JP2013228416A - Positive photosensitive resin composition and photosensitive film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition for forming a photosensitive layer, in which the photosensitive layer is excellent in adhesion with metal, developability in an exposed part and resistance to a developing solution in an unexposed part, and can be repeatedly developed with a weak alkali developing solution, and to provide a photosensitive film using the composition.SOLUTION: There is provided a positive photosensitive resin composition comprising: (A) a novolac type phenolic resin obtained from ortho-cresol modified by a compound having an unsaturated hydrocarbon group or obtained from meta-cresol or para-cresol modified by a compound having an unsaturated hydrocarbon group; (B) a novolac type phenolic resin obtained from an aromatic thiol and a phenolic resin modified by a compound having an unsaturated hydrocarbon group; (C) a novolac type phenolic resin obtained from ortho-cresol; (D) a novolac type phenolic resin obtained from an aromatic thiol and ortho-cresol; and (E) a compound that generates an acid by light.

Description

  The present invention relates to a positive photosensitive resin composition and a photosensitive film using the same.

  A positive photosensitive resin composition containing a novolac-type phenolic resin and a 1,2-quinonediazide compound as an image forming method used for patterning of electronic parts such as semiconductor integrated circuits, liquid crystal display elements, and printed wiring boards. A method using a positive photoresist as a raw material is known (see, for example, Patent Documents 1 to 4).

  When this positive photosensitive resin composition is applied to a substrate or the like to form a photosensitive layer, the film thickness is generally 0.5 to several μm. When such a positive photosensitive resin composition is used, it is possible to form an image pattern over a wide range of dimensions. 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 hundred μm. This makes it possible to finely process a wide variety of substrate surfaces.

Japanese Patent No. 3224602 Japanese Patent No. 3968177 JP 2010-39214 A JP 2008-112134 A Japanese Patent Application No. 2011-123562

  The positive photosensitive resin composition has a characteristic that a portion irradiated with light (exposed portion) can be removed with an alkaline aqueous solution, and a portion not irradiated with light (unexposed portion) remains as a film. A pattern can be formed by irradiating light again. Therefore, the step of etching the metal layer after exposing and developing the photosensitive layer is repeatedly performed on the substrate having two or more metal layers using the positive photosensitive resin composition, and the metal layer is formed on the substrate. Formation of a pattern has been studied.

  So far, a positive-type photosensitive resin composition that is sufficiently excellent in developability of an exposed area and developer resistance of an unexposed area and that forms a photosensitive layer that can be repeatedly developed with a weak alkaline developer, and the same have been used. A photosensitive film has been studied (see, for example, Patent Document 5).

  However, in image forming method applications used for patterning of electronic components such as semiconductor integrated circuits, liquid crystal display elements, and printed wiring boards, various metal layers have been used in accordance with recent miniaturization of wiring, miniaturization, and energy saving. Since the method has been diversified, the conventional method of adding an adhesion-imparting agent cannot provide sufficient adhesion to the substrate.

  Accordingly, the present invention is a positive type that forms a photosensitive layer that is excellent in adhesion to metal, sufficiently developable in exposed areas and sufficiently resistant to developer in unexposed areas, and can be repeatedly developed with a weak alkaline developer. It aims at providing the photosensitive resin composition and the photosensitive film using the same.

  The present invention relates to (A) orthocresol modified with a compound having an unsaturated hydrocarbon group, or a novolac type phenol resin obtained from meta-paracresol modified with a compound having an unsaturated hydrocarbon group, (B) A novolak-type phenol resin obtained from an aromatic thiol and a phenol resin modified with a compound having an unsaturated hydrocarbon group, (C) a novolak-type phenol resin obtained from ortho-cresol, (D) an aromatic thiol, and ortho-cresol And (E) a compound that generates an acid by light, and a positive photosensitive resin composition.

  The positive photosensitive resin composition of the present invention contains two types of novolak type phenol resins as components (A) and (C), and includes two types of novolak type phenol resins containing aromatic thiols (B) and ( D) It is contained as a component and combined with the component (E) that is a photosensitizer, so that it has excellent adhesion to metal, sufficiently develops the exposed area and develops the unexposed area, and is weakly alkaline. A photosensitive layer that can be repeatedly developed with a liquid can be formed.

  Furthermore, when the weight average molecular weights of the components (A) and (B) are 3000 to 50000, the balance between the developability of the exposed area when the photosensitive layer is formed and the developer resistance of the unexposed area is balanced. It can be improved further.

  Further, when the weight average molecular weight of the components (C) and (D) is 500 to 5000, the solubility of the exposed portion in the alkaline aqueous solution can be improved while maintaining the mechanical strength of the photosensitive layer.

  From the viewpoint of achieving both mechanical strength and developability of the photosensitive layer, the content ratio of the component (A) is based on the total amount of the components (A), (B), (C), and (D). It is preferable that it is 50-80 mass%.

  From the viewpoint of coexistence of developability of the photosensitive layer and adhesion to the substrate, the content ratio of the component (C) is the total amount of the components (A), (B), (C), and (D). It is preferable that it is 20-50 mass% with respect to it.

  From the viewpoint of improving the flexibility of the photosensitive layer, the component (A) preferably contains a phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms.

  Moreover, the said photosensitive resin composition can improve the peelability from the support body film of a photosensitive layer by further containing (F) fluorine-type surfactant.

  Furthermore, the said photosensitive resin composition can further improve the adhesiveness to the board | substrate etc. of the resist pattern formed through an exposure and image development process by further containing (G) adhesiveness imparting agent.

  The present invention also includes a support film having a release treatment on at least one surface, a photosensitive layer made of the positive photosensitive resin composition, and a protective film, which are laminated in this order. It is related with the photosensitive film in which the layer is formed on the mold release process surface of the said support body film.

