KR101739730B1 - Dry film photoresist - Google Patents

Abstract

The present invention relates to a dry film photoresist. More specifically, the dry film photoresist according to the present invention can be subjected to an exposure process in a state in which a support film is removed, thereby improving the resolution by preventing the exposure effect of the support film from being adversely affected . Particularly, when the dry film photoresist is used for pattern formation, when the laminated dry film photoresist is separated again after the exposure process, the photosensitive resin layer is not damaged or transferred due to the adhesive force between the films, have.

Description

DRY FILM PHOTORESIST < RTI ID = 0.0 >

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

Dry film photoresist was developed by DuPont of USA in 1968 under the trade name of 'RISTON' and is used as an important material in the current electric and electronic industry, especially printed circuit board.

As a photoresist material used for forming a circuit on a printed circuit board, about 50% of the total is used for a photosensitive screen printing ink. However, in the production of printed circuit boards of double-sided and multilayer boards requiring high density and high reliability, A resist is inevitably used.

Such a dry film photoresist is mainly laminated with a two-layer structure of a base film and a photosensitive resin layer. In order to protect the photosensitive resin layer before the dry film photoresist is used, .

In general, the support film uses a polyester film such as polyethylene terephthalate and has a thickness of about 25 mu m. Such a support film serves as a support for the photosensitive resin layer during the production of the dry film photoresist, and facilitates handling of the photosensitive resin layer having adhesive force during exposure.

The photosensitive resin is divided into a negative type and a positive type by a reaction mechanism by light. In the case of a negative type photosensitive resin, a photocrosslinking reaction occurs in the exposed portion, an unexposed portion is washed away with alkali to leave a resist pattern, In the case of a photosensitive resin, photodegradation reaction occurs at the exposed site and is developed to alkali, and the unexposed area remains to form a resist pattern.

The photosensitive resin layer is made to meet 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 mu m, which is suitable for use after being applied. Such a photosensitive resin layer has various compositions depending on conditions such as mechanical and chemical properties required for the photoresist and processing.

On the other hand, the protective film serves as a protective covering for protecting the photosensitive resin layer from foreign substances such as dust and preventing the damage of the resist during handling, and is laminated on the back surface of the photosensitive resin layer on which the support film is not formed.

As an example of a pattern forming method using such a dry film photoresist, when a protective film is applied on a printed circuit board, the protective film is first peeled off, laminated on a copper clad laminate (CCL) Exposed to ultraviolet (UV) light, and then developed using a suitable solvent to wash off the unhardened portions.

In general, when a dry film photoresist having such a composition is used, since the photosensitive resin layer adheres to the photosensitive resin layer during exposure, the photosensitive resin layer and the mask are spaced apart from each other by the thickness of the support film. As a result, have. In addition, when exposure is performed by irradiating ultraviolet light, ultraviolet rays are transmitted through the support film to affect the ultraviolet transmittance, and ultraviolet scattering due to particles inside the support film limits the realization of high resolution.

In order to solve this problem, the support film may be peeled off and exposed. However, since the photosensitive resin layer has adhesiveness, if the support film is peeled off, the mask adheres to the photosensitive resin layer, so that the photosensitive resin layer is damaged. As a result, There is a problem that the resolution is lowered, the mask is contaminated, and the life of the mask is shortened.

Therefore, in practice, exposure after the support film is peeled off is difficult to achieve, and the problem of resolution deterioration still remains.

Further, as the density of the printed circuit board is increased and the density of the circuit line is increased as the semiconductor packaging technology is developed, there is an urgent need for a high-resolution dry film photoresist applicable to such a microcircuit substrate.

The present invention can improve the resolution by allowing the exposure process to be performed in a state in which the support film is removed and having an optimal development time, and when the photosensitive resin layer is stored after being laminated after the exposure process, the photosensitive resin layer is not damaged or transferred And to provide a dry film photoresist capable of achieving high resolution.

One embodiment of the present invention is a dry film photoresist comprising a support film, a resin protective layer and a photosensitive resin layer sequentially laminated, wherein the support film is formed by laminating one side of the resin protective layer in the dry film photoresist, Was laminated at 110 ° C at a speed of 2 m / min and at a pressure of 4 kgf / cm 2 to contact one surface of the resin protective layer in the dry film photoresist from which the dry film photoresist was removed, The dry film photoresist having an adhesive force between one side of the protective layer and one side of the other resin protective layer is 0.01 N / cm or less.

In another embodiment of the present invention, the resin protective layer is a dry film photoresist having a haze of 3.0% or less.

In another embodiment of the present invention, the resin protective layer is a dry film photoresist having a development time per 1 mu m of 10 seconds or less.

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

In another embodiment of the present invention, the resin protective layer is a dry film photoresist having a thickness of 10 mu m or less.

In another embodiment of the present invention, the resin protective layer is a dry film photoresist comprising polyvinyl alcohol having a weight average molecular weight of 5,000 to 300,000.

In another embodiment of the present invention, the polyvinyl alcohol is a dry film photoresist having a degree of saponification of 75 to 97%.

In another embodiment of the present invention, the resin protective layer is a dry film photoresist further comprising polysilicon.

In another embodiment of the present invention, the resin protective layer is a dry film photoresist containing 0.01 to 3 parts by weight of polysilicon with respect to 100 parts by weight of polyvinyl alcohol.

In another embodiment of the present invention, the polysilicon is a dry film photoresist having a particle size of 1 탆 or less when 0.1 g of polysilicon is dissolved in 100 g of any one solvent selected from water, alcohols and mixtures thereof.

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

The dry film photoresist according to the present invention can be subjected to an exposure process in a state in which the support film is removed, thereby preventing the exposure effect of the support film from being adversely affected and ultimately improving the resolution.

