KR20110034553A - Dry film photoresist - Google Patents

Abstract

The present invention relates to a dry film photoresist, specifically, the dry film photoresist according to the present invention is capable of performing the exposure process with the support film removed, thereby improving the resolution by preventing adverse effects of the exposure effect by the support film. Can be. Furthermore, even if exposure is performed in a state where the resin protective layer is present, a decrease in transparency or a developing speed due to the resin protective layer do not occur and high resolution can be achieved. In addition, mixing between the resin protective layer and the photosensitive resin layer according to the present invention does not occur, so that the glossiness of the surface of the photosensitive resin layer is excellent even after development.

Description

Dry Film Photoresist {DRY FILM PHOTORESIST}

The present invention relates to a dry film photoresist having a multilayer structure.

Dry film photoresist has been used as an important material for the current electrical and electronic industries, especially printed circuit boards, since it was developed under the name RISTON by DuPont in 1968.

About 50% of photoresist is used as a photoresist material for forming circuits on printed circuit boards, but dry film photo is used for the production of printed circuit boards of double-sided and multilayer boards requiring high density and high reliability. Resist is essentially used.

The dry film photoresist is mainly laminated in a two-layer structure of a base film and a photosensitive layer, and further a protective film is used to protect the photosensitive resin layer until the dry film photoresist is used. Include.

Generally, the support film uses a polyester film such as polyethylene terephthalate, and its thickness is about 25 μm. Such a support film serves as a support of the photosensitive resin layer during the manufacture of the dry film photoresist, and facilitates handling during exposure of the photosensitive resin layer having adhesive force.

Photosensitive resin is divided into negative type and positive type by the reaction mechanism by light. In the case of negative type photosensitive resin, photocrosslinking reaction occurs at the exposed part, and unexposed part is washed with alkali, leaving a resist pattern. In the case of the photosensitive resin, a photolysis reaction occurs at an exposure site and is developed in an alkali, and an unexposed site remains to form a resist pattern.

The photosensitive resin layer is prepared to suit the purpose, including a photopolymerizable monomer, a photopolymerization initiator, a binder polymer, and the like. Such a photosensitive resin layer is applied on a support film, and has a thickness of 15 to 100 µm, after application, to suit the purpose of use. Such a photosensitive resin layer has various compositions according to the mechanical and chemical properties required for the photoresist and the conditions such as processing.

On the other hand, the protective film prevents damage to the resist during handling and serves as a protective cover to protect the photosensitive resin layer from foreign substances such as dust, and is laminated on the back surface where the support film of the photosensitive resin layer is not formed.

As an example of a pattern forming method using such a dry film photoresist, a protective film is first peeled off and laminated on a copper clad laminate (CCL) when applied to a printed circuit board, followed by a mask having a desired pattern. Is exposed by irradiation with ultraviolet (UV) light and then developed using a suitable solvent to wash away the uncured parts.

In general, in the case of using a dry film photoresist having such a composition, since the support film is attached to the photosensitive resin layer during exposure, the photosensitive resin layer and the mask are separated by the thickness of the support film, and as a result, there is a limit to improving the resolution. have. In addition, when irradiated with ultraviolet light to expose the ultraviolet light is transmitted through the support film affects the ultraviolet transmittance, there is a limit in implementing a high resolution by ultraviolet scattering by the particles inside the support film.

In order to solve this problem, the support film may be peeled off and then exposed, but the photosensitive resin layer may be tacky, and when the support film is peeled off, the mask may stick to the photosensitive resin layer, resulting in damage to the photosensitive resin layer. The problem is that the resolution is lowered, the mask is contaminated, and the life of the mask is shortened.

Therefore, in reality, the exposure after peeling off the support film is difficult to be achieved, and thus the problem of resolution reduction remains.

Furthermore, as the density of printed circuit boards and semiconductor packaging technologies have increased, the density of circuit lines has been increased, so there is an urgent need for high resolution dry film photoresists applicable to such microcircuit boards.

The present invention provides a dry film photoresist having excellent glossiness of the photosensitive resin layer after development, by improving the resolution by allowing the exposure process to be carried out in a state where the support film is removed and without mixing between the resin protective layer and the photosensitive resin layer. .

One embodiment of the present invention comprises a support film, a resin protective layer and a photosensitive resin layer by laminating sequentially, the resin protective layer comprises a water-soluble polymer having a weight average molecular weight of 5000 to 300000, the haze of the resin protective layer Is 3.0% or less, and the developing time per micrometer of the resin protective layer is 10 seconds or less.

Another embodiment of the present invention is a dry film photoresist wherein the water-soluble polymer comprises polyvinyl alcohol having a degree of saponification of 75 to 97%.

Another embodiment of the present invention is a dry film photoresist in which the resin protective layer comprises polysilicon.

Another embodiment of the present invention is a dry film photoresist wherein the resin protective layer is contained in an amount of 0.01 to 3 parts by weight of polysilicon based on 100 parts by weight of the water-soluble polymer.

According to another embodiment of the present invention, the polysilicon has a particle size of 1 μm or less upon dissolving 0.1 g of polysilicon under a condition of 80 ° C. for 6 hours in 100 g of any one solvent selected from water, alcohols, and mixtures thereof. Film photoresist.

Another embodiment of the present invention is a dry film photoresist wherein the resin protective layer is less than 10㎛ thickness.

Another embodiment of the present invention is a dry film photoresist having an adhesive force of 0.0005 to 0.01 N / cm between the support film and the resin protective layer.

Another embodiment of the present invention is a dry film photoresist wherein the photosensitive resin layer has a glossiness after development of 15 or more at 20 ° and 60 or more at 60 °.

Another embodiment of the present invention is a dry film photoresist further comprising a protective film on one surface of the photosensitive resin layer.

The dry film photoresist according to the present invention can be subjected to the exposure process with the support film removed, thereby ultimately improving the resolution by preventing adverse effects of the exposure effect by the support film.

Furthermore, even if exposure is performed in a state where the resin protective layer is present, a decrease in transparency or a developing speed due to the resin protective layer do not occur and high resolution can be achieved.

In addition, mixing between the resin protective layer and the photosensitive resin layer according to the present invention does not occur, so that the glossiness of the surface of the photosensitive resin layer is excellent even after development.

1 is an electron micrograph taken at 1200 times magnification of the surface of a printed circuit board after the developing process manufactured in Example 1 of the present invention.
FIG. 2 is an electron micrograph taken at 1200 times magnification of the surface of a printed circuit board after the developing process manufactured in Comparative Example 1. FIG.

