Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/022—Quinonediazides
  • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/16—Coating processes; Apparatus therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

• the present invention relates to a thermosetting photosensitive composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device.
• Resins such as polyimide and polybenzoxazole are applied to various applications because they have excellent heat resistance and insulating properties.
• the above application is not particularly limited, and examples of a semiconductor device for mounting include use as a material for an insulating film or a sealing material, or as a protective film. It is also used as a base film and coverlay for flexible substrates.
• thermosetting photosensitive compositions containing these resins or precursors thereof.
• a thermosetting photosensitive composition is applied to a base material by, for example, coating, and then exposed, developed, heated, etc., if necessary, to form a cured resin on the base material.
• the thermosetting photosensitive composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the thermosetting photosensitive composition to be applied. It can be said that it has excellent manufacturing adaptability.
• the industrial application of thermosetting photosensitive compositions containing these resins or their precursors is expanding. It is expected more and more.
• Patent Document 1 describes a photosensitive resin composition containing (a) a polyimide resin or a precursor thereof, (b) a quinonediazide compound, (c) a solvent and (d) a surfactant, and (d). )
• the surfactant contains (d1) a silicon-based surfactant and (d2) a surfactant having a fluorine atom, and the content of (d1) in the photosensitive resin composition is X% by mass, and (d2) is contained.
• the amount is Y mass%, X> Y (Y ⁇ 0), and (d) the total amount of the surfactant is 0.005 mass% or more and 0.10 mass% or less in the photosensitive resin composition.
• a photosensitive resin composition is described.
• thermosetting photosensitive composition containing at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor is applied to a substrate to prepare a cured film, it is obtained.
• Other layers such as other thermosetting photosensitive layers may be further formed on the cured film.
• a base material to which such a thermosetting photosensitive composition is applied a non-uniform base material having a step or the like may be used. Therefore, in the thermosetting photosensitive composition, when a cured film is prepared by applying it to a non-uniform substrate such as having a step, and another layer is further formed on the obtained cured film. Even if there is, it is desired to provide a thermosetting photosensitive composition in which defects are suppressed from occurring in other layers.
• the present invention is applied to a non-uniform substrate to prepare a cured film, and even when another layer is further formed on the obtained cured film, the occurrence of defects in the other layer is suppressed.
• Thermosetting photosensitive composition, a cured film obtained by curing the thermosetting photosensitive composition, a laminate containing the cured film, a method for producing the cured film, and the cured film or the laminate It is an object of the present invention to provide a semiconductor device including.
• thermosetting photosensitive composition used for forming a thermosetting photosensitive layer.
• the surface free energy of the cured film A and the surface of the cured film B calculated from the contact angle of water and the contact angle of diiodomethane with respect to the surface of the cured film A and the surface of the cured film B using the following formula (1).
• the absolute value of the difference in surface free energy is 30% or less of the surface free energy of the cured film A below.
• Thermosetting photosensitive composition Cured film A: When a coating film of the thermosetting photosensitive composition is formed on a flat support with a film thickness of 150% of the average thickness of the thermosetting photosensitive layer and then heated at 250 ° C. for 120 minutes.
• ⁇ s d is the dispersion component of the surface free energy of the cured film
• the gamma s h a polar component of surface free energy of the cured film
• gamma L d is the variance of the surface free energy of water or diiodomethane
• ⁇ L h represents the polar component of the surface free energy of water or diiodomethane
• ⁇ L tl represents the surface free energy of water or diiodomethane
• c technicallys ⁇ represents the contact angle of water or diiodomethane
• the surface free energy is represented by the sum of the dispersion component and the polar component
• the dispersion component of the surface free energy of water is 21.7 mJ / m 2
• the polar component of the surface free energy of water is 50.8 mJ / m 2 .
• thermosetting photosensitive composition according to ⁇ 1>, wherein the content of the surfactant is more than 0.1% by mass with respect to the total mass of the composition.
• thermosetting photosensitive composition Described in any one of ⁇ 1> to ⁇ 4>, wherein the content of the hydrocarbon-based surfactant in the composition is 50% by mass or more with respect to the total content of the surfactant.
• Thermosetting photosensitive composition ⁇ 6> The thermosetting photosensitive composition according to any one of ⁇ 1> to ⁇ 5>, wherein the resin contains at least one resin selected from the group consisting of polyimide and a polyimide precursor.
• thermosetting photosensitive composition according to any one of ⁇ 1> to ⁇ 6> which is used for forming a thermosetting photosensitive layer by a slit coating method.
• thermosetting photosensitive composition according to any one of ⁇ 1> to ⁇ 6> which is used for forming a thermosetting photosensitive layer by a spin coating method.
• thermosetting photosensitive composition according to any one of ⁇ 1> to ⁇ 8> which is used for forming an interlayer insulating film for a rewiring layer.
• ⁇ 10> A cured film obtained by curing the thermosetting photosensitive composition according to any one of ⁇ 1> to ⁇ 9>.
• ⁇ 11> A laminate containing two or more layers of the cured film according to ⁇ 10> and containing a metal layer between any of the cured films.
• ⁇ 12> A method for producing a cured film, which comprises a film forming step of applying the thermosetting photosensitive composition according to any one of ⁇ 1> to ⁇ 9> to a substrate to form a film.
• the method for producing a cured film according to ⁇ 12> which comprises an exposure step of exposing the film and a developing step of developing the film.
• a semiconductor device comprising the cured film according to ⁇ 10> or the laminate according to ⁇ 11>.
• thermosetting photosensitive composition in which the above is suppressed, a cured film obtained by curing the thermosetting photosensitive composition, a laminate containing the cured film, a method for producing the cured film, and the cured film or the above.
• a semiconductor device including a laminate is provided.
• the present invention is not limited to the specified embodiments.
• the numerical range represented by using the symbol “ ⁇ ” means a range including the numerical values before and after “ ⁇ ” as the lower limit value and the upper limit value, respectively.
• the term "process” means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
• the notation not describing substitution and non-substituent includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
• the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• exposure includes not only exposure using light but also exposure using particle beams such as an electron beam and an ion beam. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
• (meth) acrylate means both “acrylate” and “methacrylate”, or either
• (meth) acrylic means both “acrylic” and “methacryl”, or
• (meth) acryloyl means both “acryloyl” and “methacryloyl”, or either.
• Me in the structural formula represents a methyl group
• Et represents an ethyl group
• Bu represents a butyl group
• Ph represents a phenyl group.
• the total solid content means the total mass of all the components of the composition excluding the solvent.
• the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
• the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
• GPC measurement gel permeation chromatography
• the weight average molecular weight (Mw) and the number average molecular weight (Mn) for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
• the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as “upper”.
• the opposite direction is referred to as "down”.
• the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component.
• the content of each component in the composition means the total content of all the compounds corresponding to the component.
• the temperature is 23 ° C. and the atmospheric pressure is 101,325 Pa (1 atm).
• the combination of preferred embodiments is a more preferred embodiment.
• thermosetting photosensitive composition of the present invention is a thermosetting photosensitive composition used for forming a thermosetting photosensitive layer, and is a group consisting of a polyimide, a polyimide precursor, polybenzoxazole and a polybenzoxazole precursor. Contains at least one resin (hereinafter, also referred to as “specific resin”), a photosensitizer, a surfactant, and a solvent selected from the above, and water for each of the surface of the following cured film A and the surface of the following cured film B.
• the absolute value of the difference between the surface free energy of the following cured film A and the surface free energy of the following cured film B calculated from the contact angle and the contact angle of diiodomethane using the equation (1) is the surface free energy of the following cured film A. It is 30% or less.
• Cured film A When a coating film of the heat-curable photosensitive composition is formed on a flat support with a thickness of 150% of the average thickness of the heat-curable photosensitive layer and then heated at 250 ° C. for 120 minutes.
• Cured film of the heat-curable photosensitive composition obtained in the above B The coating film of the heat-curable photosensitive composition is flat with a thickness of 50% of the average thickness of the heat-curable photosensitive layer.
• the thermosetting photosensitive composition of the present invention preferably contains a specific resin, a photopolymerization initiator as the photosensitive agent, a surfactant, and a solvent.
• the thermosetting photosensitive composition of the present invention in the first aspect is preferably further containing a radical cross-linking agent.
• the embodiment further containing a thermal cross-linking agent is preferable, and the embodiment further containing a thermal cross-linking agent and a thermal acid generator is also more preferable.
• the thermosetting photosensitive composition of the present invention preferably contains a specific resin, a photoacid generator as the photosensitizer, a surfactant, and a solvent.
• thermosetting photosensitive composition of the present invention in the second aspect is preferably further containing a thermosetting agent.
• the thermosetting photosensitive composition of the present invention may be a negative type thermosetting photosensitive composition or a positive type thermosetting photosensitive composition.
• the negative thermosetting photosensitive composition is a composition in which a non-exposed portion is removed by development when it is subjected to development after exposure.
• the positive thermosetting photosensitive composition is a composition in which the exposed portion is removed by development when it is subjected to development after exposure.