  According to the present invention, a positive type that forms a photosensitive layer that has excellent adhesion to a substrate, is sufficiently excellent in developability of an exposed area and developer resistance of an unexposed area, and can be repeatedly developed with a weak alkaline developer. A photosensitive resin composition and a photosensitive film using the same can be provided.

It is a schematic cross section showing one embodiment of a photosensitive 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.

  The positive photosensitive resin composition of the present invention comprises (C) ortho-cresol modified with a compound having an unsaturated hydrocarbon group as component (A), or meta-paracresol modified with a compound having an unsaturated hydrocarbon group. A novolak-type phenol resin obtained from the above, a novolak-type phenol resin obtained from a phenol resin modified with a compound having an aromatic thiol and an unsaturated hydrocarbon group as component (B), and ortho as a component (C) It contains a novolak-type phenol resin obtained from cresol, an aromatic thiol as component (D), a novolac-type phenol resin obtained from ortho-cresol, and a compound that generates acid by light as component (E).

Hereinafter, each component constituting the positive photosensitive resin composition of the present invention will be described in detail.
<(A) component>
The component (A) is generally a polycondensation product of ortho-cresol or a phenol derivative containing meta-cresol and para-cresol as main components and aldehydes. The polycondensation is performed in the presence of a catalyst such as an acid.

  The mass ratio of metacresol to paracresol is preferably from 50/50 to 70/30, preferably from 55/35 to 65/45, from the viewpoint of developability and developer resistance. More preferably.

  (A) As a phenol derivative used in order to obtain a component, phenol derivatives other than cresol can be copolymerized. Examples of phenol derivatives other than cresol include phenol; 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2-butylphenol, 3-butylphenol, 4-butylphenol, 2,3-xylenol, and 2,4-xylenol. Alkylphenols such as 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol; methoxyphenol, 2 -Alkoxyphenol such as methoxy-4-methylphenol; alkenylphenol such as vinylphenol and allylphenol; aralkylphenol such as benzylphenol; alkoxycarbonylphenol such as methoxycarbonylphenol; Benzoyloxy phenol arylcarbonyl phenols, halogenated phenols chlorophenol and the like; catechol, resorcinol, and a polyhydroxy benzene pyrogallol. These are used singly or in combination of two or more. These phenol derivatives can be added within a range that does not impair the effects of the present invention, and the addition amount is 30% by mass or less based on the total amount of phenol derivatives used to obtain the component (A). It is preferable.

  Examples of aldehydes include formaldehyde, acetaldehyde, acetone, glyceraldehyde, and methyl glyoxylate. Moreover, you may use the precursor of formaldehyde, such as paraformaldehyde and trioxane, for reaction with a phenol derivative. These are used singly or in combination of two or more.

  Component (A) is a novolak type phenol resin obtained by reacting with a compound having an unsaturated hydrocarbon group (hereinafter referred to as “modified with a compound having an unsaturated hydrocarbon group” from the viewpoint of improving the flexibility of the photosensitive layer. It is preferable to include a “modified phenol resin”.

  The modified phenolic resin having an unsaturated hydrocarbon group is generally a compound having the above cresol and an unsaturated hydrocarbon group (preferably having 4 to 100 carbon atoms) (hereinafter referred to simply as “an unsaturated hydrocarbon group-containing compound”). )) And a polycondensation product of an aldehyde with a reaction product (hereinafter referred to as “unsaturated hydrocarbon group-modified phenol derivative”), or the above-mentioned novolak type phenol resin and an unsaturated hydrocarbon group-containing compound. It is a reaction product.

  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 viewpoints of adhesion of the resist pattern and flexibility of the photosensitive layer. 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, in the reaction between paracresol or metacresol, or a novolac type phenol resin and a vegetable oil, it is necessary to use a non-drying oil from the viewpoint of preventing gelation accompanying the progress of excessive reaction and improving the yield. preferable. 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 a phenol resin modified with a compound having an unsaturated hydrocarbon group, 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. 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 from the viewpoint of improving the flexibility of the photosensitive layer. It is preferably 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 phenol resin modified with the unsaturated hydrocarbon group-containing compound can also be obtained by reacting the novolak type phenol resin with the unsaturated hydrocarbon group-containing compound.

  As the unsaturated hydrocarbon group-containing compound to be reacted with the novolac-type phenol resin, the same compounds as the unsaturated hydrocarbon group-containing compound described above can be used.

  The reaction between the novolac type phenol resin and the unsaturated hydrocarbon group-containing compound is usually preferably carried out at 50 to 130 ° C. The reaction ratio between the phenol resin 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 resin from the viewpoint of improving the flexibility of the photosensitive layer. It is preferable that it is 2-70 mass parts, and it is still more preferable that it is 5-50 mass parts. 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 (A) 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. In addition, the said acid value was measured based on JISK5601-2.

  The molecular weight of component (A) is preferably 5,000 to 50,000 in terms of weight average molecular weight (Mw), considering the solubility in aqueous alkali solution and the balance between the photosensitive properties (sensitivity and resolution) and mechanical properties. More preferably, it is -33000, and it is especially preferable that it is 10000-23000.

Here, the weight average molecular weight in the present specification is a value obtained by measuring by gel permeation chromatography (GPC) and converting from a standard polystyrene calibration curve. The measurement conditions in GPC are as follows.
Pump: L-6200 type (manufactured by Hitachi, Ltd., trade name)
Column: TSKgel-G5000HXL (trade name, manufactured by Tosoh Corporation)
Detector: L-3300RI type (manufactured by Hitachi, Ltd., trade name)
Eluent: Tetrahydrofuran Temperature: 30 ° C
Flow rate: 1.0 mL / min

  In addition, from the viewpoint of achieving both mechanical strength and developability of the photosensitive layer, the content ratio of the component (A) in the photosensitive resin composition is as follows: (A) component, (B) component, (C) component, and It is preferable that it is 50-80 mass% with respect to the total amount of (D) component, and it is more preferable that it is 45-60 mass%.

