JP5741179B2 - Photosensitive film - Google Patents

Description

  The present invention relates to a positive photosensitive film.

  As an image forming method used for patterning of semiconductor integrated circuits, liquid crystal display elements, printed wiring boards and the like, a positive type using a photosensitive resin composition containing a novolac type phenolic resin and a 1,2-quinonediazide compound as a raw material A method using a photoresist is known (see, for example, Patent Documents 1 and 2).

  When a positive photoresist is formed through application of the photosensitive resin composition, the application thickness is generally about 0.5 to 15 μm. When this positive photoresist is used, an image pattern over a wide size range is formed. The size range is wide, for example, from a sub-half micron region of about 0.3 μm to a considerably large size width of about several tens to several hundreds of μm. This makes it possible to finely process a wide variety of substrate surfaces.

  The positive photoresist can be developed with an aqueous alkaline solution, and is more widely used than a photoresist that requires development with a solvent, for example, a rubber-based negative photoresist. This is because positive photoresists have better resolution than conventional rubber-based negative photoresists, and the positive photoresists have better acid / etching resistance and are suitable for development. This is because, since no solvent is used, the problem of waste liquid treatment is smaller than when a solvent is used.

  And, the biggest factor is that the above-mentioned positive photoresist has a very small change in image size due to swelling during development, and the size controllability is relatively easy. Is mentioned.

  In recent years, positive photoresists can be processed into dry films using a resist hot roll laminating method because they can be processed at the same time on both sides when laminating a resist layer on a substrate and because they have excellent followability to flexible substrates. Lamination is highly desired.

  However, when a conventional photosensitive resin composition mainly composed of a phenol novolac resin is formed into a dry film, the adhesive force with the support film tends to be increased, so that a laminator is used for pressure bonding onto a substrate. At the time of thermal transfer, the photosensitive layer made of the photosensitive resin composition partially remains on the support film, and defects may occur in the image pattern formed using the photoresist.

  On the other hand, in Patent Document 3, it has been studied to add a release agent to the photosensitive resin composition to improve the peelability between the photosensitive layer and the support film.

JP-A-6-27657 JP 2000-105466 A Special table 2008-529080 gazette

  However, it is difficult to achieve both releasability from the support film and photosensitive performance only by adding a release agent to the photosensitive resin composition. According to the study by the present inventors, if the amount of the release agent added to the photosensitive layer is small, the peelability from the support film is not sufficient, and if the amount of the release agent added is increased, the photosensitive layer sensitivity, resolution and other photosensitive characteristics Has been confirmed to decrease.

  Therefore, the present invention has been made in view of the above circumstances, and a photosensitive film having a sufficiently high peelability from a support film of a photosensitive layer made of a photosensitive resin composition and capable of forming a resist pattern having no defects. The purpose is to provide.

  The present invention relates to a photosensitive resin composition comprising a support film having at least one surface subjected to a release treatment, and (a) a phenol resin, (b) a 1,2-quinonediazide compound, and (c) a fluorosurfactant. Provided is a photosensitive film in which a photosensitive layer made of a product and a protective film are laminated in this order, and the photosensitive layer is formed on a release treatment surface of a support film.

  According to the photosensitive film, a positive photosensitive resin composition containing a specific component is laminated on a support film that has been subjected to a release treatment, thereby comprising the support film and the photosensitive resin composition. Adhesive strength with the photosensitive layer can be sufficiently controlled, and the photosensitive layer can be transferred to the substrate without the photosensitive layer remaining on the support film.

  From the viewpoint of achieving both adhesiveness and transferability of the photosensitive layer, the content of (c) the fluorosurfactant in the photosensitive resin composition is such that (a) the phenolic resin and (b) the 1,2-quinonediazide compound. It is preferable that it is 0.1-5 mass parts with respect to 100 mass parts of total amounts.

  When the surface tension at 23 ° C. of the release treatment surface of the support film is 20 to 45 mN / m, the photosensitive layer is easily transferred to the substrate without remaining the photosensitive layer on the support film.

  In the photosensitive film of the present invention, the peel strength between the photosensitive layer and the protective film is 2.0 N / m or less, and the peel strength is smaller than the peel strength between the photosensitive layer and the support film. preferable.

  ADVANTAGE OF THE INVENTION According to this invention, the peelability from the support body film of the photosensitive layer which consists of photosensitive resin compositions can be provided sufficiently, and the photosensitive film which can form a resist pattern without a defect can be provided.

It is a schematic cross section which shows one Embodiment of the photosensitive film of this invention.

  The photosensitive film of the present invention is a photosensitive layer comprising a support film having at least one surface release-treated, and a photosensitive resin composition containing a phenol resin, a 1,2-quinonediazide compound, and a fluorosurfactant. And a protective film are laminated in this order, and the photosensitive layer is formed on the release treatment surface of the support film.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of the photosensitive film of the present invention. The photosensitive film 1 shown in FIG. 1 has a structure in which a photosensitive layer 14 is laminated on a support film 10 and a protective film 15 is laminated on the surface of the photosensitive layer 14 opposite to the support film 10. The photosensitive layer 14 is a layer made of a photosensitive resin composition of the present embodiment described later.

<Support film>
At least one surface of the support film 10 according to the present embodiment is subjected to a release treatment. Here, the mold release treatment in this embodiment is supported by a silicone surfactant, a silicone compound such as a silicone resin, a fluorine surfactant, a fluorine-containing compound such as a fluorine resin, or a mold release agent such as an alkyd resin. It refers to a physical treatment such as a chemical treatment for thinly coating the surface of a body film or a corona treatment for a support film.

  When a release agent is coated on the support film, it is preferable to coat thinly as long as the release effect can be obtained. After coating, the release agent may be fixed to the support film by heat or UV treatment. More preferably, an undercoat layer is applied to the support film before coating the release agent.