Particularly, when the dry film photoresist is used for pattern formation, when the laminated dry film photoresist is separated again after the exposure process, the photosensitive resin layer is not damaged or transferred due to the adhesive force between the films, have.

Fig. 1 is an electron micrograph taken magnified 1200 times the surface of a printed circuit board after the development process produced in Example 1 of the present invention. Fig.
Fig. 2 is an electron microscope photograph obtained by enlarging the surface of the printed circuit board after the development process manufactured in Comparative Example 1 by 1200 times. Fig.

According to one embodiment of the present invention, there is provided a dry film photoresist comprising a support film, a resin protective layer, and a photosensitive resin layer sequentially laminated, wherein the support film, The laminate was laminated at 110 ° C at a speed of 2 m / min and at a pressure of 4 kgf / cm 2 so as to contact one surface of the resin protective layer in the dry film photoresist from which the support film had been removed. A dry film photoresist having an adhesive force of 0.01 N / cm or less between one surface of the resin protective layer and one surface of the other resin protective layer

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 may further include a protective film, if necessary.

Since the support film serves as a support for the resin protective layer and the photosensitive resin layer, it is preferable that the support film has sufficient mechanical properties. More specifically, examples of the support film include a polyester film such as a polyethylene terephthalate film and a polyethylene naphthalate film; A polyolefin-based film such as a polyethylene film, and a polypropylene film; A polyvinyl-based film such as a copolymer film of polyvinyl chloride and vinyl acetate, a polytetrafluoroethylene film, and a polytrifluoroethylene film; Polyimide-based films; Polyamide-based films such as 6,6-nylon; A cellulose acetate film, a cellulose triacetate film, and a cellulose diacetate film; Polyacrylate-based films such as alkyl poly (meth) acrylate films; A polyacrylic film such as a (meth) acrylic acid ester copolymer film; Among them, polyethylene terephthalate is preferably used in consideration of mechanical properties and economical efficiency.

The thickness of the support film can be selected according to any purpose within the range of 10 to 100 占 퐉.

The surface of the resin protective layer in the dry film photoresist from which the support film was removed and the other side of the resin protective layer in the dry film photoresist from which the support film had been removed were contacted at 110 ° C at a speed of 2 m / min and a pressure of 4 kgf / cm 2 It is preferable that the adhesive strength between one side of the resin protective layer and one side of the other resin protective layer when the dry film photoresist is separated again is 0.01 N / cm or less, and the lower the adhesive strength is The lower limit value of the adhesive force is meaningless in that the transfer phenomenon is eliminated.

That is, when the adhesion force between the resin protective layers of the dry film photoresist according to the present invention is within the above range, there is an advantage that the resin protective layers are cleanly separated from each other without transferring at the time of separation after contact between the resin protective layers. Cm, there is a problem that the photosensitive resin protective layer or the photosensitive resin layer is damaged due to the transfer phenomenon between them.

Specifically, when the dry film photoresist is used in the pattern formation method, the support film is removed, and a mask of a desired pattern is exposed on the resin protective layer by irradiating ultraviolet rays (UV). At this time, since there is no adhesion between the mask and the resin protective layer, they easily fall off and there is no mutual transfer. After this exposure, the deposited dry film photoresist after lamination is separated again to undergo the developing process. At this time, there is a problem that the photosensitive resin layer is separated due to the large adhesive force between the dry film photoresist at the time of separation, and a part of the resin protective layer may be transferred, which causes a difference in development time, Problems will arise.

In the present invention, when the adhesive force between the resin protective layers is within the above range, such an effect of preventing the problem can be obtained.

On the other hand, in consideration of the case where the support film is removed, the resin protective layer is required to have an adhesion strength with the support film at an appropriate level. Normally, the resin protective layer must be stably stuck to the support film laminated, It is preferable that the adhesive strength between the support film and the resin protective layer is 0.0005 to 0.01 N / cm in that the surface of the resin protective layer should not be damaged when the resin film is removed from the support. Specifically, when the adhesive force is in the above range, there is an advantage that the support film and the resin protective layer are not separated when the protective film is removed when the lamination is performed, and when the film is removed before the exposure, There is an advantage in that it can be removed without giving any influence.

The resin protective layer may have a haze of 3.0% or less and a developing time per 1 탆 of 10 seconds or less.

In the dry film photoresist according to the present invention, a dry film photoresist, in which a support film, a resin protective layer, and a photosensitive resin layer are sequentially laminated, The protective film is peeled off and laminated so that one side of the photosensitive resin layer comes into contact with the upper side of the CCL. Then, the support film is removed, a mask of a desired pattern is placed on the resin protective layer, exposure is performed by irradiating ultraviolet rays (UV), and a developing process of washing the uncured portions using an appropriate current solution is performed It goes through.

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

Particularly, as the weight average molecular weight of the polyvinyl alcohol as the water-soluble polymer contained in the resin protective layer increases, the solubility decreases and the extent to which the polyvinyl alcohol is washed away from the developer may be reduced.

This development is also affected by the development time. It is better that the development time of the resin protective layer is faster. However, if the development time of the resin protective layer is slow, a large difference in development time occurs depending on the thickness variation of the resin protective layer, The adhesion may be deteriorated by washing more than necessary, or since the resolution may be deteriorated due to less washing, the development time of the resin protective layer should be appropriately determined considering the development of the photosensitive resin layer in order to form a precise pattern.

Therefore, the resin protective layer contains polyvinyl alcohol having an appropriate level of weight average molecular weight to improve developability, and has an appropriate level of development time so as not to leave any residue and damage to the cured portion of the photosensitive resin layer It is important to have.