According to an embodiment of the present invention, the support film, the resin protective layer and the photosensitive resin layer are sequentially laminated, and the resin protective layer includes a water-soluble polymer having a weight average molecular weight of 5000 to 300000, and the resin protective layer It is to provide a dry film photoresist having a haze of 3.0% or less and a developing time per μm of the resin protective layer of 10 seconds or less.

The dry film photoresist of the present invention has a structure in which a support film, a resin protective layer and a photosensitive resin layer are sequentially laminated and included.

Since the support film serves as a support of the resin protective layer and the photosensitive resin layer, it is preferable to have sufficient mechanical properties. More specifically, the support film includes a polyester film such as polyethylene terephthalate film and polyethylene naphthalate film; Polyolefin-based films such as polyethylene films, and polypropylene films; Polyvinyl-based films such as copolymer films of polyvinylchloride and vinyl acetate, polytetrafluoroethylene films, and polytrifluoroethylene films; Polyimide film; Polyamide-based films such as 6,6-nylon; Polyacetate-based films such as cellulose triacetate film and cellulose diacetate film; Polyacrylate-based films such as alkyl poly (meth) acrylate films; Polyacrylic films such as (meth) acrylic acid ester copolymer films; These etc. are mentioned, Preferably, a polyethylene terephthalate is mentioned in consideration of mechanical properties and economics.

The thickness of a support film can be selected according to arbitrary objectives in the range of 10-100 micrometers.

The resin protective layer contains a water-soluble polymer having a weight average molecular weight of 5000 to 300000, the resin protective layer has a haze of 3.0% or less, and a developing time per μm of the resin protective layer is 10 seconds or less.

In the case of using the dry film photoresist according to the present invention in the pattern forming method, an example is described. First, a protective film on one surface of the photosensitive resin layer in a dry film photoresist in which a support film, a resin protective layer and a photosensitive resin layer are sequentially laminated. If present, peel off the protective film and lamination so that one surface of the photosensitive resin layer and the upper part of the copper clad laminate (CCL) are in contact with each other. Then, the support film is removed, the mask of the desired pattern is applied on the resin protective layer, exposed by ultraviolet (UV) exposure, and the developing process of washing off the uncured portion using a suitable supernatant is performed. Rough

The developer is mostly composed of a water-soluble solvent. It is important that the resin protective layer is well dissolved in the water-soluble solvent of the developer so that the residue does not remain in the photosensitive resin layer after development, and this is one of the factors that improve the developability.

In particular, the water-soluble polymer included in the resin protective layer may decrease the solubility of the water-soluble polymer as the weight average molecular weight increases, so that the degree of washing in the developer.

This developability is also affected by the developing speed. The faster the developing speed of the resin protective layer is, the better. However, when the developing speed of the resin protective layer is slow, a large difference in developing time due to the thickness deviation of the resin protective layer is caused. Since the adhesive force may be reduced by washing more than necessary, or the resolution may be reduced by less washing, the developing speed of the resin protective layer should have an appropriate speed in consideration of the phenomenon of the photosensitive resin layer in order to form a precise pattern.

Therefore, the resin protective layer includes a water-soluble polymer having an appropriate weight average molecular weight in order to improve developability, and has an appropriate level of developing speed so that no residue remains and no damage is caused to the cured portion of the photosensitive resin layer. It is important.

On the other hand, as one of the methods for improving the resolution, it is important to form the pattern more precisely. In order to form a fine pattern, the light scattering degree to the resin protective layer during exposure should be low, so the haze value is required to be low. This is because light passes through the resin protective layer when the photosensitive resin layer is exposed in the dry film photoresist.

In the present invention, by including a resin protective layer having a haze of 3.0% or less, preferably 0.001 to 3.0%, and a developing time per micrometer of 10 seconds or less, preferably 0.1 to 10 seconds, the light transmittance at the time of exposure is increased and optimized With developing speed, resolution can be improved.

Specifically, since the haze of the resin protective layer is required to have a low value in order to lower the light scattering degree, the lower limit value is preferably lower, and in the case of more than 3%, the shape of the photosensitive resin layer that has been exposed and developed ( The side wall is not smooth and rough.

In addition, the developing speed of the resin protective layer is required to have a low value in order to improve the developability, the lower the lower limit is preferable, and if the developing time per 1㎛ exceeds 10 seconds according to the thickness deviation of the resin protective layer There is a problem that the difference in the development speed is generated so that the photosensitive resin layer is washed much more than necessary so that the adhesion may be reduced, or the less the washing, the lower the resolution.

In addition, the dry film photoresist of the present invention has a structure in which the resin protective layer is laminated between the support film and the photosensitive resin layer. Therefore, the support film is removed by removing the support film before the exposure process so that the exposure process can be performed. When the exposure process is performed in a state, damage on the photosensitive resin layer and contamination of the mask generated due to contact with the mask can be prevented, and an effect of preventing adverse effects due to particles contained in the support film can also be obtained.

On the other hand, the above-mentioned resin protective layer is required to have an adhesive force with an appropriate level in consideration of the case where the support film is removed, it should not damage the surface of the resin protective layer when removing the support film from the resin protective layer. It is preferable that the adhesive force between a support film and a resin protective layer is 0.0005-0.01 N / cm at the point. In detail, when the adhesive force is within the range, the support film and the resin protective layer are not separated when the protective film is removed during lamination, and the resin protective layer is damaged when the support film is removed before exposure. There is an advantage that can be removed without giving.

In addition, the resin protective layer comprises a water-soluble polymer having a weight average molecular weight of 5000 to 300000, preferably 5000 to 15000, more preferably 5000 to 10000. If the weight average molecular weight is less than 5000, the coating on the film becomes difficult, and the strength is weak, so that it is difficult to perform the protective function of the photosensitive resin layer. There is a risk of damage when peeling.

It does not specifically limit as a method of forming such a resin protective layer, The composition for resin protective layer formation can be melt | dissolved in the solvent containing the organic solvent and water, and can be formed by apply | coating and drying on a support film.

Examples of the water-soluble polymer include polyvinyl ether maleic anhydride, cellulose ether, carboxyl alkyl cellulose, carboxyl alkyl starch, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyamide, polyacrylic acid, polyethylene glycol, It may be formed from a composition containing a water-soluble polymer such as polypropylene glycol, gelatin, ethylene oxide polymer, starch and water-soluble salts thereof.