  From the viewpoint of the applicability of the photosensitive resin composition and the peelability of the photosensitive layer, the surface tension (wetting tension) at 23 ° C. of the release treatment surface of the support film is preferably 20 to 45 mN / m. It is more preferably 30 to 45 mN / m, and still more preferably 35 to 45 mN / m.

  Further, from the viewpoint of the peelability of the photosensitive layer, the 180 ° C. peel strength at 23 ° C. of the release treatment surface of the support film is preferably 5 to 300 g / inch (1.97 to 118 g / cm). More preferably, it is -200 g / inch (1.97-78.7 g / cm), More preferably, it is 100-200 g / inch (39.4-78.7 g / cm). The 180 ° peel strength can be measured by a general method (for example, a method based on JIS K6854-2) using an adhesive tape (manufactured by Nitto Denko Corporation, trade name: “NITTO31B”).

  The support film before the release treatment is not particularly limited as long as the surface is smooth. For example, a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used. (Hereinafter referred to as “PET film”) is preferable.

  As a PET film in which at least one surface is release-treated with a silicone compound, for example, trade names “A31-25”, “A51-25” and “A53-38” manufactured by Teijin DuPont Film Co., Ltd. are commercially available. It is available.

  The thickness of the support film 10 is preferably 15 to 50 μm, and more preferably 25 to 40 μm. If the thickness of the support film 10 is less than 15 μm, distortion during the mold release process may remain or wrinkles may occur when the film is wound, and if it exceeds 50 μm, At the time of thermocompression bonding when the photosensitive layer 14 is laminated, bubbles tend to be easily caught between the base material and the photosensitive layer 14.

<Photosensitive layer>
The photosensitive layer 14 comprises a photosensitive resin composition containing a phenol resin as the component (a), a 1,2-quinonediazide compound as the component (b), and a fluorosurfactant as the component (c) as a support film. It was formed by applying to the surface of 10 mold release treatments. Hereinafter, each component will be described in detail.

[(A) component: phenol resin]
The phenol resin is a polycondensation product of phenol or a derivative thereof and aldehydes. The polycondensation is performed in the presence of a catalyst such as an acid or a base. A phenol resin obtained when an acid catalyst is used is particularly referred to as a novolak type phenol resin. Specific examples of novolak resins include phenol / formaldehyde novolak resins, cresol / formaldehyde novolak resins, xylylenol / formaldehyde novolak resins, resorcinol / formaldehyde novolak resins and phenol-naphthol / formaldehyde novolak resins.

  Examples of the phenol derivative used for obtaining the phenol resin include o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol and 3 Alkylphenols such as 4,4,5-trimethylphenol, alkoxyphenols such as methoxyphenol and 2-methoxy-4-methylphenol, alkenylphenols such as vinylphenol and allylphenol, aralkylphenols such as benzylphenol, metho Alkoxycarbonylphenol such as sicarbonylphenol, arylcarbonylphenol such as benzoyloxyphenol, halogenated phenol such as chlorophenol, polyhydroxybenzene such as catechol, resorcinol and pyrogallol, bisphenol such as bisphenol A and bisphenol F, α- or β -Naphthol derivatives such as naphthol, hydroxyalkylphenols such as p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol and p-hydroxyphenyl-4-butanol, hydroxyalkylcresols such as hydroxyethylcresol, monos of bisphenol Alcohol-containing hydroxyl group-containing compounds such as ethylene oxide adducts and bisphenol monopropylene oxide adducts Carboxyl groups such as diol derivatives, p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylbutanoic acid, p-hydroxycinnamic acid, hydroxybenzoic acid, hydroxyphenylbenzoic acid, hydroxyphenoxybenzoic acid and diphenolic acid Examples thereof include phenol derivatives. Further, methylolated products of the above phenol derivatives such as bishydroxymethyl-p-cresol may be used as the phenol derivative.

  Furthermore, the phenol resin may be a product obtained by polycondensing the above-described phenol or phenol derivative with an aldehyde together with a compound other than phenol such as m-xylene. In this case, the molar ratio of the compound other than phenol to the phenol derivative used for the condensation polymerization is preferably less than 0.5.

  Compounds other than the above-described phenol derivatives and phenol compounds are used singly or in combination of two or more.

  The aldehydes used to obtain the phenol resin are, for example, formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, acetone, glyceraldehyde , Glyoxylic acid, methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, formylacetic acid, methyl formylacetate, 2-formylpropionic acid and methyl 2-formylpropionate. In addition, a formaldehyde precursor such as paraformaldehyde or trioxane may be used in the reaction. Furthermore, keto acids such as pyruvic acid, levulinic acid, 4-acetylbutyric acid, acetone dicarboxylic acid, and 3,3′-4,4′-benzophenone tetracarboxylic acid can be used to obtain a phenol resin. These are used singly or in combination of two or more.

  The weight average molecular weight of the component (a) is preferably 500 to 500,000, more preferably 500 to 100,000, and still more preferably 1,000 to 50,000. Here, the weight average molecular weight is a value obtained by measuring by a gel permeation chromatography method and converting from a standard polystyrene calibration curve.

  The component (a) includes (a1) a modified phenolic resin having an unsaturated hydrocarbon group (hereinafter sometimes referred to as “component (a1)”) from the viewpoint of further improving the flexibility of the photosensitive layer 14. Can do. In addition, as the component (a1), a phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms is used from the viewpoint of improving mechanical properties (elongation at break, elastic modulus, etc.). preferable.

  (A1) A modified phenolic resin having an unsaturated hydrocarbon group is generally a compound having phenol or a derivative thereof and an unsaturated hydrocarbon group (preferably having 4 to 100 carbon atoms) (hereinafter sometimes referred to simply as “unsaturated”). A reaction product with a hydrocarbon group-containing compound ”(hereinafter referred to as“ unsaturated hydrocarbon group-modified phenol derivative ”) and a condensation polymerization product of an aldehyde or a phenol resin and an unsaturated hydrocarbon group. It is a reaction product with the containing compound.

  As the phenol derivative, the same phenol derivative as described above can be used as a raw material for the phenol resin as the component (a).