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

The resin protective layer may have a haze value of 3.0% or less, preferably 0.001 to 3.0%. When the haze is within the above range, the light transmittance can be increased during exposure to improve the resolution.

Specifically, the haze of the resin protective layer is required to have a low value in order to lower the light scattering degree. Therefore, when the lower limit value is lower, the haze of the resin protective layer is preferably as low as possible. When the haze is more than 3%, the shape of the photosensitive resin layer side walls are not smooth and rough.

The resin protective layer may have a development time per 1 μm of 10 seconds or less, preferably 0.1 to 10 seconds, and if it is within the above range, the resolution can be improved with an optimal development time.

Specifically, the development time of the resin protective layer is required to have a low value in order to improve developability. Therefore, it is preferable that the lower limit value is lower, and when it exceeds 10 seconds, the development time A large amount of difference is generated, and the photosensitive resin layer is washed away more than necessary, so that the adhesion may be deteriorated or the resolution may be deteriorated to deteriorate the resolution.

In addition, since the dry film photoresist of the present invention can be subjected to the exposure process by removing the support film before the exposure process, it is possible to obtain an effect of preventing adverse effects due to the particles contained in the support film.

The resin protective layer has a thickness of 10 mu m or less, preferably 0.001 to 10 mu m, more preferably 0.001 to 5 mu m.

When the dry film photoresist is used in the pattern forming method, the mask is irradiated with light during the exposure process. The closer the distance between the mask and the photosensitive resin layer, the higher the resolution can be realized. For this purpose, it is best to expose a photosensitive resin layer with a mask on top, but since the photosensitive resin layer adheres to the mask due to stickiness, not only the photosensitive resin layer is damaged but also the mask is contaminated. There was a limit.

Since the resin protective layer is required to have a low thickness in order to realize high resolution, the lower the lower limit value is, the more desirable it is. Therefore, by using the resin protective layer having a thickness of 10 탆 or less, And even when the support film is removed and the exposure is performed, the damage of the photosensitive resin layer and the contamination of the mask do not occur, thereby overcoming the limitations of improving the conventional resolution, and thus realizing a high resolution.

The resin protective layer includes polyvinyl alcohol having a weight average molecular weight of 5000 to 300000, preferably 5000 to 150000, more preferably 5000 to 100000. When the weight average molecular weight is within the above range, the coating on the film is well performed, the strength can be realized at a level that can perform the protective function of the photosensitive resin layer, the developing time is suitably set, It is possible to prevent the problem that the support film is damaged when the support film is peeled after lamination.

In particular, the polyvinyl alcohol according to the present invention preferably has a degree of saponification of 75% to 97%. When the degree of saponification is within the above-mentioned range, the degree of saponification has an effect of preventing a decrease in adhesion and a decrease in resolution in forming a photosensitive resin layer due to a proper development time of the resin protective layer.

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

The polysilicon serves to impart releasability to the resin protective layer and may affect the adhesion force and the 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 soluble in an organic solvent, it is insoluble in water, alcohol, or a mixed solvent thereof, and the particle size is remarkably increased, which is not preferable in the present invention.

The polysilicon is a solution type particle size analyzer, and has a particle size of 1 탆 or less when dissolved in 100 g of the solvent. The lower the lower limit of the particle size is, the more preferable it is to dissolve all the polysilicon. When the particle size of the polysilicon is within the above range, the haze can be prevented from lowering and the shape of the photosensitive resin layer during formation of the circuit can be prevented from being lowered.

The resin protective layer of the present invention may contain 0.01 to 3 parts by weight of polysilicon relative to 100 parts by weight of the above-mentioned polyvinyl alcohol. The content of polysilicon with respect to 100 parts by weight of the polyvinyl alcohol is preferably within the above range in view of easiness of application on the support film and haze of the resin protective layer after drying.

In particular, when the content of the polysilicon is within the above range, the adhesive force between one surface of the resin protective layer and one surface of the other resin protective layer may be in a range of 0.01 N / cm or less, The resin protective layers are cleanly separated from each other without transferring during the separation after the contact between the resin protective layers, thereby preventing the damage of the photosensitive resin layer and the unintentional transfer to the photosensitive resin layer.

Specifically, polysilicon generally has a property as a releasing agent. When the content of polysilicon is less than that of polyvinyl alcohol constituting the resin protective layer, that is, less than 0.01 part by weight of polysilicon is contained in the resin protective layer The adhesion between the resin protective layers exceeds 0.01 N / cm, so that when the resin protective layers are separated after contact, the surface of the laminated photosensitive resin layer may come in contact with the resin protective layer, A transfer phenomenon may occur and unintended transfer to the photosensitive resin layer may occur. When the amount of the polysilicon exceeds 3 parts by weight, there arises a problem that circuit properties are deteriorated due to an increase in haze.

In the present invention, the content of polysilicon with respect to polyvinyl alcohol is included within the above-mentioned range, so that the adhesive force between the resin protective layers is kept within a range of 0.01 N / cm or less to prevent such a problem.

On the other hand, 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 can be generally selected by a photosensitive resin composition widely known in the field to which the present invention belongs.

For example, when the dry film photoresist is of the negative type, the photosensitive resin layer may include a binder resin, an ethylenically unsaturated compound as a photopolymerizable 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 copolymers, which are a type of acrylic polymer, are preferred. If desired, copolymers of ethylenically unsaturated carboxylic acid and other monomers may be used. As the methacrylic copolymer, a methacrylic copolymer including an acetoacetyl group may also be used. Examples of the methacrylic monomer usable for synthesizing the methacrylic copolymer include methylmethacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, But are not limited to, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzylmethacrylate, Dimethylaminoethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, and the like can be given. have. As the ethylenically unsaturated carboxylic acid, monoacrylic acid such as acrylic acid, methacrylic acid, and crotonic acid is widely used. In addition, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, anhydrides thereof, and half esters thereof may be used. Of these, acrylic acid and methacrylic acid are preferred. Other copolymerizable monomers include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, a-methylstyrene, acrylonitrile, Vinyl acetate, alkyl vinyl ether, and the like.