<(B) component>
The component (B) is a polycondensation product with aldehydes in which a part of the cresol contained in the component (A) is substituted with an aromatic thiol. The polycondensation is performed in the presence of a catalyst such as an acid.

  Examples of aromatic thiols include benzenethiol, 2-toluenethiol, 3-toluenethiol, 4-toluenethiol, 2-ethylbenzenethiol, 3-ethylbenzenethiol, 4-ethylbenzenethiol, 2-butylbenzenethiol, and 3-butyl. Benzenethiol, 4-butylbenzenethiol, 2,3-xylenol, 2,4-xylenethiol, 2,5-xylenethiol, 2,6-xylenethiol, 3,4-xylenethiol, 3,5-xylenethiol, Alkylbenzenethiol such as 2,3,5-trimethylbenzenethiol and 3,4,5-trimethylbenzenethiol; alkoxybenzenethiol such as methoxybenzenethiol and 2-methoxy-4-methylbenzenethiol; vinylbenzenethiol, Alkenylbenzene thiol such as rilbenzenethiol; aralkylbenzenethiol such as benzylthiol; alkoxycarbonylbenzenethiol such as methoxycarbonylbenzenethiol; arylcarbonylbenzenethiol such as benzoyloxybenzenethiol; halogenated benzenethiol such as chlorobenzenethiol; Examples thereof include hydroxybenzene thiol, 3-hydroxybenzene thiol, 4-hydroxybenzene thiol, and polyhydroxybenzene thiol.

  As a phenol derivative and aldehydes, the thing similar to the aldehydes illustrated by (A) component can be illustrated.

  The amount of cresol substitution with an aromatic thiol is preferably 5 to 30% by mass from the viewpoint of developability.

The molecular weight of the component (B) is preferably 5,000 to 50,000 in terms of weight average molecular weight (Mw) in consideration of solubility in an aqueous alkali solution and balance between photosensitive characteristics (sensitivity and resolution) and mechanical characteristics, Is more preferably ˜25000, and particularly preferably 10000 to 15000.
Moreover, from the viewpoint of achieving both mechanical strength and developability of the photosensitive layer, the content ratio of the component (B) in the photosensitive resin composition is as follows: (A) component, (B) component, (C) component, and It is preferable that it is 5-30 mass% with respect to the total amount of (D) component, and it is more preferable that it is 10-20 mass%.

<(C) component>
Component (C) is a polycondensation product of a phenol derivative containing ortho-cresol as a main component and aldehydes. The polycondensation is performed in the presence of a catalyst such as an acid.

  As the phenol derivative used to obtain the component (C), a phenol derivative other than orthocresol can be copolymerized. For example, phenol; metacresol, paracresol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2-butylphenol, 3-butylphenol, 4-butylphenol, 2,3 -Xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol Alkylphenols such as methoxyphenol, 2-methoxy-4-methylphenol, etc .; Alkenylphenols such as vinylphenol and allylphenol; Aralkylphenols such as benzylphenol; Alkoxycarbonyl phenol; benzoyloxy oxy phenol arylcarbonyl phenol; chlorophenol halogenated such as phenol; catechol, resorcinol, and a polyhydroxy benzene pyrogallol. These are used singly or in combination of two or more. These phenol derivatives can be added within a range that does not impair the effects of the present invention, and the addition amount is 15% by mass or less based on the total amount of the phenol derivatives used to obtain the component (B). It is preferable.

  Examples of aldehydes include the same compounds as those exemplified for the component (A).

The molecular weight of the component (C) is preferably 500 to 5000, more preferably 800 to 4000 in terms of weight average molecular weight, from the viewpoint of improving the developer resistance of the unexposed area and the developability of the exposed area in the photosensitive layer in a well-balanced manner. 1000 to 3000 are particularly preferred.
From the viewpoint of coexistence of developability of the photosensitive layer and adhesion to the substrate, the content ratio of the component (C) is based on the total amount of the components (A), (B), (C), and (D). It is preferably 20 to 50% by mass, and more preferably 30 to 45% by mass.

<(D) component>
The component (D) is a polycondensation product of a phenol derivative containing ortho-cresol as a main component, in which a part of ortho-cresol contained in the component (C) is substituted with an aromatic thiol, and aldehydes. The polycondensation is performed in the presence of a catalyst such as an acid.

  Examples of the aromatic thiol, the phenol derivative, and the aldehyde include the same compounds as those exemplified for the component (C).

  The molecular weight of the component (D) is preferably 500 to 5000, more preferably 800 to 4000 in terms of weight average molecular weight, from the viewpoint of improving the developer resistance of the unexposed part and the developability of the exposed part in the photosensitive layer in a well-balanced manner. 1000 to 3000 are particularly preferred.

  Content of (D) component in the photosensitive resin composition is 1-30 mass% with respect to the total amount of (A) component, (B) component, (C) component, and (D) component. Preferably, it is 3-20 mass%, More preferably, it is 4-10 mass%.

<(E) component>
The compound (E) which generates an acid by light is used as a photosensitizer. Such a component (E) has a function of generating an acid by light irradiation and increasing the solubility of the light irradiated portion in an alkaline aqueous solution. As the component (E), a compound generally called a photoacid generator can be used. Specific examples of the component (E) include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, and the like. Of these, 1,2-quinonediazide compounds are preferred because of their high sensitivity.