  The unsaturated hydrocarbon group of the unsaturated hydrocarbon group-containing compound preferably contains two or more unsaturated groups from the viewpoint of the adhesion of the resist pattern and the flexibility of the photosensitive layer 14. In addition, from the viewpoint of compatibility with the resin composition and the flexibility of the cured film, the unsaturated hydrocarbon group-containing compound preferably has 8 to 80 carbon atoms, more preferably 10 to 60 carbon atoms. preferable.

  Examples of the unsaturated hydrocarbon group-containing compound include unsaturated hydrocarbons having 4 to 100 carbon atoms, polybutadiene having a carboxyl group, epoxidized polybutadiene, linoleyl alcohol, oleyl alcohol, unsaturated fatty acid, and unsaturated fatty acid ester. . Suitable unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, α-linolenic acid, eleostearic acid, stearidone Examples include acids, arachidonic acid, eicosapentaenoic acid, sardine acid and docosahexaenoic acid. Among these, an ester of an unsaturated fatty acid having 8 to 30 carbon atoms and a monovalent to trivalent alcohol having 1 to 10 carbon atoms is more preferable, and an unsaturated fatty acid having 8 to 30 carbon atoms and a trivalent alcohol are preferable. Especially preferred are esters with glycerin.

  Esters of unsaturated fatty acids having 8 to 30 carbon atoms and glycerin are commercially available as vegetable oils. Vegetable oils include non-drying oils with an iodine value of 100 or less, semi-drying oils with more than 100 and less than 130, or 130 or more drying oils. Non-drying oils include, for example, olive oil, Asa seed oil, cashew oil, potato oil, camellia oil, castor oil, and peanut oil. Examples of semi-drying oils include corn oil, cottonseed oil, and sesame oil. Examples of the drying oil include paulownia oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, camellia oil and coconut oil. Moreover, you may use the processed vegetable oil obtained by processing these vegetable oils.

  Among the above vegetable oils, it is preferable to use a non-drying oil from the viewpoint of preventing gelation accompanying the progress of excessive reaction and improving the yield in the reaction of phenol or a derivative thereof or a phenol resin with a vegetable oil. On the other hand, it is preferable to use drying oil from the viewpoint of improving the adhesion and mechanical properties of the resist pattern. Among the drying oils, tung oil, linseed oil, soybean oil, walnut oil and safflower oil are preferable, and tung oil and linseed oil are more preferable because the effects of the present invention can be more effectively and reliably exhibited.

  These unsaturated hydrocarbon group-containing compounds are used singly or in combination of two or more.

  In preparing the component (a1), first, the phenol derivative and the unsaturated hydrocarbon group-containing compound are reacted to produce an unsaturated hydrocarbon group-modified phenol derivative. It is preferable to perform the said reaction at 50-130 degreeC. From the viewpoint of improving the flexibility of the photosensitive layer 14, the reaction ratio between the phenol derivative and the unsaturated hydrocarbon group-containing compound is 1 to 100 parts by mass of the unsaturated hydrocarbon group-containing compound with respect to 100 parts by mass of the phenol derivative. It is preferable that it is 5 to 50 parts by mass. In the above reaction, if necessary, p-toluenesulfonic acid, trifluoromethanesulfonic acid, or the like may be used as a catalyst.

  A phenol resin modified with an unsaturated hydrocarbon group-containing compound is produced by polycondensation of an unsaturated hydrocarbon group-modified phenol derivative produced by the above reaction with an aldehyde. As the aldehydes, those described above as the aldehydes used for obtaining the phenol resin can be used.

  The reaction between the aldehydes and the unsaturated hydrocarbon group-modified phenol derivative is a polycondensation reaction, and conventionally known synthesis conditions for phenol resins can be used. The reaction is preferably performed in the presence of a catalyst such as an acid or a base, and an acid catalyst is more preferably used. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid. These acid catalysts can be used alone or in combination of two or more.

  The above reaction is preferably carried out usually at a reaction temperature of 100 to 120 ° C. Moreover, although reaction time changes with kinds and quantity of a catalyst to be used, it is 1 to 50 hours normally. After completion of the reaction, the reaction product is dehydrated under reduced pressure at a temperature of 200 ° C. or lower to obtain a phenol resin modified with the unsaturated hydrocarbon group-containing compound. In the reaction, a solvent such as toluene, xylene, or methanol can be used.

  A phenol resin modified with an unsaturated hydrocarbon group-containing compound can also be obtained by polycondensing the unsaturated hydrocarbon group-modified phenol derivative with an aldehyde together with a compound other than phenol such as m-xylene. . In this case, the molar ratio of the compound other than phenol to the compound obtained by reacting the phenol derivative with the unsaturated hydrocarbon group-containing compound is preferably less than 0.5.

  The component (a1) can also be obtained by reacting the phenol resin of the component (a) with an unsaturated hydrocarbon group-containing compound.

  The unsaturated hydrocarbon group-containing compound to be reacted with the phenol resin can be the same as the unsaturated hydrocarbon group-containing compound described above.

  The reaction between the phenol resin and the unsaturated hydrocarbon group-containing compound is usually preferably performed at 50 to 130 ° C. In addition, the reaction ratio between the phenol resin and the unsaturated hydrocarbon group-containing compound is 1 to 100 masses of the unsaturated hydrocarbon group-containing compound with respect to 100 parts by mass of the phenol resin from the viewpoint of improving the flexibility of the photosensitive layer 14. Part, preferably 2 to 70 parts by weight, and more preferably 5 to 50 parts by weight. At this time, if necessary, p-toluenesulfonic acid, trifluoromethanesulfonic acid or the like may be used as a catalyst. In addition, solvents, such as toluene, xylene, methanol, tetrahydrofuran, can be used for reaction.

