Photosensitive resin composition, photosensitive resin coating, photosensitive dry film, and pattern forming method

Abstract

This invention provides a photosensitive resin composition and a method for forming a pattern thereon, which can form fine patterns and, even when the process is completed by developing, the cured film exhibits excellent dielectric properties, high reliability, and resistance to copper migration. [Solution] A photosensitive resin composition comprising (A) a polymer having repeating units represented by the following formula (A1) and repeating units represented by the following formula (A2), having a group represented by the following formula (A3) at both ends, and having a weight-average molecular weight of 3,000 to 100,000, and (B) a photoradical generator. TIFF2026092148000024.tif30124 TIFF2026092148000025.tif2279

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a photosensitive resin coating, a photosensitive dry film, and a pattern forming method. [Background technology]

[0002] Conventionally, photosensitive polyimide compositions, photosensitive epoxy resin compositions, and photosensitive silicone compositions have been used as protective films for photosensitive semiconductor elements and insulating films for multilayer printed circuit boards. Among these, it has become clear that the cured film obtained from the photosensitive silicone composition for optical devices described in Patent Document 1 has low dielectric properties.

[0003] However, recently, there has been a demand for cured films with even lower dielectric properties to accommodate high-frequency devices, but the dielectric properties of cured films obtained from the above composition are insufficient, and improvement has been desired. Furthermore, since crosslinking does not proceed without a post-exposure heating (PEB) process when forming patterns in cured films obtained from the above composition, the PEB process is essential, which causes the catalytic acid to thermally diffuse into the unexposed areas, making it difficult to miniaturize patterns. In recent years, there has also been an increasing demand to complete the process with development in order to reduce the thermal load on the device side. However, while the above composition has high reliability and copper migration resistance when post-cured at 190°C or higher after exposure and development, on the other hand, when the process is completed with exposure and development, reliability and copper migration resistance are significantly reduced. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-90649 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention has been made in view of the above circumstances, and an object thereof is to provide a photosensitive resin composition capable of forming a fine pattern and having excellent dielectric properties, high reliability, and copper migration resistance in a cured film even when the process is completed by development, and a method for forming a pattern thereof.

Means for Solving the Problems

[0006] As a result of repeated studies to achieve the above object, the present inventors have found that the above object can be achieved by a photosensitive resin composition containing (A) a polymer having a norbornene skeleton, a silylene skeleton, and a siloxane skeleton in the main chain and having (meth)acryloyl groups at both ends and having a weight average molecular weight of 3000 to 100,000, and (B) a photo radical generator, and have completed the present invention.

[0007] That is, the present invention provides the following photosensitive resin composition, photosensitive resin film, photosensitive dry film, and pattern forming method. 1. A polymer containing a repeating unit represented by the following formula (A1) and a repeating unit represented by the following formula (A2), having a group represented by the following formula (A3) at both ends, and having a weight average molecular weight of 3000 to 100,000, and (B) A photo radical generator A photosensitive resin composition containing the same.

Chemical formula

Chemical formula

Advantages of the Invention

[0008] The photosensitive resin composition of the present invention can form a fine pattern, and even when the process is completed by development, it can provide a cured film having excellent dielectric properties, high reliability, and resistance to copper migration. Further, since the cured film has the above-described properties, it can be suitably used as a material for forming a film for protecting various electric and electronic components such as circuit boards, semiconductor elements, and display elements.

Embodiments for Carrying Out the Invention

[0009] The photosensitive resin composition of the present invention contains (A) a polymer having a norbornane skeleton, a silylene skeleton, and a siloxane skeleton in the main chain and having (meth)acryloyl groups at both ends, with a weight average molecular weight of 3,000 to 100,000, and (B) a photo radical generator.

[0010] [(A) Polymer] The polymer of component (A) contains a repeating unit represented by the following formula (A1) and a repeating unit represented by the following formula (A2).

Chemical formula

[0011] In formula (A), R 1 ~R 4 are each independently a hydrocarbyl group having 1 to 8 carbon atoms, preferably a methyl group. k is an integer of 1 to 600. a and b represent the composition ratio (molar ratio) of each repeating unit, and are numbers satisfying 0 < a < 1, 0 < b < 1, and a + b = 1. Preferably, k, a, and b are selected so that the silicone content is 20 to 80% by mass, more preferably 30 to 70% by mass.

[0012] In formulas (A1) and (A2), X is a divalent group represented by the following formula (X). [Chemical formula]

[0013] In formula (X), R 11 and R 12 are each independently a saturated hydrocarbyl group having 1 to 20 carbon atoms which may contain a hydrogen atom or a heteroatom. R 11 and R 12 are preferably a hydrogen atom or a methyl group. m is an integer from 0 to 10, preferably 0, 1 or 2. The dashed line is a bond to the Si atom.

[0014] Also, the polymer of component (A) has groups represented by the following formula (A3) at both ends. [Chemical formula]

[0015] In formula (A3), R 21 is a hydrogen atom or a methyl group. R 22 is a saturated hydrocarbyl group having 1 to 20 carbon atoms which may contain a hydrogen atom or a heteroatom. R 22 is preferably a hydrogen atom or a methyl group. n is an integer from 1 to 10, preferably 1, 2 or 3. The dashed line is a bond to the Si atom.

