JP4840068B2 - Photosensitive resin composition and photosensitive element - Google Patents

Description

  The present invention relates to a photosensitive resin composition and a photosensitive element.

  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. When a positive photoresist is formed through application of the photosensitive resin composition, the application thickness is generally 0.5 to several 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.

  Also in the field of LCD and the like, the line width of an image becomes narrower with the progress of technologies such as TFT and STN, and the tendency of miniaturization is increasing. For example, the conventional device using TN or STN liquid crystal has an image design size of about 200 μm to several hundred μm, but recently, the minimum design size of an image has become 100 μm or less due to the development of a new technology. . Further, in the TFT display element having good responsiveness or image quality, the image design dimension is improved to a level of several μm.

  The characteristics expected for the photoresist material include the maintenance of the above-mentioned fine processing capability and the ability to increase the area. That is, it corresponds to a liquid crystal display whose substrate has been enlarged in recent years, a PDP or the like oriented from the beginning to a large screen. In these substrates, it is becoming an important technique to further improve the in-plane film thickness uniformity. In addition, common problems in large-area displays include further cost reduction and liquid saving of the photoresist used during manufacturing.

  Among the above-mentioned problems, in order to further improve the film thickness uniformity in the surface of the photoresist and achieve liquid-saving of the photoresist raw material, the investigation of the coating method has been continued. As a result, a new slit coating has been developed as an alternative to the conventional spin coating. These technologies are now expected to be compatible with substrates having a size of 550 mm × 680 mm or less. However, application of these technologies is expected to be difficult when aiming for a larger substrate.

  By the way, in the field of printed wiring boards, so-called negative-type dry film photoresists are widely used. The sheet used as the material for the dry film photoresist is coated with a negative alkali-developable photopolymerizable resin usually having a thickness of 10 to 80 μm on a polyester film having a thickness of 20 to 25 μm as a temporary support. Further, a polyolefin film having a thickness of 4 to 20 μm is laminated as a protective film. This dry film photoresist technique is also applied to a printed wiring board having a width of about 600 mm. However, when used in the field of printed wiring boards, the resolution required for photoresist is at most about 30 to 300 μm. When developing such a photoresist, a weak alkaline aqueous solution typified by a sodium carbonate aqueous solution having a concentration of 1% is generally used. Thereafter, a conductor such as copper on the substrate is etched with a cupric chloride aqueous solution. Then, all of the photoresist is stripped and removed with a caustic soda aqueous solution or a caustic potassium aqueous solution having a concentration of 2 to 3%.

  However, as described above, the image processing technique required when manufacturing TFTs for LCDs is, for example, about 2 to 10 μm, and the resolution is much higher than the field of printed wiring boards. In addition, there is also a need for meta-ion-free development, stripping with an organic stripping solution, etching of metal thin films such as ITO, Ta, and Al and inorganic thin films such as SiNx and ITO. In order to cope with these, the photoresist has a film thickness of several μm, improved adhesion to various sputtered metal thin films and inorganic thin films, further improved film thickness uniformity, and unevenness of about 1 μm. There are demands for improving the followability to the TFT leading pattern and increasing the laminating speed of the substrate having a width of 1 to 2 m, which completely exceeds the limit of the conventional dry film photoresist. That is, in order to meet the demands in the LCD and PDP industries, there is a limit to the conventional method of directly applying a positive liquid resist to a substrate or the method of transferring a negative dry film resist to a substrate. In order to solve such problems, it is conceivable to employ a positive dry film resist, but there is still no practical one.

  Examples of conventional positive photoresist materials include those having a phenol novolac resin as a main component and 1,2-quinonediazide sulfonic acid ester as a photosensitive component (see, for example, Patent Documents 1 and 2). However, a dry film formed from this material has a difficulty in making it into a roll-like product because the film quality is brittle and lacks flexibility. Moreover, even if it is manufactured as a roll-shaped product, problems are likely to occur when it is used. Therefore, a positive dry film photoresist using this material has not been put into practical use. Details will be described below.