  A phenolic resin that has been acid-modified by further reacting a polybasic acid anhydride with the phenolic hydroxyl group remaining in the phenolic resin modified by the unsaturated hydrocarbon group-containing compound produced by the method as described above (a1) It can also be used as a component. By acid-modifying with a polybasic acid anhydride, a carboxy group is introduced, and development with a weak alkaline aqueous solution (developer) can be facilitated.

  The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of a carboxy group of a polybasic acid having a plurality of carboxy groups. Examples of the polybasic acid anhydride include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride Dibasic acid anhydrides such as acid, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride, biphenyl Tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride and benzophenone teto Aromatic tetrabasic acid dianhydride, such as a carboxylic acid dianhydride. You may use these individually by 1 type or in combination of 2 or more types. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably at least one selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride. In this case, there is an advantage that a resist pattern having a better shape can be formed.

  The reaction between the phenolic hydroxyl group and the polybasic acid anhydride can be carried out at 50 to 130 ° C. In this reaction, the polybasic acid anhydride is preferably reacted with 0.10 to 0.80 mol, more preferably 0.15 to 0.60 mol with respect to 1 mol of the phenolic hydroxyl group, More preferably, the reaction is performed at 20 to 0.40 mol. If the polybasic acid anhydride is less than 0.10 mol, the developability tends to decrease, and if it exceeds 0.80 mol, the alkali resistance of the unexposed area tends to decrease.

  In addition, you may contain a catalyst in the said reaction as needed from a viewpoint of performing reaction rapidly. Examples of the catalyst include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, and phosphorus compounds such as triphenylphosphine.

  The acid value of the phenol resin further modified with polybasic acid anhydride is preferably 30 to 200 mgKOH / g, more preferably 40 to 170 mgKOH / g, and further preferably 50 to 150 mgKOH / g. . When the acid value is less than 30 mgKOH / g, it tends to require a longer time for alkali development than when the acid value is in the above range, and when it exceeds 200 mgKOH / g, the acid value is in the above range. In comparison with the above, the developer resistance of the unexposed portion tends to be lowered.

  The molecular weight of the component (a1) is a weight average molecular weight of 500 to 150,000 in consideration of solubility in an alkaline aqueous solution and a balance between photosensitive characteristics (sensitivity and resolution) and mechanical characteristics (breaking elongation, elastic modulus and residual stress). It is preferable that it is 500, 100,000 is more preferable, and it is especially preferable that it is 1000-50000.

  Moreover, (a) component can also contain the phenol resin which made the polybasic acid anhydride react with the phenolic hydroxyl group of the phenol resin which is not modified | denatured by the unsaturated hydrocarbon group containing compound.

  The content of the component (a) in the photosensitive resin composition is preferably 50 to 95 parts by mass when the total amount of the components (a) and (b) is 100 parts by mass, and 55 to 90 parts by mass. It is more preferable that it is 60-85 mass parts. When the content of the component (a) is less than 50 parts by mass, the photosensitive layer 14 tends to become brittle and easily peeled compared to the case where the content is in the above range. Compared with the case where the content is in the above range, the photosensitivity of the photosensitive layer 14 tends to decrease.

[(B) component: 1,2-quinonediazide compound]
The component (b) is a 1,2-quinonediazide compound, which is 1,2-quinonediamide and / or a derivative thereof. Such a 1,2-quinonediazide compound is obtained by reacting a 1,2-quinonediazide compound having a sulfo group and / or a sulfonyl chloride group with an organic compound having a hydroxyl group or an amino group (hereinafter simply referred to as “organic compound”). Compound. At this time, the hydroxyl group or amino group of the organic compound is bonded to the sulfo group or sulfonyl chloride group of the 1,2-quinonediazide compound. Note that at least one bond may be present in the molecule of the 1,2-quinonediazide compound obtained.

  Examples of the 1,2-quinonediazide compound having a sulfo group and / or a sulfonyl chloride group include 1,2-naphthoquinone-2-diazide-4-sulfonic acid and 1,2-naphthoquinone-2-diazide-5-sulfone. Examples include acids, orthoanthraquinone diazide sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, and orthoanthraquinone diazide sulfonyl chloride. Among these, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and 1 , 2-naphthoquinone-2-diazide-5-sulfonyl chloride is preferably one or more compounds selected from the group consisting of. These 1,2-quinonediazide compounds having a sulfo group and / or a sulfonyl chloride group are well dissolved in a solvent, so that the reaction efficiency with an organic compound can be increased.

  Examples of the organic compound include polyhydroxybenzophenones, bis [(poly) hydroxyphenyl] alkanes, tris (hydroxyphenyl) methanes or methyl-substituted products thereof, bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methanes, or Its methyl substitution product, phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, aniline, p-aminodiphenylamine, 4,4 ′ -Diaminobenzophenone, novolak, pyrogallol-acetone resin, p-hydroxystyrene homopolymer or a copolymer with a monomer copolymerizable therewith. These are used singly or in combination of two or more.

  Examples of the polyhydroxybenzophenones include 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2′-methylbenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3 ′, 4,4 ', 6-pentahydroxybenzophenone, 2,2', 3,4,4'-pentahydroxybenzophenone, 2,2 ', 3,4,5-pentahydroxybenzophenone, 2,3', 4,4 ', 5 ', 6-hexahydroxybenzophenone and 2,3,3', 4,4 ', 5'-hexahydroxybenzophenone And the like. These are used singly or in combination of two or more.

  Examples of bis [(poly) hydroxyphenyl] alkanes include bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, and 2- (4-hydroxyphenyl) -2. -(4'-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ', 4'-dihydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2 -(2 ', 3', 4'-trihydroxyphenyl) propane, 4,4 '-{1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol and 3, And 3'-dimethyl- {1- [4- [2- (3-methyl-4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol. That. These are used singly or in combination of two or more.

  Examples of tris (hydroxyphenyl) methanes or methyl-substituted products thereof include tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, and bis (4- Hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl)- 2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane and bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane Can be mentioned. These are used singly or in combination of two or more.