• thermosetting photosensitive composition of the present invention it is a case where a cured film is produced by applying it to a non-uniform substrate, and another layer is further formed on the obtained cured film.
• a cured film is produced by applying it to a non-uniform substrate, and another layer is further formed on the obtained cured film.
• the occurrence of defects in other layers is suppressed.
• the mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
• thermosetting photosensitive composition is used for applications such as forming a thermosetting photosensitive layer by applying it to a substrate or the like and then drying it if necessary, and then obtaining a cured film by heating or the like. .. Further, if necessary, patterning may be performed by exposure and development, for example, before heating. As a result of diligent studies, the present inventors formed a thermosetting photosensitive layer on a non-uniform substrate such as having a step, and after obtaining a cured film, further formed another layer on the cured film. It was found that if this is done, defects may occur in other layers.
• thermosetting photosensitive layer Since the solvent is present in the thermosetting photosensitive layer before drying, at least a part of the components in the thermosetting photosensitive composition (for example, components that easily move in the composition film such as a surfactant). Is thought to move to the surface of the composition film.
• a base material in which the physical shape of the surface of the base material is not uniform such as a base material having a step on the surface or a base material having an inclination on the surface, or one of the surfaces.
• the thickness of the thermosetting photosensitive layer is uniform. It may not be.
• thermosetting photosensitive layer in a substrate having a step on the surface, the thermosetting photosensitive layer is thin at the convex portion of the substrate surface, and the thermosetting photosensitive layer is thick at the concave portion of the substrate surface.
• thermosetting photosensitive layer in a substrate having an inclination on the surface, the thermosetting photosensitive layer becomes thick at a portion where the inclination is low, and the thermosetting photosensitive layer becomes thick at a portion where the inclination is high.
• the thermosetting photosensitive layer in a substrate in which only a part of the surface is difficult to be compatible with the composition, the thermosetting photosensitive layer is thin because the composition is easily spread in the portion that is easily compatible with the composition, and the composition is not compatible with the composition. The thermosetting photosensitive layer becomes thick because it is difficult to spread.
• thermosetting photosensitive layer Since the components such as the surfactant move from the inside of the thermosetting photosensitive layer, many of the above components move to the surface in the portion where the thermosetting photosensitive layer is thick, and the surface in the portion where the thermosetting photosensitive layer is thin. It is considered that the above-mentioned component that moves to is small.
• thermosetting photosensitive composition having a different distribution of components depending on its position on the surface is cured to form a cured film and another layer is formed on the cured film, it depends on the position on the surface of the cured film. Since the coatability and the like when forming the other layer are different, it is considered that defects occur in the other layer.
• the composition of the present invention is a composition capable of obtaining a cured film having a small difference in surface free energy with respect to a change in film thickness. Therefore, it is presumed that the occurrence of defects in the other layers may be suppressed. The suppression of the occurrence of the above defects is considered to be particularly remarkable when the thermosetting photosensitive layer is formed by a method such as a slit coating method that takes a long time to dry after coating.
• Patent Document 1 does not describe or suggest a thermosetting photosensitive composition in which the above-mentioned difference in surface free energy is a specific value.
• thermosetting photosensitive composition of the present invention and the components contained therein will be described in detail.
• the heat-curable photosensitive composition of the present invention is the cured film calculated from the contact angle of water and the contact angle of diiodomethane with respect to the surface of the cured film A and the surface of the cured film B, respectively, using the formula (1).
• the surface free energy is a value calculated from the contact angle of water and the contact angle of diiodomethane using the formula (1).
• the surface free energy is set as a value that satisfies the following formula for each contact angle by contacting 1 ⁇ l of water and diiodomethane with the cured film A or B and measuring their respective contact angles. It is the required energy. For example, it can be calculated using the functional integrated analysis software FAMAS (manufactured by Kyowa Surface Chemistry Co., Ltd.).
• ⁇ s d is the dispersion component of the surface free energy of the cured film
• the gamma s h a polar component of surface free energy of the cured film
• gamma L d is the variance of the surface free energy of water or diiodomethane
• ⁇ L h represents the polar component of the surface free energy of water or diiodomethane
• ⁇ L tl represents the surface free energy of water or diiodomethane
• c technicallys ⁇ represents the contact angle of water or diiodomethane
• the surface free energy is represented by the sum of the dispersion component and the polar component
• the dispersion component of the surface free energy of water is 21.7 mJ / m 2
• the polar component of the surface free energy of water is 50.8 mJ / m 2 .
• the average thickness of the thermosetting photosensitive layer is an average value of the thickness of the entire surface of the thermosetting photosensitive layer applied to the base material.
• a thermosetting photosensitive layer having a thickness of T1 was formed.
• the area where the thermosetting photosensitive layer having a thickness T2 is formed is S2
• the sum of the areas S1 and S2 is the total area of the thermosetting photosensitive layer, it is calculated by the following formula.
• Average thickness T1 x S1 / (S1 + S2) + T2 x S2 / (S1 + S2)
• the area where the thermosetting photosensitive layer of n kinds of thickness Ti is formed is Si (i is an integer of 1 to n, and S1 + S2 + ...
• thermosetting photosensitive layer is the total area of the thermosetting photosensitive layer.
• the above average thickness is calculated by the following formula.
• the thickness of the thermosetting photosensitive layer such as the thicknesses T1, T2, and Ti is measured using, for example, an ellipsometer (KT-22 manufactured by Foothill).
• the surface free energy of the cured film A is preferably 10 to 50 mJ / m 2 , more preferably 15 to 40 mJ / m 2 , and even more preferably 20 to 35 mJ / m 2 .
• the surface free energy of the cured film B is preferably 10 to 50 mJ / m 2 , more preferably 15 to 40 mJ / m 2 , and even more preferably 20 to 35 mJ / m 2 .
• the absolute value of the difference between the surface free energy of the cured film A and the surface free energy of the cured film B is 30% or less, more preferably 20% or less of the surface free energy of the cured film A. It is more preferably% or less.
• the lower limit is not particularly limited, and may be 0% or more.
• the ratio of the absolute value of the difference between the surface free energy of the cured film A and the surface free energy of the cured film B to the surface free energy of the cured film A is a value determined by the composition of the thermosetting photosensitive composition. For example, it is considered to be determined by the amount of the surfactant in the thermosetting photosensitive composition, the type of the surfactant, and the like.
• the method for producing the coating film in the cured film A and the cured film B is not particularly limited, but the method is the same as the method for producing the coating film in the formation of the thermosetting photosensitive layer using the thermosetting photosensitive composition of the present invention. It is preferably produced.
• the thermosetting photosensitive layer is produced by the slit coating method, it is preferable that the coating films in the cured film A and the cured film B are also produced by the slit coating method.
• the absolute value of the difference between the surface free energy of the cured film C below and the surface free energy of the cured film D below is 30% or less of the surface free energy of the cured film C below. It is preferably 20% or less, more preferably 10% or less.
• the lower limit is not particularly limited and may be 0% or more.
• Cured film C The thermosetting photosensitive composition obtained when a coating film of the thermosetting photosensitive composition is formed on a flat support with a film thickness of 45 ⁇ m and then heated at 250 ° C. for 120 minutes.
• Cured film D The thermosetting photosensitive composition obtained when a coating film of the thermosetting photosensitive composition is formed on a flat support with a film thickness of 15 ⁇ m and then heated at 250 ° C. for 120 minutes.
• the thermosetting photosensitive composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor.
• the specific resin preferably contains at least one resin selected from the group consisting of polyimide and a polyimide precursor. Further, it is preferable that the resin contains a polymerizable group and the photosensitive resin composition contains a polymerizable compound.
• the polyimide and polybenzoxazole contained in the resin layer in the laminate of the present invention preferably contain a partial structure represented by -Ar-L-Ar-.
• Ar is an aromatic group independently
• L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, ⁇ CO ⁇ , —S—. , -SO 2- or -NHCO-, or a group consisting of a combination of two or more of the above.
• Ar is a phenylene group is preferably, L is an aliphatic hydrocarbon group having a fluorine atom in 1 carbon atoms which may be substituted or 2, -O -, - CO - , - S- or -SO 2 - is preferred .
• the aliphatic hydrocarbon group here is preferably an alkylene group.
• polyimide precursor The type of the polyimide precursor used in the present invention is not particularly specified, but it is preferable that the polyimide precursor contains a repeating unit represented by the following formula (2). Equation (2) In formula (2), A 1 and A 2 independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, and R 113. And R 114 each independently represent a hydrogen atom or a monovalent organic group.
• a 1 and A 2 in the formula (2) independently represent an oxygen atom or NH, and an oxygen atom is preferable.
• R 111 in the formula (2) represents a divalent organic group.
• the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms.
• a cyclic aliphatic group of 6 to 20, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
• a group represented by -Ar-L-Ar- is exemplified.
• Ar is an aromatic group independently
• L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, ⁇ CO ⁇ , —S—. , -SO 2- or -NHCO-, or a group consisting of a combination of two or more of the above.