As the ethylenically unsaturated compound as the photopolymerizable monomer, a monofunctional, bifunctional or trifunctional or multifunctional monomer may be used. Examples of the polyfunctional monomer include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, But are not limited to, 1,6-hexane glycoldimethacrylate, trimethyolpropane trimethacrylate, glycerin dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate, Pentaerythritol trimethacrylate, Dipentaerythritol pentamethacrylate, 2,2-bis (4-methacryloxydiethoxyphenyl) propane, 2-hydroxy-3-methane 2-hydroxy-3-methacryloyloxypropyl methacrylate, ethylene glycol diglycidylether dimethacrylate, diethylene glycol diglycidyl ether dimethacrylate (also referred to as " diethylene glycol diglycidyl ether dimethacrylate, phthalic acid diglycidyl ester dimethacrylate, glycerin polyglycidyl ether polymethacrylate, and the like. Examples of the monofunctional monomer include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxypropyl methacrylate, 2-methacryloyloxy-2-hydroxypropyl phthalate, 3-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, glycerin monomethacrylate, 2-methacryloyloxyethyl acid phosphate, 2-methacryloyloxypropyl methacrylate, Methacrylates 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-dimethy-4 (3,3-dimethyl-4-methoxybenzophenone), benzophenone, p, p'-bis (dimethylamino) benzophenone, p, p, p'-diethylaminobenzophenone, pivalate ethyl (p-diethylamino) benzophenone, p, p'-diethylaminobenzophenone, ether, 1,1-dichloroacetophenone, pt-butyldichloroacetophenone, hexaaryl- Dimer of hexaaryl-imidazole, 2,2'-diethoxyacetophenone, 2,2'-diethoxy-2-phenylacetophenone, 2-phenylacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, phenyl glyoxylate, a-hydroxy-isobutylphenone a-hydroxyisobutylphenone, dibenzospan, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-

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

As the additive, a softener such as vinyl chloride resin may be included. Specific examples of the phthalic ester include, but are not limited to, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, but are not limited to, phthalate, diisodecyl phthalate, butylbenzyl phthalate, diisononyl phthalate, ethylphthalylethyl glycolate, dimethylisophthalate, dichlorohexyl phthalate, dichlorohexyl phthalate, and the like, and esters of fatty acids and arimatic acid such as dioctyl adipate, diisobutyl adipate, dibutyl adipate, Diisodecyl adipate, dibutyl diglyco < RTI ID = 0.0 > l

adipate, dibutyl sebacate, dioctyl sebacate, and the like. In the present invention, glycerol triacetate, trimethyl phosphate, triethyl 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, tricetylphosphate, , Tristearyl phosphate phosphate, trioleyl phosphate, triphenyl phosphite, tris-tridecyl phosphite, dibutyl hydrogen phosphite, dibutyl-butylphosphate, Dibutyl-butyl phosphonate, di (2-ethylhexyl) 2-ethylhexyl phosphonate, 2-ethylhexyl-2 methylhexylphosphonate, 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).

Other volatile organic compounds such as glycerin, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol dipropylene glycol or lower alkyl ethers thereof, lower fatty acid esters, higher fatty acids or esters thereof, higher fatty acid alcohols or esters thereof may also be used as the softening agent of the present invention.

The binder resin, the photopolymerizable compound, the photopolymerization initiator and the additive contained in the above-mentioned negative-working photosensitive resin can be appropriately mixed and used according to any purpose.

On the other hand, when the dry film photoresist is of a positive type, the photosensitive resin layer may include an alkali-soluble resin and a diazide-based photosensitive compound. Specifically, a novolak resin may be used as the alkali-soluble resin, And may contain a boric resin. The novolak resin can be obtained by polycondensation reaction of phenol alone or in combination with an aldehyde and an acidic catalyst.

The phenol is not particularly limited, and phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4- 2-t-butylphenol, 3-t-butylphenol, 4-methyl-2-t-butylphenol, A monovalent phenol; Dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, resorcinol, pyrocatechol, hydroquinone, bisphenol A, fluoroglucinol, Pyrogallol, and the like, and they may be used alone or in combination of two or more. Particularly, a combination of m-cresol and p-cresol is preferable.

The aldehydes include, but are not limited to, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, alpha or beta-phenylpropylaldehyde, o-, m- or p- Hydroxybenzaldehyde, glutaraldehyde, terephthalaldehyde and the like, which may be used alone or in combination of two or more.

The cresol novolak resin preferably has a weight average molecular weight (based on GPC measurement method) of 2,000 to 30,000, and the cresol novolac resin has properties such as a photosensitizing time and a residual film ratio depending on the content ratio of meta / , It may be preferable that the meta / para-cresol content is mixed in a ratio of 4: 6 to 6: 4 on a weight basis. When the content of the methacresol in the cresol novolac resin exceeds the above range, the photosensitive time is accelerated and the residual film rate is drastically lowered. When the content of the para-cresol exceeds the above range, the photosensitive time is slowed down. The cresol novolak resin may be used singly as a cresol novolak resin having a meta / para-cresol content of 4: 6 to 6: 4 by weight, more preferably, a mixture of different resins may be used. In this case, it is preferable that the cresol novolak resin is mixed and used in a ratio of cresol novolak resin having a weight average molecular weight of 8,000 to 30,000 and novolak resin having a weight average molecular weight of 2,000 to 8,000 in a ratio of 7: 3 to 9: 1 .