[0016] The weight average molecular weight (Mw) of the polymer of component (A) is from 3000 to 100000, preferably from 5000 to 50000. In the present invention, Mw is a polystyrene equivalent measurement value by gel permeation chromatography (GPC) using tetrahydrofuran as an elution solvent.

[0017] [Method for producing polymer] The aforementioned polymer can be produced by addition polymerization of the compound represented by formula (1), the compound represented by formula (2), and the compound represented by formula (3) in the presence of a metal catalyst, and then reacting them with the compound represented by formula (4). [ka]

[0018] [ka] (In the formula, R 1 ~R 4 (and k are the same as above.)

[0019] [ka] (In the formula, R 11 , R 12 (and m are the same as above.)

[0020] [ka] (In the formula, R 21 , R 22 (And n are the same as above.)

[0021] The aforementioned metal catalysts include elemental platinum group metals such as platinum (including platinum black), rhodium, and palladium; platinum chloride, chloroplatinic acid, and chloroplatinate salts such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2, and Na2HPtCl4·xH2O (where x is preferably an integer from 0 to 6, and particularly preferably 0 or 6); and alcohol-modified chloroplatinic acid (for example, as described in U.S. Patent No. 3,220,972). ); complexes of chloroplatinic acid and olefins (for example, those described in U.S. Patent No. 3,159,601, U.S. Patent No. 3,159,662, and U.S. Patent No. 3,775,452); platinum group metals such as platinum black and palladium supported on a carrier such as alumina, silica, or carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (so-called Wilkinson catalyst); complexes of platinum chloride, chloroplatinic acid, or chloroplatinate salts with vinyl group-containing siloxanes (especially vinyl group-containing cyclic siloxanes), etc. can be used.

[0022] The amount of catalyst used is a catalytic amount, and is preferably 0.001 to 0.1% by mass of the total amount of the compounds represented by formula (1), formula (2), formula (3), and formula (4) as platinum group metals. In the polymerization reaction, a solvent may be used as needed. As the solvent, hydrocarbon solvents such as toluene and xylene are preferred. As the polymerization conditions, the polymerization temperature is preferably 40 to 150°C, and particularly 60 to 120°C, from the viewpoint that the catalyst will not be deactivated and polymerization can be completed in a short time. The polymerization time depends on the type and amount of polymer, but in order to prevent moisture from entering the polymerization system, it is preferable to complete the process in about 0.5 to 100 hours, and particularly 0.5 to 30 hours. After the polymerization reaction is completed in this way, if a solvent was used, it can be removed by distillation to obtain the polymer.

[0023] The reaction method is not particularly limited, but it is preferable to first heat the compound represented by formula (3), then add a metal catalyst to the mixed solution, then add the compound represented by formula (1) and the compound represented by formula (2) dropwise over 0.1 to 5 hours, allow to mature for 1 to 10 hours, then add the compound represented by formula (4) dropwise over 0.1 to 5 hours, allow to mature for 1 to 10 hours.

[0024] Each starting compound is prepared such that (total hydrosilyl groups of the compound represented by formula (1) and the compound represented by formula (2)) / (total alkenyl groups of the compound represented by formula (3)) > 1 (molar ratio). This creates a state where hydrosilyl groups remain at the terminals, and by reacting these with the alkenyl groups of the compound represented by formula (4), (meth)acrylic groups are introduced at the terminals. Therefore, after adding the compound represented by (4), (total hydrosilyl groups) / (total alkenyl groups (excluding (meth)acryloyl groups)) ≤ 1 (molar ratio).

[0025] [(B) Photoradical Generator] The photoradical generator of component (B) is not particularly limited as long as it is a compound that generates radicals upon exposure, and specific examples include acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, oxime compounds, etc.

[0026] Specific examples of the aforementioned acetophenone compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one.

[0027] Specific examples of the aforementioned benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

[0028] Specific examples of the thioxanthone compounds mentioned above include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

[0029] Specific examples of the benzoin compounds mentioned above include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

[0030] Specific examples of the aforementioned triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-to Examples include lyazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-s-triazine, and 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine.

[0031] Specific examples of the aforementioned oxime compounds include 1,2-octanedione, O-acyl oxime compounds, 2-(O-benzoyl oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyl oxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane, and O-ethoxycarbonyl-α-oxyamino-1-phenylpropane-1-one. Specific examples of the O-acyloxime compounds include 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine-4-ylphenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butan-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-one oxime-O-acetate, and 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O-acetate.

[0032] Specific examples of the phosphine oxide compounds mentioned above include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0033] (B) In addition to the above-mentioned compounds, other photoradical generators that can be used include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, non-imidazole compounds, fluorene compounds, etc.

[0034] In the photosensitive resin composition of the present invention, the content of (B) photoradical generator is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of component (A). When the content of the photoradical generator is within the above range, an excellent balance between sensitivity and developability during exposure is obtained, a pattern with excellent resolution without residual film is obtained, and in addition, a highly reliable cured film is obtained. (B) photoradical generator may be used alone or in combination of two or more types.

[0035] [(C) Crosslinking agent] The photosensitive resin composition of the present invention may further contain a crosslinking agent as component (C). The crosslinking agent (C) is a component that undergoes a crosslinking reaction with the silicone resin (A) to facilitate the formation of a pattern with a good shape, and a crosslinking agent having two or more (meth)acryloyl groups is preferred.