• R 111 is preferably derived from diamine.
• the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof. It is preferable that the diamine contains the above, and more preferably the diamine contains a group consisting of an aromatic group having 6 to 20 carbon atoms. Examples of groups containing aromatic groups include:
• diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- Or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl;
• diamines (DA-1) to (DA-18) shown below are also preferable.
• a diamine having at least two or more alkylene glycol units in the main chain is also mentioned as a preferable example. More preferably, it is a diamine containing two or more ethylene glycol chains, one or both of propylene glycol chains in one molecule, and more preferably, the above diamine, which does not contain an aromatic ring. Specific examples include Jeffamine® KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000.
• x, y, and z are average values.
• R 111 is preferably represented by —Ar—L—Ar— from the viewpoint of the flexibility of the obtained cured film.
• Ar is an aromatic group independently
• L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, ⁇ CO ⁇ , —S—. , -SO 2- or -NHCO-, or a group consisting of a combination of two or more of the above.
• Ar is a phenylene group is preferably, L is an aliphatic hydrocarbon group having a fluorine atom in 1 carbon atoms which may be substituted or 2, -O -, - CO - , - S- or -SO 2 - is preferred .
• the aliphatic hydrocarbon group here is preferably an alkylene group.
• R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-ray transmittance.
• a divalent organic group represented by the formula (61) is more preferable.
• Equation (51) In formula (51), R 50 to R 57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or trifluoro. It is a methyl group, and each of * independently represents a bond site with a nitrogen atom in the formula (2).
• the monovalent organic group of R 50 to R 57 includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.
• R 58 and R 59 are independently fluorine atoms or trifluoromethyl groups, respectively.
• Examples of the diamine compound giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-. Examples thereof include bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.
• diamines can also be preferably used.
• R 115 in the formula (2) represents a tetravalent organic group.
• a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
• 2- , -NHCO-, and a group selected from a combination thereof are preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-,- More preferably, it is a group selected from CO-, -S- and -SO 2- , -CH 2- , -C (CF 3 ) 2- , -C (CH 3 ) 2- , -O-, More preferably, it is a divalent group selected from the group consisting of -CO-, -S- and -SO 2- .
• R 115 examples include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
• the tetracarboxylic dianhydride is preferably represented by the following formula (O). Equation (O) In formula (O), R 115 represents a tetravalent organic group.
• a preferred range of R 115 has the same meaning as R 115 in formula (2), and preferred ranges are also the same.
• tetracarboxylic dianhydride examples include pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-.
• PMDA pyromellitic dianhydride
• 3,3', 4,4'-biphenyltetracarboxylic dianhydride 3,3', 4,4'-.
• DAA-1 to DAA-5 tetracarboxylic dianhydrides
• DAA-5 tetracarboxylic dianhydrides
• R 111 and R 115 has an OH group. More specifically, as R 111 , a residue of a bisaminophenol derivative can be mentioned.
• R 113 and R 114 independently represent a hydrogen atom or a monovalent organic group, and the monovalent organic group includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy. It preferably contains a group, more preferably a polyalkyleneoxy group. Further, it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and it is more preferable that both contain a polymerizable group. As the polymerizable group, a radically polymerizable group is preferable because it is a group capable of undergoing a cross-linking reaction by the action of heat, radicals and the like.
• the polymerizable group examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, a methylol group and an amino.
• the group is mentioned.
• a group having an ethylenically unsaturated bond is preferable.
• Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a group represented by the following formula (III).
• R200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and a hydrogen atom or a methyl group is more preferable.
• R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH (OH) CH 2- or a polyoxyalkylene group having 4 to 30 carbon atoms. Examples of suitable R 201 are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group.
• alkylene group -CH2CH (OH) CH2-
• ethylene group propylene group, trimethylene group, -CH2CH (OH) CH2-
• R 200 is a methyl group
• R 201 is an ethylene group.
• R 113 and R 114 are independently hydrogen atoms or monovalent organic groups.
• the monovalent organic group include an aromatic group and an aralkyl group in which an acidic group is bonded to one, two or three carbons constituting the aryl group, preferably one.
• Specific examples thereof include an aromatic group having an acidic group having 6 to 20 carbon atoms and an aralkyl group having an acidic group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned.
• the acidic group is preferably an OH group. It is also more preferable that R 113 or R 114 is a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group and a 4-hydroxybenzyl group.
• R 113 or R 114 is preferably a monovalent organic group.
• the monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and an alkyl group substituted with an aromatic group is more preferable.
• the alkyl group preferably has 1 to 30 carbon atoms.
• the alkyl group may be linear, branched or cyclic.
• linear or branched alkyl group examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group and octadecyl group.
• Isobutyl group isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, 2-ethylhexyl group 2- (2- (2-methoxyethoxy) ethoxy) ethoxy group, 2- (2- (2) -Ethoxyethoxy) ethoxy) ethoxy) ethoxy group, 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethoxy group, and 2- (2- (2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) Ethoxy group is mentioned.
• the cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group.
• Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
• Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Of these, the cyclohexyl group is most preferable from the viewpoint of achieving both high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferable.
• aromatic group examples include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, inden ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene.
• the benzene ring is most preferable.
• R 113 is a hydrogen atom or R 114 is a hydrogen atom
• R 113 is a hydrogen atom
• R 114 is a hydrogen atom
• the polyimide precursor forms a salt with a tertiary amine compound having an ethylenically unsaturated bond.
• the tertiary amine compound having such an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.
• the polyimide precursor has a fluorine atom in the structural unit.
• the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
• the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
• the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.
• the repeating unit represented by the formula (2) is preferably the repeating unit represented by the formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by the formula (2-A). With such a structure, the width of the exposure latitude can be further widened. Equation (2-A) In formula (2-A), A 1 and A 2 represent oxygen atoms, R 111 and R 112 each independently represent a divalent organic group, and R 113 and R 114 each independently. Representing a hydrogen atom or a monovalent organic group, at least one of R 113 and R 114 is a group containing a polymerizable group, and it is preferable that both are groups containing a polymerizable group.
• a 1, A 2, R 111 , R 113 and R 114 each independently have the same meaning as A 1, A 2, R 111 , R 113 and R 114 in formula (2), and preferred ranges are also the same .
• R 112 has the same meaning as R 112 in formula (5), and preferred ranges are also the same.
• the polyimide precursor may contain one type of repeating unit represented by the formula (2), but may contain two or more types. Further, it may contain a structural isomer of a repeating unit represented by the formula (2). Needless to say, the polyimide precursor may contain other types of repeating units in addition to the repeating unit of the above formula (2).
• polyimide precursor in the present invention a polyimide precursor in which 50 mol% or more of all repeating units, more 70 mol% or more, particularly 90 mol% or more is a repeating unit represented by the formula (2) is used. Illustrated.
• the weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and even more preferably 22,000 to 25,000.
• the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
• the degree of dispersion of the molecular weight of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more.
• the upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly defined, but for example, 4.5 or less is preferable, 4.0 or less is more preferable, 3.8 or less is further preferable, and 3.2 or less is further preferable. Preferably, 3.1 or less is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is particularly preferable.
• the weight average molecular weight (Mw) is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. Is.
• the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
• the degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.8 or more, more preferably 2.0 or more, and further preferably 2.2 or more.
• the upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly determined, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.
• the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.
• the polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide that is soluble in a developing solution containing an organic solvent as a main component.
• the alkali-soluble polyimide means a polyimide that dissolves 0.1 g or more at 23 ° C. in 100 g of a 2.38 mass% tetramethylammonium aqueous solution, and 0.5 g or more from the viewpoint of pattern forming property.
• a polyimide that dissolves is preferable, and a polyimide that dissolves 1.0 g or more is more preferable.
• the upper limit of the dissolved amount is not particularly limited, but is preferably 100 g or less.
• the polyimide is preferably a polyimide having a plurality of imide structures in the main chain from the viewpoint of the film strength and the insulating property of the obtained cured film.
• the "main chain” refers to the relatively longest binding chain among the molecules of the polymer compound constituting the resin, and the “side chain” refers to other binding chains.
• the polyimide preferably has a fluorine atom.
• the fluorine atom is preferably contained in, for example, R 132 in the repeating unit represented by the formula (4) described later, or R 131 in the repeating unit represented by the formula (4) described later, and is preferably contained in the formula (4) described later. It is more preferable that it is contained as an alkyl fluoride group in R 132 in the repeating unit represented by 4) or R 131 in the repeating unit represented by the formula (4) described later.
• the amount of fluorine atoms with respect to the total mass of the polyimide is preferably 1 to 50 mol / g, and more preferably 5 to 30 mol / g.
• the polyimide preferably has a silicon atom.
• the silicon atom is preferably contained in R 131 in the repeating unit represented by the formula (4) described later, and is organically modified (poly) in R 131 in the repeating unit represented by the formula (4) described later. ) It is more preferable that it is contained as a siloxane structure. Further, the silicon atom or the organically modified (poly) siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
• the amount of silicon atoms with respect to the total mass of the polyimide is preferably 0.01 to 5 mol / g, more preferably 0.05 to 1 mol / g.