  The 1,2-quinonediazide compound 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. . 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, 3'-dimethyl- {1- [4- [2- (3-methyl-4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol. 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 general formulas (4) to (6) include the following methods. That is, for example, a compound represented by any one of the above general formulas (4) to (6) and 1,2-naphthoquinone-2-diazide-sulfonyl chloride are mixed with a solvent such as dioxane or THF (tetrahydrofuran). Examples thereof include a method in which the reaction is carried out in the presence of an alkali catalyst such as triethylamine, triethanolamine, alkali carbonate or alkali hydrogencarbonate. At this time, a 1,2-quinonediazide compound in which the hydroxyl group of the compounds represented by the general formulas (4) to (6) and the sulfonyl group of 1,2-naphthoquinone-2-diazide-sulfonyl chloride are condensed is synthesized. The In addition, in the molecule | numerator of the 1,2-quinonediazide compound obtained, the hydroxyl group of the compound represented by General formula (4)-(6) and the sulfonyl group of 1,2-naphthoquinone-2-diazide-sulfonyl chloride. There may be at least one bond.

  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 (E) in the photosensitive resin composition is the components (A), (B), (C), (D), and (E) from the viewpoints of photosensitive properties and mechanical properties. The total amount is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and particularly preferably 10 to 20% by mass.

<(F) component>
Photosensitive resin for the purpose of improving the coating property, defoaming property, leveling property, etc. of the positive photosensitive resin composition and improving the peelability of the photosensitive layer from the support film when it is used as a photosensitive film. The composition can contain a fluorosurfactant as the component (F).

  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, “Megafuck” is a registered trademark); Florad FC-135, Fluorard FC-170C, Fluorard FC-430, Fluorard FC-431, Novec FC-4430, Novec FC-4432 (trade name, manufactured by Sumitomo 3M Limited); Surflon S-112, Surflon S-113, Surflon S- 131, Surflon S-141, Surflon S-145 ( On, manufactured by Asahi Glass Co., Ltd., product name, "Sarfron" can be used the registered trademark.), And the like of the commercially available product. 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.

  When the component (F) is blended in the photosensitive resin composition, the total content of the component (A), component (B), component (C), component (D), and component (E) is 100 parts by mass. Is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 2 parts by mass, and still more preferably 0.3 to 1 part by mass. When the content ratio of the component (F) exceeds 5 parts by mass, the image contrast tends to decrease.

<(G) component>
From the viewpoint of further improving the coating property to the support film, the adhesion of the formed photosensitive layer to the substrate and the developability after exposure, the photosensitive resin composition comprises an adhesion imparting agent as the component (G). Can be contained.

  As the component (G), adhesion promoters such as nitrogen-containing compounds, silane coupling agents, and aluminum chelating agents and / or solubility modifiers such as organic acids and high-boiling solvents can be used.

  The nitrogen-containing compound preferably has an azole group, amino group, amide group, imino group, imide group, etc., for example, triazole compounds such as imidazole, pyrazole, benzimidazole, benzotriazole, mercaptotriazole, alkyl Amine, piperidine, piperazine, morpholine, aniline, ethylenediamine, catecholamine, ethylenediaminetetraacetic acid, bipyridine, terpyridine and phenanthroline.

  The silane coupling agent preferably has a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. For example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, Examples include vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

  Examples of the aluminum chelating agent include aluminum ethyl acetoacetate / diisopropylate, aluminum trisethyl acetoacetate, aluminum bisethyl acetoacetate / monoacetylacetonate, and aluminum trisacetylacetonate.

  Among these adhesion assistants, nitrogen-containing compounds are preferred, triazole compounds are more preferred, and mercaptotriazoles are particularly preferred from the viewpoint of developability.

  Content in the case of mix | blending an adhesion assistant in the photosensitive resin composition is (A) component, (B) component, (C) component, (D) component, and the total amount of (E) component is 100 mass parts. On the other hand, it is preferably 0.1 to 5 parts by mass, preferably 0.2 to 3 parts by mass, and more preferably 0.3 to 2 parts by mass.

  Examples of the organic acid include monocarboxylic acid, hydroxymonocarboxylic acid, expensive carboxylic acid and acid anhydride.

  Examples of monocarboxylic acids include acetic acid, propionic acid, n-butyric acid, iso-butyric acid, n-valeric acid, iso-valeric acid, benzoic acid and cinnamic acid.

  Examples of the hydroxy monocarboxylic acid include lactic acid, hydroxybutyric acid, salicylic acid, hydroxybenzoic acid, hydroxycinnamic acid, hydroxyisophthalic acid, and syringic acid.

  Examples of the polyvalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, cyclohexanetricarboxylic acid, Examples include merit acid and pyromellitic acid.

  Examples of the acid anhydride include itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, 1, 2,3,4-butanetetracarboxylic acid, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitic anhydride and glycerine tris anhydrous trimellitate Is mentioned.

  The high boiling point solvent represents a solvent having a boiling point of 150 ° C. or higher under normal pressure, for example, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, dihexyl ether , Caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, γ-butyrolactone and phenyl cellosolve acetate.

  The blending amount of the solubility modifier can be appropriately adjusted according to the application and application method, and is not particularly limited as long as the blending amount allows the photosensitive resin composition to be uniformly mixed. It is preferably 60% by mass or less, and more preferably 40% by mass or less, based on the total amount of the object.

<Other ingredients>
In the photosensitive resin composition of the present embodiment, a sensitizer, a light absorber (dye), a cross-linking agent, a plasticizer, a pigment, a filler, a flame retardant, a stabilizer, a peeling accelerator, and an antioxidant are added as necessary. You may contain additives, such as an agent, a fragrance | flavor, an imaging agent, and a thermal crosslinking agent. These can be used individually by 1 type or in combination of 2 or more types. Although the compounding quantity of these additives will not be restrict | limited especially if it is a range which does not impair the characteristic of the said photosensitive resin composition, It is preferable that it is 50 mass% or less with respect to the photosensitive resin composition whole quantity.

