JP2013505483A - Dry film photoresist - Google Patents

Abstract

  The present invention relates to dry film photoresists. Specifically, since the dry film photoresist according to the present invention can be subjected to the exposure process with the support film removed, the resolution can be improved by preventing the adverse effect of the exposure effect by the support film. it can. Moreover, even if the exposure is carried out in the presence of the resin protective layer, high transparency can be achieved because the transparency or the development speed does not decrease due to the resin protective layer.

Description

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

  Dry film photoresist has been developed by DuPont in the United States under the trade name “RISTON” around 1968, and has been used as an important material in the current electrical and electronic industries, especially for processing printed circuit boards. ing.

  Photoresist screen printing ink is used for the photoresist material used for circuit formation on the printed circuit board. About 50% of the total is a double-sided board and multilayer board that requires high density and high reliability. Dry film photoresist is essential for the production of printed circuit boards.

  Such a dry film photoresist is mainly laminated in a two-layer structure of a support film (base film) and a photosensitive resin layer (photosensitive layer), and protects the photosensitive resin layer until the dry film photoresist is used. In addition, a protective film is further included.

  In general, a polyester film such as polyethylene terephthalate is used as the support film and has a thickness of about 25 μm. Such a support film serves as a support for the photosensitive resin layer during the production of the dry film photoresist, and is handled during exposure of the photosensitive resin layer having adhesive force. make it easier.

  The photosensitive resin is classified into a negative type and a positive type according to a reaction mechanism by light. In the case of negative photosensitive resin, a photo-crosslinking reaction occurs in the exposed part, and the unexposed part is washed away with alkali to leave a resist pattern. In the case of positive photosensitive resin, a photodecomposition reaction occurs in the exposed part. The resist pattern is formed by leaving the unexposed area remaining.

  The photosensitive resin layer includes a photopolymerizable monomer, a photopolymerization initiator, a binder polymer, and the like and is manufactured according to the purpose. Such a photosensitive resin layer is apply | coated on a support body film, and has a thickness of 15-100 micrometers according to the intended purpose after application | coating. Such a photosensitive resin layer has various compositions according to mechanical and chemical properties required for the photoresist and processing conditions.

  On the other hand, the protective film serves as a protective cover that prevents damage to the resist during handling and protects the photosensitive resin layer from foreign matters such as dust, and is formed by a support film of the photosensitive resin layer. Laminated on the back side that is not.

  An example of a pattern formation method using such a dry film photoresist is, when applied on a printed circuit board, first peeled off the protective film, laminated on a copper clad laminate (CCL), A mask having a desired pattern is applied and exposed by irradiating with ultraviolet rays (UV), and a developing process is performed to wash away uncured portions using an appropriate solvent.

  Usually, when a dry film photoresist having such a composition is used, since the support film is attached to the photosensitive resin layer at the time of exposure, the photosensitive resin layer and the mask are the thickness of the support film. There is a limit in improving the resolution as a result of the separation. In addition, when exposure is performed by irradiating with ultraviolet light, the ultraviolet light passes through the support film and affects the ultraviolet transmittance, and there is a limit to the realization of high resolution due to ultraviolet scattering by particles in the support film. .

  In order to solve such a point, it is conceivable to perform exposure after peeling off the support film, but the photosensitive resin layer has adhesiveness, and when the support film is peeled off, the mask is Since it adheres to the photosensitive resin layer, 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, it is difficult to perform exposure after actually peeling off the support film, and the problem of resolution reduction due to this still remains.

  Moreover, as the density of printed circuit boards increases and the development of semiconductor packaging technology, the density of circuit lines increases, so high-resolution dry film photoresists that can be applied to such fine circuit boards. The demand for is urgently required.

  It is an object of the present invention to provide a dry film photoresist that improves the resolution by enabling the exposure process to be performed with the support film removed.

  In one embodiment of the present invention, a support film, a resin protective layer, and a photosensitive resin layer are sequentially laminated. The resin protective layer includes a water-soluble polymer having a weight average molecular weight of 5,000 to 300,000. Is 3.0% or less, and a dry film photoresist having a development time of 10 seconds or less per 1 μm is provided.

  In another embodiment of the present invention, a dry film photoresist is provided in which the water-soluble polymer includes polyvinyl alcohol having a saponification degree of 75 to 97%.

  In another embodiment of the present invention, a dry film photoresist is provided in which the resin protective layer includes polysilicon.

  In another embodiment of the present invention, a dry film photoresist is provided in which the resin protective layer includes 0.01 to 3 parts by weight of polysilicon with respect to 100 parts by weight of the water-soluble polymer.

  In another embodiment of the present invention, 0.1 g of polysilicon is added to 100 g of any one solvent selected from water, alcohols, and a mixture thereof at 80 ° C. for 6 hours. Provided is a dry film photoresist having a particle size of 1 μm or less when dissolved.

  In another embodiment of the present invention, a dry film photoresist is provided in which the resin protective layer has a thickness of 10 μm or less.

  In another embodiment of the present invention, the resin protective layer includes a water-soluble polymer and provides a dry film photoresist having a thickness of 10 μm or less and a thickness deviation of 1 μm or less.

  In another embodiment of the present invention, a dry film photoresist is provided in which the UV protective layer has a UV transmittance of 70% or more at 355 nm and 405 nm, respectively.

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

In another embodiment of the present invention, one surface of the resin protective layer in the dry film photoresist from which the support film has been removed and one surface of the resin protective layer in the dry film photoresist from which the other support film has been removed include After laminating at 110 ° C. at a speed of 2 m / min and a pressure of 4 kgf / cm ² so as to come into contact, when further separating the dry film photoresist, between one side of the resin protective layer and one side of another resin protective layer A dry film photoresist having an adhesive strength of 0.01 N / cm or less is provided.

  In another embodiment of the present invention, the photosensitive resin layer provides a dry film photoresist having a gloss after development of 15 or more at 20 ° and 60 or more at 60 °.

  In another embodiment of the present invention, a dry film photoresist is provided in which the support film in contact with the resin protective layer has a surface roughness Ra of 0.01 or less.

  In another embodiment of the present invention, a dry film photoresist is provided that further includes a protective film on one surface of the photosensitive resin layer.

  The dry film photoresist according to the present invention can perform the exposure process in a state where the support film is removed, and ultimately improves the resolution by preventing the adverse effect of the exposure effect by the support film. be able to.

  In addition, according to the present invention, even when exposure is performed in a state where a resin protective layer is present, high resolution can be achieved because the transparency of the resin protective layer or the development speed does not decrease.

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

  Also, when using dry film photoresist for pattern formation, when dry film film photoresist is laminated and stored after the exposure process, even if the laminated dry film photoresist is further separated, due to the adhesive force between the films Since the photosensitive resin layer is not damaged and the transfer phenomenon does not occur, high resolution can be achieved.