From the photoresist material, a roll-shaped product having a desired film width is obtained as follows. First, a wide roll is usually formed by applying a photoresist material to a temporary support. Next, the roll is cut by a slit so that the roll has a desired film width. In order to laminate a dry film on a substrate on which an image pattern is formed, the dry film is usually drawn out from the roll-shaped product and thermally transferred while being pressed onto the substrate using a laminator. During or after the lamination, the dry film is cut into a predetermined length in the longitudinal direction of the substrate.
JP-A-6-27657 JP 2000-105466 A

  However, in the case of a brittle film-like dry film, chips are generated at the time of the slit. Further, when the dry film is cut to a predetermined length in the longitudinal direction of the substrate, chips are easily generated from the dry film. These chips become dust, contaminate the operating environment of the substrate and laminator, and adhere to the photoresist laminated on the substrate. As a result, defects are likely to occur in an image pattern formed using a photoresist.

  Therefore, the present invention has been made in view of the above circumstances, and when formed as a dry film, a photosensitive resin composition in which generation of chips is sufficiently suppressed even when the film is cut, and the It aims at providing the photosensitive element using this.

  In order to achieve the above object, the present invention provides a photosensitive resin containing (A) component: a compound obtained by reacting a phenol resin and a drying oil, and (B) component: 1,2-quinonediazide compound. A composition is provided. The factor by which the photosensitive resin composition of the present invention can achieve the above-mentioned object has not yet been clarified in detail. As one of the factors, the present inventors include the component (A) together with the component (B), so that the dry film formed from the photosensitive resin composition of the present invention is suppressed in brittleness and is flexible. I think that it comes to have sex. However, the factor is not limited to this.

  Moreover, the photosensitive resin composition of this invention shows the high softness | flexibility in the dry film formed from it. Furthermore, this photosensitive resin composition is excellent in photosensitivity, image contrast and resolution, and its cured product has high adhesion to the substrate.

  The present invention provides a photosensitive element comprising a support and a photosensitive layer made of the above-described photosensitive resin composition formed on the support. Since this photosensitive element uses the photosensitive resin composition of the present invention, generation of chips is sufficiently suppressed even when the photosensitive layer is cut.

  ADVANTAGE OF THE INVENTION According to this invention, when formed as a dry film, even if the film is cut | disconnected, the photosensitive resin composition by which generation | occurrence | production of chips is suppressed sufficiently can be provided.

  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 photosensitive resin composition in this embodiment contains (A) component: the compound obtained by making a phenol resin and dry oil react, and (B) component: 1,2-quinonediazide compound. Hereinafter, the component (A) and the component (B) will be described in detail.

((A) component)
(A) A component is a compound obtained by making a phenol resin and dry oil react. The phenol resin is obtained, for example, by a polycondensation reaction using a phenol compound and an aldehyde and / or ketone as raw materials.

  Examples of the phenol compound include phenol, cresol, xylenol; alkylphenols such as ethylphenol, butylphenol and trimethylphenol; alkoxyphenols such as methoxyphenol and 2-methoxy-4-methylphenol; alkenylphenols such as vinylphenol and allylphenol. Arylphenols such as phenylphenol; aralkylphenols such as benzylphenol; alkoxycarbonylphenols such as methoxycarbonylphenol; arylcarbonylphenols such as benzoyloxyphenol; halogenated phenols such as chlorophenol; polyhydroxybenzenes such as catechol and resorcinol; Bisphenols such as bisphenol A and bisphenol F; and α Or naphthol compounds such as β- naphthol. Moreover, you may use the methylolation thing of the said phenolic compounds, such as bishydroxymethyl-p-cresol, as a phenolic compound.