In particular, the water-soluble polymer according to the present invention may include polyvinyl alcohol having a saponification degree of 75 to 97%. The degree of saponification is a factor that affects the developability. When the degree of saponification is within the above range, the resin protective layer has an appropriate developing time to form the photosensitive resin layer, thereby reducing the adhesion and the resolution.

In addition, the resin protective layer is 10 micrometers or less, Preferably it is 0.001-10 micrometers, More preferably, it is 0.001-5 micrometers in thickness.

The resin protective layer described above is prepared by dissolving a water-soluble polymer and optionally polysilicon in an aqueous solvent including an organic solvent and water. Due to this aqueous solvent system can be washed well in the developer solution consisting of most water-soluble solvents. In addition, since the photosensitive resin layer in contact with the aqueous resin protective layer is made of an oil-based solvent system, it is possible to fundamentally prevent mixing between the aqueous resin protective layer and the oil-based photosensitive resin layer. If the resin protective layer is mixed with the photosensitive resin layer, the components of the resin protective layer remain in the photosensitive resin layer even after development or part of the photosensitive resin layer cured by exposure is developed, and thus the glossiness of the photosensitive resin layer is reduced. The problem that developability deteriorates may arise.

In the present invention, as the resin protective layer has an aqueous composition, it can be washed well in the developing solution, and the mixing with the photosensitive resin layer which is oil-based can be prevented. You can.

In the present invention, the glossiness of the photosensitive resin layer is measured after development, and is measured by using a gloss meter reading. The glossiness is according to KS definition (KS M ISO 2813: 2007).

Specifically, the glossiness (specular gloss) is the luminous flux and the refractive index irradiated by an object placed in the specular direction when the light source and the light receiving unit are set at a prescribed angle. When the glass having an index of 1.567 is placed on the reflecting surface, the mirror gloss values such as 20 °, 60 °, and 85 ° of the polished black glass having a refractive index of 1.567 are respectively 100. It is defined as

In this regard, it is preferable that the surface of the photosensitive resin layer has a glossiness of 20 ° to 15 or more and 60 ° to 60 or more after development, and mixing between the resin protective layer and the photosensitive resin layer does not occur when the glossiness is in the above range. It does not impair developability.

On the other hand, while irradiating light to the mask during the above-described exposure process, the closer the distance between the mask and the photosensitive resin layer can implement a high resolution. For this purpose, it is best to expose the mask on top of the photosensitive resin layer, but since the adhesiveness of the photosensitive resin layer causes the mask to adhere to the mask, not only the photosensitive resin layer is damaged but also the mask is contaminated. There was a limit to.

The present invention is required to have a low value of the thickness of the resin protective layer in order to implement a high resolution, the lower the lower limit is preferable, and therefore, by using a resin protective layer having a thickness of 10 ㎛ or less, to minimize the separation distance with the mask In addition, even when the support film is removed and subjected to exposure, damage to the photosensitive resin layer and contamination of the mask do not occur, so that the limitations of the conventional resolution can be overcome, and high resolution can thus be realized.

Meanwhile, the resin protective layer according to the present invention may include polysilicon.

The polysilicon serves to impart releasability to the resin protective layer, and may also affect adhesion and haze between the support film and the resin protective layer.

Such polysilicon is soluble in any one solvent selected from water, alcohols and mixtures thereof. If the polysilicon is dissolved in an organic solvent, it does not dissolve in water and alcohols or a mixed solvent thereof, so that the particle size is significantly increased, which is not preferable in the present invention.

The polysilicon has a particle size of 1 μm or less when dissolved in 0.1 g of polysilicon under conditions of 80 ° C. for 6 hours in a solution-type particle size measuring device, and it is preferable to dissolve all polysilicon. The lower the lower limit of the particle size, the better. When the particle size of the polysilicon is in the above range, it is possible to prevent a decrease in haze and to prevent a side wall from being lowered during circuit formation of the photosensitive resin layer.

The resin protective layer of the present invention may be included in an amount of 0.01 to 3 parts by weight of polysilicon based on 100 parts by weight of the aforementioned water-soluble polymer. The content of polysilicon relative to 100 parts by weight of the water-soluble polymer is preferably carried out within the above range in consideration of ease of application on the support film and haze of the resin protective layer after drying.

Meanwhile, the composition of the photosensitive resin layer may vary depending on whether the dry film photoresist is applied in a negative type or a positive type. The composition of the photosensitive resin layer according to such a negative type or positive type dry film photoresist may be generally selected as a photosensitive resin composition well known in the art.

For example, when the dry film photoresist is negative, the photosensitive resin layer may include an binder resin, a photopolymerizable compound, an ethylenically unsaturated compound, a photopolymerization initiator, and an additive.

As the binder resin, an acrylic polymer, polyester, polyurethane, or the like may be used. Of these, methacrylic copolymer (methacrylic copolymer) which is a kind of acrylic polymer is preferable. Copolymers of ethylenically unsaturated carboxylic acids and other monomers can be used as desired. As the methacrylic copolymer, a methacrylic copolymer including an acetoacetyl group may also be used. Methacrylic monomers usable for synthesizing the methacrylic copolymers include methyl methacrylate, methyl methacrylate, propyl methacrylate and butyl methacrylate. Butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, Dimethylaminoethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, and the like. have. As the ethylenically unsaturated carboxylic acid, monoacrylic acid (monoacrylic acid) such as acrylic acid, methacrylic acid, and crotonic acid is used. In addition, maleic acid, fumaric acid, dicarboxylic acids such as itaconic acid, or anhydrides thereof, half esters, and the like may also be used. Of these, acrylic acid and methacrylic acid are preferable. Other copolymerizable monomers include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, a-methylstyrene, Vinyl acetate, alkyl vinyl ether, and the like.