It is a figure which shows roughly the thickness deviation which concerns on this invention. It is the electron micrograph which expanded and imaged the surface of the printed circuit board after the image development process manufactured in Example 1 of this invention 1200 times. 4 is an electron micrograph taken by enlarging the surface of a printed circuit board manufactured in Comparative Example 1 after a development process at a magnification of 1200 times.

  According to an embodiment of the present invention, a support film, a resin protective layer, and a 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 300,000. Provided is a dry film photoresist wherein the haze of the resin protective layer is 3.0% or less and the development time per 1 μm of the resin protective layer is 10 seconds or less.

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

  Since the support film serves as a support for the resin protective layer and the photosensitive resin layer, it is preferable to have sufficient mechanical properties. More specifically, the support film includes polyester films such as polyethylene terephthalate film and polyethylene naphthalate film; polyolefin films such as polyethylene film and polypropylene film; copolymer films of polyvinyl chloride and vinyl acetate, polytetra Polyvinyl film such as fluoroethylene film and polytrifluoroethylene film; Polyimide film; Polyamide film such as 6,6-nylon; Polyacetate film such as cellulose triacetate film and cellulose diacetate film; Alkyl poly (meta ) Polyacrylate films such as acrylate films; (meth) acrylic acid ester copolymer films Polyacrylic film; and the like can be illustrated, in consideration of the mechanical properties and economy, preferable examples thereof include polyethylene terephthalate.

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

  The surface roughness Ra of the support film surface in contact with the resin protective layer is preferably 0.01 or less.

  The surface roughness of the portion in contact with the resin protective layer in the support film forms the surface roughness of the resin protective layer coated on the support film, and the surface roughness of the resin protective layer causes light scattering of the resin protective layer. Through which the haze is increased. Therefore, the surface roughness of the portion in contact with the resin protective layer in the support film is an important factor of the present invention. From such a viewpoint, in order to increase haze, the surface roughness Ra of the support film surface in contact with the resin protective layer is preferably 0.01 or less.

  The resin protective layer contains a water-soluble polymer having a weight average molecular weight of 5,000 to 300,000, has a haze of 3.0% or less, and a development time per 1 μm of 10 seconds or less.

  When the dry film photoresist according to the present invention is used in a pattern forming method, an example will be described. First, a dry film photoresist in which a support film, a resin protective layer, and a photosensitive resin layer are sequentially laminated is photosensitive. When there is a protective film on one side of the resin layer, the protective film is peeled off, and lamination is performed so that one side of the photosensitive resin layer and the upper part of the copper clad laminate (CCL) are in contact. Thereafter, the support film is removed, a mask having a desired pattern is placed on the resin protective layer, exposed to ultraviolet rays (UV), exposed, and an uncured portion is washed away using an appropriate developer. Go through.

  Most of the developer is made of a water-soluble solvent, but it is important that the resin protective layer is dissolved in the water-soluble solvent of the developer and washed well so that no residue remains on the photosensitive resin layer after development. This is one of the factors that enhance developability.

  In particular, the solubility of the water-soluble polymer contained in the resin protective layer decreases as the weight average molecular weight increases, and the degree of washing away by the developer may decrease.

  Such developability is affected by the development speed, but the higher the development speed of the resin protective layer, the better. If the development speed of the resin protective layer is slow, the difference in development time due to the thickness deviation of the resin protective layer can be reduced. Therefore, if the photosensitive resin layer is washed away more than necessary, the adhesive force is lowered, or if the photosensitive resin layer is washed away less, the resolution is lowered. Therefore, in order to form a precise pattern, the development speed of the resin protective layer must have an appropriate speed in consideration of development of the photosensitive resin layer.

  Therefore, the resin protective layer contains a water-soluble polymer having an appropriate level of weight average molecular weight in order to improve developability, and is suitable so that there is no residue and damage does not occur in the cured portion of the photosensitive resin layer. It is important to have a level of development speed.

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

  In the present invention, it includes a resin protective layer having a haze of 3.0% or less, preferably 0.001 to 3.0%, and a development time per 1 μm of 10 seconds or less, preferably 0.1 to 10 seconds. This increases the light transmittance during exposure and has an optimum development speed, so that the resolution can be improved.

  Specifically, the haze of the resin protective layer is required to have a low value in order to reduce the light scattering degree. When the haze of the resin protective layer exceeds 3%, there is a problem that the shape (side wall) of the photosensitive resin layer that has undergone the exposure and development processes becomes rough and rough.

  In addition, the developing speed of the resin protective layer is required to have a low value for improving the developability, so the lower limit value is preferable. When the development time per 1 μm of the resin protective layer exceeds 10 seconds, the difference in the development speed due to the thickness deviation of the resin protective layer is large, so that the adhesive force decreases when the photosensitive resin layer is washed away more than necessary. However, if the degree of washing of the photosensitive resin layer is small, there is a problem that the resolution is lowered.

  In addition, the dry film photoresist of the present invention has a structure in which the resin protective layer is laminated between a support film and a photosensitive resin layer. Therefore, the support film is removed before the exposure step to expose the dry film photoresist. Since the process can be performed, when the exposure process is performed with the conventional support film removed, damage on the photosensitive resin layer caused by contact with the mask and contamination of the mask can be prevented. The effect which prevents the bad influence by the particle | grains contained in the body film can also be acquired.

2 m / min at 110 ° C. so that one surface of the resin protective layer in the dry film photoresist from which the support film was removed and one surface of the resin protective layer in the dry film photoresist from which the other support film was removed were in contact with each other. When laminating at a speed of 4 kgf / cm ² and then further separating the dry film photoresist, the adhesive force between one surface of the resin protective layer and one surface of the other resin protective layer is 0.01 N. The lower limit of the adhesive force is meaningless because the transfer phenomenon is eliminated as the adhesive strength is lower.

  That is, if the adhesive force between the resin protective layers of the dry film photoresist according to the present invention is within the above range, when the resin protective layers are brought into contact with each other and then separated, the resin protective layers are clean without any transfer phenomenon. If the adhesive strength between the resin protective layers exceeds 0.01 N / cm, the photosensitive resin protective layer or the photosensitive resin layer is damaged by the transfer phenomenon between the resin protective layers. There is a problem.

  Specifically, when dry film photoresist is used in the pattern formation method, the support film is removed, a mask having a desired pattern is applied on the resin protective layer, and ultraviolet light (UV) is irradiated for exposure. I do. At this time, since there is no adhesive force between the mask and the resin protective layer, the mask and the resin protective layer are easily separated from each other, and there is no transfer between them. Thereafter, the film is stacked and stored, and the dry film photoresist that has been stacked and stored after such exposure is further separated for the development process. At this time, the adhesive force between the dry film photoresists is large during separation, and the photosensitive resin layer may be peeled off, or partial transfer of the resin protective layer may occur. As a result, there arises a problem that the resolution is lowered.

  In this invention, when the adhesive force between resin protective layers exists in the said range, the effect which prevents such a problem can be acquired.