  Examples of bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methanes or methyl-substituted products thereof include bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenylmethane and bis (3-cyclohexyl-4-hydroxyphenyl). ) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis ( 5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2- Droxyphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -3 -Hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl) -2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -2-hydroxyphenylmethane and bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -4-Hide Hydroxyphenyl methane and the like. These are used singly or in combination of two or more.

  Among these, organic compounds are polyhydroxybenzophenones, bis [(poly) hydroxyphenyl] alkanes, tris (hydroxyphenyl) methanes, and / or bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methanes. It is preferable.

  The organic compound is more preferably a compound represented by any one of the following general formulas (1) to (3). In this case, since the difference in solubility in the developer before and after the light irradiation to the photosensitive resin composition becomes large, there is an advantage that the image contrast is more excellent. These are used singly or in combination of two or more.

Here, in the formulas (1) to (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, and X represents a single bond, an oxygen atom, or a phenylene group. .

  When the organic compound is a compound represented by any one of the above general formulas (1) to (3), a 1,2-quinonediazide compound having a sulfo group and / or a sulfonyl chloride group is 1,2-naphthoquinone-2. -Diazide-4-sulfonic acid, 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride, and / or 1,2-naphthoquinone-2-diazide It is preferably -5-sulfonyl chloride. Since the 1,2-quinonediazide compounds having these sulfo groups and / or sulfonyl chloride groups have good compatibility with the compounds represented by the general formulas (1) to (3), the component (a) And the component (b) can be reduced in the amount of agglomerates generated when the components are mixed. In addition, when a photosensitive resin composition containing these is used as a photosensitive component of a positive photoresist, the sensitivity, image contrast, and heat resistance are excellent.

  The compounds represented by the general formulas (1) to (3) are more preferably compounds represented by any one of the following chemical formulas (4) to (6). In this case, there is an advantage that it is more excellent in light sensitivity.

  Examples of the synthesis method of the 1,2-quinonediazide compound using the compounds represented by the chemical formulas (4) to (6) include the following methods. That is, for example, a compound represented by any one of the above chemical formulas (4) to (6) and 1,2-naphthoquinone-2-diazide-sulfonyl chloride are added to a solvent such as dioxane or THF. , Triethylamine, triethanolamine, alkali carbonate, alkali hydrogen carbonate or the like in the presence of an alkali catalyst. At this time, a 1,2-quinonediazide compound in which the hydroxyl group of the compound represented by the chemical formulas (4) to (6) is condensed with the sulfonyl group of 1,2-naphthoquinone-2-diazide-sulfonyl chloride is synthesized. . In addition, in the molecule | numerator of the 1,2-quinonediazide compound obtained, the coupling | bonding of the hydroxyl group of the compound represented by Chemical formula (4)-(6) and the sulfonyl group of 1,2-naphthoquinone-2-diazide-sulfonyl chloride. There must be at least one.

  As 1,2-naphthoquinone-2-diazide-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride or 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride is preferable. You may use these individually by 1 type or in combination of 2 or more types.

  The content of the component (b) in the photosensitive resin composition is preferably 5 to 50 parts by mass, and 10 to 45 parts by mass, with the total amount of the component (a) and the component (b) being 100 parts by mass. More preferred is 15 to 40 parts by mass. When the content is less than 5 parts by mass, the photosensitivity tends to be lower than when the content is in the above range. When this content exceeds 50 parts by mass, when the photosensitive resin composition is used as a resist film as compared with the case where the content is in the above range, the resist film becomes brittle and tends to peel off. .

[(C) component: fluorinated surfactant]
(C) A component is mix | blended in order to improve the applicability | paintability of a photosensitive resin composition, defoaming property, leveling property, etc., and to improve the peelability from the support body film 10 of the photosensitive layer 14. FIG.

  Examples of the fluorosurfactant include BM-1000, BM-1100 (trade name, manufactured by BM Chemie); Megafuck F142D, Megafuck F172, Megafuck F173, Megafuck F183, Megafuck R-08 , Megafuck R-30, Megafuck R-90PM-20, Megafuck BL-20 (above, Dainippon Ink & Chemicals, trade name); Fluorard FC-135, Fluorard FC-170C, Fluorard FC-430, Fluorad FC-431, Novec FC-4430, Novec FC-4432 (above, trade name, manufactured by Sumitomo 3M Limited); Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 Using commercial products such as (Asahi Glass Co., Ltd., trade name) It is possible. Among these, Novec FC-4430 and Novec FC-4432, which are fluorosurfactants having a perfluorobutanesulfonic acid skeleton, are preferable from the viewpoint of further improving the crack generation after exposure. These are used singly or in combination of two or more.

  The content of the component (c) in the photosensitive resin composition is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b), 0.2 to It is preferably 2 parts by mass, and more preferably 0.3 to 1 part by mass. When the content of the component (c) exceeds 5 parts by mass, the image contrast tends to decrease.

[Other ingredients]
The photosensitive resin composition of the present embodiment may contain an adhesion assistant in order to improve adhesion with a substrate or the like. As the adhesion assistant, a functional silane coupling agent is preferable. Here, the functional silane coupling agent means a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group.

  Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, trimethoxysilylpropyl isocyanate and 1,3,5-N-tris (trimethoxysilylpropyl) isocyanate. These are used singly or in combination of two or more.

  When using the said adhesion assistant, it is preferable in content to be 20 mass parts or less with respect to 100 mass parts of total amounts of (a) component and (b) component. When this content exceeds 20 parts by mass, a development residue tends to be generated as compared with the case where the content is in the above range.

  The photosensitive resin composition may contain a solubility adjusting agent such as an acid or a high boiling point solvent for the purpose of finely adjusting the solubility in an alkali developer.

  Examples of the acid include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, iso-butyric acid, n-valeric acid, iso-valeric acid, benzoic acid, cinnamic acid, lactic acid, 2-hydroxybutyric acid, 3-hydroxy Hydroxy monocarboxylic acids such as butyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid and syringic acid; Acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, tri Merit acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1 Polycarboxylic acid such as 2,5,8-naphthalenetetracarboxylic acid, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydro anhydride Phthalic acid, hymic anhydride, 1,2,3,4-butanetetracarboxylic acid, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene Acid anhydrides such as glycol bis anhydride trimellitate and glycerin tris anhydride trimellitate are listed.