As the photopolymerizable monomer, an ethylenically unsaturated compound may be a monofunctional, bifunctional, trifunctional or higher polyfunctional monomer. The polyfunctional monomers include ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and propylene glycol dimethacrylate. (propylene glycol dimethacrylate), polypropylene glycol dimethacrylate, butylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexane 1,6-hexane glycoldimethacrylate, trimethylolpropane trimethacrylate, glycerin dimethacrylate, pentaerythritol dimethacrylate, penta Erythritol trimethacrylate (pentaerythritol trimethacrylate), Dipentaerythritol pentamethacrylate (dipentaerythritolpentamethacrylate), 2,2-bis (4-methacryloxydiethoxyphenyl) propane (2,2-bis (4-methacryloxydiethoxyphenyl) propane), 2-hydroxy-3-meta 2-hydroxy-3-methacryloyloxypropyl methacrylate, ethylene glycol diglycidylether dimethacrylate, diethylene glycol diglycidyl ether dimethacrylate (2-hydroxy-3-methacryloyloxypropyl methacrylate) diethylene glycol diglycidyl ether dimethacrylate, phthalic acid diglycidyl ester dimethacrylate, glycerine polyglycidyl ether polymethacrylate, and the like. The monofunctional monomers include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, and 2-hydroxybutyl methacrylate. 2-phenoxy-2-hydroxypropyl methacrylate, 2-methacryloyloxy-2 hydroxypropyl phthalate, 3 3-chloro-2-hydroxypropyl methacrylate, glycerin monomethacrylate, 2-methacryloyloxyethyl acid phosphate, Methacrylic acid of phthalic acid derivatives, N-methylol methacrylamide, and the like can be used. The monofunctional monomer may be used together with the multifunctional monomer.

Examples of the photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, Benzoin phenyl ether, benzyl diphenyl disulfide, benzyl dimethyl ketal, anthraquinone, naphthoquinone, 3,3-dimethyl- 4-methoxybenzophenone (3,3-dimethyl-4-methoxybenzophenone), benzophenone, p, p'-bis (dimethylamino) benzophenone (p, p'-bis (dimethylamino) benzophenone), p, p'-bis (diethylamino) benzophenone (p, p'-bis (diethylamino) benzophenone), p, p'-diethylaminobenzophenone (p, p'-diethylaminobenzophenone), pivalon ethyl ether ( pivalone ethyl ether), 1,1-dichloroacetophenone, pt-butyldichloroacetophenone, hexaaryl- Dimer of hexaaryl-imidazole, 2,2'-diethoxyacetophenone, 2,2'-diethoxy-2-phenylacetophenone (2,2'-diethoxy -2-phenylacetophenone), 2,2'-dichloro-4-phenoxyacetophenone, phenyl glyoxylate, a-hydroxy-isobutylphenone (2,2'-dichloro-4-phenoxyacetophenone) a-hydroxyisobutylphenone), dibenzospan, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-propanone (1- (4-

isopropylphenyl) -2-hydroxy-2-methyl-1-propanone), 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone (2-methyl- [4- (methylthio ) phenyl] -2-morpholino-1-propanone), tri-bromophenylsulfone, tribromomethylphenylsulfone, and the like can be used.

As the additive, a softening agent such as vinyl chloride resin may be included. Specific examples of the phthalic ester include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, and dioctyl phthalate. phthalate, diisodecyl phthalate, butylbenzyl phthalate, diisononyl phthalate, ethylphthalyl ethyl glycolate, dimethyl isophthalate, dimethylisophthalate, dichlorohexyl phthalate dichlorohexyl phthalate, and esters of fatty acids or arimatic acid, such as dioctyl adipate, diisobutyl adipate, dibutyl adipate, Diisodecyl adipate, dibutyl diglycodiate l

adipate), dibutyl sebacate, dioctyl sebacate, and the like. In the present invention, glycerol triacetate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributyl phosphate, trioctylphosphate, tributoxyethyl phosphate phosphate, tris-chloroethylphosphate, tris-dichloropropyl phosphate, triphenylphosphate, tricresyl phosphate, trixylenyl phosphate ), Cresyl diphenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, trilauryl phosphate, tricetyl phosphate , Tristearyl phosphate phosphate, trioleyl phosphate, triphenyl phosphite, tris-tridecyl phosphite, dibutyl hydrogen phosphite, dibutyl-butyl phosphate Dibutyl-butyl phosphonate, di (2-ethylhexyl) 2-ethylhexyl phosphonate, 2-ethylhexyl-2-ethylhexyl phosphonate (2-ethylhexyl-2 -ethylhexylphosphonate, methyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, dibutyl acid phosphate, monobutyl acid phosphate ), Octyl acid phosphate, dioctyl phosphate, isodecyl acid phosphate, monoisodecyl phosphate, decanoic acid phosphate It may also be used, such as softeners (decanol acid phosphate).

In addition, volatile organic glycerol (glycerin), trimethylolpropane (ethylene glycol), ethylene glycol (ethylene glycol), diethylene glycol (diethylene glycol), triethylene glycol (propylene glycol), dipropylene glycol (dipropylene glycol) or lower alkyl ethers thereof, lower fatty acid esters, higher fatty acids or their esters, higher fatty alcohols or esters thereof and the like can also be used as the softening agent of the present invention.

The binder resin, the photopolymerizable compound, the photoinitiator, and the additive contained in the negative photosensitive resin described above can be appropriately mixed and used according to any purpose.

Dry film photoresist according to an embodiment of the present invention may further include a protective film on one surface of the photosensitive resin layer. The protective film serves to protect the photosensitive resin layer from the outside, and when the dry film photoresist is easily applied to the post-process, the protective film needs proper release property and adhesion so as not to be released during storage and distribution.

Hereinafter, preferred examples and comparative examples of the present invention will be described. However, the following examples are only preferred embodiments of the present invention and the present invention is not limited to the following examples.

Example  1 to 6 and Comparative example  1 to 6

≪ Example 1 >

(a) 20 g of polyvinyl alcohol (KURARAY, PVA205) having a weight average molecular weight of 22000, saponification degree of 87%, and 0.1 g of polysilicon were dissolved in 100 g of butoxyethanol for 6 hours under the condition of 80 ° C. When the particle size of 0㎛ polysilicon (BYK, BYK-349, 0.25% of the solid content after drying) 0.05g was added to 100g of distilled water and stirred for 6 hours at 80 ℃ completely to prepare a composition for the resin protective layer. This was coated on a support film having a thickness of 16 μm (haze 2.3%, no surface treatment, polyethylene terephthalate film, FDFR-16 μm, KOLON) using a coating bar, and then dried at 80 ° C. for 10 minutes using a hot air oven to obtain a thickness. The resin protective layer of 3 micrometers was formed. In this case, when the polysilicon was dissolved in the solvent for 6 hours at 80 ° C., the particle size of 0 μm means that the polysilicon was almost completely dissolved in the solvent and no particulate was found. Unless otherwise specified, 'particle size 0 μm' means the same meaning as described above.