  On the other hand, the resin protective layer is required to have an appropriate level of adhesive strength with the support film in consideration of the case where the support film is removed. However, the flat film is stably attached to the laminated support film, and at the same time, when removing the support film from the resin protective layer, the surface of the resin protective layer must not be damaged. And the adhesive strength between the resin protective layers is preferably 0.0005 to 0.01 N / cm. Specifically, if the adhesive strength is within the above range, when removing the protective film during lamination, there is an advantage that the support film and the resin protective layer are not separated, and before exposure. When the support film is removed, there is an advantage that it can be removed without damaging the resin protective layer.

  The resin protective layer contains a water-soluble polymer having a weight average molecular weight of 5,000 to 300,000, preferably 5,000 to 15,000, and more preferably 5,000 to 10,000. If the weight average molecular weight is less than 5,000, coating on a film becomes difficult, and it is not preferable because the strength is weak and it is difficult to perform a protective function of the photosensitive resin layer. If the weight average molecular weight exceeds 300,000, The development time becomes longer, and there is a risk of damage when the support film is peeled off after being laminated on the copper clad laminate.

  The method for forming such a resin protective layer is not particularly limited, and the resin protective layer-forming composition is dissolved in a solvent containing an organic solvent and water, and applied and dried on a support film. Thus, a resin protective layer can be formed.

  Examples of the water-soluble polymer include polyvinyl ether maleic anhydride, cellulose ether, carboxyl alkyl cellulose, carboxyl alkyl starch, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamides, polyamide, polyacrylic acid, polyethylene glycol, polypropylene glycol, gelatin. , Ethylene oxide polymers, starches and water-soluble polymers such as 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 saponification degree is a factor that affects the developability. When the saponification degree is within the above range, the resin protective layer forms the photosensitive resin layer with an appropriate development time, but there is an effect that the adhesion strength and the resolution are not lowered.

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

  When a dry film photoresist is used for the pattern forming method, a mask is applied to irradiate the light during the exposure process, and higher resolution can be realized as the distance between the mask and the photosensitive resin layer is shorter. For this reason, it is most preferable to expose the mask by applying a mask to the upper part of the photosensitive resin layer, but the photosensitive resin layer sticks to the mask due to the adhesiveness of the photosensitive resin layer. Due to such problems, there has been a limit in improving the resolution in the past.

  In the present invention, in order to achieve high resolution, the resin protective layer is required to have a low thickness. Therefore, the lower limit value is preferably as low as possible, and therefore a resin protective layer having a thickness of 10 μm or less is used. Therefore, even if exposure is performed after removing the support film after minimizing the separation distance from the mask, the photosensitive resin layer will not be damaged and the mask will not be contaminated. As a result, high resolution can be realized.

  The resin protective layer has a thickness defined such that the thickness deviation is 1 μm or less. Specifically, the thickness of the resin protective layer in the present invention means an average thickness based on an arithmetic average value, and is defined by the following formula 1.

<Formula 1>

In the formula, m represents an average thickness, and in a set of n numbers (x ₁ , x ₂ , x ₃ ,..., X _n ), n represents the number of times the thickness was measured, and x is The numerical value which measured thickness is shown.

The thickness deviation includes the absolute value (| mx- _max |) obtained by subtracting the maximum value (x _max ) of the numerical value for measuring the thickness from the average thickness (m) and the minimum value of the numerical value for measuring the thickness. It means 1/2 of the sum of the absolute value (| m−X _min |) obtained by subtracting the value (x− _min ) from the average thickness (m), and is defined by the following formula 2.

<Formula 2>
Thickness deviation = (| mx- _max | + | mx- _min |) / 2
In order to make the thickness of the resin protective layer uniform, it is preferable that the lower limit of the thickness deviation is as low as possible. When the thickness deviation exceeds the above range, the circuit implementation capability is due to the difference in the development time for each part of the photosensitive resin layer. There is a problem of off contact of a mask for forming a circuit during exposure.

  This will be described with reference to FIG. 1. m indicates the average thickness, a indicates that the value of mx has a positive value, and b indicates that the value of mx has a negative value. Indicates.

  When the absolute values a (| a |) and b (| b |) increase, the thickness corresponding to a and b becomes thicker or thinner from the surface of the photosensitive resin, and the thickened portion is the average of the resin protective layer. The development time is longer than the thickness, and conversely, the portion where the development is thinner is shorter than the average thickness of the resin protective layer, and the development time for each part of the resin protective layer is different. For example, when development is performed with the development time set on the basis of the average thickness of the resin protective layer, the portion where the resin protective layer is thicker than the average thickness is washed away with less resin protective layer, and the photosensitive layer located below the resin protective layer is washed away. There is a possibility that the photosensitive resin layer may not be developed, and in the portion where the resin protective layer is thinner than the average thickness, the resin protective layer may be washed away more than necessary, and the surface of the photosensitive resin layer may be damaged.

  Accordingly, as the absolute values a and b, that is, the thickness deviation obtained from them are lower, the development time is uniformly applied to the resin protective layer, and the difference in the development time for each part of the photosensitive resin layer is minimized. As a result, high resolution can be realized.

  Further, when the thickness deviation is within the above range, the surface of the resin protective layer is uniform, and the effect of improving the properties such as haze and UV transmittance of the resin protective layer can be obtained.

  The above-mentioned resin protective layer is produced by dissolving a water-soluble polymer and polysilicon selectively in an aqueous solvent containing an organic solvent and water. By such an aqueous solvent system, it is washed away with a developer mainly composed of a water-soluble solvent.

  In addition, since the photosensitive resin layer in contact with the aqueous resin protective layer is manufactured in an oil-based solvent system, it is possible to fundamentally prevent contamination between the aqueous resin protective layer and the oil-based photosensitive resin layer. Can do. If mixing between the resin protective layer and the photosensitive resin layer occurs, the components of the resin protective layer remain in the photosensitive resin layer even after development, or a part of the exposed and cured photosensitive resin layer is developed. As a result, the glossiness of the photosensitive resin layer is lowered, and thus the developability may be lowered.

  In the present invention, since the resin protective layer has an aqueous composition, the resin protective layer can be easily washed away with a developer and can be prevented from being mixed with the oil-based photosensitive resin layer. The glossiness of the surface is excellent and the developability can be improved.

  In the present invention, the glossiness of the photosensitive resin layer was measured after development using a glossiness measuring instrument (Gloss Meter Reading). The glossiness conforms to the KS definition (KS M ISO 2813: 2007).

  More specifically, the glossiness (specular gloss) is irradiated by an object located in the specular direction when the light source and the light receiving unit are set at a predetermined angle. The ratio between the speed of light and the speed of light reflected when a glass with a refractive index of 1.567 is placed on the reflecting surface, 20 °, 60 °, 85 ° of polished black glass with a refractive index of 1.567 Each of the specular gloss values is defined as 100.

  In this respect, the surface of the photosensitive resin layer after development is preferably 15 or more at 20 ° and 60 or more at 60 °, and if the gloss is within the above range, the resin protection Since mixing between the layer and the photosensitive resin layer does not occur, developability is not hindered.