  Examples of the high boiling point solvent include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl. Ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, Examples include propylene carbonate and phenyl cellosolve acetate.

  These solubility regulators can be used alone or in combination of two or more. The content of the solubility adjuster is not particularly limited as long as it can be adjusted according to the application and application method and can be uniformly mixed in the photosensitive resin composition. For example, the content of the solubility modifier is preferably 60% by mass or less, and more preferably 40% by mass or less, based on the total amount of the photosensitive resin composition. In this case, there exists an advantage that the characteristic of the photosensitive resin composition is not impaired.

  In the photosensitive resin composition, if necessary, a sensitizer, a light absorber (dye), a crosslinking agent, a plasticizer, a pigment, a filler, a flame retardant, a stabilizer, an adhesion promoter, a release accelerator, You may contain additives, such as antioxidant, a fragrance | flavor, an imaging agent, and a thermal crosslinking agent. These additives may be used alone or in combination of two or more.

  Preparation of the photosensitive resin composition should just be performed by mixing and stirring by a normal method. In addition, when a filler, a pigment, or the like is added to the photosensitive resin composition, it may be dispersed and mixed using a disperser such as a dissolver, a homogenizer, or a three roll mill. Furthermore, you may filter using a mesh, a membrane filter, etc. as needed.

<Protective film>
As the protective film 15, for example, a polymer film such as polyethylene, polypropylene, polyethylene terephthalate, or polyester can be used. Moreover, you may use the polymer film which gave the mold release process similarly to a support body film. From the viewpoint of flexibility when the photosensitive film is rolled up, a polyethylene film is particularly preferable as the protective film 15. Moreover, it is preferable that the protective film 15 is a film with a low fish eye so that dents on the surface of the photosensitive layer can be reduced.

  The peel strength between the protective film 15 and the photosensitive layer 14 is preferably 2.0 N / m or less. In order to easily peel the protective film 15 from the photosensitive layer 14, it is preferable to select the protective film so that the peel strength is smaller than the peel strength between the photosensitive layer 14 and the support film 10.

  The thickness of the protective film 15 is preferably 10 to 100 μm, and particularly preferably 15 to 80 μm.

  Next, the manufacturing method of the photosensitive film 1 of this embodiment is demonstrated.

  The photosensitive layer 14 can be formed by applying the photosensitive resin composition as a liquid resist on the support film 10. When the photosensitive resin composition is applied onto the support film 10, if necessary, the photosensitive resin composition is dissolved in a predetermined solvent to obtain a solution having a solid content of 30 to 60% by mass. You may use as a coating liquid.

  Examples of such solvents include methanol, ethanol, propanol, ethylene glycol, propylene glycol, octane, decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, toluene, xylene. , Tetramethylbenzene, N, N-dimethylformamide, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene Glycol mono Chill ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate , Organic solvents such as dipropylene glycol monomethyl ether acetate, or a mixed solvent thereof.

  Examples of the coating method include a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, and a bar coater. The solvent can be removed by heating, for example. In this case, the heating temperature is preferably about 70 to 150 ° C., and the heating time is preferably about 5 to about 30 minutes.

  The amount of the remaining organic solvent in the photosensitive layer 14 thus formed is preferably 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.

  Moreover, although the thickness of the photosensitive layer 14 changes with uses, it is preferable that the thickness after removing a solvent is about 1-30 micrometers. Moreover, when using a photosensitive film in roll shape, it is preferable that the thickness of the photosensitive layer 14 shall be 1-5 micrometers from a viewpoint which can reduce the crack of the photosensitive layer 14. FIG. When producing a thick photosensitive film with the thickness of the photosensitive layer 14 being 5 μm to 30 μm, by using a modified phenol resin having (a1) an unsaturated hydrocarbon group as the component (a), The crack of the photosensitive layer 14 can be suppressed.

  The photosensitive film 1 includes intermediate layers such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer between the support film 10 and the photosensitive layer 14 and / or between the photosensitive layer 14 and the protective film 15. Alternatively, a protective layer may be further provided.

  The photosensitive film 1 can be wound around, for example, a cylindrical core and stored in a roll form. The core is not particularly limited as long as it is conventionally used. For example, plastic such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer), etc. Etc. At the time of storage, it is preferable to wind up so that a support body film may become the outermost side. Moreover, it is preferable to install an end face separator from the viewpoint of protecting the end face on the end face of the photosensitive film (photosensitive film roll) wound in a roll shape, and in addition, a moisture-proof end face separator is installed from the viewpoint of edge fusion resistance. It is preferable to do. Moreover, when packaging the photosensitive film 1, it is preferable to wrap it in a black sheet with low moisture permeability.

  Next, a resist pattern forming method will be described.

  The resist pattern is formed by laminating the photosensitive film 1 on a substrate so that the photosensitive layer 14 is in close contact, and irradiating an active ray in an image form to remove an exposed portion by development. . The portion that is not irradiated with actinic rays does not dissolve in alkali because the 1,2-quinonediazide compound interacts with the phenol resin and acts as a dissolution inhibitor. However, in the portion irradiated with actinic rays, the 1,2-quinonediazide compound is photolyzed and loses the dissolution inhibiting effect. Thereby, the exposed part irradiated with actinic light becomes alkali-soluble.

As a method for laminating the photosensitive layer 14 on the substrate, the protective film 15 is removed, and then the photosensitive layer 14 is heated to about 70 to 130 ° C. while being heated to about 0.1 to 1 MPa (1 to 10 kgf / cm). ^And a method of pressure bonding using a laminator or the like at a pressure of about ² ). Such a lamination process may be performed under reduced pressure. The surface of the base material on which the photosensitive layer 14 is laminated is not particularly limited.