The "weight average molecular weight" above and below is defined as a polystyrene equivalent conversion value determined by gel permeation chromatography (GPC) unless otherwise specified.

On the other hand, in the photoresist layer composition, the diazide-based photosensitive compound functions as a dissolution inhibitor which decreases the solubility of the alkali-soluble resin in alkali, and when the light is irradiated, it turns into an alkali-soluble substance and increases the alkali solubility of the alkali- do. Due to such a change in solubility due to light irradiation, the exposed region of the film-type photodegradable transfer material of the present invention is developed.

The diazide-based photosensitive compound can be synthesized by an esterification reaction of a polyhydroxy compound with a quinone diazide sulfonic acid compound. The esterification reaction for obtaining a diazide-based photosensitive compound is preferably carried out by reacting a polyhydroxy compound and a quinonediazide sulfonic acid compound in a solvent such as dioxane, acetone, tetrahydrofuran, methyl ethyl ketone, N-methylpyrrolidone, chloroform, triethylamine, N -Methylmorpholine, N-methylpiperazine or 4-dimethylaminopyridine, and then the obtained product is washed, purified and dried.

Examples of the quinonediazide sulfonic acid compound include 1,2-benzoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid, 1,2-benzoquinonediazide- O-quinonediazidesulfonic acid compounds such as 1,2-naphthoquinonediazide-5-sulfone and other quinonediazide sulfonic acid derivatives. The quinone diazide sulfonic acid compound itself has a function as a dissolution inhibitor which lowers the solubility of the alkali-soluble resin in alkali. However, it has a property of decomposing for the alkali solubility at the time of exposure, thereby promoting the dissolution of the alkali-soluble resin in the alkali.

Examples of the polyhydroxy compound include trihydroxybenzophenone such as 2,3,4-trihydroxybenzophenone, 2,2 ', 3-trihydroxybenzophenone and 2,3,4'-trihydroxybenzophenone. Currents; 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,5-tetrahydroxybenzophenone, etc., tetrahydroxybenzophenone Currents; 2,2 ', 3,4,4'-pentahydroxybenzophenone, 2,2', 3,4,5-pentahydroxybenzophenone edpentahydroxybenzophenones; Hexahydroxybenzophenones such as 2,3,3 ', 4,4', 5'-hexahydroxybenzophenone, 2,2 ', 3,3', 4,5'-hexahydroxybenzophenone; Gallic acid alkyl esters; Oxyflavones and the like.

Specific examples of the diazide-based photosensitive compound obtained therefrom include 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4-tri Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate and (1- [1- (4-hydroxyphenyl) isopropyl] -4- [ Phenyl) ethyl] benzene) -1,2-naphthoquinonediazide-5-sulfonate.

Such a diazide-based photosensitive compound may be advantageous from the viewpoint of developability and solubility in the range of 30 to 80 parts by weight based on 100 parts by weight of the alkali-soluble resin in the photoresist layer composition.

The above-mentioned positive photosensitive resin layer may contain a sensitivity enhancing agent for improving sensitivity. Examples thereof include 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone and 1- [1- (4-hydroxyphenyl) isopropyl] -4- [ 1,1-bis (4-hydroxyphenyl) ethyl] benzene. When the sensitivity enhancer is included, the content of the sensitizer is preferably 3 to 15 parts by weight based on 100 parts by weight of the alkali-soluble resin.

In addition, the positive-type photosensitive resin layer may contain other components such as leveling agents, fillers, antioxidants, and additives.

On the other hand, a composition containing an alkali-soluble resin, a diazide-based photosensitive compound and the like is dispersed in a certain amount of a solvent and applied to the coating solution. Examples of the solvent include ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate, glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, acetone, methyl ethyl ketone, ethyl alcohol, methyl alcohol, propyl alcohol, isopropyl alcohol, benzene, toluene, cyclopentanone, cyclohexanone, ethylene glycol, Glycol monoethyl ether, and diethylene glycol monoethyl ether.

The dry film photoresist according to an embodiment of the present invention may further include a protective film on one side of the photosensitive resin layer. The protective film serves to protect the photosensitive resin layer from the outside. When the dry film photoresist is applied to a post-process, it is easily separated, and it is required to have appropriate releasability and tackiness so as not to be released during storage and circulation.

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

Example  1 to 4 and Comparative Example  1 to 2

≪ Example 1 >

(a) 20 g of polyvinyl alcohol (KURARAY, PVA205) having a weight average molecular weight of 22000 and a degree of saponification of 87%, and 0.1 g of polysilicon in 100 g of butoxyethanol solvent, 0.05 g of silicone (BYK, BYK-349, 0.25% of solid content after drying) was added to 100 g of distilled water and stirred at 80 ° C for 6 hours to completely dissolve the resin composition. This was coated on a support film having a thickness of 16 μm (haze of 2.3%, no surface treatment, polyethylene terephthalate film, FDFR-16 μm, KOLON) using a coating bar and dried at 80 ° C. for 10 minutes using a hot air oven 3.0 占 퐉, and a thickness deviation of 0.4 占 퐉 was formed

 In this case, when the polysilicon is dissolved in the solvent, the particle size of 0 占 퐉 means that the polysilicon is almost completely dissolved in the solvent and the particle phase is not found. Unless otherwise specified, the particle size is 0 占 퐉 'Means the same meaning as above.

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

(c) The photosensitive resin composition was coated on a protective film having a thickness of 19 占 퐉 (polyethylene terephthalate film of silicone-modified type, CY201-19um, KOLON) using a coating bar, Minute to form a photosensitive resin layer having a thickness of 15 mu m.