[0036] Specific examples of crosslinking agents having two or more (meth)acryloyl groups include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropyl glycol di(meth)acrylate, and trimethylolpropyl glycol di(meth)acrylate. Pantri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate (T)Acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate diglycidyl ester di(meth)acrylate, glycerin triacrylate, glyceryl Examples include polyglycidyl ether poly(meth)acrylate, urethane(meth)acrylate (i.e., reaction products of tolylene diisocyanate, trimethylhexamethylene diisocyanate or hexamethylene diisocyanate, etc. with 2-hydroxyethyl(meth)acrylate), methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, polyfunctional monomers such as condensates of polyhydric alcohols with N-methylol(meth)acrylamide, and triacrylic formal.

[0037] If the photosensitive resin composition of the present invention contains (C) a crosslinking agent, its content is preferably 0.5 to 100 parts by mass, and more preferably 1 to 50 parts by mass, per 100 parts by mass of component (A). The (C) crosslinking agent may be used alone or in combination of two or more types.

[0038] [(D) Solvent] The photosensitive resin composition of the present invention may contain a solvent as component (D). The solvent (D) is not particularly limited as long as it can dissolve and disperse the aforementioned components (A) to (C) and other various additives.

[0039] (D) As solvents, organic solvents are preferred, and examples include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monotert-butyl ether acetate, and γ-butyrolactone.

[0040] (D) As solvents, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclopentanone, and mixed solvents thereof are preferred, as they have particularly good solubility for (A) silicone resin and (B) photoradical generator.

[0041] (D) The content of component (D) is preferably 25 to 85% by mass, and more preferably 30 to 80% by mass, relative to the total amount of the photosensitive resin composition, from the viewpoint of compatibility and viscosity of the photosensitive resin composition. (D) Solvent may be used alone or as a mixture of two or more types.

[0042] The photosensitive resin composition of the present invention can be prepared by conventional methods. For example, the photosensitive resin composition of the present invention can be prepared by stirring and mixing the components, and then filtering out the solids as needed using a filter or the like.

[0043] The photosensitive resin composition of the present invention prepared in this manner can be suitably used, for example, as a protective film-forming material for various electrical and electronic components such as circuit boards, semiconductor elements, and display elements.

[0044] [Pattern formation method using photosensitive resin composition] The pattern forming method using the photosensitive resin composition of the present invention is: (i) A step of forming a photosensitive resin film on a substrate using the photosensitive resin composition of the present invention, (ii) A step of exposing the photosensitive resin film, and (iii) A step of developing the exposed photosensitive resin film using a developer to remove unexposed areas and form a pattern. It includes.

[0045] Step (i) is a step of forming a photosensitive resin film on a substrate using the photosensitive resin composition. Examples of the substrate include silicon wafers, silicon wafers for through electrodes, silicon wafers thinned by backside polishing, plastic or ceramic substrates, and substrates having metals such as Ni or Au on the entire surface or in part by ion sputtering or plating. In addition, substrates with uneven surfaces may also be used.

[0046] One method for forming a photosensitive resin film is to apply the photosensitive resin composition onto a substrate and preheat (pre-bake) it as needed. The application method can be any known method, such as the dip method, spin coating method, or roll coating method. The amount of the photosensitive resin composition applied can be appropriately selected depending on the purpose, but it is preferable to apply it so that the resulting photosensitive resin film thickness is preferably 0.1 to 200 μm, more preferably 1 to 150 μm.

[0047] To improve film thickness uniformity on the substrate surface, a solvent may be dropped onto the substrate before applying the photosensitive resin composition (pre-wetting method). The solvent to be dropped and its amount can be appropriately selected depending on the purpose. Preferred solvents include alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, and glycols such as PGME, but solvents used in photosensitive resin compositions can also be used.

[0048] To ensure efficient photocuring, pre-baking may be performed to evaporate solvents and other substances beforehand, if necessary. Pre-baking can be carried out, for example, at 40-140°C for 1 minute to 1 hour.

[0049] Next, (ii) the photosensitive resin film is exposed to light. At this time, exposure is preferably carried out with light of a wavelength of 10 to 600 nm, and more preferably with light of 190 to 500 nm. Examples of such wavelengths of light include various wavelengths of light generated by a radiation generator, such as ultraviolet rays (g-rays, h-rays, i-rays, etc.) and far-ultraviolet rays (248 nm, 193 nm). Of these, light of a wavelength of 248 to 436 nm is particularly preferred. The exposure amount is 10 to 10000 mJ / cm². 2 It is preferable.

[0050] Exposure may be performed via a photomask. The photomask may, for example, have a desired pattern cut out of it. The material of the photomask is not particularly limited, but it is preferably one that blocks light of the aforementioned wavelength, and for example, one that has chromium or the like as a light-shielding film is preferably used.

[0051] Furthermore, in this invention, the crosslinking reaction proceeds in the exposed area without performing the PEB process, forming an insoluble pattern that is insoluble in the organic solvent used as the developer. By omitting the PEB process, the catalyst species generated in the exposed area are prevented from thermally diffusing to the unexposed area, making it possible to achieve finer pattern formation.