  The photosensitive resin composition can be prepared by mixing and stirring by a usual method. When a filler, a pigment, or the like is added, it is dispersed and mixed using a disperser such as a dissolver, a homogenizer, or a three roll mill. That's fine. Moreover, you may further filter using a mesh, a membrane filter, etc. as needed.

[Photosensitive film]
The photosensitive film according to the present embodiment is a photosensitive film comprising a support film having at least one surface subjected to a release treatment, and the positive photosensitive resin composition formed on the release treatment surface of the support film. A layer. A protective film can be laminated | stacked on the surface on the opposite side to the support body film of a photosensitive layer as needed.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of a photosensitive film. 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 the photosensitive resin composition of the present embodiment.

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

  When a release agent is applied (coated) to the support film, it is preferably thinly applied (coated) as long as the release effect is obtained. After coating (coating), the release agent may be fixed to the support film by heat or UV treatment. It is more preferable to apply an undercoat layer to the support film before coating (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 5 to 300 gf / inch (1.97 to 118 gf / cm or 19.3 to 1156.4). × 10 ⁻³ N / cm), preferably 5 to 200 gf / inch (1.97 to 78.7 gf / cm or 19.3 to 771.3 × 10 ⁻³ N / cm). Preferably, it is 100-200 gf / inch (39.4-78.7 gf / cm or 386.1-771.3 * 10 < ^-3 > N / cm). The 180 ° peel strength can be measured by a general method (for example, a method according to 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.

  Examples of PET films on which at least one surface has been release-treated with a silicone compound include, for example, trade names “Purex A53”, “A31-25”, “A51-25” and “A53-” manufactured by Teijin DuPont Films Ltd. 38 "is commercially available (" Purex "is a registered trademark).

  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.

<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 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, a solution having a solid content of 20 to 90% by mass is prepared by dissolving the photosensitive resin composition in a predetermined solvent. You may use as a coating liquid.
Examples of such solvents include methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, octane, decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, acetone, methyl isobutyl ketone, diethyl ketone, diisobutyl ketone. , Methyl amyl ketone, methyl ethyl ketone, cyclohexanone, toluene, xylene, tetramethylbenzene, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoryl amide, tetramethylene sulfone , Γ-butyrolactone, 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 monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, triethylene glycol mono Ethyl ether, ethyl acetate, butyl acetate, ethyl lactate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol An organic solvent such as rumonoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, 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. In the case of producing a thick photosensitive film with the photosensitive layer 14 having a thickness of 5 μm to 30 μm, a modified phenol resin having an unsaturated hydrocarbon group is used as the component (A). Cracks 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.

[Method of forming resist pattern]
Next, a resist pattern forming method will be described.
The method for forming a resist pattern includes a step of exposing a photosensitive layer made of the above-described positive photosensitive resin composition, and a step of developing and patterning the exposed photosensitive layer with an alkaline aqueous solution. The photosensitive layer formed from the positive photosensitive resin composition of the present invention can be repeatedly exposed and developed.

  As the substrate for forming the resist pattern, a substrate having a multilayer metal layer can be used. As a base material, the base material provided with two or more metal layers on the board | substrate comprised from the raw material which is not melt | dissolved in the etching liquid for a metal use is mentioned, for example. As said board | substrate, what is comprised from organic compounds, such as metal oxides, such as glass, titanium oxide, an alumina, semiconductors, such as a silicon | silicone, polyethylene terephthalate, a polypropylene, polyethylene, polyester, a polycarbonate, can be used, for example. Examples of the metal layer include a layer made of a metal such as gold, silver, copper, aluminum, iron, tungsten, molybdenum, titanium, or nickel, or a metal oxide such as indium tin oxide (ITO) or zinc oxide. The metal layer can be formed by laminating these metals or metal oxides on the substrate by vacuum vapor deposition, sputtering, electrolytic plating, electroless plating, or chemical vapor deposition using plasma.

  A method for forming a photosensitive layer on a substrate using the photosensitive film 1 will be described. The resist pattern is formed by laminating the photosensitive film 1 on a base material so that the photosensitive layer 14 is in close contact, irradiating an active ray in an image form, and removing an exposed portion by development. The part not irradiated with actinic rays works as a dissolution inhibitor by causing the (E) component which is a photosensitive agent to interact with the phenol resin which is the (A), (B), (C) and (D) component. So it does not dissolve in alkali. However, in the portion irradiated with actinic rays, the component (E) 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 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 film 10 present on the photosensitive layer 14 is transparent to the active light, the active light can be irradiated through the support film 10, and the support film 10 can be applied to the active light. In the case where the light shielding property is exhibited, the photosensitive layer 14 is irradiated with actinic rays after the support film 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 film 10 is present on the photosensitive layer 14, the support film 10 is removed with an auto peeler or the like, and a developing solution such as an alkaline aqueous solution, an aqueous developer, or an organic solvent is used. Examples include a method in which an exposed portion is removed and developed by wet development or dry development.

  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 pH is preferably in the range of 9 to 12 from the viewpoint of reducing the environmental load. 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 is 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.

  In this embodiment, the positive photosensitive resin composition can be directly applied onto the substrate and dried to form a photosensitive layer. In this case, the positive photosensitive resin composition is spin-coated on the above-described substrate using a spinner or the like to form a coating film. The substrate on which the coating film is formed is dried using a hot plate, an oven or the like. Thereby, a photosensitive layer is formed on the substrate. The subsequent exposure step and development step can be performed in the same manner as when the photosensitive film 1 is used.