  It is preferable that the UV transmittance of the resin protective layer is 70% or more at 355 nm and 405 nm, respectively. If the UV transmittance of the resin protective layer is less than 70%, the amount of exposure necessary to obtain the same sensitivity increases, the workability decreases, and light distortion such as scattering and refraction becomes severe, resulting in high light. It acts as an impediment when the resolution is realized.

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

  The polysilicon plays a role of imparting releasability to the resin protective layer, and also affects the adhesive force and haze between the support film and the resin protective layer.

  Such polysilicon has solubility in any one solvent selected from water, alcohols, and mixtures thereof. If polysilicon is soluble in an organic solvent, it will not dissolve in water, alcohols, or a solvent in which these are mixed.

  The polysilicon has a particle size of 1 μm or less when 0.1 g of polysilicon is dissolved in 100 g of the solvent at 80 ° C. for 6 hours when measured with a solution type particle size measuring instrument. Since it is preferable to dissolve all of the polysilicon, the lower the lower limit of the particle size, the better. When the grain size of the polysilicon is within the above range, haze can be prevented from being lowered, and the side wall can be prevented from being inferior during circuit formation of the photosensitive resin layer.

  The resin protective layer of the present invention may contain 0.01 to 3 parts by weight of polysilicon with respect to 100 parts by weight of the water-soluble polymer. The content of polysilicon with respect to 100 parts by weight of the water-soluble polymer is preferably within the above range in consideration of the ease of application on the support film and the haze of the resin protective layer after drying.

  More specifically, in general, polysilicon has a property as a release agent. However, when the content of polysilicon is small compared to polyvinyl alcohol forming the resin protective layer, that is, polysilicon is 0. When it is contained in the resin protective layer at less than 0.01 parts by weight, the adhesive strength between the resin protective layers exceeds 0.01 N / cm, and during the separation after contact between the resin protective layers, the photosensitive resin layer is damaged or By causing a transfer phenomenon between the resin protective layers, unintended transfer to the photosensitive resin layer may occur. In addition, when polysilicon exceeds 3 parts by weight, there is a problem that the physical properties of the circuit are deteriorated due to an increase in haze.

  In the present invention, such a problem is prevented by setting the content of polysilicon to polyvinyl alcohol within the above range so that the adhesive strength between the resin protective layers is within a range of 0.01 N / cm or less. Can do.

  Meanwhile, the composition of the photosensitive resin layer may be changed by applying a dry film photoresist as a negative type or a positive type. As a composition of the photosensitive resin layer by such a negative type or positive type dry film photoresist, the composition of a known photosensitive resin in the field to which the present invention belongs can be usually selected.

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

  As the binder resin, acrylic polymer, polyester, polyurethane and the like can be used, and among these, methacrylic copolymer which is a kind of acrylic polymer is preferable. If necessary, a copolymer of ethylenically unsaturated carboxylic acid and other monomers can be used. As the methacrylic copolymer, a metaclick copolymer containing an acetoacetyl group can also be used. Examples of methacrylic monomers that can be used to synthesize the methacrylic copolymer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate ( hexyl methacrylate), 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, dimethylaminoethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate methacrylate), glycidyl methacrylate and the like. As the ethylenically unsaturated carboxylic acid, monoacrylic acid such as acrylic acid, methacrylic acid, and crotonic acid is frequently used. Also, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, or anhydrides and half esters thereof can be used. Among these, acrylic acid and methacrylic acid are preferable. Other copolymerizable monomers include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, Examples thereof include alkyl vinyl ether.

  The ethylenically unsaturated compound as the copolymerizable monomer may be a monofunctional monomer or a bifunctional, trifunctional or higher polyfunctional monomer. Examples of the polyfunctional monomer include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, and polypropylene glycol dimethacrylate. Methacrylate (polypropylene glycol dimethacrylate), Butylene glycol dimethacrylate, Neopentyl glycol dimethacrylate, 1,6-hexane glycol dimethacrylate, Trimethylolpropane trimethacrylate (trimethylolpropane trimethacrylate), glycerin dimethacrylate, pentaerythritol dimethacrylate (Pentaerythritol dimethacrylate), pentaerythritol trimethacrylate, dipentaerythritol pentamethacrylate, 2,2-bis (4-methacryloxydiethoxyphenyl) propane (2,2-bis (4-methacryloxydiethoxyphenyl) propane), 2-hydroxy-3-methacryloyloxypropyl methacrylate, ethylene glycol diglycidyl ether dimethacrylate, diethylene glycol diglycidyl ether dimethacrylate , Phthalic acid diglycidyl ester dimethacrylate, glycerin polyglycidyl ether polymethacrylate yl ether polymethacrylate). Examples of the polyfunctional monomer include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, and 2-phenoxy-2-hydroxy. Propyl methacrylate (2-phenoxy-2-hydroxypropyl methacrylate), 2-methacryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl methacrylate (3-chloro-2-hydroxypropyl methacrylate) Hydroxypropyl methacrylate, glycerin monomethacrylate, 2-methacryloyloxyethyl acid phosphate, methacrylates of phthalic acid derivatives, N-methylol methacrylamide and the like can be used. The monofunctional monomer can be used together with the polyfunctional monomer.

  Examples of the photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, and benzoin phenyl 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 (diethylamino) benzophenone (p, p ') -bis (diethylamino) benzophenone), p, p'-diethylaminobenzophenone ( p, p'-diethylaminobenzophenone), pivalone ethyl ether, 1,1-dichloroacetophenone, pt-butyldichloroacetophenone, hexaaryl-imidazole (hexaaryl) -imidazole) dimer, 2,2'-diethoxyacetophenone, 2,2'-diethoxy-2-phenylacetophenone, 2,2 '-Dichloro-4-phenoxyacetophenone (2,2'-dichloro-4-phenoxyacetophenone), 2,2'-dichloro-4-phenoxyacetophenone (2,2'-dichloro-4-phenoxyacetophenone), phenylglyoxylate ( phenyl glyoxylate), a-hydroxy-isobutylphenone, dibenzospan, 1- (4-isopropylphenyl) -2-hydro 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.

  The additive may include a softening agent such as vinyl chloride resin. Specific examples include phthalic ester types such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, and dioctyl phthalate ( dioctyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, diisononyl phthalate, ethylphthalylethyl glycolate, dimethylisophthalate, dichlorohexyl phthalate ) And esters of fatty acids or aromatic acids, such as dioctyl adipate, diisobutyl adipate, dibutyl adipate, diisodecyl adipa te), dibutyl diglycol adipate, dibutyl sebacate, dioctyl sebacate, and the like. In the present invention, glycerol triacetate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate (tributoxyethyl phosphate) , Tris-chloroethyl phosphate, tris-dichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl Diphenyl phosphate (cresyl diphenyl phosphate), octyl diphenyl phosphate, xylenyl diphenyl phosphate, trilauryl phosphate Trilauryl phosphate, tricetyl phosphate, tristearyl phosphate, trioleyl phosphate, triphenyl phosphite, tris-tridecyl phosphite Dibutyl hydrogen phosphite, dibutyl-butyl phosphonate, di (2-ethylhexyl) phosphonate, 2-ethylhexyl-2-ethylhexylphosphonate ( 2-ethylhexyl-2-ethylhexyl phosphonate), methyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, dibutyl acid phosphate, monobutyl acid phosphate ( monobutyl acid phosphate) Softeners such as octyl acid phosphate, dioctyl phosphate, isodecyl acid phosphate, monoisodecyl phosphate, decanol acid phosphate, etc. It can also be used.