(d) A dry film photoresist having a thickness of 53 탆 was prepared by laminating the dried photosensitive resin layer of the film (c) and the resin protective layer of the above (a) so as to be in contact with each other at 50 캜 under a pressure of 4 kgf / cm 2.

≪ Example 2 >

A dry film photoresist having a thickness of 60 占 퐉 was prepared in the same manner as in Example 1, except that the following procedure was employed.

(a) 20 g of polyvinyl alcohol (KURARAY Co., PVA205) having a weight average molecular weight of 22000 and a degree of saponification of 87% and 0.1 g of polysilicon in 100 g of butoxyethanol solvent were mixed to prepare a polysilicon (BYK 0.05 g of BYK-349, 0.25% of the solid content after drying) was added to 100 g of distilled water and stirred at 80 ° C for 6 hours to completely dissolve the resin composition. This was coated on a support film having a thickness of 16 μm (haze of 2.3%, no surface treatment, polyethylene terephthalate film, FDFR-16 μm, KOLON) using a coating bar and dried at 80 ° C. for 20 minutes using a hot air oven 10.0 mu m, and a thickness variation of 0.8 mu m was formed

≪ Example 3 >

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

(a) 20 g of polyvinyl alcohol (KURARAY Co., PVA205) having a weight average molecular weight of 22000 and a degree of saponification of 87% and 0.1 g of polysilicon in 100 g of butoxyethanol solvent were mixed to prepare a polysilicon (BYK 0.2 g of BYK-349, 1.0% of solid after drying) was added to 100 g of distilled water and stirred at 80 ° C for 6 hours to completely dissolve the resin composition. This was coated on a support film having a thickness of 16 μm (haze of 2.3%, no surface treatment, polyethylene terephthalate film, FDFR-16 μm, KOLON) using a coating bar and dried at 80 ° C. for 20 minutes using a hot air oven 3.0 占 퐉, and a thickness deviation of 0.4 占 퐉 was formed

<Example 4>

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

(a) 10 g of polyvinyl alcohol (KURARAY, PVA217) having a weight average molecular weight of 75000 and a degree of saponification of 87%, and 0.1 g of polysilicon in 100 g of butoxyethanol solvent were mixed to prepare a polysilicon (BYK 0.025 g of BYK-349, 0.25% of solid after drying) was added to 100 g of distilled water and stirred at 80 ° C for 6 hours to completely dissolve the resin composition. This was coated on a 16 μm thick support film (haze 2.3%, no surface treatment, polyethylene terephthalate film, FDFR-16 μm, KOLON) using a coating bar and dried at 80 ° C. for 10 minutes using a hot air oven to obtain a thickness of 3.0 Mu m, and a thickness deviation of 0.4 mu m was formed

&Lt; Comparative Example 1 &

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

(b) The above photosensitive resin composition was coated on a support film having a thickness of 16 탆 (haze of 2.3%, no surface treatment, polyethylene terephthalate film, FDFR-16 탆, KOLON) using a coating bar, Lt; 0 &gt; C for 10 minutes to form a photosensitive resin layer having a thickness of 15 mu m.

(c) A photosensitive resin layer of the dried (b) film and a release film of a protective film having a thickness of 19 μm (silicone-modified polyethylene terephthalate film, CY201-19 μm, KOLON) / Cm &lt; 2 &gt; to prepare a film-type photosensitive transfer material having a thickness of 50 mu m.

&Lt; Comparative Example 2 &

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

(a) 20 g of polyvinyl alcohol (KURARAY, PVA205) having a weight average molecular weight of 22000 and a degree of saponification of 87%, and 0.1 g of polysilicon in 100 g of butoxyethanol solvent, 0.0016 g of silicone (BYK, BYK-349, after drying, 0.008% by weight) was added to 100 g of distilled water and stirred at 80 캜 for 6 hours to completely dissolve the resin composition. This was coated on a support film having a thickness of 16 μm (haze of 2.3%, no surface treatment, polyethylene terephthalate film, FDFR-16 μm, KOLON) using a coating bar and dried at 80 ° C. for 10 minutes using a hot air oven 0.5 占 퐉, and a thickness deviation of 0.1 占 퐉.

The weight average molecular weight and degree of saponification of the polyvinyl alcohol as the water-soluble polymer of Examples 1 to 4 and Comparative Example 2 were measured by the following methods.

Weight average molecular weight measurement

The weight average molecular weight of the polyvinyl alcohol was determined by gel permeation chromatography (GFC) using PEO (Polymer Standards Service, Mp 25300, 44000, 73500, 176000, 252000, 613000, 1010000) as reference materials.

Saponification degree  Measure

The saponification degree of polyvinyl alcohol was measured according to JIS K6726 method.

The adhesion of the dry film photoresist prepared in Examples 1 to 4 and Comparative Examples 1 and 2 was measured as follows.

Adhesion measurement

&Lt; Adhesion between resin protective layers >

After removing the protective film of the dry film photoresist sample having a width of 3 cm and a length of 20 cm, two samples were prepared by lamination to FCCL at a rate of 2 m / min and a pressure of 4 kgf / cm 2 at 110 ° C. Thereafter, the support film of two samples was released and laminated at a speed of 2 m / min and a pressure of 4 kgf / cm &lt; 2 &gt; at 110 DEG C with the resin protective layers facing each other. The force required for releasing the sample using a 10N load cell was measured using a UTM (4303 series, Instron) at a time of 100 mm / min from 5 cm to 8 cm from the starting point while releasing the attached sample.