• the polyimide preferably has an ethylenically unsaturated bond.
• the polyimide may have an ethylenically unsaturated bond at the end of the main chain or at the side chain, but it is preferably provided at the side chain.
• the ethylenically unsaturated bond preferably has radical polymerization property.
• the ethylenically unsaturated bond is preferably contained in R 132 in the repeating unit represented by the formula (4) described later or in R 131 in the repeating unit represented by the formula (4) described later, and is preferably contained in the formula described later.
• R 132 in the repeating unit represented by (4) or R 131 in the repeating unit represented by the formula (4) described later is contained as a group having an ethylenically unsaturated bond.
• ethylenically unsaturated bond ethylene R 131 in the repeating unit represented by the preferably contained in R 131 in the repeating unit represented by the formula (4) described later, which will be described later Equation (4) It is more preferably contained as a group having a sex unsaturated bond.
• Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acrylamide group and a (meth) group. Examples thereof include an acryloyloxy group and a group represented by the following formula (III).
• R200 represents a hydrogen atom or a methyl group, an ethyl group or a methylol group, and a hydrogen atom or a methyl group is more preferable.
• (Poly) oxyalkylene group having 2 to 30 carbon atoms the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12 and 1 ⁇ 6 is more preferable, and 1 to 3 are particularly preferable), or a group in which two or more of these are combined is represented.
• the (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
• R 201 is preferably a group represented by any of the following formulas (R1) to (R3), and more preferably a group represented by the formula (R1).
• L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly) oxyalkylene group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded
• X Indicates an oxygen atom or a sulfur atom
• * represents a binding site with another structure
• ⁇ represents a binding site with an oxygen atom to which R 201 in the formula (III) is bonded.
• a preferred embodiment of the alkylene group having 2 to 12 carbon atoms in L or the (poly) oxyalkylene group having 2 to 30 carbon atoms is the above-mentioned R 201 having 2 to 12 carbon atoms. This is the same as the preferred embodiment of the 12 alkylene group or the (poly) oxyalkylene group having 2 to 30 carbon atoms.
• X is preferably an oxygen atom.
• * is synonymous with * in formula (III), and the preferred embodiment is also the same.
• the structure represented by the formula (R1) comprises, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group and a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate). Obtained by reacting.
• the structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate).
• the structure represented by the formula (R3) is obtained by reacting, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate). can get.
• * represents a binding site with another structure, and is preferably a binding site with the main chain of polyimide.
• the amount of the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.
• the polyimide may have a crosslinkable group other than the ethylenically unsaturated bond.
• the crosslinkable group other than the ethylenically unsaturated bond include a cyclic ether group such as an epoxy group and an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
• the crosslinkable group other than the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by the formula (4) described later, for example.
• the amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol / g, and more preferably 0.1 to 5 mol / g.
• the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 mgKOH / g or more from the viewpoint of improving the developability. Is more preferable.
• the acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.
• the acid value of the polyimide is preferably 2 to 35 mgKOH / g, and 3 to 30 mgKOH. / G is more preferable, and 5 to 20 mgKOH / g is further preferable.
• the acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992.
• an acid group having a pKa of 0 to 10 is preferable, and an acid group having a pKa of 3 to 8 is more preferable, from the viewpoint of achieving both storage stability and developability.
• the pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is expressed by its negative common logarithm pKa.
• pKa is a value calculated by ACD / ChemSketch (registered trademark) unless otherwise specified.
• the values published in "Revised 5th Edition Chemistry Handbook Basics" edited by the Chemical Society of Japan may be referred to.
• the acid group is a polyvalent acid such as phosphoric acid
• the above pKa is the first dissociation constant.
• the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.
• the polyimide preferably has a phenolic hydroxy group.
• the polyimide may have a phenolic hydroxy group at the end of the main chain or at the side chain.
• the phenolic hydroxy group is preferably contained in, for example, R 132 in the repeating unit represented by the formula (4) described later, or R 131 in the repeating unit represented by the formula (4) described later.
• the amount of the phenolic hydroxy group with respect to the total mass of the polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.
• the polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but preferably contains a repeating unit represented by the following formula (4), and is represented by the formula (4). It is more preferable that the compound contains a repeating unit and has a polymerizable group.
• Equation (4) In formula (4), R 131 represents a divalent organic group and R 132 represents a tetravalent organic group. When having a polymerizable group, the polymerizable group may be located at at least one of R 131 and R 132 , or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2). It may be located in.
• Equation (4-1) In formula (4-1), R 133 is a polymerizable group, and the other groups are synonymous with formula (4). Equation (4-2) At least one of R 134 and R 135 is a polymerizable group, when it is not a polymerizable group, it is an organic group, and the other group is synonymous with the formula (4).
• the polymerizable group has the same meaning as the polymerizable group described in the above-mentioned polymerizable group possessed by the polyimide precursor and the like.
• R 131 represents a divalent organic group. Examples of the divalent organic group include those similar to R 111 in the formula (2), and the preferred range is also the same. Further, as R 131 , a diamine residue remaining after removal of the amino group of diamine can be mentioned. Examples of the diamine include aliphatic, cyclic aliphatic or aromatic diamines. Specific examples include the example of R 111 in the formula (2) of the polyimide precursor.
• R 131 is a diamine residue having at least two or more alkylene glycol units in the main chain from the viewpoint of more effectively suppressing the occurrence of warpage during firing. More preferably, it is a diamine residue containing two or more ethylene glycol chains, one or both of propylene glycol chains in one molecule, and more preferably, a diamine residue containing no aromatic ring.
• diamines containing two or more ethylene glycol chains and / or both of propylene glycol chains in one molecule include Jeffamine® KH-511, ED-600, ED-900, ED-2003, and EDR. -148, EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2-aminopropoxy) ethoxy) Examples thereof include, but are not limited to, propoxy) propane-2-amine and 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine.
• R 132 represents a tetravalent organic group.
• examples of the tetravalent organic group include those similar to R 115 in the formula (2), and the preferred range is also the same.
• R 132 includes a tetracarboxylic acid residue remaining after removal of an anhydride group from the tetracarboxylic dianhydride.
• Specific examples include an example of R 115 in the polyimide precursor formula (2).
• R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
• R 131 and R 132 It is also preferable to have an OH group in at least one of R 131 and R 132 . More specifically, as R 131 , 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2- Bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and (DA-1) to (DA-18) above are preferable examples. As R 132 , the above (DAA-1) to (DAA-5) are more preferable examples.
• the polyimide has a fluorine atom in its structure.
• the content of fluorine atoms in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.
• the polyimide may be copolymerized with an aliphatic group having a siloxane structure.
• the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.
• the main chain end of polyimide may be sealed with an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound.
• an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound.
• monoamine acid anhydride
• monocarboxylic acid monoacid chloride compound or monoactive ester compound.
• monoactive ester compound preferable.
• monoamine it is more preferable to use monoamine, and preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7.
• the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, the insulating property, etc. of the obtained cured film. More preferably, it is 90% or more.
• the upper limit of the imidization rate is not particularly limited, and may be 100% or less.
• the imidization rate is measured by, for example, the following method. The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 near 1377 cm -1, which is the absorption peak derived from the imide structure. Next, after heat-treating the polyimide at 350 ° C.
• the polyimide may contain repeating units of the above formula (4), all containing one type of R 131 or R 132 , of the above formula (4) containing two or more different types of R 131 or R 132 . It may include repeating units. Further, the polyimide may contain other types of repeating units in addition to the repeating unit of the above formula (4).
• the polyimide is, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound (partially replaced with a terminal capping agent which is monoamine) at a low temperature, or a tetracarboxylic acid dianhydride (partly an acid) at a low temperature.
• a method of reacting a diamine compound with an anhydride or a monoacid chloride compound or a terminal capping agent which is a monoactive ester compound) a diester is obtained by tetracarboxylic acid dianhydride and an alcohol, and then diamine (partly monoamine) is obtained.
• a polyimide precursor is obtained by using a method such as a method of reacting with an end-capping agent (replaced with an end-capping agent), which is completely imidized by a known imidization reaction method, or an imide in the middle.
• Synthesis using a method of stopping the conversion reaction and introducing a partially imidized structure and further, a method of introducing a partially imidized structure by blending a completely imidized polymer with its polyimide precursor.
• a method of introducing a partially imidized structure by blending a completely imidized polymer with its polyimide precursor.
• Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide5218 (manufactured by HUNTSMAN Co., Ltd.).
• the weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, still more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing can be improved. In order to obtain a cured film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more types of polyimide are contained, the weight average molecular weight of at least one type of polyimide is preferably in the above range. On the other hand, from the viewpoint of chemical resistance, the weight average molecular weight (Mw) of polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 15,000. It is 40,000.
• the polybenzoxazole precursor used in the present invention is not particularly defined for its structure and the like, but preferably contains a repeating unit represented by the following formula (3).