  Other volatile organic substances 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, and the like can also be used as the softening agent of the present invention.

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

  The 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 plays a role of protecting the photosensitive resin layer from the outside, and is easily removed when a dry film photoresist is applied to a subsequent process, while being released during storage and distribution. In order to prevent this, an appropriate releasability and adhesion are required.

  Hereinafter, preferred examples and comparative examples of the present invention will be described. However, the following embodiment is only a preferred embodiment of the present invention and does not limit the present invention.

Examples 1-6 and Comparative Examples 1-7

<Example 1>
(A) Polysilicone having a particle size of 0 μm when dissolved in 0.1 g of polysilicon in 100 g of polyvinyl alcohol (KURARAY, PVA205) having a weight average molecular weight of 22000 and a saponification degree of 87%, and 100 g of butoxyethanol solvent (BYK, BYK-349, 0.25% with respect to 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 protective layer composition. . This 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 heated at 80 ° C. using a hot air oven. A resin protective layer having a thickness of 3 μm and a thickness deviation of 0.4 μm was formed by drying for 5 minutes. At this time, when the polysilicon is dissolved in the solvent for 6 hours under the condition of 80 ° C., the particle size is 0 μm because the polysilicon is almost completely dissolved in the solvent and the particle shape is not found. Unless otherwise stated, “particle size 0 μm” has the same meaning as described above.

  (B) The photosensitive resin composition was manufactured with the composition and content which were used for UH-9200 series (Kolon). Specifically, after photoinitiators are dissolved in methyl ethyl ketone and methyl alcohol as solvents, photopolymerizable oligomers and binder polymer are added and mixed for 1 hour using a mechanical stirrer. Thus, a photosensitive resin composition was produced.

  (C) After coating the photosensitive resin composition on a 19 μm-thick protective film (polyethylene terephthalate film from which silicone has been released, CY201-19um, KOLON) using a coating bar, using a hot air oven A photosensitive resin layer having a thickness of 15 μm was formed by drying at 80 ° C. for 6 minutes.

(D) A dry film photoresist was produced by laminating at 50 ° C. under a pressure of 4 kgf / cm ² so that the photosensitive resin layer of the dried (c) film and the resin protective layer of (a) were in contact with each other.

<Example 2>
A dry film photoresist was produced in the same manner as in Example 1 except for the following.

  (A) Polyvinyl alcohol (KURARAY, PVA217) having a weight average molecular weight of 75,000 and a saponification degree of 87%, and polysilicon having a particle size of 0 μm (BYK, BYK-349, 0.25% based on the solid content after drying) 0.025g was put into 100g of distilled water, and it stirred at 80 degreeC for 6 hours, and manufactured the composition for resin protective layers. This 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 heated at 80 ° C. using a hot air oven. A resin protective layer having a thickness of 3.0 μm and a thickness deviation of 0.4 μm was formed by drying for 5 minutes.

<Example 3>
A dry film photoresist was produced in the same manner as in Example 1 except that the following was carried out.

  (A) Polyethylene glycol (manufacturer: Sigma-Aldrich, weight average molecular weight 20,000), and polysilicon having a particle size of 0 μm (BYK, BYK-349, 0.25% based on solid content after drying) 0 0.025 g was put in 100 g of distilled water, and stirred at 80 ° C. for 6 hours to completely dissolve the resin protective layer 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 then heated at 80 ° C. using a hot air oven. By drying for a minute, a resin protective layer having a thickness of 3.0 μm and a thickness deviation of 0.4 μm was formed.

<Example 4>
A dry film photoresist was produced in the same manner as in Example 1 except for the following.

  (A) 20 g of polyvinyl alcohol (KURARAY, PVA205) having a weight average molecular weight of 22000 and a saponification degree of 87%, and polysilicon having a particle size of 0 μm (BYK, BYK-349, 1.0% based on the solid content after drying) 0.2 g was put into 100 g of distilled water and stirred at 80 ° C. for 6 hours to completely dissolve the resin protective layer composition. This was coated with a coating bar on the ILC opposite surface of a 16 μm-thick support film (0.7% haze, ILC (in-line coating) on one side, polyethylene terephthalate film, SDFR-16 μm, KOLON). Then, it dried for 10 minutes at 80 degreeC using hot air oven, and formed the resin protective layer of thickness 3.0micrometer and thickness deviation 0.4micrometer.

<Example 5>
A dry film photoresist was produced in the same manner as in Example 1 except for the following.

  (A) 20 g of polyvinyl alcohol (KURARAY, PVA205) having a weight average molecular weight of 22000 and a saponification degree of 87%, and polysilicon having a particle size of 0 μm (BYK, BYK-349, 0.25% based on the solid content after drying) 0.05 g was put into 100 g of distilled water, and stirred at 80 ° C. for 6 hours to completely dissolve the resin protective layer composition. This 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 heated at 80 ° C. using a hot air oven. By drying for 5 minutes, a resin protective layer having a thickness of 6 μm and a thickness deviation of 0.6 μm was formed.

<Example 6>
A dry film photoresist was produced in the same manner as in Example 1 except for the following.

  (A) 20 g of polyvinyl alcohol (KURARAY, PVA205) having a weight average molecular weight of 22000 and a saponification degree of 87%, and polysilicon having a particle size of 0 μm (BYK, BYK-349, 0.25% based on the solid content after drying) 0.05 g was put into 100 g of distilled water, and stirred at 80 ° C. for 6 hours to completely dissolve the resin protective layer 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 then heated at 80 ° C. using a hot air oven. By drying for minutes, a resin protective layer having a thickness of 10.0 μm and a thickness deviation of 0.8 μm was formed.

<Comparative Example 1>
(A) The photosensitive resin composition was manufactured by the composition and content which were used for UH-9200 series (Kolon). Specifically, after photoinitiators are dissolved in methyl ethyl ketone and methyl alcohol as solvents, photopolymerizable oligomers and a binder polymer are added and mixed for 1 hour using a mechanical stirrer, thereby obtaining photosensitivity. A resin composition was produced.

  (B) After coating the photosensitive resin composition on a 16 μm-thick support film (haze 2.3%, no surface treatment, polyethylene terephthalate film, FDFR-16 μm, KOLON) using a coating bar, A photosensitive resin layer having a thickness of 15 μm was formed by drying at 80 ° C. for 10 minutes using an oven.