  Examples of the phenol compound include hydroxyalkylphenols such as p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol, and p-hydroxyphenyl-4-butanol; hydroxyalkylcresols such as hydroxyethylcresol; bisphenol Monoethylene oxide adducts; alcoholic hydroxyl group-containing phenolic compounds such as bisphenol monopropylene oxide adducts; and p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylbutanoic acid, p-hydroxycinnamic acid Also included are carboxyl group-containing phenol compounds such as hydroxybenzoic acid, hydroxyphenylbenzoic acid, hydroxyphenoxybenzoic acid, and diphenolic acid.

  Furthermore, the phenol resin may be a condensation polymerization product of the above-described phenol compound and a compound other than phenol such as m-xylene. In this case, the molar ratio of the compound other than phenol to the phenol compound used for the condensation polymerization is preferably less than 0.5.

  The above-mentioned phenol compound and compounds other than the phenol compound are used singly or in combination of two or more.

  Examples of the aldehyde and / or ketone include formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, acetone, and glyceraldehyde. . Examples of the aldehyde and / or ketone include glyoxylic acid, methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, formylacetic acid, methyl formylacetate, 2-formylpropionic acid, methyl 2-formylpropionate, and pyruvic acid. , Repric acid, 4-acetylbutyric acid, acetone dicarboxylic acid, and 3,3′-4,4′-benzophenone tetracarboxylic acid. Formaldehyde precursors such as paraformaldehyde and trioxane may also be used. These are used singly or in combination of two or more.

  It is preferable to use an acidic catalyst for the condensation polymerization reaction. By using this acidic catalyst, a novolac-type phenol resin can be easily obtained, and generation of chips can be more effectively prevented. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid. These are used singly or in combination of two or more. The synthesis conditions for the phenol resin may be known conditions.

  The content of the aldehyde and / or ketone in the raw material is preferably 0.7 to 1 mol with respect to 1 mol of the phenol compound. In this case, the polycondensation reaction can proceed more rapidly.

  Examples of the dry oil to be reacted with the phenol resin include tung oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, coconut oil and coconut oil. Moreover, you may use the processing dry oil obtained by processing these drying oils as a raw material as needed. Among the above-mentioned drying oils, tung oil, linseed oil, soybean oil, walnut oil and safflower oil are preferable, and tung oil and linseed oil are more preferable from the viewpoint of more effectively and reliably achieving the above-described effects of the present invention. These drying oils are used alone or in combination of two or more.

  The reaction between the phenol resin and the drying oil is usually preferably performed at 50 to 130 ° C. Moreover, the reaction ratio of the phenol resin and the drying oil is 1 to 50 parts by mass of the drying oil with respect to 100 parts by mass of the phenol resin from the viewpoint of further preventing generation of chips and improving the adhesion. It is preferably 5 to 25 parts by mass. When the reaction ratio of the drying oil is less than 1 part by mass, chips are more likely to be generated and chipping resistance tends to be lower than in the above range. Moreover, when the reaction ratio of drying oil exceeds 50 mass parts, compared with the case where it exists in the said range, it exists in the tendency for the adhesiveness with respect to the foundation | substrate of hardened | cured material to fall. At this time, if necessary, p-toluenesulfonic acid, trifluoromethanesulfonic acid or the like may be used as a catalyst.

  The weight average molecular weight in terms of polystyrene by gel permeation chromatography of the component (A) is preferably 300 to 100,000, and preferably 1,000 to 20,000 from the viewpoint of improving the coating properties and suppressing the decrease in developability. More preferred. If the weight average molecular weight is less than 300, the coating properties tend to be lower than in the above range. On the other hand, when the weight average molecular weight exceeds 1000000, the developability tends to be lower than that in the above range. However, the weight average molecular weight is not limited to the above numerical range.

  When the weight average molecular weight of the phenol resin is small, the phenol resin may be multimerized using a chain extender to increase the molecular weight so that the weight average molecular weight is within the range. Examples of the chain extender include diepoxy compounds and dioxazoline compounds that can react with a carboxyl group, and diisocyanate compounds that can react with a hydroxyl group.