• Equation (3) R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group. Represent.
• R 123 and R 124 are synonymous with R 113 in formula (2), respectively, and the preferred range is also the same. That is, at least one is preferably a polymerizable group.
• R 121 represents a divalent organic group.
• the divalent organic group a group containing at least one of an aliphatic group and an aromatic group is preferable.
• the aliphatic group a linear aliphatic group is preferable.
• R 121 is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.
• a dicarboxylic acid residue a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
• a dicarboxylic acid containing an aliphatic group a dicarboxylic acid containing a linear or branched (preferably straight chain) aliphatic group is preferable, and a linear or branched (preferably straight chain) aliphatic group and two -COOH.
• a dicarboxylic acid composed of is more preferable.
• the number of carbon atoms of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, and 4 to 20. It is more preferably 15, and particularly preferably 5 to 10.
• the linear aliphatic group is preferably an alkylene group.
• dicarboxylic acid containing a linear aliphatic group examples include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-Dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-Dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelliic acid, 2,2,6,6-tetramethylpimelic acid, suberin Acid, dodecafluorosveric acid, azelaic acid, sebacic acid, hexa
• Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).
• dicarboxylic acid containing an aromatic group a dicarboxylic acid having the following aromatic groups is preferable, and a dicarboxylic acid consisting of only a group having the following aromatic groups and two -COOH is more preferable.
• A is -CH 2- , -O-, -S-, -SO 2- , -CO-, -NHCO-, -C (CF 3 ) 2- , and -C (CH 3 ) 2- Represents a divalent group selected from the group consisting of.
• dicarboxylic acid containing an aromatic group examples include 4,4'-carbonyl dibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.
• R 122 represents a tetravalent organic group.
• the tetravalent organic group has the same meaning as R 115 in the above formula (2), and the preferable range is also the same.
• R 122 is also preferably a group derived from a bisaminophenol derivative, and examples of the group derived from the bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'.
• bisaminophenol derivatives having the following aromatic groups are preferable.
• X 1 represents -O-, -S-, -C (CF 3 ) 2- , -CH 2- , -SO 2- , -NHCO-.
• R 1 is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO 2- , -CO-, -NHCO-, single bond, or the following formula (A-). It is an organic group selected from the group of sc).
• R 2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.
• R 3 is any of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.
• R 2 is an alkyl group and R 3 is an alkyl group has high transparency to i-rays and a high cyclization rate when cured at a low temperature. The effect can be maintained, which is preferable.
• R 1 is an alkylene or a substituted alkylene.
• Specific examples of the alkylene and the substituted alkylene according to R 1 include -CH 2- , -CH (CH 3 )-, -C (CH 3 ) 2- , -CH (CH 2 CH 3 )-, and -C.
• the polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (3). It is preferable to include a diamine residue represented by the following formula (SL) as another type of repeating structural unit in that the occurrence of warpage due to ring closure can be suppressed.
• SL diamine residue represented by the following formula
• Z has an a structure and a b structure
• R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
• R 2s is a hydrocarbon group having 1 to 10 carbon atoms.
• at least one of R 3s , R 4s , R 5s , and R 6s is an aromatic group
• the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different.
• the polymerization of the a structure and the b structure may be block polymerization or random polymerization.
• the mol% of the Z portion is 5 to 95 mol% for the a structure, 95 to 5 mol% for the b structure, and 100 mol% for a + b.
• preferred Z includes those in which R 5s and R 6s in the b structure are phenyl groups.
• the molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000.
• the tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride is used as the repeating structural unit. It is also preferable to include it. Examples of such a tetracarboxylic acid residue include the example of R 115 in the formula (2).
• the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further, when used in the compositions described below. It is preferably 22,000 to 28,000.
• the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
• the degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more.
• the upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly determined, but for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and 2.3 or less. Is more preferable, and 2.2 or less is even more preferable.
• the polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X). It is more preferable that the compound has a polymerizable group.
• R 133 represents a divalent organic group and R 134 represents a tetravalent organic group.
• the polymerizable group may be located at at least one of R 133 and R 134 , or polybenzoxazole as shown in the following formula (X-1) or formula (X-2). It may be located at the end of.
• Equation (X-1) In formula (X-1), at least one of R 135 and R 136 is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group is synonymous with formula (X).
• Equation (X-2) In formula (X-2), R 137 is a polymerizable group, the other is a substituent, and the other group is synonymous with formula (X).
• the polymerizable group is synonymous with the polymerizable group described in the polymerizable group possessed by the polyimide precursor and the like described above.
• R 133 represents a divalent organic group.
• the divalent organic group include an aliphatic group and an aromatic group.
• Specific examples include the example of R 121 in the formula (3) of the polybenzoxazole precursor. A preferred example thereof is the same as that of R 121 .
• R 134 represents a tetravalent organic group.
• the tetravalent organic group include R 122 in the formula (3) of the polybenzoxazole precursor. A preferred example thereof is the same as that of R 122 .
• four conjugates of a tetravalent organic group exemplified as R 122 combine with a nitrogen atom and an oxygen atom in the above formula (X) to form a condensed ring.
• R 134 when R 134 is the following organic group, it forms the following structure.
• Polybenzoxazole preferably has an oxazoleization rate of 85% or more, and more preferably 90% or more.
• the upper limit is not particularly limited and may be 100%.
• the oxazoleization rate is 85% or more, the membrane shrinkage due to ring closure that occurs when oxazoled by heating is reduced, and the occurrence of warpage can be suppressed more effectively.
• Polybenzoxazole everything may include repeating structural units of formula (X) comprising one of R 131 or R 132, 2 or more different types of R 131 or the formula comprising R 132 ( It may include the repeating unit of X). Further, the polybenzoxazole may contain other types of repeating structural units in addition to the repeating unit of the above formula (X).
• the resulting polybenzoxazole for example, a bis-aminophenol derivative, a dicarboxylic acid or the dicarboxylic acid containing R 133, is reacted with a compound selected from such dicarboxylic acid dichloride and dicarboxylic acid derivatives, the polybenzoxazole precursor ,
• a compound selected from such dicarboxylic acid dichloride and dicarboxylic acid derivatives the polybenzoxazole precursor .
• This can be obtained by oxazole using a known oxazole reaction method.
• an active ester-type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like.
• the weight average molecular weight (Mw) of polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing can be improved. In order to obtain a cured film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more kinds of polybenzoxazole are contained, it is preferable that the weight average molecular weight of at least one kind of polybenzoxazole is in the above range.
• a polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine.
• the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent and then reacting it with a diamine.
• an organic solvent in the reaction.
• the organic solvent may be one kind or two or more kinds.
• the organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
• the polyimide may be produced by synthesizing a polyimide precursor and then cyclizing it by a method such as thermal imidization or chemical imidization (for example, promotion of cyclization reaction by acting a catalyst), or directly. , Polyimide may be synthesized.
• the end of the polyimide precursor or the like is used as an end sealant such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound or a monoactive ester compound. It is preferable to seal. It is more preferable to use monoalcohol, phenol, thiol, thiophenol, and monoamine as the terminal encapsulant.
• Preferred compounds of monoalcohols include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, flufuryl alcohol, and isopropanol.
• Preferred compounds of phenols include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol and the like.
• Preferred compounds of monoamine are aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene.
• sealing agents for amino groups include carboxylic acid anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic acid anhydride and the like, and carboxylic acid anhydride and carboxylic acid chloride are more preferable. preferable.
• Preferred compounds of the carboxylic acid anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride and the like.
• Preferred compounds for the carboxylic acid chloride include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, and 1-adamantancarbonyl chloride. , Heptafluorobutyryl chloride, stearate chloride, benzoyl chloride, and the like.
• a step of precipitating a solid may be included in the production of the polyimide precursor or the like.
• the polyimide precursor or the like in the reaction solution is precipitated in water, and the polyimide precursor or the like such as tetrahydrofuran is dissolved in a soluble solvent to cause solid precipitation.
• the polyimide precursor or the like can be dried to obtain a powdery polyimide precursor or the like.
• the content of the specific resin in the thermosetting photosensitive composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total solid content of the thermosetting photosensitive composition. It is more preferably 40% by mass or more, and even more preferably 50% by mass or more.
• the content of the specific resin in the thermosetting photosensitive composition of the present invention is preferably 99.5% by mass or less, preferably 99% by mass or less, based on the total solid content of the thermosetting photosensitive composition. It is more preferably 98% by mass or less, further preferably 97% by mass or less, and even more preferably 95% by mass or less.
• the thermosetting photosensitive composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.
• thermosetting photosensitive composition contains a photosensitizer.
• photosensitizer when the thermosetting photosensitive layer is exposed to light, chemical changes such as generation of radicals and generation of acids occur, and the development solution of the thermosetting photosensitive layer changes with the above structural changes.
• the compound is not particularly limited as long as it has an action of changing the solubility of the substance, and examples thereof include a photopolymerization initiator and a photoacid generator.