(b) A photosensitive resin composition was prepared in the composition and content used for UH-9200 series (Kolon). Specifically, photoinitiators were dissolved in methyl ethyl ketone and methyl alcohol as solvents, and then photopolymerizable oligomers and binder polymers were added and mixed for 1 hour using a mechanical stirrer to prepare a photosensitive resin composition.

(c) coating the photosensitive resin composition on a 19 μm thick protective film (silicon-released polyethylene terephthalate film, CY201-19um, KOLON) using a coating bar, and then using a hot air oven at 80 ° C. It dried for 1 minute and formed the photosensitive resin layer of 15 micrometers in thickness.

(d) Lamination was carried out at a pressure of 4kgf / ㎠ at 50 ℃ to contact the photosensitive resin layer of the film (c) film is dried and the resin protective layer of (a) to prepare a dry film photoresist having a thickness of 53㎛.

<Example 2>

A dry film photoresist having a thickness of 53 μm was prepared in the same manner as in Example 1, except that the following procedure was performed.

(a) Polysilicon (BYK) having a particle size of 0 μm when 10 g of polyvinyl alcohol (KURARAY Co., PVA217) having a weight average molecular weight of 75000, saponification degree 87%, and 0.1 g of polysilicon are dissolved in 100 g of butoxyethanol solvent. Inc., BYK-349, and 0.025 g of 0.25% to solids after drying was added to 100 g of distilled water and stirred at 80 ° C. for 6 hours to completely dissolve to prepare a resin protective layer composition. It was coated on a 16 μm thick support film (2.3% haze, no surface treatment, polyethylene terephthalate film, FDFR-16 μm, KOLON) using a coating bar, and then dried at 80 ° C. for 10 minutes using a hot air oven to obtain a thickness of 3 μm. A micrometer resin protective layer was formed.

<Example 3>

A dry film photoresist having a thickness of 53 μm was prepared in the same manner as in Example 1, except that the following procedure was performed.

(a) 10 g of polyethylene glycol (manufacturer: Sigma-Aldrich, 20,000 weight average molecular weight) and 0.1 g of polysilicon dissolved in 100 g of butoxyethanol solvent (BYK, BYK-349, dry) After 0.25% compared to the solid content) 0.025g into 100g of distilled water and stirred for 6 hours at 80 ℃ completely dissolved to prepare a composition for a resin protective layer. This was coated on a support film having a thickness of 16 μm (haze 2.3%, no surface treatment, polyethylene terephthalate film, FDFR-16 μm, KOLON) using a coating bar, and then dried at 80 ° C. for 20 minutes using a hot air oven to obtain a thickness. The resin protective layer of 3 micrometers was formed.

<Example 4>

A dry film photoresist having a thickness of 53 μm was prepared in the same manner as in Example 1, except that the following procedure was performed.

(a) Polysilicon (BYK) having a particle size of 0 µm when 20 g of polyvinyl alcohol (KURARAY, PVA205) having a weight average molecular weight of 22000 and a saponification degree of 87%, and 0.1 g of polysilicon are dissolved in 100 g of butoxyethanol solvent. Inc., BYK-349, 1.0 g of the solid content after drying) 0.2 g of distilled water was added to 100 g of distilled water and stirred at 80 ° C. for 6 hours to completely dissolve to prepare a resin protective layer composition. It was coated on the opposite side of the ILC of the support film (haze 0.7%, ILC (in-line coating) on one side, polyethylene terephthalate film, SDFR-16㎛, KOLON) having a thickness of 16 μm by using a coating bar, followed by a hot air oven. It was dried for 10 minutes at 80 ℃ using to form a resin protective layer of 3㎛ thickness.

Example 5

A dry film photoresist having a thickness of 56 μm was manufactured in the same manner as in Example 1, except that the following procedure was performed.

(a) Polysilicon (BYK) having a particle size of 0 µm when 20 g of polyvinyl alcohol (KURARAY, PVA205) having a weight average molecular weight of 22000 and a saponification degree of 87%, and 0.1 g of polysilicon are dissolved in 100 g of butoxyethanol solvent. Inc., BYK-349, 0.25% of solids after drying) 0.05g of distilled water was added to 100g of distilled water and stirred at 80 ° C for 6 hours to completely dissolve to prepare a resin protective layer composition. This was coated on a support film having a thickness of 16 μm (haze 2.3%, no surface treatment, polyethylene terephthalate film, FDFR-16 μm, KOLON) using a coating bar, and then dried at 80 ° C. for 10 minutes using a hot air oven to obtain a thickness. The resin protective layer of 6 micrometers was formed.

<Example 6>

A dry film photoresist having a thickness of 60 μm was manufactured in the same manner as in Example 1, except that the following procedure was performed.

(a) Polysilicon (BYK) having a particle size of 0 µm when 20 g of polyvinyl alcohol (KURARAY, PVA205) having a weight average molecular weight of 22000 and a saponification degree of 87%, and 0.1 g of polysilicon are dissolved in 100 g of butoxyethanol solvent. Inc., BYK-349, 0.25% of solids after drying) 0.05g of distilled water was added to 100g of distilled water and stirred at 80 ° C for 6 hours to completely dissolve to prepare a resin protective layer composition. This was coated on a support film having a thickness of 16 μm (haze 2.3%, no surface treatment, polyethylene terephthalate film, FDFR-16 μm, KOLON) using a coating bar, and then dried at 80 ° C. for 20 minutes using a hot air oven to obtain a thickness. A resin protective layer of 10 mu m was formed.

Comparative Example 1

(a) A photosensitive resin composition was prepared in the composition and content used for UH-9200 series (Kolon). Specifically, photoinitiators were dissolved in methyl ethyl ketone and methyl alcohol as solvents, and then photopolymerizable oligomers and binder polymers were added and mixed for 1 hour using a stirring machine to prepare a photosensitive resin composition.

(b) coating the photosensitive resin composition on a support film having a thickness of 16 μm (haze 2.3%, no surface treatment, polyethylene terephthalate film, FDFR-16 μm, KOLON) using a coating bar, and then using a hot air oven. It dried at 10 degreeC for 10 minutes, and formed the photosensitive resin layer of 15 micrometers in thickness.

(c) pressure of 4 kgf at 50 ° C. such that the photosensitive resin layer of the dried film (b) and the release layer of the protective film having a thickness of 19 μm (silicon release treated polyethylene terephthalate film, CY201-19 μm, KOLON) are in contact with each other. Lamination at / cm 2 to prepare a dry film photoresist having a thickness of 50㎛.