  In the present embodiment, the above-described exposure and development can be repeated twice or more as necessary with a photosensitive layer formed on a substrate. That is, by using the positive photosensitive resin composition of the present invention, the resist pattern once formed when etching two or more metal layers by repeating the exposure and development steps is peeled off from the substrate, and again exposed to new photosensitive material. The step of forming the layer on the substrate can be omitted. Thereby, since the process at the time of etching the metal layer of a base material using a resist pattern can be shortened, it is useful also in terms of cost and environment.

  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 is given and this invention is demonstrated in more detail, this invention is not limited to these Examples.
[(A) component]
As the component (A), a novolac type phenol resin obtained from cresol was synthesized.

(Synthesis Example A1)
To 490 parts by mass of cresol mixed with metacresol and para-cresol at a mass ratio of 60:40, 210 parts by mass of linseed oil was added and stirred, and then 1.12 parts by mass of a 50% by mass aqueous trifluoroacetic acid solution was added. Reacted for hours. After the reaction, the mixture was cooled to room temperature (25 ° C., the same applies hereinafter), 81 parts by mass of 92% paraformaldehyde, 18 parts by mass of methanol and 1 part by mass of oxalic acid were added and stirred at 90 ° C. for 3 hours. The cresol of the reaction was removed to obtain a 30% linseed oil-modified novolac type phenol resin (A1). The Mw of (A1) was 12000.

(Synthesis Example A2)
A novolac phenol resin (A2) was obtained in the same manner as in Synthesis Example A1, except that the amount of 92% paraformaldehyde added was changed to 76 parts by mass. The Mw of (A2) was 8000.

(Synthesis Example A3)
After 210 parts by weight of linseed oil was added to 490 parts by weight of orthocresol and stirred, 1.12 parts by weight of a 50% by weight aqueous trifluoroacetic acid solution was added and reacted at 120 ° C. for 2 hours. After the reaction, the reaction mixture was cooled to room temperature, added with 92 parts of 92% paraformaldehyde, 18 parts by weight of methanol and 1 part by weight of oxalic acid, stirred at 90 ° C. for 3 hours, and then distilled under reduced pressure to remove unreacted cresol. A 30% linseed oil-modified novolak phenol resin (A3) was obtained. The Mw of (A3) was 3300.

(Synthesis Example A4)
A novolac type phenol resin (A4) was obtained in the same manner as in A3 except that the amount of 92% paraformaldehyde added was changed to 109 parts by mass. Mw of (A4) was 15000.

(Synthesis Example A5)
45 parts by mass of the above (A1), 45 parts by mass of propylene glycol monomethyl ether acetate (hereinafter abbreviated as “PGMEA”) and 17.6 parts by mass of succinic anhydride are placed in a flask and while flowing nitrogen at a flow rate of 300 mL / min. Stir at 100 ° C. After the succinic anhydride was completely dissolved, the flask was cooled to room temperature, 0.9 parts by mass of diazabicycloundecene (hereinafter abbreviated as “DBU”) diluted with 17.6 parts by mass of PGMEA was added, The reaction was carried out at 2 ° C. for 2 hours. After completion of the reaction, the system was cooled to 30 ° C. or lower, and then the nitrogen atmosphere was released to obtain a novolac type phenol resin (A5) component. Mw of (A5) was 18000.

  As the component (B), a novolac type phenol resin obtained from aromatic thiol and cresol was synthesized.

(Synthesis Example B1)
To 465 parts by mass of cresol mixed with metacresol and paracresol at a mass ratio of 60:40, 25 parts by mass of benzenethiol and 210 parts by mass of linseed oil were added and stirred, and then 1.12 parts by mass of a 50% by mass aqueous trifluoroacetic acid solution. In addition, it reacted at 120 ° C. for 2 hours. After the reaction, the reaction mixture was cooled to room temperature, added with 92 parts of 92% paraformaldehyde, 18 parts by weight of methanol and 1 part by weight of oxalic acid, stirred at 90 ° C. for 3 hours, and then distilled under reduced pressure to remove unreacted cresol. A 30% linseed oil-modified novolak phenol resin (B1) was obtained. The Mw of (B1) was 12000.

(Synthesis Example B2)
A novolac-type phenol resin (B2) was obtained in the same manner as in B1, except that cresol was changed to 343 parts by mass and benzenethiol was changed to 147 parts by mass. Mw of (B2) was 10,000.

[Component (C)]
As the component (C), a novolac type phenol resin obtained from orthocresol was synthesized.

(Synthesis Example C1)
After adding 112 parts by mass of 92% paraformaldehyde and 1.2 parts by mass of oxalic acid to 336 parts by mass of ortho-cresol, the mixture was stirred at 120 ° C. for 4 hours, and then distilled under reduced pressure to remove unreacted ortho-cresol. (C1) was obtained. The Mw of (C1) was 3000.

(Synthesis Example C2)
Except having changed the compounding quantity of 92% paraformaldehyde into 86 mass parts, operation similar to the synthesis example B1 was performed, and the novolak-type phenol resin (C2) was obtained. Mw of (C2) was 1000.

(Synthesis Example C3)
45 parts by mass of the above (C1), 45 parts by mass of PGMEA solvent and 11.3 parts by mass of succinic anhydride were placed in a flask and stirred at 100 ° C. while flowing nitrogen at a flow rate of 300 mL / min. After the succinic anhydride was completely dissolved, the flask was cooled to room temperature, 0.9 part by weight of DBU diluted with 12.5 parts by weight of PGMEA was added, and the reaction was carried out at 120 ° C. for 2 hours. After completion of the reaction, the system was cooled to 30 ° C. or lower and then the nitrogen atmosphere was released to obtain a novolac type phenol resin (C3) component. The Mw of (C3) was 3000.