• photopolymerization initiator examples include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferable.
• thermosetting photosensitive composition of the present invention preferably contains a photoradical polymerization initiator.
• a photoradical polymerization initiator by containing a photoradical polymerization initiator and a radical cross-linking agent described later, radical polymerization proceeds and the exposed portion of the thermosetting photosensitive layer becomes insoluble in a developing solution, thereby forming a negative pattern. can do.
• the photoradical polymerization initiator is not particularly limited and may be appropriately selected from known compounds, for example.
• a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.
• the photoradical polymerization initiator is a compound having at least a molar extinction coefficient of about 50 L ⁇ mol -1 ⁇ cm -1 with respect to light having a wavelength in the range of about 300 to 800 nm (preferably 330 to 500 nm). It is preferable that one type is contained.
• the molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
• a known compound can be arbitrarily used.
• halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
• acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like.
• Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned.
• paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification.
• ketone compound for example, the compound described in paragraph 0087 of JP2015-087611A is exemplified, and the content thereof is incorporated in the present specification.
• KayaCure DETX manufactured by Nippon Kayaku Co., Ltd.
• Nippon Kayaku Co., Ltd. is also preferably used.
• a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.
• IRGACURE 184 (IRGACURE is a registered trademark)
• DAROCUR 1173 As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.
• aminoacetophenone-based initiator commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF), Omnirad 907, Omnirad 369, and Omnirad 379 (all manufactured by IGM Resin). ) Can be used.
• the compound described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.
• acylphosphine-based initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
• commercially available products such as IRGACURE-819, IRGACURE-TPO (trade name: all manufactured by BASF), Omnirad 819 and Omnirad TPO (all manufactured by IGM Resins) can be used.
• metallocene compound examples include IRGACURE-784 (manufactured by BASF).
• An oxime compound is more preferable as the photoradical polymerization initiator.
• the exposure latitude can be improved more effectively.
• the oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.
• the compound described in JP-A-2001-233842 the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.
• Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.
• thermosetting photosensitive composition of the present invention it is particularly preferable to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator.
• IRGACURE OXE 01 IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PUTMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Laid-Open No. 2012-014052).
• a radical polymerization initiator 2) is also preferably used.
• TR-PBG-304 manufactured by Changshu Powerful Electronics New Materials Co., Ltd.
• ADEKA ARCLUDS NCI-831 ADEKA ARCULDS NCI-930
• DFI-091 manufactured by Daito Chemix Corp.
• An oxime compound having the following structure can also be used.
• an oxime compound having a fluorine atom examples include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.
• Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.
• the photoradical polymerization initiator includes a trihalomethyltriazine compound, a benzyldimethylketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, and a triaryl.
• a trihalomethyltriazine compound Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxaziazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.
• More preferable photoradical polymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds.
• At least one compound selected from the group consisting of trihalomethyltriazine compounds, ⁇ -aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable, and oxime compounds are even more preferable. Is even more preferable.
• the photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone).
• 2-benzyl such as benzophenone
• -2-morpholino-aromatic ketones such as propanol-1, alkylanthraquinone, etc.
• benzoin ether compounds such as benzoin alkyl ether
• benzoin compounds such as benzoin and alkyl benzoin
• benzyl derivatives such as benzyl dimethyl ketal.
• a compound represented by the following formula (I) can also be used.
• RI00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like.
• RI01 is a group represented by the formula (II). It is the same group as R I00, and R I02 to R I04 are independently alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogen atoms.
• R I05 to R I07 are the same as R I 02 to R I 04 of the above formula (I).
• the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/1254669 can also be used.
• the content of the photoradical polymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the thermosetting photosensitive composition of the present invention. Yes, more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photoradical polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photoradical polymerization initiators are contained, the total is preferably in the above range.
• thermosetting photosensitive composition of the present invention may further contain a thermal radical polymerization initiator.
• a thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the radical polymerization reaction further proceeds during heating, so that the crosslink density may be further improved.
• thermal radical polymerization initiator examples include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.
• thermoradical polymerization initiator When the thermoradical polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 30% by mass, based on the total solid content of the thermosetting photosensitive composition of the present invention. It is 20% by mass, more preferably 5 to 15% by mass. Only one type of thermal radical polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal radical polymerization initiators are contained, the total is preferably in the above range.
• thermosetting photosensitive composition of the present invention preferably contains a photoacid generator.
• a photoacid generator for example, acid is generated in the exposed portion of the thermosetting photosensitive layer, the solubility of the exposed portion in a developing solution (for example, an alkaline aqueous solution) is increased, and the exposed portion is developed. A positive relief pattern that is removed by the solution can be obtained.
• the thermosetting photosensitive composition contains a photoacid generator and a heat-crosslinking agent described later, for example, the cross-linking reaction of the heat-crosslinking agent is promoted by the acid generated in the exposed part, and the exposed part is exposed. Can be made more difficult to be removed by the developing solution than the non-exposed portion. According to such an aspect, a negative type relief pattern can be obtained.
• photoacid generator examples include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts and the like.
• the quinonediazide compound includes a polyhydroxy compound in which quinonediazide sulfonic acid is ester-bonded, a polyamino compound in which quinonediazide sulfonic acid is conjugated with a sulfonamide, and a polyhydroxypolyamino compound in which quinonediazide sulfonic acid is ester-bonded and a sulfonamide bond.
• Examples include those bound by at least one of the above. In the present invention, for example, it is preferable that 50 mol% or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.
• the quinone diazide either a 5-naphthoquinone diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group is preferably used.
• the 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
• the 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure.
• a 4-naphthoquinone diazidosulfonyl ester compound or a 5-naphthoquinone diazidosulfonyl ester compound depending on the wavelength to be exposed.
• a naphthoquinone diazidosulfonyl ester compound having a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group may be contained in the same molecule, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound may be contained. It may be contained.
• the naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxy group and a quinone diazido sulfonic acid compound, and can be synthesized by a known method.
• the resolution, sensitivity, and residual film ratio are further improved by using these naphthoquinone diazide compounds.
• the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the thermosetting photosensitive composition of the present invention. It is by mass, more preferably 5 to 15% by mass. Only one type of photoacid generator may be contained, or two or more types may be contained. When two or more photoacid generators are contained, the total is preferably in the above range.
• thermosetting photosensitive composition of the present invention may contain a thermosetting agent.
• the thermoacid generator is not particularly limited as long as it is a compound that generates an acid by heat, but for example, an onium salt such as a sulfonium salt, an ammonium salt, or a phosphonium salt, a carboxylic acid ester compound, a sulfonic acid ester compound, or a phosphoric acid. Examples thereof include ester compounds such as ester compounds.
• Examples of the acid generated from the thermal acid generator by heating include sulfonic acid, phosphoric acid, and carboxylic acid, with sulfonic acid being preferable and aromatic sulfonic acid being more preferable.
• the pKa of the acid generated from the thermoacid generator is preferably -15 to 3, more preferably -10 to 0.
• the acid generation temperature of the thermoacid generator is preferably 40 to 300 ° C, more preferably 80 to 260 ° C, further preferably 120 to 220 ° C, and 120 ° C to 200 ° C. Is particularly preferable, and the temperature is most preferably 140 ° C to 180 ° C.
• the acid generation temperature is determined as the peak temperature of the exothermic peak, which is the lowest temperature when the thermoacid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule. Examples of the device used for measuring the acid generation temperature include Q2000 (manufactured by TA Instruments). Further, the acid generation temperature of the thermosetting agent is preferably lower than the boiling point of the solvent contained in the thermosetting photosensitive composition.
• thermoacid generators examples include Sun Aid SI series manufactured by Sanshin Kagaku Kogyo, CPI series manufactured by Sun Appro, and K-PURE TAG series manufactured by King. Further, Japanese Patent Application Laid-Open No. 2003-277353, Japanese Patent Application Laid-Open No. 2-001470, Japanese Patent Application Laid-Open No. 2-255646, Japanese Patent Application Laid-Open No. 3-011044, Japanese Patent Application Laid-Open No. 2003-183313, Japanese Patent Application Laid-Open No. 2003-277352, Japanese Patent Application Laid-Open No. 58-037003. No., known thermoacid generators described in JP-A-58-198532 and the like can also be used.
• the content of the thermosetting agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the thermosetting photosensitive composition of the present invention. It is more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass. Only one type of thermoacid generator may be contained, or two or more types may be contained. When two or more types of thermoacid generators are contained, the total is preferably in the above range.
• the thermosetting photosensitive composition of the present invention contains a surfactant.
• the surfactant include nonionic surfactants such as silicone-based surfactants, hydrocarbon-based surfactants, and fluorine-based surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.
• nonionic surfactants such as silicone-based surfactants, hydrocarbon-based surfactants, and fluorine-based surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.
• Various types of surfactants can be used, and nonionic surfactants are preferable from the viewpoint of insulating properties of the cured film.
• the content of the surfactant is preferably more than 0.1% by mass with respect to the total mass of the composition.