(C) The photosensitive resin layer of the dried (b) film and the release layer of a 19 μm-thick protective film (polyethylene terephthalate film subjected to silicon release treatment, CY201-19 μm, KOLON) are in contact with each other. Lamination was performed at 0 ° C. and a pressure of 4 kgf / cm ² to produce a dry film photoresist having a thickness of 50 μm.

<Comparative Example 2>
A dry film photoresist was produced in the same manner as in Example 1 except for the following.

  (A) Polyvinyl alcohol (KURARAY, PVA205) 20 g having a weight average molecular weight of 22000 and a saponification degree of 87%, and polysilicon having a particle size of 0 μm (BYK, BYK-349, 3.0% based on the solid content after drying) A composition for a resin protective layer was produced by placing 0.7 g in 100 g of distilled water and stirring it at 80 ° C. for 6 hours to completely dissolve it. This was coated with a coating bar on the ILC opposite surface of a 16 μm-thick support film (0.7% haze, ILC (in-line coating) on one side, polyethylene terephthalate film, SDFR-16 μm, KOLON). Then, the resin protective layer having a thickness of 3 μm and a thickness deviation of 3 μm was formed by drying at 80 ° C. for 10 minutes using a hot air oven.

<Comparative Example 3>
A dry film photoresist was produced in the same manner as in Example 1 except for the following.

  (A) Polyvinyl alcohol having a weight average molecular weight of 75,000 and a saponification degree of 98% (Toyo Seikan Kagaku Co., Ltd., F17), and polysilicon having a particle size of 0 μm (BYK, BYK-349, 0.000 based on the solid content after drying). 25%) 0.01 g in 100 g of distilled water was stirred at 80 ° C. for 6 hours to completely dissolve the resin protective layer 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 then heated at 80 ° C. using a hot air oven. By drying for a minute, a resin protective layer having a thickness of 3 μm and a thickness deviation of 3 μm was formed.

<Comparative Example 4>
A dry film photoresist was produced in the same manner as in Example 1 except for the following.

  (A) 20 g of polyvinyl alcohol (KURARAY, PVA205) having a weight average molecular weight of 22000 and a saponification degree of 87%, and polysilicon having a particle size of 0 μm (BYK, BYK-349, 0.25% based on the solid content after drying) 0.05 g was put into 100 g of distilled water, and stirred at 80 ° C. for 6 hours to completely dissolve the resin protective layer 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 then heated at 80 ° C. using a hot air oven. By drying for a minute, a resin protective layer having a thickness of 16 μm and a thickness deviation of 0.9 μm was formed.

<Comparative Example 5>
A dry film photoresist was produced in the same manner as in Example 1 except for the following.

  (A) A resin protective layer composition was prepared by putting 100 g of acrylic acid polymer (KOLON, KBP116) having a weight average molecular weight of 60000 into methyl ethyl ketone 100 and stirring it at 30 ° C. for 6 hours to completely dissolve it. This 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 heated at 80 ° C. using a hot air oven. By drying for a minute, a resin protective layer having a thickness of 3 μm and a thickness deviation of 0.4 μm was formed.

<Comparative Example 6>
A dry film photoresist was produced in the same manner as in Example 1 except for the following.

  (A) 100 g of acrylic acid polymer (KOLON, KBP114) having a weight average molecular weight of 30,000 was placed in 100 g of methyl ethyl ketone, and stirred at 30 ° C. for 6 hours to completely dissolve the resin protective layer composition. This 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 heated at 80 ° C. using a hot air oven. By drying for a minute, a resin protective layer having a thickness of 3 μm and a thickness deviation of 0.4 μm was formed.

<Comparative Example 7>
A dry film photoresist was produced in the same manner as in Example 1 except for the following.

  (A) Polysilicone having a particle size of 0 μm when dissolved in 0.1 g of polysilicon in 100 g of polyvinyl alcohol (KURARAY, PVA205) having a weight average molecular weight of 22000 and a saponification degree of 87%, and 100 g of butoxyethanol solvent (BYK, BYK-349, 0.008% with respect to 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 protective layer composition. . This was coated on a 16 μm-thick support film (haze 15.1%, no surface treatment, polyethylene terephthalate film, NDFR-16 μm, KOLON) using a coating bar, and then heated at 80 ° C. using a hot air oven. By drying for a minute, a resin protective layer having a thickness of 3 μm and a thickness deviation of 0.4 μm was formed.

  The weight average molecular weights of the water-soluble polymers of Examples 1 to 6 and Comparative Examples 2 to 7 were measured by the following method.

Measurement of Weight Average Molecular Weight The weight average molecular weight of the water-soluble polymer was measured using a GFC (Gel Filtration Chromatography; Varian GPC system) at a temperature of 40 ° C., Stationary Phase: (Plgel Mixed D) × 2, Mobile Phase: THF, 1 0.1 mL / min, Injection: 100 μL, Detection: RI, PS Standard (Polymer Standards Service, Mp723000, 219000, 89300, 52200, 30300, 7000, 5000, 2960) at a concentration of 0.1% The sample was dissolved in THF and injected and measured as a reference substance. The sample was dissolved in THF at a concentration of 0.2% and then filtered through a 0.45 μm PTFE syringe filter.

  The thicknesses and thickness deviations of the resin protective layers produced in Examples 1 to 6 and Comparative Examples 2 to 7 were measured as follows.

Measurement of Thickness and Thickness Deviation of Resin Protective Layer A support film obtained by attaching a tape on a support film (PET) of dry film photoresist produced in Examples 1 to 6 and Comparative Examples 2 to 7, and then removing the support film After removing a part of the resin protective layer, the thickness of the resin protective layer appearing in the cross section of the dry film photoresist portion is measured using K351C of Anritsu (the measurement range is set to 0.1 μm). At that time, 20 points were arbitrarily set and the thickness thereof was measured, and the average thickness of the resin protective layer was obtained from the measured value by the arithmetic average value of Formula 1 according to the present invention.

  Moreover, the thickness deviation was calculated | required by Formula 2 which concerns on this invention from the average value of the resin protective layer obtained by the maximum value and minimum value and said Formula 1 among these measured values.

  The UV transmittances of the resin protective layers produced in Examples 1 to 6 and Comparative Examples 2 to 7 were measured as follows.

Measurement of UV transmittance The dry film photoresist produced in Examples 1 to 6 and Comparative Examples 2 to 7 was cut to a size of 7 cm × 7 cm, and then the protective film was peeled off to form a copper clad laminate having a size of 10 cm × 10 cm. Laminated. Then, after peeling the support film of the laminated dry film photoresist, the resin protective layer was peeled off, and the removed resin protective layer was 355 nm using a UV-3101PC (UV-VIS-NIR SCANNING SPECTROPHOTOMETER) manufactured by SHIMADZU. The UV transmittance at 405 nm was measured.