[(D) component]
As the component (D), a novolac type phenol resin obtained from aromatic thiol and orthocresol was synthesized.

(Synthesis Example D1)
After adding benzenethiol 17 parts by mass, 92% paraformaldehyde 112 parts by mass and oxalic acid 1.2 parts by mass to orthocresol 319 parts by mass and stirring at 120 ° C. for 4 hours, vacuum distillation was performed to remove unreacted orthocresol. Thus, a novolac type phenol resin (D1) was obtained. The Mw of (D1) was 3000.

(Synthesis Example D2)
Except for changing 236 parts by mass of orthocresol and 100 parts of benzenethiol, the same operation as in Synthesis Example D1 was performed to obtain a novolac type phenol resin (C2). Mw of (C2) was 1000.

[Phenol resins other than (A), (B), (C) and (D) components]
(Comparative Synthesis Example G1)
A novolac-type phenol resin (G1) was obtained in the same manner as in B1, except that cresol was changed to 245 parts by mass and benzenethiol was changed to 245 parts by mass. Mw of (G1) was 15000.

(Comparative Synthesis Example G2)
A novolac-type phenol resin (G2) was obtained in the same manner as in Synthesis Example D1 except that 168 parts by mass of orthocresol and 168 parts by mass of benzenethiol were changed. Mw of (G2) was 3000.

<Preparation of photosensitive resin composition>
Example 1
(A) component (A1) 35 parts by weight, (B) component (B1) 10 parts by weight, (C) component (C1) 35 parts by weight, (D) component (D1) 5 parts by weight, (E ) “PA-28” (trade name, manufactured by Daitokemix Co., Ltd.) as 15 parts by mass, “FC-4430” (trade name, manufactured by Sumitomo 3M Limited) as component (F), 0.5 parts by mass, (F) As a component, 3-mercapto-1,2,4-triazole (hereinafter abbreviated as “3MT”) 0.3 part by mass, methyl ethyl ketone (hereinafter abbreviated as “MEK”) 140 parts by mass and PGMEA 90 parts by mass as a solvent. It mixed and produced the photosensitive resin composition.

(Examples 2 to 7)
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the components (A) and (B) were changed so as to have the composition (unit: part by mass) shown in Table 1.

(Comparative Examples 1-3)
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the composition (unit: part by mass) shown in Table 2 was changed.

<Production of photosensitive film and evaluation of photosensitive layer>
(Examples 1-5 and Comparative Examples 1-3)
A photosensitive film was prepared using the photosensitive resin composition according to the following procedure. First, a PET film “Purex A53” (Teijin DuPont) on which one side was release-treated with a silicone compound under the conditions of 300 rpm / 10 seconds → 500 rpm / 30 seconds using a spin coater (manufactured by Daitron Technology Co., Ltd.) Release name of film company, film thickness 50μm, 180 ° peeling strength 100g / inch at 23 ° C using adhesive tape "NITTO31B" made by Nitto Denko Corporation, surface tension 44mN / m of the release treatment surface A photosensitive resin composition was applied to the treated surface. Subsequently, it dried for 5 minutes at 95 degreeC with the conveyor type dryer (RCP oven line, Dainippon Screen Co., Ltd.), and produced the photosensitive film which formed the photosensitive layer with a thickness of 4.0 micrometers.

  Using a roll laminator (manufactured by Hitachi Chemical Technoplant Co., Ltd.), laminating the photosensitive layer of the photosensitive film on the substrate under the conditions of pressure 0.5 MPa, upper and lower roll temperature 120 ° C., speed 0.5 m / min, A positive photoresist laminate was obtained. Using the obtained positive photoresist laminate, the photosensitive layer was exposed and developed in the order of the following steps 1 to 3.

(Process 1)
The PET film is peeled off from the positive photoresist laminate, and the photosensitive layer is exposed under the condition of 100 mJ / cm ² using a UV exposure machine (Dainippon Screen Co., Ltd., trade name “Large Manual Exposure Machine MAP-1200”). did. A glass mask (manufactured by Toppan Printing Co., Ltd., trade name “TOPPAN-TEST-CHART-NO1-N L78I1”) was used for pattern formation. Next, a 2.38 mass% TMAH (trimethylanilinium hydroxide) aqueous solution was used as a developing solution, and was predetermined at 30 ° C. with a spray developing device (trade name “DVW-911” manufactured by Dainippon Screen Co., Ltd.). The resist film 1 was formed by performing time development, washing with distilled water, and drying by nitrogen blowing.

(Process 2)
Half of the resist film 1 remaining in Step 1 was covered with a black sheet, and exposure was performed under the condition of 100 mJ / cm ² as in Step 1. 2. Using a TMAH developer of 2.38% by mass, developed in a spray developing machine at 30 ° C. for a predetermined time in the same manner as in Step 1, washed with distilled water, dried by nitrogen blowing, and resist film 2 Formed.

(Process 3)
The entire surface of the resist film 2 remaining in Step 2 was exposed under the condition of 100 mJ / cm ² as in Step 1. Using a 2.38 mass% TMAH aqueous solution, it was developed with a spray developer at 30 ° C. for a predetermined time in the same manner as in Step 1, and washed with distilled water. Thereafter, drying was performed by nitrogen blowing.

(Example 6)
Except that the developer used in Steps 1 to ₃ was changed from the 2.38 wt% TMAH aqueous solution to the 1.0 wt% Na ₂ CO ₃ aqueous solution, the same operation as in Example 1 was performed to expose and develop the photosensitive layer. did.