&Lt; Adhesion between the support film and the resin protective layer >

After removing the protective film of the dry film photoresist specimen having a width of 3 cm and a length of 20 cm, the laminate was laminated to the copper laminate at 110 ° C at a speed of 2 m / min and a pressure of 4 kgf / cm 2. Then, the force required for releasing the support film using a 10N load cell at a time of 100 mm / min from the starting point to the 8 cm point was measured using a UTM (4303 series, Instron) while releasing the supporting film.

&Lt; Adhesion between the photosensitive resin layer and the protective film >

The force required to release the protective film of the dry film photoresist sample of 3 cm in width and 20 cm in length using a 10 N load cell from 5 cm to 8 cm from the starting point at a time of 100 mm / , 4303 series, Instron).

&Lt; Adhesion of resin protective layer and PET after peeling off the support film >

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

Table 1 below shows the results of measurement of the adhesive force of the dry film photoresist prepared in Examples 1 to 4 and Comparative Examples 1 and 2. [

The conditions for lamination of the PET film are the same as those under which the PET film is adhered to the mask at the time of general exposure, and the adhesive force of the support film measured at this time is the adhesion between the resin protective layer and the PET film in Examples 1 to 4 and Comparative Example 2 .

Adhesion (N / cm) Adhesion between resin protective layers Adhesion between the photosensitive resin layer and the protective film Adhesion between the support film and the resin protective layer After removing the support film, the adhesive strength between the resin protective layer and PET Example One 0.0015 0.0017 0.0027 0.0010 2 0.0015 0.0017 0.0027 0.0010 3 0.0012 0.0017 0.0024 0.0010 4 0.0017 0.0017 0.0031 0.0009 Comparative Example One Not measurable 0.0017 0.0047 ^* 0.0043 ^** 2 0.0125 0.0017 0.0130 0.0007

(Note) In Table 1, * denotes the adhesive strength between the support film and the photosensitive resin layer, and ** denotes the adhesive strength between the photosensitive resin layer and the PET film after the support film is peeled off.

Character rating

Then, the dry film photoresists prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were formed on a printed circuit board in the following manner, and then the characteristics of the dry film photoresist were evaluated.

(1) Formation on a printed circuit board

A brush pre-treatment machine is used for the CCL to form a new hibernation and to form an appropriate surface roughness. Then, it was acid-treated with 5% sulfuric acid solution, washed with water, dried, and then put into a laminator. The dry film photoresist prepared in Examples 1 to 4 and Comparative Examples 1 and 2 was laminated to a copper clad laminate using a Hakuto Mach 610i laminator at a pressure of 4 kgf / cm 2 at a rate of 2 m / min at 110 ° C, . Thereafter, exposure was performed by irradiating with a UV exposure apparatus (Perkin Elmer OB-7120, 5 kW parallel light). After the exposure, the printed circuit board was developed by passing through the developing device.

In the case of Examples 1 to 4 and Comparative Example 2 including the resin protective layer, the support film was peeled off before the exposure process, and in Comparative Example 1 in which the resin protective layer was not included, the support film was peeled off before the development process.

(a) haze

The dry film photoresist prepared according to Examples 1 to 4 and Comparative Examples 1 and 2 was cut into a size of 7 cm x 7 cm and then the protective film was peeled off and laminated on a copper clad laminate having a size of 10 cm x 10 cm. Then, the support film of the laminated dry film photoresist was peeled off, the resin protective layer was peeled off, and the haze of the peeled resin protective layer was measured using Haze Meter (NIPPON DENSHOKU, NDH-2000).

 (b) Development time

When the resin protective layer is not included, the printed circuit board, on which the dry film photoresist is laminated to the copper clad laminate as in (a), is exposed to a developing solution (1% Na ₂ CO ₃ The time taken for the laminated portion to be completely washed and removed by passing through a developing device having a gap of 15 cm between the nozzle of the fan type and the substrate for spraying the photosensitive resin layer, , And 'S _min '). The actual development time (hereinafter referred to as "S _del ") of only 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 developing time (hereinafter referred to as "P _min ") of a film including the resin protective layer is determined by measuring the minimum developing time (S _min ) (Hereinafter referred to as &quot; P _del &quot;) of the film including the resin protective layer is the same as the actual development time (S _del ) of the photosensitive resin layer alone, 'P _tim '), which is expressed as in Equation 3 below.

&Quot; (3) &quot;

P _del = S _del + P _tim

= S _min x 2 + P _tim

Expression (3) is expressed differently from Expression (4).

&Lt; Equation 4 &

P _del = _Pmin + _Smin

Therefore, the minimum developing time of the film including the resin protective layer and the minimum developing time of the film not including the resin protective layer, that is, the minimum developing time of only the photosensitive resin layer are respectively measured and from these values, The actual developing time can be calculated.

Here, the minimum developing time (S _min ) of only the photosensitive resin layer is the minimum developing time for the dry film photoresist of Comparative Example 1. [

The development time (P _tim ) of only the resin protective layer is calculated from the above equations (3) and (4), and the value obtained by dividing the calculated development time by the thickness of the resin protective layer is defined as the development time per 1 μm of the resin protective layer.

(c) Sensitivity and exposure

In the case of Examples 1 to 4 and Comparative Example 2 at the time of exposure, a sensitizer (21 stage Stouffer Step Tablet) was placed on the resin protective layer in the case of Comparative Example 1 on the support film, , And the amount of exposure for obtaining the 7th stage was measured using a light amount meter (UV-351, manufactured by ORC). The values are shown in Table 2 below. The sensitivity was evaluated by the maximum number of the photosensitive resist remaining on the substrate after development.

(2) Circuit properties: resolution, session adhesion, 1/1 (line / space) resolution

Using Kolon Test Artwork, the resolution, fine wire adhesion, and 1/1 (line / space) resolution were measured to evaluate the circuit properties.

