[0131] ○: No peeling of the film, and ink components are absorbed into the tape.

[0132] ×: All the pieces fall off.

[0133] Organic solvent stripping performance evaluation

[0134] The coating films of Examples 1 to 4 and Comparative Examples 1 to 4, which were photocured as described above, were immersed in NMP (N-methyl-2-pyrrolidone) and PMA (propylene glycol methyl ether acetate), respectively, and the peeling completion time was measured and evaluated according to the following criteria, which are shown in Table 2.

[0135] ◎: Peeled off within 2 minutes

[0136] ○: Peeled off within 4 minutes

[0137] △: Peeled off within 6 minutes

[0138] ×: No peeling for 8 minutes

[0139] Separately, for the coating of Example 1, the peeling time for organic solvents was evaluated and shown in Table 3.

[0140] Table 2. Evaluation Results

[0141]

[0142] Referring to Table 2, the curable resin compositions of Examples 1 to 4 contain a monofunctional monomer but do not have an acid value, so the resulting coating film is resistant to acid or alkaline aqueous solutions, and because the crosslinking density of the coating film is low, it can be easily peeled off even with an organic solvent. In particular, the coating films of Examples 1 to 4 exhibited excellent peelability not only to NMP, a solvent known to generate toxic gases, but also to PMA, a solvent that does not generate toxic gases.

[0143] In addition, it can be confirmed that the curable resin compositions of Examples 1 to 4 are well cured even when using an LED lamp, and the resulting coating film has the characteristics of an excellent etching resist.

[0144] Table 3. Evaluation Results

[0145]

[0146] * KOCOSOL: naphtha solvent (petroleum), heavy aromatic

[0147] * DPM: Dipropylene glycol monomethyl ether

[0148] * DPM-Ac: Dipropylene glycol methyl ether acetate

[0149] * Butyl Carbitol: Diethylene glycol monobutyl ether

[0150] Referring to Table 3, it can be confirmed that the coating formed by the composition of the present invention is peelable for all various organic solvents.

Claims

1. (Meth)acrylate monofunctional monomer; and Containing a photopolymerization initiator, Does not contain polymers having a weight average molecular weight of 5000 or more, An organic solvent-released curable resin composition having no acid value.

2. An organic solvent-released curable resin composition according to claim 1, wherein the (meth)acrylate-based monofunctional monomer comprises a monomer containing at least one of a morpholino group and a hydroxyl group.

3. An organic solvent-released curable resin composition according to claim 1, wherein the (meth)acrylate-based monofunctional monomer comprises at least one water-soluble monomer and at least one water-insoluble monomer.

4. An organic solvent peelable curable resin composition according to claim 1, wherein the content of the water-soluble monomer is 15 to 50 wt% based on the total weight of the composition.

5. An organic solvent peelable curable resin composition in the first paragraph, wherein the content of the (meth)acrylate-based monofunctional monomer is 20 to 95 wt% based on the total weight of the composition.

6. An organic solvent peeling curable resin composition according to claim 1, further comprising a polyfunctional monomer, and having a viscosity of 5 to 500 cps when measured with a cone-plate viscometer at 25°C and 5 rpm.

7. An organic solvent peelable curable resin composition in claim 6, wherein the content of the multifunctional monomer is 15 wt% or less based on the total weight of the composition.

8. An organic solvent peeling type curable resin composition according to claim 1, wherein the photopolymerization initiator is at least one of a phosphine oxide type or a hydrogen abstraction type.

9. An organic solvent peelable curable resin composition according to claim 1, wherein the content of the photopolymerization initiator is 1 to 10 wt% based on the total weight of the composition.

10. An organic solvent peelable curable resin composition according to claim 1, further comprising a colorant in an amount of 0.1 to 10 wt% based on the total weight of the composition.

11. An organic solvent peelable curable resin composition having a viscosity of 1 to 50 cps at 25°C in the first paragraph.

12. An organic solvent peelable curable resin composition according to claim 1, wherein the organic solvent does not have metal corrosiveness.

13. An organic solvent-peelable curable resin composition capable of being peeled at 20°C to 40°C using an organic solvent including a glycol solvent, an alcohol solvent, an acetate solvent, or a mixture thereof, in accordance with the first paragraph.

14. An organic solvent peelable curable resin composition capable of LED curing in the first paragraph.

15. A coating film for etching resist formed by curing an organic solvent-released curable resin composition according to any one of claims 1 to 14.

16. A coating film for etching resist, wherein the curing can be performed using only a UV LED lamp in the 15th paragraph.

17. A coating film for etching resist that can be peeled off in an organic solvent in the 15th paragraph.

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