  (A) A component is used individually by 1 type or in combination of 2 or more types. Examples of the phenol resin used in combination of two or more types include, for example, two or more types of phenol resins obtained from different types of monomers, two or more types of phenol resins having different weight average molecular weights, and Two or more types of phenol resins having different degrees of dispersion can be mentioned.

  The blending ratio of the component (A) in the photosensitive resin composition is preferably 50 to 95 parts by mass with the total amount of the component (A) and the component (B) being 100 parts by mass, and is 55 to 90 parts by mass. It is more preferable, and it is especially preferable that it is 60-85 mass parts. When this blending ratio is less than 50 parts by mass, when the photosensitive resin composition is used as a resist film, the resist film tends to become brittle and easily peeled, compared to the case where the blending ratio is in the above range. It is in. When the blending ratio exceeds 95 parts by mass, the photosensitivity of the resist film tends to be lower than when the blending ratio is in the above range.

((B) component)
The component (B) is a 1,2-quinonediazide compound and 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 One or more compounds selected from the group consisting of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride are preferred. 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'-hexahydroxybenzopheno 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 , 3'-dimethyl- {1- [4- [2- (3-methyl-4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol It is. 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 Is 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-H B 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 they 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 added to a solvent such as dioxane or THF. And a reaction 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.

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

  The blending ratio 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 preferably, it is 15-40 mass parts. When the blending ratio is less than 5 parts by mass, the photosensitivity tends to be lower than when the blending ratio is in the above range. When the blending ratio exceeds 50 parts by mass, when the photosensitive resin composition is used as a resist film, the resist film becomes brittle and tends to be peeled as compared with the case where the blending ratio is in the above range. .

(Other ingredients)
In addition to the component (A) described above, the photosensitive resin composition of the present embodiment may contain a phenol resin that has not been modified with a drying oil. Known phenol resins not modified with drying oil can be used. Examples of such phenol resins include novolak-type phenol resins, resol-type phenol resins, bisphenol resins, polyphenol compounds obtained by addition reaction of phenol compounds with diolefin compounds such as divinylbenzene and dicyclopentadiene, phenol compounds and aralkyl halides. , Polyphenol compounds obtained by reaction with aralkyl alcohol or derivatives thereof, and triazinephenol novolac resins. These are used singly or in combination of two or more.

  Moreover, you may make the photosensitive resin composition of this embodiment contain surfactant for the purpose of improving applicability | paintability, antifoaming property, leveling property, etc. as needed. Such a surfactant is not particularly limited, but is preferably a fluorosurfactant. Examples of such a fluorosurfactant include BM-1000 and BM-1100 (manufactured by BM Chemie); Megafuck F142D, Megafuck F172, Megafuck F173, Megafuck F183, and Megafuck R-08. , MegaFac R-30, MegaFac R-90PM-20, MegaFac BL-20 (above, manufactured by Dainippon Ink & Chemicals, Inc.); Fluorard FC-135, Fluorard FC-170C, Fluorard FC-430, Fluorard FC- 431, Florard FC-4430 (Sumitomo 3M, Inc.); Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 (above, Asahi Glass Co., Ltd.); SH-28PA , SH-190, SH-193, SZ-6032 SF-8428 (Toray Ltd. Silicone Co., Ltd.) may be commercially available, such as. These are used singly or in combination of two or more.

  The blending ratio of the surfactant is preferably 5 parts by mass or less with respect to 100 parts by mass of the total amount of the component (A) and the component (B). When the blending ratio exceeds 5 parts by mass, the image contrast tends to be lower than when the blending ratio is in the above range.

  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 such an 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.

  The blending ratio of the adhesion assistant is preferably 20 parts by mass or less with respect to 100 parts by mass of the total amount of the component (A) and the component (B). When the blending ratio exceeds 20 parts by mass, a development residue tends to be generated as compared with a case where the blending ratio is in the above range.