[0052] After exposure, (iii) the exposed photosensitive resin film is developed using a developer to remove unexposed areas and form a pattern. As the developer, organic solvents such as alcohols such as IPA, ketones such as cyclohexanone, and glycols such as PGME are preferred, but solvents used in the photosensitive resin composition can also be used. As for the development method, a conventional method can be used, such as immersing the patterned substrate in the developer. The unexposed areas are dissolved and removed by organic solvent development, thereby forming a pattern. After that, washing, rinsing, drying, etc. are performed as necessary to obtain a resin film having the desired pattern. In this invention, even if the process is completed by development, a cured film with excellent dielectric properties, high reliability, and resistance to copper migration can be obtained.

[0053] Furthermore, the (iv) patterned film can be post-cured at a low temperature of 40-150°C using an oven or hot plate. A post-curing temperature of 40-150°C increases the crosslinking density of the photosensitive resin composition without damaging the laminated semiconductor elements, ensuring high chemical resistance, copper migration resistance, and reliability of the cured film. The post-curing time is preferably 10 minutes to 12 hours, and more preferably 1 hour to 6 hours. Using the photosensitive resin composition of the present invention, a film with excellent cured film properties can be obtained even with post-curing at a low temperature of around 40-150°C. The film thickness of the cured film after post-curing is typically 1-200 μm, preferably 5-50 μm.

[0054] If it is not necessary to form a pattern, for example, if it is simply desired to form a uniform film, the film can be formed in step (ii) of the pattern formation method by exposing the material to light of an appropriate wavelength without using the photomask.

[0055] [Photosensitive dry film] The photosensitive dry film of the present invention comprises a support film and a photosensitive resin coating obtained from the photosensitive resin composition on the support film.

[0056] The photosensitive dry film (support film and photosensitive resin coating) is solid, and the photosensitive resin coating does not contain solvents, so there is no risk of bubbles remaining inside the photosensitive resin coating and between it and the uneven substrate due to its volatilization.

[0057] The thickness of the photosensitive resin coating is preferably 5 to 200 μm, and more preferably 10 to 100 μm, from the viewpoint of flatness on an uneven substrate, step coverage, and substrate stacking spacing.

[0058] Furthermore, the viscosity and fluidity of the photosensitive resin film are closely related. The photosensitive resin film can exhibit appropriate fluidity within an appropriate viscosity range, allowing it to penetrate deep into narrow gaps and strengthen adhesion to the substrate as the resin softens. Therefore, from the viewpoint of its fluidity, the viscosity of the photosensitive resin film is preferably 10 to 5000 Pa·s, more preferably 30 to 2000 Pa·s, and even more preferably 50 to 300 Pa·s at 80 to 120°C. In this invention, viscosity is measured using a rotational viscometer.

[0059] The photosensitive dry film of the present invention achieves high flatness when the photosensitive resin coating adheres to the uneven surface of a substrate. In particular, the photosensitive resin coating is characterized by low viscoelasticity, which allows for even higher flatness. Furthermore, adhering the photosensitive resin coating to the substrate under a vacuum environment can more effectively prevent the formation of gaps.

[0060] The photosensitive dry film of the present invention can be manufactured by applying the photosensitive resin composition onto a support film and drying it to form a photosensitive resin film. A film coater for manufacturing adhesive products can generally be used as the manufacturing apparatus for the photosensitive dry film. Examples of film coaters include comma coaters, comma reverse coaters, multi coaters, die coaters, lip coaters, lip reverse coaters, direct gravure coaters, offset gravure coaters, three-bottom reverse coaters, four-bottom reverse coaters, and the like.

[0061] A photosensitive dry film can be manufactured by unwinding a support film from the unwinding shaft of the film coater and passing it through the coater head of the film coater, applying the photosensitive resin composition to the support film to a predetermined thickness, then passing it through a hot air circulation oven at a predetermined temperature and time to dry it on the support film and form a photosensitive resin coating. Alternatively, if necessary, a photosensitive dry film with a protective film can be manufactured by passing the photosensitive dry film together with a protective film unwinding from another unwinding shaft of the film coater through a laminating roll at a predetermined pressure to bond the photosensitive resin coating on the support film with the protective film, and then winding it onto the winding shaft of the film coater. In this case, the temperature is preferably 25 to 150°C, the time is preferably 1 to 100 minutes, and the pressure is preferably 0.01 to 5 MPa.

[0062] The support film may be a single-layer film consisting of a single film, or a multilayer film formed by laminating multiple films. Examples of materials for the film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Of these, polyethylene terephthalate is preferred due to its appropriate flexibility, mechanical strength, and heat resistance. These films may have undergone various treatments, such as corona treatment or release agent coating. Commercially available products can be used, such as Therapiel WZ(RX), Therapiel BX8(R) (both manufactured by Toray Film Processing Co., Ltd.), E7302, E7304 (both manufactured by Toyobo Co., Ltd.), Purex G31, Purex G71T1 (both manufactured by Teijin DuPont Films Ltd.), PET38×1-A3, PET38×1-V8, and PET38×1-X08 (all manufactured by Nippa Co., Ltd.).

[0063] As the protective film, the same type as the support film described above can be used, but polyethylene terephthalate and polyethylene are preferred due to their appropriate flexibility. Commercially available products can be used, and examples of polyethylene terephthalate include those already exemplified, while examples of polyethylene include GF-8 (manufactured by Tamapoly Co., Ltd.) and PE film type 0 (manufactured by Nipper Co., Ltd.).