Comparative Example 2

A dry film photoresist having a thickness of 53 μm was prepared in the same manner as in Example 1, except that the following procedure was performed.

(a) Polysilicon (BYK) having a particle size of 0 µm when 20 g of polyvinyl alcohol (KURARAY, PVA205) having a weight average molecular weight of 22000 and a saponification degree of 87%, and 0.1 g of polysilicon are dissolved in 100 g of butoxyethanol solvent. Inc., BYK-349, after drying, 0.7 g of 3.0% of solids content was added to 100 g of distilled water, and stirred at 80 ° C. for 6 hours to completely dissolve to prepare a resin protective layer composition. This was coated on the opposite side of the ILC of the support film (haze 2.3%, no surface treatment, polyethylene terephthalate film, SDFR-16 μm, KOLON) having a thickness of 16 μm using a coating bar, and then heated at 80 ° C. using a hot air oven. It dried for 1 minute and formed the resin protective layer of 3 micrometers in thickness.

Comparative Example 3

A dry film photoresist having a thickness of 53 μm was prepared in the same manner as in Example 1, except that the following procedure was performed.

(a) Polysilicon having a particle size of 0 µm when 4 g of polyvinyl alcohol (F17) having a weight average molecular weight of 75000, saponification degree of 98%, and 0.1 g of polysilicon are dissolved in 100 g of butoxyethanol solvent. (BYK, BYK-349, 0.25% of the solid content after drying) 0.01g to 100g of distilled water and stirred at 80 ℃ for 6 hours to completely dissolve to prepare a composition for the resin protective layer. This was coated on a support film having a thickness of 16 μm (haze 2.3%, no surface treatment, polyethylene terephthalate film, FDFR-16 μm, KOLON) using a coating bar, and then dried at 80 ° C. for 20 minutes using a hot air oven to obtain a thickness. The resin protective layer of 3 micrometers was formed.

<Comparative Example 4>

A dry film photoresist having a thickness of 66 μm was prepared in the same manner as in Example 1, except that the following procedure was performed.

(a) Polysilicon (BYK) having a particle size of 0 µm when 20 g of polyvinyl alcohol (KURARAY, PVA205) having a weight average molecular weight of 22000 and a saponification degree of 87%, and 0.1 g of polysilicon are dissolved in 100 g of butoxyethanol solvent. Inc., BYK-349, 0.25% of solids after drying) 0.05g of distilled water was added to 100g of distilled water and stirred at 80 ° C for 6 hours to completely dissolve to prepare a resin protective layer composition. This was coated on a support film having a thickness of 16 μm (haze 2.3%, no surface treatment, polyethylene terephthalate film, FDFR-16 μm, KOLON) using a coating bar, and then dried at 80 ° C. for 20 minutes using a hot air oven to obtain a thickness. The resin protective layer of 16 micrometers was formed.

Comparative Example 5

A dry film photoresist having a thickness of 53 μm was prepared in the same manner as in Example 1, except that the following procedure was performed.

(a) 100 g of acrylic acid polymer (KOLON, KBP116) having a weight average molecular weight of 60000 was added to 100 g of methyl ethyl ketone, and stirred at 30 ° C. for 6 hours to completely dissolve to prepare a resin protective layer composition. It was coated on a 16 μm thick support film (2.3% haze, no surface treatment, polyethylene terephthalate film, FDFR-16 μm, KOLON) using a coating bar, and then dried at 80 ° C. for 10 minutes using a hot air oven to obtain a thickness of 3 μm. A micrometer resin protective layer was formed.

Comparative Example 6

A dry film photoresist having a thickness of 53 μm was prepared in the same manner as in Example 1, except that the following procedure was performed.

(a) 100 g of acrylic acid polymer (KOLON, KBP114) having a weight average molecular weight of 30000 was added to 100 g of methyl ethyl ketone, and stirred at 30 ° C. for 6 hours to completely dissolve to prepare a composition for a resin protective layer. It was coated on a 16 μm thick support film (2.3% haze, no surface treatment, polyethylene terephthalate film, FDFR-16 μm, KOLON) using a coating bar, and then dried at 80 ° C. for 10 minutes using a hot air oven to obtain a thickness of 3 μm. A micrometer resin protective layer was formed.

The weight average molecular weights of the water-soluble polymers of Examples 1 to 6 and Comparative Examples 2 to 6 were measured by the following method.

Weight average molecular weight measurement

The weight average molecular weight of the water-soluble polymer is 40 ° C using GFC (Gel Filtration Chromatography; Varian GPC system), Stationary Phase is (Plgel Mixed D) × 2, Mobile Phase: THF, 1.0ml / min, Injection: 100µl , Detection: The standard was measured by dissolving PS Standard (Polymer Standards Service, Mp 723000,219000,89300,52200,30300,7000,5000,2960) in THF at the concentration of 0.1% under the conditions of RI and 40C. . The sample was dissolved in THF at a concentration of 0.2% and filtered with a 0.45 μm PTFE syringe filter.

The adhesion of the dry film photoresist prepared by Examples 1 to 6 and Comparative Examples 1 to 6 was measured as follows.

Adhesive force measurement

<Adhesion between support film and resin protective layer>

The protective film of the dry film photoresist specimen having a width of 3 cm and a length of 20 cm was removed, and then laminated on the copper clad laminate at 110 ° C. at a speed of 2 m / min and a pressure of 4 kgf / cm 2. Then, the release force of the support film was measured using a UTM (4303 series, Instron) using a 10N load cell at a speed of 100 mm / min from a starting point of 5 cm to 8 cm at a starting point.

<Adhesion between the photosensitive resin layer and the protective film>

A universal testing machine (UTM) was used to release a protective film of a dry film photoresist specimen having a width of 3 cm and a length of 20 cm, using a 10 N load cell at a speed of 100 mm / min from a starting point of 5 cm to 8 cm. , 4303 series, Instron).

<Adhesion between resin protective layer and PET after peeling support film>

The protective film of the dry film photoresist specimen having a width of 3 cm and a length of 20 cm was removed, and the support film was removed after laminating the copper clad laminate at 110 ° C. at 4 kgf / cm 2 at a speed of 2 m / min. Herein, a PET film having a width of 4 cm, a length of 25 cm, and a thickness of 19 μm (FDFR, manufactured by Kolon Co., Ltd.) at 110 ° C. and 4 kgf / cm 2 at a rate of 2 m / min, and then releasing the PET film The force required to release using a 10N load cell at a speed of 100 mm / min from 5 cm to 8 cm from the starting point was measured using UTM (4303 series, Instron).