  The photosensitive resin composition of this embodiment may contain an acid or a high-boiling point solvent in order to finely adjust 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 are used singly or in combination of two or more.

  The mixing ratio of the above-mentioned acid or high boiling point solvent is not particularly limited as long as it can be adjusted according to the application and coating method, and can be uniformly mixed in the photosensitive resin composition. For example, the mixing ratio of these acids and high-boiling solvents is preferably 60% by mass or less, 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.

  Furthermore, the photosensitive resin composition of the present embodiment includes a sensitizer, a light absorber (dye), a crosslinking agent, a plasticizer, a pigment, a filler, a flame retardant, a stabilizer, and an adhesion imparting agent as necessary. Further, additives such as a peeling accelerator, an antioxidant, a fragrance, an imaging agent, and a thermal crosslinking agent may be contained. These additives may be used alone or in combination of two or more.

  The blending ratio of these additives is not particularly limited as long as it does not impair the characteristics of the photosensitive resin composition, but is preferably 50% by mass or less based on the total amount of the photosensitive resin composition. .

  Each of the components described above may be combined with any of those exemplified above.

  Preparation of the photosensitive resin composition of this embodiment should just be performed by mixing and stirring by a normal method. Moreover, what is necessary is just to disperse | distribute and mix using dispersers, such as a dissolver, a homogenizer, and a 3 roll mill, when adding a filler and a pigment to the photosensitive resin composition. Furthermore, you may filter using a mesh, a membrane filter, etc. as needed.

  When the photosensitive resin composition of this embodiment contains the component (A) in the photosensitive resin composition together with the component (B), the dry film obtained from the photosensitive resin composition is cut. Generation | occurrence | production of refuse can fully be prevented. In addition, the film quality of the dry film becomes flexible.

  Next, the photosensitive element of this embodiment will be described. FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention. The photosensitive element 1 shown in FIG. 1 has a structure in which a photosensitive layer 14 is laminated on a support 10. The photosensitive layer 14 is a layer made of the above-described photosensitive resin composition of the present embodiment.

  As the support 10, for example, a metal plate such as copper, a copper-based alloy, iron, or an iron-based alloy, or a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, or polyester can be used. The thickness of the support is preferably 1 to 150 μm.

  The photosensitive layer 14 can be formed by applying the photosensitive resin composition of the present embodiment on the support 10 as a liquid resist.

  When applying the photosensitive resin composition on the support 10, if necessary, the photosensitive resin composition is dissolved in a predetermined solvent to form a solution having a solid content of 30 to 60% by mass. It may be used as a 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, for example, by heating. 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 0.5-100 micrometers.

  In the photosensitive element 1, the surface F1 opposite to the support side of the photosensitive layer 14 may be covered with a protective film (not shown) as necessary.

  Examples of the protective film include polymer films such as polyethylene and polypropylene. Further, the protective film is preferably a low fish eye film, and the adhesive force between the protective film and the photosensitive layer 14 is such that the protective layer 14 and the support can be easily peeled off from the photosensitive layer 14. It is preferable that it is smaller than the adhesive force between 10.

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

  The photosensitive element 1 is, for example, in the form of a flat plate as it is or by laminating a protective film on one side of the photosensitive layer (on an exposed surface that is not protected) and wound around a cylindrical core. And can be stored in 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 that the support is wound up so as to be 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 element (photosensitive element roll) wound up 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 element 1, it is preferable to wrap it in a black sheet with low moisture permeability.

  The photosensitive element of this embodiment has the photosensitive layer 14 derived from the above-mentioned photosensitive resin composition. Therefore, generation of chips can be sufficiently prevented when the photosensitive layer 14 is cut. Further, the film quality of the photosensitive layer 14 becomes flexible.

  Next, a resist pattern forming method of this embodiment will be described.