  Table 1 below shows the results of measuring the UV transmittance of the resin protective layers produced in Examples 1 to 6 and Comparative Examples 2 to 7.

  From the measurement results, it can be seen that the transmittance does not differ greatly in the types of substances of the resin protective layer used in Examples and Comparative Examples, and the transmittance varies depending on the thickness. In particular, Example 6 has a transmittance of 70% or more, which is suitable for the purpose of the present invention, but Comparative Example 4 has a transmittance of about 60%, which is not suitable for use.

  The surface roughness of the support films produced in Examples 1 to 6 and Comparative Examples 2 to 7 was measured as follows.

Surface Roughness Measurement After the support films used in Examples 1 to 6 and Comparative Examples 2 to 7 were cut to a size of 1 cm × 1 cm, the surface roughness of the portion in contact with the resin protective layer was determined by AFM (Atomic Force Microscopy). , PSIA M5AV) using a 100 um scanning head (Park Scientific Instruments).

  Table 2 below shows the results of measuring the surface roughness of the portions in contact with the resin protective layer of the support films used in Examples 1 to 6 and Comparative Examples 2 to 7.

   From the measurement results, it can be seen that the higher the haze of the support film, the higher the surface roughness of the support film. The haze is determined by the content of particles used in the production of PET in the support film. However, if the content of particles is large, the number of particles exposed on the surface increases and the surface roughness increases. However, since the ILC-treated PET (SDFR16) used in Example 4 and Comparative Example 2 has no particles on the surface in contact with the resin protective layer, the content of particles in the ILC composition increases and haze increases. However, it can be expected that the surface roughness of the surface in contact with the resin protective layer in the support film does not change.

  The adhesive strength of the dry film photoresists produced by Examples 1-6 and Comparative Examples 1-7 was measured as follows.

Adhesion measurement
<Adhesive strength between resin protective layers>
After removing the protective film of the dry film photoresist specimen having a width of 3 cm and a length of 20 cm, two samples were prepared by laminating to FCCL at a speed of 2 m / min at 110 ° C. and a pressure of 4 kgf / cm ² . Thereafter, the support films of the two samples were released, and the resin protective layers were laminated to face each other at 110 ° C. at a speed of 2 m / min and a pressure of 4 kgf / cm ² . Then, while releasing the adhered sample, the force required to release the sample using 10N Load cell at a speed of 100 mm / min from the start point to the 5 cm point to the 8 cm point is applied to UTM (4303 series, Instron). ).

<Adhesive strength between support film and 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, it was laminated on a copper clad laminate at a rate of 2 m / min at 110 ° C. and a pressure of 4 kgf / cm ² . Then, UTM (4303 series, Instron) required force to release using a 10N load cell from the start point to a point of 5 cm to 8 cm at a rate of 100 mm / min while releasing the support film. It measured using.

<Adhesive strength between photosensitive resin layer and protective film>
Necessary for releasing 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 time of 100 mm / min from the start point to a point of 5 cm to 8 cm. The force was measured using UTM (4303 series, Instron).

<Adhesive strength between the resin protective layer and PET after peeling off the support film>
After removing the protective film of the dry film photoresist specimen having a width of 3 cm and a length of 20 cm and laminating at 110 ° C. under the condition of 4 kgf / cm ² at a speed of 2 m / min, the support film was removed. After laminating a PET film (FDFR, Kolon Co., Ltd.) having a width of 4 cm, a width of 25 cm, and a thickness of 19 μm at 110 ° C. and 4 kgf / cm ² at a speed of 2 m / min, the PET film was started to be released from the mold. The force required to release the mold using a 10N load cell at a speed of 100 mm / min from the start point to the 5 cm point to the 8 cm point was measured using UTM (4303 series, Instron).

  Table 3 below shows the results of measuring the adhesive strength of the dry film photoresists produced in Examples 1-6 and Comparative Examples 1-7.

  The conditions for laminating the PET film are the same as the conditions for adhering to a mask during general exposure. At this time, the measured adhesive strength of the support film is that of Examples 1 to 6 and Comparative Example 2. In the case of -7, it is the adhesive force between a resin protective layer and a PET film.

   (Ii) In Table 1, exceptionally, * means the adhesive strength between the support film and the photosensitive resin layer, and ** indicates the adhesive strength between the photosensitive resin layer and the PET film after peeling the support film. Means.

  From the measurement results, it can be seen that, except for Comparative Example 3, 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 within a range that does not impair the workability. Moreover, it turns out that the adhesive force between the resin protective layer and PET after peeling a support body film is remarkably low compared with the comparative example 1.

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

Characteristic Evaluation After the dry film photoresist produced in Examples 1 to 6 and Comparative Examples 1 to 7 was formed on a printed board by the following method, the characteristics of the dry film photoresist were evaluated.

(1) Formation on a printed circuit board A new copper surface is formed on a copper clad laminate (CCL) using a brush pretreatment machine to form an appropriate surface roughness. Then, after acid treatment with a 5% sulfuric acid solution, it was washed with water and dried, and put into a laminator. Using a Hakuto Mach 610i as a laminator, the dry film photoresist produced in Examples 1-6 and Comparative Examples 1-7 was applied to a copper clad laminate at 110 ° C. at a pressure of 4 kgf / cm ² and a speed of 2 m / min. Laminated. At this time, preheating is not performed. Thereafter, exposure was performed by irradiation with a UV exposure machine (Perkin Elmer OB-7120, 5 KW parallel light). The exposed printed circuit board was developed through a developing machine.

  In this case, in Examples 1 to 6 including the resin protective layer, the support film is peeled off before the exposure step, whereas in Comparative Example 1 in which the resin protective layer is not included, the support film is removed before the development step. Peeled off.

(A) Haze After the dry film photoresist produced by Examples 1-6 and Comparative Examples 1-7 was cut into a size of 7 cm × 7 cm, the protective film was peeled off and laminated to a copper-clad laminate of size 10 cm × 10 cm did. Then, after peeling off the support film of the laminated dry film photoresist, the resin protective layer is peeled off, and the haze of the peeled resin protective layer is measured using a haze meter (Nippon Denshoku Co., Ltd., NDH-2000). did.

(B) Development time When a resin protective layer is not included, a printed circuit board obtained by laminating a dry film photoresist on a copper clad laminate as in (a) above is developed at a pressure of 1.5 kgf / cm ² at a temperature of 30 ° C. Pass the fan-type nozzle that sprays the solution (1% Na ₂ CO ₃ aqueous solution) through a developing machine with a distance of 15 cm between the substrate and measure the time that the laminated part is completely washed away by the developer and removed. This was defined as the minimum development time of only the photosensitive resin layer (hereinafter referred to as “S _min ”). Further, the actual development time of only the photosensitive resin layer (hereinafter referred to as “S _del ”) 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 the same as the method of measuring the minimum development time (S _min ) of only the photosensitive resin layer. Measured. The actual development time of the film including the resin protective layer (hereinafter referred to as “P _del ”) is the actual development time of the photosensitive resin layer only (S _del ) and the development time of the resin protective layer only (hereinafter referred to as “P _tim ”). This must be added, and this is expressed by the following formula 1.