• the thermosetting photosensitive composition of the present invention comprises a group consisting of a hydrocarbon-based surfactant described later, a surfactant having a fluorine atom described later, and a surfactant having a silicon atom described later. It can contain at least one selected surfactant. When two or more kinds of surfactants are contained, the total is preferably in the above range.
• the lower limit of the content is more preferably 0.101% by mass or more, and preferably 0.105% by mass or more.
• the upper limit of the content is preferably 5% by mass or less, and more preferably 1% by mass or less.
• thermosetting photosensitive layer is a thin portion in a non-uniform substrate
• the surface of the thermosetting photosensitive layer is subjected to a large amount of the surfactant. Is thought to be covered. Therefore, the difference in the amount of surfactant present on the surface of the thermosetting photosensitive layer becomes small between the thick portion and the thin portion of the thermosetting photosensitive layer, and the surface free energy of each of the cured film A and the cured film B becomes small.
• the content of the surfactant is preferably less than 0.005% by mass with respect to the total mass of the composition.
• the thermosetting photosensitive composition of the present invention comprises a group consisting of a hydrocarbon-based surfactant described later, a surfactant having a fluorine atom described later, and a surfactant having a silicon atom described later. It can contain at least one selected surfactant. When two or more kinds of surfactants are contained, the total is preferably in the above range.
• the lower limit of the content is more preferably 0.0001% by mass or more, and preferably 0.0005% by mass or more.
• the upper limit of the content is preferably 0.0045% by mass or less, and more preferably 0.0042% by mass or less.
• the thermosetting photosensitive layer may be a thin portion or a thick portion, and may be thermosetting photosensitive. It is believed that the amount of surfactant that moves to the surface of the layer will be reduced. Therefore, the difference in the amount of surfactant present on the surface of the thermosetting photosensitive layer becomes small between the thick portion and the thin portion of the thermosetting photosensitive layer, and the surface free energy of each of the cured film A and the cured film B becomes small.
• the thermosetting photosensitive composition of the present invention preferably contains a surfactant having no fluorine atom and silicon atom.
• the surfactant having no fluorine atom and silicon atom include hydrocarbon-based surfactants described later.
• a surfactant having a fluorine atom or a silicon atom moves to the surface of the thermosetting photosensitive layer, it is considered that the surface free energy of the cured film tends to decrease. Therefore, by including a surfactant having no fluorine atom and silicon atom as the surfactant, the amount of the surfactant present on the surface of the thermosetting photosensitive layer in the thick portion and the thin portion of the thermosetting photosensitive layer.
• the content of the hydrocarbon-based surfactant in the composition is preferably 50% by mass or more with respect to the total content of the surfactant.
• the thermosetting photosensitive composition of the present invention has at least one type of surfactant selected from the group consisting of a surfactant having a fluorine atom described later and a surfactant having a silicon atom described later.
• the agent may be further included.
• the content is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more.
• the upper limit is not particularly limited and may be 100% by mass.
• the total is preferably in the above range. Details of the hydrocarbon-based surfactant will be described later. It is considered that the hydrocarbon-based surfactant does not easily reduce the surface free energy of the cured film even if it moves to the surface of the thermosetting photosensitive layer. Therefore, when the content of the hydrocarbon-based surfactant in the composition is 50% by mass or more with respect to the total content of the surfactant, the heat-curable photosensitive layer is formed in a thick portion and a thin portion. Even if there is a difference in the amount of surfactant present on the surface of the heat-curable photosensitive layer, it is considered that the difference in surface free energy between the cured film A and the cured film B is small. As a result, even when a cured film is produced by applying it to a non-uniform substrate and another layer is further formed on the obtained cured film, the generation of defects in the other layer is suppressed. It is considered easy.
• the hydrocarbon-based surfactant may be a surfactant whose hydrophobic portion is a hydrocarbon group, and may be an acetylene-based surfactant, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, or polyoxyethylene stearyl ether, which will be described later.
• Polyoxyethylene alkyl ethers such as, or esters such as phosphates thereof, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether, polyoxyethylene stearate and the like.
• Solbitan alkyl esters such as polyoxyethylene alkyl esters, sorbitan monolaurates, sorbitan monostearates, sorbitan distearates, sorbitan monooleates, sorbitans sesquioleates, sorbitan trioleates, glycerol monostearates, glycerol monooletes.
• Monoglyceride alkyl esters such as ate, nonionic surfactants such as polynuclear phenol ethoxylates; Alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, alkylnaphthalene sulfonates such as sodium butylnaphthalene sulfonate, sodium pentylnaphthalene sulfonate, sodium hexylnaphthalene sulfonate, sodium octylnaphthalene sulfonate, alkyl sulphate such as sodium lauryl sulphate.
• Anionic surfactants such as salts, alkyl sulfonates such as sodium dodecyl sulfonate, sulfosuccinate salts such as sodium dilauryl sulfosuccinate; Cationic surfactants such as quaternary ammonium salt type alkyl cations; Examples thereof include, but are not limited to, amphoteric surfactants such as alkyl betaines such as lauryl betaine and stearyl betaine.
• the number of acetylene groups in the molecule in the acetylene-based surfactant is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and further 1 to 2. preferable.
• the molecular weight of the acetylene-based surfactant is preferably relatively small, preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,000 or less. There is no particular lower limit, but it is preferably 200 or more.
• the acetylene-based surfactant is preferably a compound represented by the following formula (9).
• R 91 and R 92 are independently an alkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, or an aromatic heterocyclic group having 4 to 15 carbon atoms. ..
• the number of carbon atoms of the aromatic heterocyclic group is preferably 1 to 12, more preferably 2 to 6, and even more preferably 2 to 4.
• the aromatic heterocycle is preferably a 5-membered ring or a 6-membered ring.
• the hetero atom contained in the aromatic heterocycle is preferably a nitrogen atom, an oxygen atom, or a sulfur atom.
• R 91 and R 92 may each independently have a substituent, and examples of the substituent include the following substituent T.
• an alkyl group preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms
• an arylalkyl group preferably 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms. , 7-11 is more preferable
• an alkenyl group (2 to 24 carbon atoms is preferable, 2 to 12 is more preferable, 2 to 6 is more preferable
• an alkynyl group (2 to 12 carbon atoms is preferable, 2 to 6 is preferable).
• 2 to 3 are more preferable), hydroxy group, amino group (preferably 0 to 24 carbon atoms, more preferably 0 to 12 and further preferably 0 to 6), thiol group, carboxy group, aryl group (carbon).
• the number 6 to 22 is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), an alkoxyl group (1 to 12 carbon atoms is preferable, 1 to 6 is more preferable, 1 to 3 is more preferable), and aryloxy.
• Group preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10
• acyl group preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3
• Acyloxy group preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms
• allylloyl group preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11 carbon atoms).
• allyloyloxy group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11), carbamoyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, 1).
• ⁇ 3 is more preferable
• sulfamoyl group preferably 0 to 12 carbon atoms, more preferably 0 to 6 and even more preferably 0 to 3
• sulfo group, alkylsulfonyl group preferably 1 to 12 carbon atoms 6 is more preferable, 1 to 3 is more preferable
• an arylsulfonyl group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable
• a heterocyclic group (1 to 12 carbon atoms is more preferable).
• RN is a hydrogen atom or an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), and a hydrogen atom, a methyl group, an ethyl group, or a propyl group is preferable.
• the alkyl moiety, alkenyl moiety, and alkynyl moiety contained in each substituent may be chain or cyclic, and may be linear or branched.
• the substituent T is a group capable of taking a substituent, it may further have a substituent T.
• the alkyl group may be an alkyl halide group, a (meth) acryloyloxyalkyl group, an aminoalkyl group or a carboxyalkyl group.
• the substituent is a group capable of forming a salt such as a carboxy group or an amino group, the group may form a salt.
• the compound represented by the formula (9) is preferably a compound represented by the following formula (91).
• R 93 to R 96 are each independently a hydrocarbon group having 1 to 24 carbon atoms, n9 is an integer of 1 to 6, m9 is an integer twice n9, and n10 is an integer of 1 to 6. It is an integer, m10 is an integer twice n10, and l9 and l10 are independently numbers of 0 or more and 12 or less.
• R 93 to R 96 are hydrocarbon groups, among which alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms) and alkenyl groups (2 to 12 carbon atoms are preferable).
• 2 to 6 are more preferable, 2 to 3 are more preferable), an alkynyl group (2 to 12 carbon atoms are preferable, 2 to 6 are more preferable, 2 to 3 are more preferable), and an aryl group (6 to 6 carbon atoms is more preferable).
• 22 is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), and an arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable, and 7 to 11 is further preferable).
• the alkyl group, alkenyl group, and alkynyl group may be linear or cyclic, and may be linear or branched.
• R 93 to R 96 may have a substituent T as long as the effects of the present invention are exhibited. Further, R 93 to R 96 may be bonded to each other or form a ring via the above-mentioned linking group L. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to the hydrocarbon group in the formula with or without the following linking group L to form a ring.