[0064] The thickness of the support film and protective film is preferably 10 to 100 μm, more preferably 25 to 50 μm, from the viewpoint of stability in the production of the photosensitive dry film and prevention of curling on the core.

[0065] [Pattern formation method using photosensitive dry film] The pattern formation method using the photosensitive dry film of the present invention is: (i') A step of forming the photosensitive resin film on the substrate using the photosensitive dry film, (ii) A step of exposing the photosensitive resin film, and (iii) A step of developing the exposed photosensitive resin film using a developer to remove unexposed areas and form a pattern. It is characterized by including.

[0066] First, in step (i'), a photosensitive resin film is formed on the substrate using a photosensitive dry film. Specifically, the photosensitive resin film of the photosensitive dry film is attached to the substrate to form the photosensitive resin film. If the photosensitive dry film has a protective film, the protective film is peeled off from the photosensitive dry film before attaching the photosensitive resin film of the photosensitive dry film to the substrate. The attachment can be performed, for example, using a film attachment device.

[0067] The substrate is the same as that described in the pattern formation method using a photosensitive resin composition. A vacuum laminator is preferred as the film bonding apparatus. For example, the protective film of the photosensitive dry film is peeled off, and the exposed photosensitive resin film is pressed onto the substrate on a table at a predetermined temperature using a bonding roll at a predetermined pressure in a vacuum chamber at a predetermined vacuum level. The temperature is preferably 60 to 120°C, the pressure is preferably 0 to 5.0 MPa, and the vacuum level is preferably 50 to 500 Pa.

[0068] To obtain a photosensitive resin coating of the required thickness, the film may be applied multiple times as needed. For example, applying the film 1 to 10 times can yield a photosensitive resin coating with a thickness of approximately 10 to 1000 μm, and especially 100 to 500 μm.

[0069] To efficiently carry out the photocuring reaction of the photosensitive resin film and to improve the adhesion between the photosensitive resin film and the substrate, pre-baking may be performed as needed. Pre-baking can be performed, for example, at 40 to 140°C for about 1 minute to 1 hour.

[0070] A photosensitive resin film attached to a substrate can be used to form a pattern by (ii) exposing the photosensitive resin film to light, (iii) developing the exposed photosensitive resin film with a developer to remove unexposed areas, and (iv) performing a post-curing treatment as necessary, similar to the pattern-forming method using the photosensitive resin composition. The support film for the photosensitive dry film is removed before pre-baking or by other means, depending on the process.

[0071] The film obtained from the photosensitive resin composition and the photosensitive dry film provides a cured film with excellent dielectric properties, high reliability, and resistance to copper migration, even when the process is completed by developing. It can be suitably used as a protective film-forming material for various electrical and electronic components such as circuit boards, semiconductor elements, and display elements. [Examples]

[0072] The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, Mw was measured by gel permeation chromatography (GPC) using monodisperse polystyrene as the standard, with a TSKGEL Super HZM-H (manufactured by Tosoh Corporation) as the GPC column, under analytical conditions of flow rate 0.6 mL / min, eluent tetrahydrofuran, and column temperature 40°C. In addition, using deuterated toluene as the deuterated solvent, a Bruker AV400M was used. 1 By performing 1H-NMR measurements, the disappearance of a peak originating from the hydrosilyl group (4.7 ppm), the disappearance of a peak originating from the alkenyl group in the norbornene skeleton (6.1 ppm), and the assignment of a peak originating from the (meth)acryloyl group (5.5 ppm) confirmed that it was the polymer of the present invention.

[0073] [1] Polymer synthesis The compounds used in the synthesis of the polymer are listed below. [ka]

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] [Synthesis Example 1] Synthesis of Polymer 1 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 145.8 g (0.90 mol) of compound (S-3b) was added, followed by the addition of 2000 g of toluene, and the mixture was heated to 70°C. Then, 1.0 g of toluene chloroplatinate solution (platinum concentration 0.5% by mass) was added, and 145.5 g (0.75 mol) of compound (S-1) and 755.0 g (0.25 mol) of compound (S-2a) were added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups (excluding (meth)acryloyl groups) = 1.11 (molar ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and aged for 7 hours, and then 54.6 g (0.30 mol) of compound (S-5b) was added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups (excluding (meth)acryloyl groups) = 0.95 (molar ratio)). After the dropwise addition was complete, the mixture was aged at 100°C for 7 hours, and then toluene was removed from the reaction solution under reduced pressure to obtain polymer 1 (silicone content 68.6% by mass). 1 ¹H-NMR measurements revealed the disappearance of a peak originating from the hydrosilyl group (4.7 ppm), the disappearance of a peak originating from the alkenyl group in the norbornene skeleton (6.1 ppm), and the assignment of a peak originating from the (meth)acryloyl group (5.5 ppm), confirming that the polymer is of the present invention. Furthermore, GPC measurements showed that the Mw was 50,000.