<Formula 1>

  When the expression 1 is changed, it is expressed by the following expression 2.

<Formula 2>

  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 are measured, and from these values, the resin protective layer is included. The actual development time of the film can be calculated.

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

The development time (P _tim ) of only the resin protective layer is calculated from Equation 1 and Equation 2, 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. To do.

(C) Sensitivity and exposure amount At the time of exposure, in Examples 1 to 6 and Comparative Examples 2 to 7, on the resin protective layer, and in Comparative Example 1 on the support film, a sensitivity device (21 stages). After placing the Stuffer Step Table), the exposure amount for obtaining the sensitivity of 5, 6, and 7 steps was measured using a light meter (UV-351, manufactured by ORC). The measured values are shown in Table 4 below. At this time, the sensitivity was evaluated by the maximum number of photosensitive resists remaining on the substrate after development.

(2) Circuit physical properties: resolution, fine line adhesion, and 1/1 (Line / Space) resolution The circuit physical properties are measured by measuring the resolution, fine line adhesion, and 1/1 (Line / Space) resolution using the Kolon Test Artwork. Evaluated.

  In this experiment, the resolution is a value obtained by measuring the degree to which the line width is developed when an unexposed part is developed. The smaller the value, the higher the resolution, and the measured resolution is measured. The used mask was formed at intervals of 0.5 μm from 4 to 20 μm, and a mask made at intervals of 400 μm was used for the resolution to be realized. The value of the fine line adhesion force is a value obtained by measuring how small the line width of the exposed portion is not eroded after development to form a linear circuit, and the smaller this value, the better the fine line adhesion value. The mask used for the measurement of the measured fine line adhesion force value is formed at intervals of 0.5 μm from 4 to 20 μm, and the mask made at an interval of 400 μm to the fine line adhesion force value to be realized. It was used. The 1/1 resolution is a value obtained by measuring the minimum line width that is finely developed with an interval between circuit lines of 1: 1.

(3) Glossiness Glossiness was measured at a gloss measurement angle of 20 ° and 60 ° according to the KS definition (KS M ISO 2813: 2007) using a gloss meter reading.
In order to measure the glossiness by the above method, first, a dry film photoresist having a resin protective layer was laminated on a copper clad laminate, exposed and developed, and then the glossiness was measured. At this time, the exposure and development were carried out by the methods implemented in the above-described characteristic evaluation. The results are shown in Table 5 below.

(4) Surface analysis The printed circuit board to which the dry film photoresist of Example 1 and Comparative Example 1 was applied was exposed and developed as described above, and then the surface was photographed with an electron microscope, respectively. -Shown in FIG.

  Table 4 below shows the measurement results of circuit properties according to haze, development time, and exposure conditions.

(Ii) In Table 4, 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 time of the film including the resin protective layer ( P _del ). However, exceptionally, * means the minimum development time (S _min ) of only the photosensitive resin layer, and ** means the free development time (S _del ) of only the photosensitive resin.

  Table 5 below shows the results of measuring the glossiness of the surface of the photosensitive resin layer after development.

  As a result of the measurement, Comparative Example 1 had no resin protective layer, so haze measurement was impossible. In particular, Comparative Example 5 and Comparative Example 6 were unable to measure haze because mixing between the resin protective layer and the photosensitive resin layer occurred and the layers were not separated. In Comparative Example 3, the haze value was lower than those in Examples 4 to 6, but there was a problem that the development time was significantly increased and the circuit physical properties were lowered.

  Moreover, the exposure amount required in order to implement | achieve the same number of steps had almost no difference between Examples 1-6 and Comparative Examples 1-7. From the measurement results of the circuit physical properties, it can be seen that the examples show more excellent results including resolution.

  On the other hand, in the case of a dry film photoresist including the resin protective layer of the present invention, the resin protective layer development time was about 0.5 to 3 seconds.

  Moreover, in the case of FIG. 2 which shows the surface photograph of the printed circuit board which applied the dry film photoresist by Example 1 as a result of the surface observation by the electron micrograph of FIGS. 2-3, the case of FIG. 3 which applied the comparative example 1 It can be seen that there was almost no unevenness on the side and surface, and a very excellent pattern was formed.

  Therefore, when the dry film photoresist of the present invention is applied, it is easy to handle at the time of exposure, the resolution is improved, and mixing between the resin protective layer and the photosensitive resin layer is prevented, and the photosensitive resin is also developed after development. It can be seen that the glossiness of the layer is excellent and the developability is improved.

  Simple variations or modifications of the present invention can be easily implemented by those having ordinary skill in the art, and it can be understood that any such variations or modifications fall within the scope of the present invention.

Claims (13)

Comprising a support film, a resin protective layer and a photosensitive resin layer laminated in sequence,
The resin protective layer contains a water-soluble polymer having a weight average molecular weight of 5000 to 300,000, the haze of the resin protective layer is 3.0% or less, and the development time per 1 μm of the resin protective layer is 10 seconds or less. The dry film photoresist characterized by the above-mentioned.   The dry film photoresist of claim 1, wherein the water-soluble polymer includes polyvinyl alcohol having a saponification degree of 75 to 97%.   The dry film photoresist of claim 1, wherein the resin protective layer includes polysilicon.   The dry film photoresist of claim 1, wherein the resin protective layer includes 0.01 to 3 parts by weight of polysilicon with respect to 100 parts by weight of the water-soluble polymer.   The polysilicon has a particle size of 1 μm or less when 0.1 g of polysilicon is dissolved in 100 g of a solvent selected from water, alcohols, and a mixture thereof at 80 ° C. for 6 hours. 5. A dry film photoresist according to claim 3 or 4, characterized in that it is.   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 resin protective layer includes a water-soluble polymer and has a thickness of 10 μm or less and a thickness deviation of 1 μm or less.   The dry film photoresist according to claim 1, wherein the resin protective layer has a UV transmittance of 70% or more at 355 nm and 405 nm, respectively.   The dry film photoresist according to claim 1, wherein an adhesive force between the support film and the resin protective layer is 0.0005 to 0.01 N / cm. 2 m / min at 110 ° C. so that one surface of the resin protective layer in the dry film photoresist from which the support film has been removed is in contact with one surface of the resin protective layer in the dry film photoresist from which the other support film has been removed. After laminating at a speed 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 further separated is 0.01 N / The dry film photoresist according to claim 1, wherein the dry film photoresist is cm or less.   The dry film photoresist according to claim 1, wherein the photosensitive resin layer has a gloss after development of 15 or more at 20 ° and 60 or more at 60 °.   The dry film photoresist according to claim 1, wherein the surface roughness Ra of the support film in contact with the resin protective layer is 0.01 or less.   The dry film photoresist of claim 1, further comprising a protective film on one surface of the photosensitive resin layer.