  The photosensitive layer 14 thus laminated on the substrate is irradiated with actinic rays in an image form through a negative or positive mask pattern to form an exposed portion. At this time, when the support 10 existing on the photosensitive layer 14 is transparent to the active light, the support 10 can be irradiated with the active light, and the support 10 can block the active light. In this case, the photosensitive layer 14 is irradiated with actinic rays after the support 10 is removed.

  As the active light source, a conventionally known light source, for example, a light source that effectively emits ultraviolet light, visible light, or the like, such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, or a xenon lamp is used. Further, a laser direct drawing exposure method or the like may be used.

  After formation of the exposed portion, the resist layer is formed by removing the photosensitive layer in the exposed portion by development. As a method for removing the exposed portion, when the support 10 is present on the photosensitive layer 14, the support 10 is removed by an auto peeler or the like, and wet development with a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. Or a method of developing by removing an exposed portion by dry development or the like.

  Examples of the alkali used for wet development include weak alkali inorganic compounds such as sodium carbonate, potassium carbonate and ammonia; alkali metal compounds such as sodium hydroxide and potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide; monomethylamine Weak alkaline organic compounds such as dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethyl methacrylate, polyethyleneimine; Examples thereof include methylammonium hydroxide and tetraethylammonium hydroxide. These may be used alone or in combination of two or more as an aqueous solution. The pH of the alkaline aqueous solution is preferably in the range of 9 to 13, and the temperature is adjusted according to the developability of the photosensitive layer. Moreover, you may mix surfactant, an antifoamer, an organic solvent, etc. in alkaline aqueous solution.

  Examples of the development method include a dip method, a spray method, brushing, and slapping. In addition, as a process after image development, you may harden and use a resist pattern by performing a heating etc. of about 60-250 degreeC as needed.

  In this way, a resist pattern is obtained. By using the photosensitive film 1 of the present invention, the transfer property of the photosensitive layer 14 to the substrate is excellent, so that the support film 10 can be easily peeled and removed, and the photosensitive layer 14 can be transferred to the substrate without defects. As a result, a resist pattern with sufficiently few defects can be formed.

  Further, the exposed portion of the photosensitive layer 14 is easily dissolved in a weak alkaline aqueous solution and peeled off from the substrate, and the weak alkali developability is extremely good, so that a fine resist pattern with excellent contrast can be formed. Become.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment. The present invention can be variously modified without departing from the gist thereof.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

[Synthesis of phenol resin (A1)]
54 parts by mass of formalin, which is an aldehyde, is added to 216 parts by mass of a mixed solution in which m-cresol and p-cresol, which are phenolic compounds, are mixed at a mass ratio of 50:50, and 2.2 parts by mass of oxalic acid as a catalyst is used. Then, a condensation reaction was performed by a conventional method to obtain a novolac type phenol resin having a weight average molecular weight of 10,000.

  Next, 100 parts by mass of the novolac-type phenol resin, 10 parts by mass of tung oil as a drying oil, and 0.01 parts by mass of p-toluenesulfonic acid as an acidic catalyst were mixed and reacted at 90 ° C. The reaction solution was cooled to room temperature to obtain a tung oil-modified phenol resin (hereinafter referred to as “phenol resin A1”) as a reaction product.

[Synthesis of phenol resin (A2)]
54 parts by mass of formalin is added to 216 parts by mass of a mixed solution in which m-cresol and p-cresol are mixed at a mass ratio of 50:50, and a condensation reaction is performed by a conventional method using 2.2 parts by mass of oxalic acid. A novolak-type phenol resin (hereinafter referred to as “phenol resin A2”) having a weight average molecular weight of 10,000 was obtained.

[Preparation of positive photosensitive resin composition]
As the component (a), the phenol resin A1 and the phenol resin A2 were prepared.

  As the component (b), a 1,2-quinonediazide compound obtained by reacting 1 mol of the compound represented by the chemical formula (5) with 3 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride (hereinafter referred to as “component”). "DNQ") was prepared.

  As the component (c), trade names “Novec FC-4430” and “Novec FC-4432” manufactured by Sumitomo 3M Co., which are fluorine-based surfactants, and “MegaFak R”, trade names manufactured by Dainippon Ink and Chemicals, Inc. -08 "and" Megafuck R-30 "were prepared.

  As the component (c ′), a silicone surfactant, trade name “SH-193” manufactured by Toray Dow Corning Co., Ltd. was prepared.

  Each component, methyl ethyl ketone (MEK), and propylene glycol monomethyl ether acetate (PGMEA) were mixed so that it might become a composition (unit: mass part) shown in Table 1, and the photosensitive resin compositions 1-10 were prepared. In addition, the mass in Table 1 is a mass of non-volatile content.

The following films were prepared as a support film and a protective film.
PET film “A31-25” which has been release-treated with a silicone compound: Teijin DuPont Films, Inc., 380 mm wide, 25 μm thick, using NITTO 31B adhesive tape “NITTO 31B” at 23 ° C. 180 ° peel strength 5 g / inch. The surface tension of the mold release surface is 23 mN / m.
PET film “A53-38” release-treated with a silicone compound: Teijin DuPont Films, Inc., width 380 mm, thickness 38 μm, 180 ° peel strength 100 g / inch at 23 ° C. using “NITTO 31B”. The surface tension of the release treatment surface is 44 mN / m.
PET film “A51-25” release-treated with a silicone compound: Teijin DuPont Films, trade name, width 380 mm, thickness 25 μm, 180 ° peel strength at 23 ° C. using 200 Nt, 200 g /inch. The surface tension of the release treatment surface is 38 mN / m.
PET film “G2-38”: Teijin DuPont Films Co., Ltd., 380 mm wide, 38 μm thick, 180 ° peel strength at 23 ° C. using “NITTO 31B” exceeding 500 g / inch. Surface tension 46 mN / m.
Polyethylene film “NF-15”: manufactured by Tamapoli Co., Ltd., width 380 mm, thickness 23 μm.