Table 1 shows the results of measuring the adhesive strength of the dry film photoresist prepared by Examples 1 to 6 and Comparative Examples 1 to 6.

The conditions for laminating the PET film are the same as the conditions for bonding with the mask during normal exposure, and the adhesive force of the support film measured at this time is between Examples 1 to 6 and Comparative Examples 2 to 6 between the resin protective layer and the PET film. Adhesion.

Adhesion (N / cm) Protective film Adhesion between Support Film and Resin Protective Layer Adhesion between resin protective layer and PET after peeling support film Example One 0.0017 0.0027 0.0010 2 0.0017 0.0031 0.0009 3 0.0017 0.0028 0.0027 4 0.0017 0.0024 0.0010 5 0.0017 0.0027 0.0010 6 0.0017 0.0027 0.0010 Comparative example One 0.0017 0.0047 ^* 0.0043 ^** 2 0.0017 0.0020 0.0009 3 0.0017 0.0053 0.0008 4 0.0017 0.0027 0.0010 5 0.0017 0.0028 0.0025 6 0.0018 0.0027 0.0026

(Note) The exceptional * in Table 1 means the adhesive force between the support film and the photosensitive resin layer, ** indicates the adhesive force between the photosensitive resin layer and the PET film after peeling off the support film.

As a result of the measurement, except for Comparative Example 3, it can be seen that the release force between the photosensitive resin layer and the protective film and the release force between the resin protective layer and the support film are in a range that does not impair workability. In the case of the adhesive strength of the protective layer and PET can be seen that the case of the Example is significantly lower than in Comparative Example 1.

From this, it can be seen that the adhesive force between the resin protective layer of the embodiment and the mask material generally used in the exposure conditions is very low, and thus it is easy to handle during exposure.

Property evaluation

Thereafter, the dry film photoresist prepared in Examples 1 to 6 and Comparative Examples 1 to 6 was formed on the printed circuit board by the following method, and then the characteristics of the dry film photoresist were evaluated.

(1) Formation on a printed circuit board

A brush preprocessor is used for the copper clad laminate (CCL) to form new copper surfaces and to form the appropriate surface finish. After acid treatment in 5% sulfuric acid solution, washed with water, dried and added to the laminator. The laminator used Hakuto Mach 610i and laminating the dry film photoresist prepared in Examples 1 to 8 and Comparative Examples 1 to 6 at 110 ° C. at a pressure of 4 kgf / cm 2 and a speed of 2 m / min. Did not carry. Then, the exposure was performed by irradiating with a UV exposure machine (Perkin Elmer OB-7120, 5KW parallel light). After the exposure, the printed circuit board was developed by passing through a developer.

In this case, in Examples 1 to 6 including the resin protective layer, the support film was peeled off before the exposure process, and in Comparative Examples 2 to 6 in which the resin protective layer was not included, the support film was peeled off before the developing process.

(a) haze

The dry film photoresist prepared according to Examples 1 to 8 and Comparative Examples 1 to 6 was cut to a size of 7 cm × 7 cm, and then the protective film was peeled off and laminated on a copper clad laminate having a size of 10 cm × 10 cm. Then, after peeling off the support film of the laminated dry film photoresist, the resin protective layer was peeled off and the haze of the peeled resin protective layer was measured using a Haze Meter (NIPPON DENSHOKU, NDH-2000).

(b) Development time

When the resin protective layer is not included, the printed circuit board after lamination of the dry film photoresist on the copper-clad laminate as shown in (a) is carried out at a pressure of 1.5 kgf / cm 2 at a temperature of 30 ° C. (1% Na ₂ CO _3). After passing through a fan-type nozzle that sprays an aqueous solution) and a substrate having a distance of 15 cm, the time at which the laminated part is completely washed and removed by the developer is measured. , 'S _min '). In addition, the actual development time (hereinafter referred to as 'S _del ') only of the photosensitive resin layer was calculated to be twice the minimum development time (S _min ) of only the photosensitive resin layer.

On the other hand, in the case of a film including a resin protective layer, the minimum development time (hereinafter referred to as 'P _min ') of the film including the resin protective layer is a method of measuring the minimum development time (S _min ) of only the photosensitive resin layer and Measured in the same way, the actual development time (hereinafter referred to as' P _del ') of the film including the resin protective layer is the development time of the resin protective layer (hereinafter,' P) only in the actual development time (S _del ) of the photosensitive resin layer. _tim '), which is represented by Equation 1 below.

<Equation 1>

P _del = S _del + P _tim

= S _min × 2 + P _tim

Another expression of Equation 1 is expressed by Equation 2 below.

<Formula 2>

P _del = P _min + S _min

Therefore, the minimum development time of the film including the resin protective layer and the minimum development time of the film not including the resin protective layer, that is, the minimum development time of only the photosensitive resin layer, were measured, respectively. The actual development time can be calculated.

Here, the minimum development time (S _min ) of the photosensitive resin layer is determined by the minimum development time for the dry film photoresist of Comparative Example 1.

The developing time P _tim of only the resin protective layer is calculated from Equations 1 and 2, and the value obtained by dividing the calculated developing time by the thickness of the resin protective layer is defined as the developing time per μm of the resin protective layer.

 (c) sensitivity and exposure dose

In the case of exposure, Examples 1 to 6 and Comparative Examples 2 to 6 were placed on the resin protective layer, and in the case of Comparative Example 1 on a support film, a sensitivity (21 steps Stouffer Step Tablet) was placed, The exposure amount for obtaining 6 steps and 7 steps was measured using a photometer (UV-351, manufactured by ORC), and the values are shown in Table 2 below. At this time, the sensitivity was evaluated by the maximum number of units of the photosensitive resist remaining on the substrate after development.

(2) Circuit Properties: Resolution, Session Adhesion, 1/1 (Line / Space) Resolution

The Kolon Test Artwork was used to evaluate the circuit properties by measuring the resolution, thin line adhesion, and 1/1 (Line / Space) resolution.

In this experiment, the resolution is a measure of how small the line width was developed when the unexposed areas were developed. The smaller this value, the higher the resolution. The mask used for measuring the measured resolution was 0.5 μm up to 4 to 20 μm. The mask was formed at intervals of and a mask made with an interval of 400 μm was used for the resolution to be realized. The thin line adhesion value is a measure of how small the line width after exposure is formed to form a straight line circuit without being eroded. The smaller the value, the better the fine line adhesion value, and the mask used for measuring the measured thin line adhesion value. Was formed at intervals of 0.5 μm to 4 to 20 μm, and a mask made of 400 μm was used for the fine wire adhesion value of the value to be realized. In addition, 1/1 resolution represents the value of the cleanest developed minimum line width with the distance between the circuit line and the circuit line 1: 1.