  In this embodiment, the resist pattern is formed by laminating the photosensitive element 1 on a base material so that the photosensitive layer 14 is in close contact, irradiating actinic rays in an image form, and removing the exposed portion by development. To do. 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 of laminating the photosensitive layer 14 on the substrate, when the photosensitive element includes a protective film, the protective film is removed, and then the photosensitive layer 14 is heated to about 70 to 130 ° C. while being heated to about 0. Examples include a method of pressure bonding using a laminator or the like at a pressure of about 1 to 1 MPa (about 1 to 10 kgf / cm 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 with 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 is performed. 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 Weakly 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, the resist pattern according to this embodiment is obtained. At this time, since the photosensitive layer 14 in which generation of chips is sufficiently prevented is used, contamination of the working environment of the base material and laminator by chips is sufficiently prevented, and as a result, a resist pattern with sufficiently few defects. Can be formed. Further, by using the photosensitive element 1 of the present invention in which the exposed portion of the resist film is easily dissolved in weak alkali and peeled off from the substrate, and the weak alkali developability is extremely good, a fine resist pattern having excellent contrast can be obtained. Can be obtained.

  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]
In both cases, m-cresol and p-cresol, which are phenol compounds, were mixed at a mass ratio of 50:50. Subsequently, 54 parts by mass of formalin, which is an aldehyde, was added to 216 parts by mass of the mixed solution. Further, 2.2 parts by mass of oxalic acid as a catalyst was further added, and a condensation reaction was performed by a conventional method. Thus, a novolak type phenol resin having a weight average molecular weight of 10,000 was obtained. Next, 100 parts by weight of this novolac type phenolic resin, 10 parts by weight of tung oil as a drying oil, and 0.01 parts by weight of p-toluenesulfonic acid as an acidic catalyst are mixed and reacted at 90 ° C. to make tung oil. (A) component which is the phenol resin modified | denatured by was obtained. In addition, this (A) component is called phenol resin A1.

[Synthesis of phenol resin A2]
In both cases, m-cresol and p-cresol, which are phenol compounds, were mixed at a mass ratio of 60:40. Subsequently, 54 parts by mass of formalin, which is an aldehyde, was added to 216 parts by mass of the mixed solution. Further, 2.2 parts by mass of oxalic acid as a catalyst was further added, and a condensation reaction was performed by a conventional method. Thus, a novolak type phenol resin having a weight average molecular weight of 10,000 was obtained. Next, 100 parts by weight of this novolak type phenolic resin, 30 parts by weight of tung oil as a drying oil, and 0.01 parts by weight of p-toluenesulfonic acid as an acidic catalyst are mixed and reacted at 120 ° C. to make tung oil. (A) component which is the phenol resin modified | denatured by was obtained. In addition, this (A) component is called phenol resin A2.

[Synthesis of phenol resin A3]
In both cases, m-cresol and p-cresol, which are phenol compounds, were mixed at a mass ratio of 40:60. Subsequently, 54 parts by mass of formalin, which is an aldehyde, was added to 216 parts by mass of the mixed solution. Further, 2.2 parts by mass of oxalic acid as a catalyst was further added, and a condensation reaction was performed by a conventional method. Thus, a novolak type phenol resin having a weight average molecular weight of 10,000 was obtained. Next, 100 parts by mass of this novolak type phenol resin, 20 parts by mass of linseed oil as a drying oil, and 0.01 parts by mass of trifluoromethanesulfonic acid as an acidic catalyst were mixed and reacted at 120 ° C. to obtain linseed The component (A) which is a phenol resin modified with oil was obtained. In addition, this (A) component is called phenol resin A3.

[Synthesis of phenol resin A4]
In both cases, m-cresol and p-cresol, which are phenol compounds, were mixed at a mass ratio of 50:50. Subsequently, 54 parts by mass of formalin, which is an aldehyde, was added to 216 parts by mass of the mixed solution. Further, 2.2 parts by mass of oxalic acid as a catalyst was further added, and a condensation reaction was performed by a conventional method. Thus, a novolak type phenol resin having a weight average molecular weight of 10,000 was obtained. This novolac type phenol resin is referred to as a phenol resin A4.