(Example 7)
The photosensitive layer was exposed and developed in the same manner as in Example 1 except that the developer used in Steps 1 to 3 was changed from the 2.38 mass% TMAH aqueous solution to the 1.19 mass% TMAH aqueous solution.

(Example 8)
The photosensitive resin composition was directly applied to the substrate using a spin coater (manufactured by Daitron Technology Co., Ltd.) at 300 rpm / 10 seconds → 500 rpm / 30 seconds, and a conveyor dryer (RCP oven line, Dainippon, Japan). Except that the positive photoresist laminate was obtained by drying at 95 ° C. for 5 minutes using Screen Co., Ltd., the same operation as in Example 1 was performed to expose and develop the photosensitive layer.

<Evaluation of photosensitive layer>
The flexibility and adhesion of the photosensitive layer formed on the support film and the repeated developability of the photosensitive layer in steps 1 to 3 were evaluated according to the following criteria. The results are shown in Tables 3 and 4.

(Flexibility)
Regarding the flexibility of the photosensitive layer formed on the support film, the photosensitive film was wound around a core material having various diameters, and the presence or absence of cracks, peeling and transfer was evaluated in the following five stages.
A: Can be wound on a core material having a diameter of 1 cm B: Can be wound on a core material having a diameter of 3 cm C: Can be wound on a core material having a diameter of 5 cm D: Can be wound on a core material having a diameter of 10 cm E: Can be wound on a core material having a diameter of 20 cm

(Adhesion)
The photosensitive layer formed on the support film was laminated on a gold, palladium, silver, copper, ITO, and silica substrate by the method described above, and the adhesion with the substrate was evaluated in the following five stages.
A: The developer or the etching solution does not enter between the base material and the photosensitive layer. Pattern accuracy error is less than 5%. B: Developer or etching solution does not enter between the base material and the photosensitive layer. Pattern accuracy error is less than 10%. C: Developer or etchant wraps around the gap between the substrate and the photosensitive layer. Pattern accuracy error is less than 10%. D: Developer or etchant wraps around the gap between the substrate and the photosensitive layer. Pattern accuracy error is less than 20%. E: Peeling in developer or etchant.

(Developability)
The developability of the exposed part of the photosensitive layer in steps 1 to 3 was evaluated. Specifically, the cutability of the pattern edge portion, the development residue of the solid portion, the adhesion of the peeled pieces and thread-like residues on the substrate were evaluated in the following five criteria.
A: Good cracking at the pattern edge, no development residue at the solid part, no peeling piece, no thread residue B: Poor cracking at the pattern edge part, no development residue at the solid part, no peeling piece, no thread residue C: Poor chipperiness at the pattern edge, no development residue at the solid part, no peeling piece, with thread-like residue D: Poor cracking at the pattern edge part, development residual at the solid part, no peeling piece, with thread-like residue E: Pattern edge Poor part cracking, solid development remaining, peeling pieces, thread residue

(Developer resistance)
In Steps 1 and 2, the developer resistance of the unexposed part of the photosensitive layer was evaluated according to the following criteria. Specifically, cracking, film reduction, and surface layer peeling were evaluated in five stages.
A: No crack, no film reduction, no surface layer peeling B: No crack, no film thickness reduction, surface layer peeling C: Cracked, no film thickness reduction, no surface layer peeling D: Cracked, no film thickness reduction, surface layer peeling No peeling E: Cracking, film loss, surface peeling

(Resist appearance)
In Steps 1 and 2, the resist appearance of the unexposed portion of the photosensitive layer was evaluated according to the following criteria. Specifically, the roughness of the surface and the degree of unevenness were evaluated in five levels.
A: Almost good B: Some roughness C: Concavity and convexity D: Layer separation or cloudiness E: Substrate surface exposed

  According to the positive photosensitive resin compositions of Examples 1 to 8, a photosensitive layer that is sufficiently excellent in developability of an exposed area and developer resistance of an unexposed area and that can be repeatedly developed with a weak alkaline developer. It was confirmed that it can be formed.

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

Claims (8)

(A) orthocresol modified with a compound having an unsaturated hydrocarbon group, or a novolak type phenol resin obtained from meta-paracresol modified with a compound having an unsaturated hydrocarbon group,
(B) a novolak type phenol resin obtained from a phenol resin modified with an aromatic thiol and a compound having an unsaturated hydrocarbon group,
(C) a novolac-type phenolic resin obtained from ortho-cresol,
A positive photosensitive resin composition comprising (D) an aromatic thiol, a novolak-type phenol resin obtained from ortho-cresol, and (E) a compound that generates an acid by light.   The positive photosensitive resin composition according to claim 1, wherein the components (A) and (B) have a weight average molecular weight of 3000 to 50000.   The positive photosensitive resin composition according to claim 1 or 2, wherein the components (C) and (D) have a weight average molecular weight of 500 to 5,000.   The content rate of (A) component is 50-80 mass% with respect to the total amount of (A) component, (B) component, (C) component, and (D) component, Any one of Claims 1-3. The positive photosensitive resin composition according to Item.   The content rate of (C) component is 20-50 mass% with respect to the total amount of (A) component, (B) component, (C) component, and (D) component, Any one of Claims 1-3. The positive photosensitive resin composition according to Item.   Furthermore, the positive photosensitive resin composition as described in any one of Claims 1-5 which contains a fluorine-type surfactant as (F) component.   Furthermore, the positive photosensitive resin composition as described in any one of Claims 1-6 which contains an adhesiveness imparting agent as (G) component.   A support film having a release treatment on at least one surface thereof, a photosensitive layer made of the positive photosensitive resin composition according to any one of claims 1 to 7, and a protective film are laminated in this order. A photosensitive film in which the photosensitive layer is formed on a release treatment surface of the support film.

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