[0078] [Synthesis Example 2] Synthesis of Polymer 2 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 108.9 g (0.90 mol) of compound (S-3a) was added, followed by the addition of 2000 g of toluene, and the mixture was heated to 70°C. Then, 1.0 g of toluene chloroplatinate solution (platinum concentration 0.5% by mass) was added, and 164.9 g (0.85 mol) of compound (S-1) and 237.8 g (0.15 mol) of compound (S-2b) were added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups (excluding (meth)acryloyl groups) = 1.11 (molar ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and aged for 7 hours, and then 46.2 g (0.30 mol) of compound (S-5a) was added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups (excluding (meth)acryloyl groups) = 0.95 (molar ratio)). After the dropwise addition was complete, the mixture was aged at 100°C for 7 hours, and then toluene was removed from the reaction solution under reduced pressure to obtain polymer 2 (silicone content 42.6% by mass). 1 1H-NMR measurements revealed the disappearance of a peak originating from the hydrosilyl group (4.7 ppm), the disappearance of a peak originating from the alkenyl group in the norbornene skeleton (6.1 ppm), and the assignment of a peak originating from the (meth)acryloyl group (5.5 ppm), confirming that it is the polymer of the present invention. Furthermore, GPC measurements showed that the Mw was 10000.

[0079] [Synthesis Example 3] Synthesis of Polymer 3 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 113.4 g (0.70 mol) of compound (S-3b) was added, followed by the addition of 2000 g of toluene, and the mixture was heated to 70°C. Subsequently, 1.0 g of toluene chloroplatinate solution (platinum concentration 0.5% by mass) was added, and 164.9 g (0.85 mol) of compound (S-1) and 453.0 g (0.15 mol) of compound (S-2a) were added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups (excluding (meth)acryloyl groups) = 1.43 (molar ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and aged for 7 hours. Then, 127.4 g (0.70 mol) of compound (S-5b) was added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups (excluding (meth)acryloyl groups) = 0.95 (molar ratio)). After the dropwise addition was complete, the mixture was aged at 100°C for 7 hours. Toluene was then removed from the reaction solution under reduced pressure to obtain polymer 3 (silicone content 52.8% by mass). 1 1H-NMR measurements revealed the disappearance of a peak originating from the hydrosilyl group (4.7 ppm), the disappearance of a peak originating from the alkenyl group in the norbornene skeleton (6.1 ppm), and the assignment of a peak originating from the (meth)acryloyl group (5.5 ppm), confirming that it is the polymer of the present invention. Furthermore, GPC measurements showed that the Mw was 30000.

[0080] [Synthesis Example 4] Synthesis of Polymer 4 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 96.8 g (0.80 mol) of compound (S-3a) was added, followed by the addition of 2000 g of toluene, and the mixture was heated to 70°C. Then, 1.0 g of toluene chloroplatinate solution (platinum concentration 0.5 mass%) was added, and 174.6 g (0.90 mol) of compound (S-1) and 158.5 g (0.10 mol) of compound (S-2b) were added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups (excluding (meth)acryloyl groups) = 1.25 (molar ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and aged for 7 hours, and then 77.0 g (0.50 mol) of compound (S-5a) was added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups (excluding (meth)acryloyl groups) = 0.95 (molar ratio)). After the dropwise addition was complete, the mixture was aged at 100°C for 7 hours, and then toluene was removed from the reaction solution under reduced pressure to obtain polymer 4 (silicone content 31.3% by mass). 1 1H-NMR measurements revealed the disappearance of a peak originating from the hydrosilyl group (4.7 ppm), the disappearance of a peak originating from the alkenyl group in the norbornene skeleton (6.1 ppm), and the assignment of a peak originating from the (meth)acryloyl group (5.5 ppm), confirming that it is the polymer of the present invention. Furthermore, GPC measurements showed that the Mw was 5000.

[0081] [Comparative Synthesis Example 1] Synthesis of Comparative Polymer 1 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 79.5 g (0.30 mol) of compound (S-4) and 113.4 g (0.70 mol) of compound (S-3b) were added, followed by the addition of 2000 g of toluene, and the mixture was heated to 70°C. Then, 1.0 g of toluene chloroplatinate solution (platinum concentration 0.5% by mass) was added, and 145.5 g (0.75 mol) of compound (S-1) and 755.0 g (0.25 mol) of compound (S-2a) were added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups = 1.00 (molar ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and aged for 6 hours. Toluene was then removed from the reaction solution under reduced pressure to obtain comparative polymer 1 (silicone content 69.1% by mass). GPC measurement revealed a Mw of 50000.

[0082] [Comparative Synthesis Example 2] Synthesis of Comparative Polymer 2 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 132.5 g (0.50 mol) of compound (S-4) and 60.5 g (0.50 mol) of compound (S-3a) were added, followed by the addition of 2000 g of toluene, and the mixture was heated to 70°C. Then, 1.0 g of toluene chloroplatinate solution (platinum concentration 0.5% by mass) was added, and 174.6 g (0.90 mol) of compound (S-1) and 158.5 g (0.10 mol) of compound (S-2b) were added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups = 1.00 (molar ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and aged for 6 hours. Toluene was then removed from the reaction solution under reduced pressure to obtain comparative polymer 2 (silicone content 30.1% by mass). GPC measurement revealed a Mw of 5000.

[0083] [Comparative Synthesis Example 3] Synthesis of Comparative Polymer 3 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 79.5 g (0.30 mol) of compound (S-4) and 108.9 g (0.90 mol) of compound (S-3a) were added, followed by the addition of 2000 g of toluene, and the mixture was heated to 70°C. Then, 1.0 g of toluene chloroplatinate solution (platinum concentration 0.5% by mass) was added, and 164.9 g (0.85 mol) of compound (S-1) and 237.8 g (0.15 mol) of compound (S-2b) were added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups = 1.00 (molar ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and aged for 6 hours. Toluene was then removed from the reaction solution under reduced pressure to obtain comparative polymer 3 (silicone content 42.6% by mass). GPC measurement revealed a Mw of 10000.