(Examples 1 to 3 and Comparative Examples 1 and 2)
The photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were mixed by mixing the component (A), the component (B) and other components so as to have the composition (unit: part by mass) shown in Table 1. I got a thing. Details of the compounds in Table 1 are shown below. In addition, the mass in Table 1 is a mass of non-volatile content.
DNQ: 1,2-quinonediazide compound obtained by reacting 1 mol of the compound represented by the above chemical formula (5) with 3 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride PGMEA: propylene glycol monomethyl ether acetate MEK: Methyl ethyl ketone

[Production of photosensitive element]
Using the photosensitive resin composition solutions of Examples 1 to 3 and Comparative Examples 1 and 2, photosensitive elements were prepared according to the following procedure. First, a photosensitive resin composition solution was applied onto a polyethylene terephthalate film (hereinafter referred to as “PET film”) having a width of 380 mm and a thickness of 50 μm. Subsequently, the PET film coated with the photosensitive resin composition solution was held in a hot air convection dryer set at 100 ° C. to form a photosensitive layer. At that time, the film thickness of the photosensitive layer after heating was set to 3 μm. And the 35-micrometer-thick polyethylene film as a protective film was mounted on the formed photosensitive layer, and it pressurized with the roll. Thus, photosensitive elements of Examples 1 to 3 and Comparative Examples 1 and 2 were obtained.

[Production of sample for characteristic evaluation]
Examples 1 to 3 and Comparative Examples in which the photosensitive layers of the photosensitive elements of Examples 1 to 3 and Comparative Examples 1 and 2 were laminated on a glass plate while heating to 120 ° C., and a photosensitive layer was formed on the glass plate. Samples for characteristic evaluation 1 and 2 were obtained.

  Using the samples for characteristic evaluation of Examples 1 to 3 and Comparative Examples 1 and 2 thus obtained, the alkali resistance evaluation of the unexposed part, the developability evaluation of the exposed part, and the adhesion evaluation were performed. . Moreover, the chipping resistance of the photosensitive elements of Examples 1 to 3 and Comparative Examples 1 and 2 was also evaluated.

[Evaluation of alkali resistance of unexposed areas]
The PET film was peeled off from the sample for characteristic evaluation, and immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at room temperature (25 ° C.) for 60 seconds. The photosensitive layer after immersion was regarded as an unexposed portion of the resist film, and the state was visually evaluated according to the following criteria. The obtained results are shown in Table 2.
A: No abnormality was observed in the appearance of the photosensitive layer.
B: Peeling was observed on a part of the photosensitive layer.

[Evaluation of developability of exposed areas]
The PET 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. 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. The obtained results are shown in Table 2.
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 PET 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 placed 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 Table 2. In Table 2, the adhesion is indicated by the minimum line width, and the smaller the minimum line width is, the better the adhesion is, and the contrast between the unexposed part and the exposed part is clearer. In Table 2, “impossible to evaluate” means a state where a pattern cannot be formed due to poor developability.

[Evaluation of chipping resistance]
The photosensitive element was cut with a laminator cutter. The cut part and its periphery in the photosensitive element in that case were observed. The state was evaluated according to the following criteria. The obtained results are shown in Table 2.
A: Chip generation was not observed and chipping resistance was good.
B: Generation of chips was observed and the chipping resistance was not good.

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

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support body, 14 ... Photosensitive layer.

Claims (2)

(A) component: a compound obtained by reacting a phenol resin and a drying oil;
(B) The photosensitive resin composition containing a component: 1,2-quinonediazide compound.   A photosensitive element comprising: a support; and a photosensitive layer made of the photosensitive resin composition according to claim 1 formed on the support.

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