In this experiment, the resolution is a measure of how small the linewidth was developed when the unexposed portion was developed. The smaller the value, the higher the resolution. The mask used for measuring the measured resolution was 0.5 to And a mask having an interval of 400 mu m is used for the resolution of the value to be implemented. The fine line adhesion value is a measure of how much exposure area forms a straight line circuit without being eroded to the small line width after development. The smaller the value, the better the fine line adhesion value, and the mask used to measure the measured fine line adhesion value Was formed at an interval of 0.5 to 4 mu m to 4 to 20 mu m and a mask made of an interval of 400 mu m was used for the fine line adhesion value of the value to be implemented. Also, 1/1 resolution shows the measured minimum linewidth that was cleanly developed with a 1: 1 gap between the circuit line and the circuit line.

(3) Surface analysis

A printed circuit board to which the dry film photoresist of Example 1 and Comparative Example 2 was applied was subjected to the exposure and development processes as described above, and then the surface thereof was photographed by an electron microscope and shown in FIG. 1 and FIG. 2, respectively.

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

Hayes
(%) Development time Exposure conditions Circuit property Minimum developing time (sec) Actual developing time (sec) Exposure
Energy (mJ / cm 2) Sensitivity (sst
/ 21st) resolution
(탆) Fine line
Adhesion
(탆) 1/1
resolution
(탆) Example 1 0.80 11 19 50 5 7/7 13/14 9/9 60 6 9/9 11/11 9/8 70 7 9/9 8/8 9/9 Example 2 2.6 18 26 50 5 8/8 13/13 9/9 60 6 10/10 11/11 10/11 70 7 11/10 8/8 11/11 Example 3 1.9 11 19 50 5 8/8 13/13 9/9 60 6 10/10 11/11 10/11 70 7 10/10 8/8 10/10 Example 4 0.80 17 25 50 5 7/7 13/12 9/9 60 6 9/9 11/11 9/9 70 7 9/9 8/8 9/9 Comparative Example 1 None 8 ^* 16 ^** 50 5 8/8 13/13 10/10 60 6 11/11 13/13 11/11 70 7 13/13 8/9 13/13 Comparative Example 2 0.25 8 16 50 5 7/7 20/20 20/20 60 6 9/9 18/18 18/18 70 7 9/9 16/16 16/16

Co. physical phenomenon of the film, including the above Table 2 Minimum developing time (sec) is the resin means that the minimum processing time (P _min) of the film comprising a protective layer, and actual developing time (sec) is a resin protective layer in the Means time (P _del ). However, exceptionally * denotes the minimum developing time (S _min ) of the photosensitive resin layer alone, and ** denotes the actual developing time (S _del ) only of the photosensitive resin layer.

As a result of the measurement, the amounts of exposure required to realize the same number of steps were almost the same as those of Examples 1 to 4 and Comparative Examples 1 and 2. The results of measurement of circuit physical properties showed better results in comparison with the comparative example in resolution and fine wire adhesion .

In the case of the embodiment, it can be seen that the releasing force between the photosensitive resin layer and the protective film and the releasing force between the resin protective layer and the support film are in a range not hindering the workability.

In addition, since the adhesive strength of the resin protective film and PET is adequate after peeling off the support film, good workability is exhibited without mutual transfer even after contact with the mask. Most importantly, since the adhesion between the resin protective layers is also an appropriate level, even when laminated after exposure, they are cleanly separated without mutual transfer, and the circuit properties are good. From this, it can be seen that, in the embodiment, even after stacking the post-exposure substrates, there is no mutual transfer, and it is possible to work stably.

 The adhesion force between the resin protective layers of Comparative Example 1 was directly laminated between the photosensitive resin layers due to the absence of the resin protective layer. In Comparative Example 2, the adhesion force between the resin protective layers exceeded 0.01 N / cm, so that the adhesion strength between the layers after the exposure lamination was high, and the transfer phenomenon occurred. As a result, the adhesion of the fine wires and the resolution degraded by 1/1.

From this, it can be seen that when the dry film photoresist of the present invention is applied, a dry film photoresist which can be easily handled during exposure and can be stably operated even after lamination after exposure can be produced.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (11)

A dry film photoresist comprising a support film, a resin protective layer and a photosensitive resin layer sequentially laminated,
The surface of the resin protective layer in the dry film photoresist from which the support film was removed and the other side of the resin protective layer in the dry film photoresist from which the support film had been removed were contacted at 110 ° C at a speed of 2 m / min and a pressure of 4 kgf / cm 2 , The adhesive force between one surface of the resin protective layer and one surface of the other resin protective layer when the dry film photoresist is separated again is 0.01 N / cm or less,
Wherein the resin protective layer comprises 0.01 to 3 parts by weight of polysilicon relative to 100 parts by weight of polyvinyl alcohol. The dry film photoresist according to claim 1, wherein the resin protective layer has a haze of 0.001 to 3.0%. The dry film photoresist according to claim 1, wherein the resin protective layer has a development time per 1 mu m of 0.1 to 10 seconds. The dry film photoresist according to 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 resin protective layer has a thickness of 0.001 to 10 탆. The dry film photoresist according to claim 1, wherein the resin protective layer comprises polyvinyl alcohol having a weight average molecular weight of 5000 to 300000. The dry film photoresist according to claim 6, wherein the polyvinyl alcohol has a degree of saponification of 75 to 97%. delete delete The dry film photoresist according to claim 1, wherein the polysilicon has a particle size of 0 to 1 탆 when dissolving 0.1 g of polysilicon in 100 g of any one solvent selected from water, alcohols and mixtures thereof. The dry film photoresist according to claim 1, further comprising a protective film on one surface of the photosensitive resin layer.

Images