Here, the surface tension of the release treatment surface of the support film is a value measured as follows.
When a commercially available liquid mixture for wet tension test (manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the mold release surface of the support film using a cotton swab under the condition of 23 ° C., the liquid was not repelled. The minimum value of the test liquid mixture number to get wet was defined as the surface tension (wetting tension). For comparison, a PET film “G2-38” that was not subjected to release treatment was also evaluated in the same manner.

[Preparation of photosensitive film]
Example 1
A photosensitive film was prepared using the solution of the photosensitive resin composition 1 according to the following procedure. First, “A31-25” which is a release-treated PET film was used as a support film, and a solution of the photosensitive resin composition 1 was applied on the release-treated surface. Next, the PET film coated with the solution of the photosensitive resin composition 1 was held in a hot air convection dryer set at 100 ° C. to form a photosensitive layer. At that time, the thickness of the photosensitive layer after heating was set to 3 μm. Then, “NF-15” was placed as a protective film on the formed photosensitive layer and pressed with a roll. Thus, the photosensitive film of Example 1 was obtained.

(Examples 2 to 7)
Each photosensitive film was produced according to the same procedure as Example 1 using the support film shown in Table 2, the solution of the photosensitive resin composition, and the protective film.

(Comparative Examples 1-6)
Each photosensitive film was produced according to the same procedure as Example 1 using the support film shown in Table 3, the solution of the photosensitive resin composition, and the protective film.

[Applicability to support film]
A solution of the photosensitive resin composition was applied on the support film so that the thickness of the photosensitive layer after drying was 3 μm, and the coating property was evaluated according to the following criteria.
A: A solution of the photosensitive resin composition can be uniformly applied.
B: There are many repels (there is an uncoated part).

[Peelability of protective film]
After the photosensitive films prepared in Examples and Comparative Examples were stored at 23 ° C. for 20 hours, the peel strength was measured from the photosensitive layer when the protective film was peeled off at an angle of 180 °, and the peelability was determined according to the following criteria. Evaluated.
A: The peel strength is 2.0 N / m or less, and the peelability is good.
B: The protective film is firmly adhered to the photosensitive layer, and a part or all of the photosensitive layer is peeled off from the support film.

[Peelability of support film]
The protective film was removed from the photosensitive films prepared in Examples and Comparative Examples, respectively, and the photosensitive layer was laminated on a glass plate while being heated to 120 ° C., thereby preparing a sample for property evaluation in which the photosensitive layer was transferred. Subsequently, the support film was peeled off from the sample for property evaluation, and the transfer state of the photosensitive layer was visually evaluated.
A: Peeling and removal are possible without the photosensitive layer adhering to the support film.
B: Peeling with the photosensitive layer adhering to the support film over a part or the entire surface of the photosensitive layer.

[Developability of exposed area]
The support film is peeled off from the sample for characteristic evaluation, and the photosensitive layer is exposed at an exposure amount of 100 mJ / cm ² using an exposure machine (trade name “HMW-590” manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp. A resist film was obtained by exposure. After the exposure, development was performed at 30 ° C. for 60 seconds using a 2.38 mass% tetramethylammonium hydroxide aqueous solution, and the state of the resist film in the exposed portion was visually evaluated based on the following criteria.
A: Resist film did not remain on the glass surface, and developability was good.
B: Resist film remained on the glass surface, and developability was not good.

[Evaluation of adhesion]
The support film was peeled off from the characteristic evaluation sample, and a phototool having a wiring pattern with a line / space of 3/50 to 30/50 (unit: μm) was disposed on the photosensitive layer. Next, the photosensitive layer was exposed through a photo tool at an exposure amount of 100 mJ / cm ² using an exposure machine having a high-pressure mercury lamp (trade name: HMW-590, manufactured by Oak Manufacturing Co., Ltd.). After the exposure, development was carried out by spraying an aqueous 2.38 mass% tetramethylammonium hydroxide solution (30 ° C.). After the development, the minimum line width (μm) of the line remaining without peeling was measured to evaluate the adhesion. The obtained results are shown in Tables 2 and 3. In Tables 2 and 3, the adhesion is indicated by the minimum line width, and the smaller the minimum line width, the better the adhesion, and the clearer the contrast between the unexposed part and the exposed part.

[Crack generation after exposure]
The support film was peeled off from the sample for characteristic evaluation. Next, the photosensitive layer was exposed at an exposure amount of 100 mJ / cm ² using an exposure machine having a high-pressure mercury lamp lamp (trade name: HMW-590, manufactured by Oak Manufacturing Co., Ltd.) to obtain a resist film. The surface of the obtained resist film was visually observed, and crack generation was evaluated according to the following criteria.
A: There is no crack in the resist film.
B: There is a crack in the resist film.

  DESCRIPTION OF SYMBOLS 1 ... Photosensitive film, 10 ... Support film, 14 ... Photosensitive layer, 15 ... Protective film.

Claims (4)

A support film on which at least one surface is subjected to a release treatment;
A photosensitive layer comprising a photosensitive resin composition containing (a) a phenol resin, (b) a 1,2-quinonediazide compound and (c) a fluorosurfactant;
A protective film;
Are stacked in this order,
The photosensitive layer is formed on the release-treated surface of the support film ;
The photosensitive film whose content of the said (c) fluorine-type surfactant is 0.1-5 mass parts with respect to 100 mass parts of total amounts of (a) phenol resin and (b) 1,2-quinonediazide compound. . The photosensitive film of Claim 1 whose thickness of the said photosensitive layer is 1-5 micrometers.   The photosensitive film of Claim 1 or 2 whose surface tension in 23 degreeC of the mold release process surface of the said support body film is 20-45 mN / m.   The peel strength between the photosensitive layer and the protective film is 2.0 N / m or less, and the peel strength is smaller than the peel strength between the photosensitive layer and the support film. The photosensitive film as described in any one of Claims.

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