(3) glossiness

Glossiness was measured at 20 ° and 60 ° gloss angles according to KS definition (KS M ISO 2813: 2007) using Gloss Meter Reading.

In order to measure the glossiness according to the above method, first, a dry film photoresist having a resin protective layer was laminated on the copper clad laminate, and then the glossiness was measured after exposure and development. In this case, the exposure and development were carried out by the method performed on the above-described characteristic evaluation. The results are shown in Table 3 below.

(4) surface analysis

Printed circuit boards to which the dry film photoresist of Example 1 and Comparative Example 1 were applied were subjected to the exposure and development processes as described above, and the surfaces thereof were photographed with an electron microscope, respectively, as shown in FIGS. 1 to 2.

Table 2 shows the measurement results of the circuit properties according to the haze, development time and exposure conditions, respectively.

Hayes
(%) Developing time Exposure conditions Circuit properties Minimum developing time (sec) Actual development time (sec) Exposure
Energy (mJ / ㎠) Sensitivity (sst
/ 21sst) resolution
(Μm) Thin line
Adhesion
(Μm) 1/1
resolution
(Μm) Example 1 0.80 11 19 50 5 7 13 9 60 6 9 11 9 70 7 9 8 9 Example 2 0.80 17 25 50 5 7 13 9 60 6 9 11 9 70 7 9 8 9 Example 3 0.81 10 18 50 5 7 13 9 60 6 9 11 9 70 7 9 8 9 Example 4 1.9 11 19 50 5 8 13 9 60 6 10 11 10 70 7 10 8 10 Example 5 1.9 14 22 50 5 8 13 9 60 6 10 11 10 70 7 10 8 10 Example 6 2.6 18 26 50 5 8 13 9 60 6 10 11 10 70 7 11 8 11 Comparative Example 1 None 8 ^* 16 ^** 50 5 8 13 10 60 6 11 13 11 70 7 13 8 13 Comparative Example 2 3.2 11 19 50 5 8 13 10 60 6 11 13 11 70 7 13 9 13 Comparative Example 3 0.89 59 67 50 5 8 18 18 60 6 11 19 19 70 7 13 17 16 Comparative Example 4 3.3 24 32 50 5 8 13 10 60 6 11 13 11 70 7 13 8 13 Comparative Example 5 None 9 16 50 5 9 15 16 60 6 12 13 13 70 7 14 11 13 Comparative Example 6 None 13 20 50 5 9 17 16 60 6 12 14 13 70 7 14 10 13

Note: In Table 2, the minimum development time (sec) means the minimum development time (P _min ) of the film including the resin protective layer, and the actual development time (sec) is the actual development of the film including the resin protective layer. It means time (P _del ). However, exceptionally * indicates the minimum development time (S _min ) of the photosensitive resin layer only, ** ** means the actual development time (S _del ) of the photosensitive resin layer only.

Table 3 below shows the results of measuring the glossiness of the surface of the photosensitive resin layer after development.

division Glossiness 20 ° 60 ° Example 1 87 94 Example 2 80 95 Example 3 83 93 Example 4 84 90 Example 5 75 81 Example 6 70 76 Comparative Example 1 84 92 Comparative Example 2 81 90 Comparative Example 3 49 67 Comparative Example 4 58 71 Comparative Example 5 12 53 Comparative Example 6 7 36

As a result of the measurement, the haze measurement was not possible because Comparative Example 1 does not have a resin protective layer, in particular, Comparative Examples 5 and 6 was mixed between the resin protective layer and the photosensitive resin layer was not separated from the layer and the haze measurement was not possible. In Comparative Example 3, the haze value was lower than that of Examples 4 to 6, but the development time was remarkably long, resulting in a problem that the circuit physical properties were lowered.

In addition, the amount of exposure required to implement the same number of stages was almost no difference between Examples 1 to 6 and Comparative Examples 1 to 4, and it can be seen that the measurement results of the physical properties of the Example showed better results including resolution.

On the other hand, in the dry film photoresist including the resin protective layer of the present invention it can be seen that the development time of the resin protective layer is about 0.5 to 3 seconds.

In addition, as a result of surface observation through the electron micrographs of FIGS. 1 to 2, in the case of FIG. 1, which is a surface photograph of the printed circuit board to which the dry film photoresist according to Example 1 is applied, the side and the surface of FIG. It can be seen that there is almost no irregularities and a very good pattern is formed.

Therefore, when the dry film photoresist of the present invention is applied, not only the handling is easy during exposure but the resolution is improved, and the mixing of the resin protective layer and the photosensitive resin layer is prevented, so that the glossiness of the photosensitive resin layer is excellent even after development. It can be seen that can be improved.

All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (9)

A support film, a resin protective layer, and a photosensitive resin layer are sequentially laminated and included,
The resin protective layer comprises a water-soluble polymer having a weight average molecular weight of 5000 to 300000, the haze of the resin protective layer is 3.0% or less, the developing speed per 1㎛ of the resin protective layer is 10 seconds or less Resist. The dry film photoresist of claim 1, wherein the water-soluble polymer comprises polyvinyl alcohol having a degree of saponification of 75% to 97%. The dry film photoresist of claim 1, wherein the resin protective layer comprises polysilicon. The dry film photoresist of claim 1, wherein the resin protective layer comprises 0.01 to 3 parts by weight of polysilicon based on 100 parts by weight of the water-soluble polymer. The polysilicon of claim 3 or 4, wherein the polysilicon has a particle size of 1 μm or less upon dissolving 0.1 g of polysilicon in a condition of 80 ° C. for 6 hours in 100 g of any one of water, alcohols, and mixtures thereof. Dry film photoresist. The dry film photoresist of claim 1, wherein the resin protective layer has a thickness of 10 μm or less. The dry film photoresist of claim 1, wherein the adhesive force between the support film and the resin protective layer is 0.0005 to 0.01 N / cm. The dry film photoresist according to claim 1, wherein the photosensitive resin layer has a glossiness after development of 15 or more at 20 ° and 60 or more at 60 °. The dry film photoresist of claim 1, further comprising a protective film on one surface of the photosensitive resin layer.

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