[0084] [2] Preparation of photosensitive resin composition [Examples 1-8 and Comparative Examples 1-6] Each component was mixed according to the proportions listed in Tables 1 and 2, then stirred and dissolved at room temperature. Finally, the mixture was microfiltered using a 1.0 μm Teflon® filter to prepare the photosensitive resin compositions of Examples 1-8 and Comparative Examples 1-6.

[0085] [Table 1]

[0086] [Table 2]

[0087] In Tables 1 and 2, the photoradical generators B1, B2, B'1, and B'2 are as follows: [ka]

[0088] In Tables 1 and 2, the crosslinking agents C1, C2, C'1, and C'2 are as follows: [ka]

[0089] [3] Preparation of photosensitive dry film A die coater was used as the film coater, and a polyethylene terephthalate film (75 μm thick) was used as the support film. The photosensitive resin compositions described in Tables 1 and 2 were applied to the support film, respectively. The films were then dried by passing them through a hot air circulation oven (4 m long) set to 100°C for 5 minutes to form a photosensitive resin film on the support film, obtaining a photosensitive dry film. A polyethylene film (50 μm thick) was then laminated onto the photosensitive resin film using a laminating roll at a pressure of 1 MPa to produce a photosensitive dry film with a protective film. The film thickness of each photosensitive resin film was 100 μm. The film thickness of the photosensitive resin film was measured using an optical interference film thickness analyzer (F50-EXR, manufactured by Filmetrics Co., Ltd.).

[0090] [4] Evaluation of resin coating (1) Pattern formation and evaluation thereof The photosensitive dry film with protective film was prepared by removing the protective film and using a vacuum laminator TEAM-100RF (manufactured by Takatori Co., Ltd.) to set the vacuum level in the vacuum chamber to 80 Pa. The photosensitive resin film on the support film was then pressed into contact with a migration test substrate (a comb-shaped electrode substrate with copper conductive material, conductive area spacing and width of 20 μm, and conductive area thickness of 4 μm). The temperature was set to 100°C. After returning to atmospheric pressure, the substrate was removed from the vacuum laminator and the support film was removed. Next, to improve adhesion to the substrate, preheating was performed at 120°C for 5 minutes using a hot plate. To form line-and-space patterns and contact hole patterns on the obtained photosensitive resin film, exposure was performed using a contact aligner type exposure apparatus with an exposure condition of wavelength 405 nm via a mask. After exposure, only the comparative example underwent PEB at 140°C for 5 minutes using a hot plate, followed by cooling. Subsequently, spray development was performed with PGMEA for 300 seconds to form the patterns.

[0091] Subsequently, the cross-sections of the formed 150 μm, 100 μm, 50 μm, and 30 μm contact hole patterns were observed using a scanning electron microscope (SEM), and the smallest hole pattern in which the holes penetrated to the bottom of the film was defined as the limiting resolution. Furthermore, the perpendicularity of the 150 μm contact hole pattern was evaluated from the obtained cross-sectional images, with ◎ indicating a perfectly perpendicular pattern, ○ indicating slight reverse taper or fitting, △ indicating strong reverse taper or fitting, and × indicating poor aperture. The results are shown in Tables 3 and 4.

[0092] (2) Evaluation of electrical properties (copper migration) A substrate with a pattern formed by method (1) was used as a substrate for evaluating copper migration, and tests were conducted. The copper migration tests were performed under the conditions of a temperature of 130°C, humidity of 85%, and applied voltage of 10V, and the time during which a short circuit occurred was checked, with a maximum of 1000 hours. The results are shown in Tables 3 and 4.

[0093] (3) Evaluation of reliability (adhesion, crack resistance) The aforementioned photosensitive dry film with protective film was prepared by removing the protective film and using a vacuum laminator TEAM-100RF (manufactured by Takatori Co., Ltd.) to set the vacuum level in the vacuum chamber to 80 Pa. The photosensitive resin film on the support film was then pressed into contact with a CCL substrate on which 10 mm x 10 mm square silicon chips were laminated. The temperature was set to 100°C. After returning to atmospheric pressure, the substrate was removed from the vacuum laminator and the support film was removed. Next, to improve adhesion to the substrate, preheating was performed at 120°C for 5 minutes using a hot plate. The resulting photosensitive resin film was exposed using a contact aligner type exposure apparatus at a wavelength of 405 nm without using a mask. After exposure, only the comparative example underwent PEB at 140°C for 5 minutes using a hot plate, followed by cooling. Subsequently, spray development was performed with PGMEA for 300 seconds. After development, the substrate was cut using a dicing saw equipped with a dicing blade (DISCO DAD685, spindle speed 40,000 rpm, cutting speed 20 mm / sec) to obtain 20 mm x 20 mm square test pieces so that the outer circumference of the silicon chip was 5 mm. The obtained test pieces (10 pieces each) were subjected to a heat cycle test (held at -30°C for 10 minutes, held at 130°C for 10 minutes, repeated 1000 times), and the delamination state of the resin film from the wafer and the presence or absence of cracks were checked after the heat cycle test. A circle (○) indicated no delamination or cracking, a cross (×) indicated that at least one delamination occurred, and a cross (×) indicated that at least one crack occurred. The presence or absence of delamination and cracking was confirmed by top-down observation with an optical microscope and cross-sectional SEM observation. The results are shown in Tables 3 and 4.

[0094] (4) Evaluation of relative permittivity and dielectric loss tangent The aforementioned photosensitive dry film with protective film was exposed using a contact aligner type exposure apparatus at a wavelength of 405 nm without using a mask, after removing the protective film. After exposure, only the comparative example underwent PEB at 140°C for 5 minutes using a hot plate, followed by cooling. Subsequently, it was spray developed with PGMEA for 300 seconds. After removing the support film, the relative permittivity (10 GHz, 25°C) and dielectric loss tangent (10 GHz, 25°C) were measured. The relative permittivity and dielectric loss tangent were measured using the cavity resonator method with an AET apparatus. The results are shown in Tables 3 and 4.

[0095] (5) Evaluation of flexibility The cured film prepared in (4) was wrapped around a plastic cylinder with an outer diameter of 8.5 cm, left to stand for 10 seconds, then the film was returned to its original position and checked for any abnormalities on the film. If cracks or other abnormalities occurred, it was marked with "×", and if there was no change, it was marked with "○". The results are shown in Tables 3 and 4.

[0096] (6) Evaluation of warping stress The aforementioned photosensitive dry film with protective film was prepared by removing the protective film, setting the vacuum level in the vacuum chamber to 80 Pa using a TEAM-100RF vacuum laminator (manufactured by Takatori Co., Ltd.), laminating the photosensitive resin film on the support film onto an 8-inch silicon wafer, and preheating at 120°C for 5 minutes using a hot plate. Subsequently, exposure was performed using a contact aligner type exposure apparatus at a wavelength of 405 nm without using a mask. After exposure, only the comparative example underwent PEB at 140°C for 5 minutes using a hot plate, followed by cooling. Then, spray development was performed with PGMEA for 300 seconds. After that, the warpage stress (25°C) was measured using a thin-film stress measuring device (FLX-2320-S, manufactured by Toho Technology Co., Ltd.). The results are shown in Tables 3 and 4.

[0097] [Table 3]

[0098] [Table 4]

[0099] Based on the above results, the photosensitive resin composition of the present invention can form fine patterns, and even when the process is completed by developing, the cured film exhibits excellent dielectric properties, flexibility, low stress properties, high reliability, and copper migration resistance. Furthermore, because the cured film has the above-mentioned properties, it can be suitably used as a protective coating material for various electrical and electronic components such as circuit boards, semiconductor elements, and display elements.

Claims

1. (A) A polymer comprising repeating units represented by the following formula (A1) and repeating units represented by the following formula (A2), having a group represented by the following formula (A3) at both ends, and having a weight-average molecular weight of 3,000 to 100,000, and (B) Photoradical Generator A photosensitive resin composition containing [a specific substance]. 【Chemistry 1】 [In the formula, R 1 ~R 4 Each of these is an independent hydrocarbyl group having 1 to 8 carbon atoms. k is an integer from 1 to 600. a and b represent the composition ratio (molar ratio) of each repeating unit, and are numbers that satisfy 0 < a < 1, 0 < b < 1, and a + b = 1. X is a divalent group represented by the following formula (X). 【Chemistry 2】 (In the formula, R 11 and R 12 Each of these is an independent saturated hydrocarbyl group having 1 to 20 carbon atoms, which may contain a hydrogen atom or a heteroatom. m is an integer from 0 to 10. The dashed lines represent bonds with Si atoms. 【Transformation 3】 (In the formula, R 21 R is a hydrogen atom or a methyl group. 22 This is a saturated hydrocarbyl group having 1 to 20 carbon atoms, which may contain hydrogen atoms or heteroatoms. n is an integer from 1 to 10. The dashed lines represent bonds with Si atoms.

2. Furthermore, the photosensitive resin composition according to claim 1 further comprises a crosslinking agent having two or more (meth)acryloyl groups.

3. Furthermore, the photosensitive resin composition according to claim 1, further comprising (D) a solvent.

4. A photosensitive resin film obtained from the photosensitive resin composition according to any one of claims 1 to 3.

5. A photosensitive dry film comprising a support film and a photosensitive resin coating according to claim 4 on the support film.

6. (i) A step of forming a photosensitive resin film on a substrate using the photosensitive resin composition according to any one of claims 1 to 3, (ii) A step of exposing the photosensitive resin film, and (iii) A step of developing the exposed photosensitive resin film using a developer to remove unexposed areas and form a pattern. A pattern formation method including the following.

7. Furthermore, the pattern forming method according to claim 6, further comprising the step of (iv) post-curing the photosensitive resin film, which has been patterned by development, at a temperature of 40 to 150°C.

8. (i') A step of forming the photosensitive resin film on the substrate using the photosensitive dry film according to claim 5, (ii) A step of exposing the photosensitive resin film, and (iii) A step of developing the exposed photosensitive resin film using a developer to remove unexposed areas and form a pattern. A pattern formation method including the following.

9. Furthermore, the pattern forming method according to claim 8, further comprising the step of (iv) post-curing the photosensitive resin film, which has been patterned by development, at a temperature of 40 to 150°C.

10. A photosensitive resin composition according to any one of claims 1 to 3, which is a material for a protective coating for electrical and electronic components.

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