• R 93 and R 94 are preferably alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms). Of these, a methyl group is preferable.
• R 95 and R 96 are preferably alkyl groups (preferably 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 3 to 6 carbon atoms). Of these, ⁇ (C n11 R 98 m11 ) -R 97 is preferable. R 95 and R 96 are particularly preferably isobutyl groups. n11 is an integer of 1 to 6, and an integer of 1 to 3 is preferable. m11 is twice the number of n11. R 97 and R 98 are each independently preferably a hydrogen atom or an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms).
• n9 is an integer of 1 to 6, and an integer of 1 to 3 is preferable.
• m9 is an integer that is twice n9.
• n10 is an integer of 1 to 6, and an integer of 1 to 3 is preferable.
• m10 is an integer that is twice n10.
• l9 and l10 are independently numbers from 0 to 12. However, l9 + l10 is preferably a number of 0 to 12, more preferably a number of 0 to 8, more preferably a number of 0 to 6, further preferably a number of more than 0 and less than 6, and more than 0. A number of 3 or less is even more preferable.
• the compound of the formula (91) may be a mixture of compounds having different numbers, and in that case, the numbers of l9 and l10, or l9 + l10 are the numbers including the decimal point. You may.
• the compound represented by the formula (91) is preferably a compound represented by the following formula (92).
• R 93 , R 94 , and R 97 to R 100 are each independently a hydrocarbon group having 1 to 24 carbon atoms, and l11 and l12 are each independently a number of 0 or more and 12 or less.
• R 93 , R 94 , and R 97 to R 100 are alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms) and alkenyl groups (preferably 2 to 12 carbon atoms).
• alkyl group, alkenyl group, and alkynyl group may be chain or cyclic, and may be linear or branched.
• R 93 , R 94 , and R 97 to R 100 may have a substituent T as long as the effects of the present invention are exhibited. Further, R 93 , R 94 , and R 97 to R 100 may be bonded to each other or form a ring via a linking group L. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to the hydrocarbon group in the formula with or without the linking group L to form a ring.
• R 93 , R 94 , and R 97 to R 100 are each independently preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms).
• a methyl group is preferable.
• the number of l11 + l12 is preferably 0 to 12, more preferably 0 to 8, more preferably 0 to 6, more preferably more than 0 and less than 6, more preferably more than 0 and 5 or less.
• the number of is even more preferable, the number of more than 0 and less than 4 is even more preferable, the number of more than 0 and less than 3 or more than 0 and less than or equal to 1.
• l11 and l12 may be a mixture of compounds having different numbers in the compound of the formula (92), and in that case, the numbers of l11 and l12, or l11 + l12 are the numbers including the decimal point. May be good.
• Surfynol 104 series (trade name, Nissin Chemical Industry Co., Ltd.), acetylenol E00, E40, E13T, 60 (trade name, Kawaken Fine Chemicals)
• Surfinol 104 series, Acetyleneol E00, E40 and E13T are preferable, and Acetyleneol E40 and E13T are more preferable.
• the Surfinol 104 series and acetylenol E00 are surfactants having the same structure.
• hydrocarbon-based surfactant a commercially available product may be used, and as the commercially available product, Adecator LB, LA, OA, TN, TO, UA, LO, SO, SP, PC, Adecanol NK, AP, Adeka Estor OEG, TL, S, T, Adekasol CO, COA, Adeka Hope MS, YES, TR, Adeka Call TS, CS, PS, EC, Adekamin 4MAC, 4DAC, MT, Adeka Surfact PB, AB, etc. ) Made by ADEKA), etc., but is not limited to this.
• surfactant with fluorine atom examples include a surfactant having a fluorocarbon chain and the like.
• the PF series of Kitamura Chemical Industry Co., Ltd. the "Mega Fuck (registered trademark)” series of Dainippon Ink Industry Co., Ltd., the Florard series of Sumitomo 3M Ltd., and the "Surflon” of AGC Inc. (Registered Trademark) ”series,“ Asahi Guard (Registered Trademark) ”series, Mitsubishi Material Electronics Chemicals Co., Ltd. EF Series, Omniova Solution Co., Ltd. Polyfox Series, etc., but are not limited to these. ..
• Examples of the surfactant having a silicon atom include a surfactant having a polysiloxane chain which may be modified.
• silicone-based surfactants Toshiba Dow Corning Silicone Co., Ltd. SH series, SD series, ST series, Big Chemie Japan Co., Ltd. "BYK” series, Shinetsu Silicone Co., Ltd. KP series, KF Series, Disform series of Nippon Oil & Fats Co., Ltd., TSF series of Toshiba Silicone Co., Ltd., etc., but are not limited to these.
• thermosetting photosensitive composition of the present invention may contain other surfactants as the surfactants.
• Other surfactants include, but are limited to, acrylic / methacrylic resin-based surfactants such as Kyoeisha Chemical's Polyflow series and Kusumoto Kasei's "Disparon (registered trademark)" series. It's not a thing.
• the thermosetting photosensitive composition of the present invention contains a solvent.
• a solvent a known solvent can be arbitrarily used.
• the solvent is preferably an organic solvent.
• the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, and alcohols.
• esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and ⁇ -butyrolactone.
• alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate, etc.)
• 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)
• 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, ethyl 2-alkyl
• ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol.
• Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, and propylene glycol monopropyl ether acetate.
• ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like are preferable.
• cyclic hydrocarbons for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene are preferable.
• sulfoxides for example, dimethyl sulfoxide is preferable.
• N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylisobutyramide, 3-methoxy-N, N- Dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide and the like are preferable.
• Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, Examples thereof include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
• the solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.
• the mixed solvent to be mixed is preferable.
• the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
• the content of the solvent is preferably such that the total solid content concentration of the thermosetting photosensitive composition of the present invention is 5 to 80% by mass, and is 5 to 75% by mass.
• the amount is more preferably 10 to 70% by mass, further preferably 20 to 70% by mass, and further preferably 40 to 70% by mass. More preferred.
• the solvent content may be adjusted according to the desired thickness of the coating film and the coating method.
• the solvent may contain only one type, or may contain two or more types. When two or more kinds of solvents are contained, the total is preferably in the above range.
• the thermosetting photosensitive composition of the present invention preferably further contains a radical cross-linking agent.
• the radical cross-linking agent is a compound having a radically polymerizable group.
• a group containing an ethylenically unsaturated bond is preferable.
• the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group.
• the (meth) acryloyl group is preferable as the group containing the ethylenically unsaturated bond, and the (meth) acryloyl group is more preferable from the viewpoint of reactivity.
• the radical cross-linking agent may be a compound having one or more ethylenically unsaturated bonds, but is more preferably a compound having two or more ethylenically unsaturated bonds.
• the compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the above ethylenically unsaturated bonds.
• the thermosetting photosensitive composition of the present invention preferably contains a compound having three or more ethylenically unsaturated bonds as a radical cross-linking agent.
• the compound having 3 or more ethylenically unsaturated bonds a compound having 3 to 15 ethylenically unsaturated bonds is preferable, and a compound having 3 to 10 ethylenically unsaturated bonds is more preferable, and 3 to 6 compounds are more preferable.
• the compound having is more preferable.
• the compound having three or more ethylenically unsaturated bonds is preferably a compound having three or more groups containing the ethylenically unsaturated bond, and more preferably a compound having 3 to 15 ethylenically unsaturated bonds.
• a compound having 3 to 10 is more preferable, and a compound having 3 to 6 is particularly preferable.
• the thermosetting photosensitive composition of the present invention comprises a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferable to include and.
• the radical cross-linking agent is particularly preferably a compound having two ethylenically unsaturated bonds.
• the molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
• the lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.
• radical cross-linking agent examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and are preferable.
• an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group.
• a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
• an addition reaction product of an unsaturated carboxylic acid ester or amide having a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amines or thiols, and a halogeno group.
• Substitution reactions of unsaturated carboxylic acid esters or amides having a releasable substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable.
• radical cross-linking agent a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable.
• examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
• a compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0371993.
• Urethane (meth) acrylates such as those described in JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490, the polyester acrylates, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable.
• a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.
• a preferable radical cross-linking agent other than the above it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like.
• a compound having two or more groups having two or more groups and a cardo resin can also be used.
• dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.) ), A-TMMT: Shin-Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) ) Acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are mediated by ethylene glycol residues or propylene glycol residues. A structure that is bonded together is preferable
• SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer
• SR-209 manufactured by Sartmer which is a bifunctional methacrylate having four ethyleneoxy chains.
• DPCA-60 a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd.
• TPA-330 a trifunctional acrylate having 3 isobutyleneoxy chains
• urethane oligomer UAS-10 are examples of the radical cross-linking agent.
• UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (Japan) Chemicals Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.
• radical cross-linking agent examples include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765.
• Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.
• radical cross-linking agent a compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 is used. You can also do it.
• the radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group.
• the radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride.
• a radical cross-linking agent provided with is more preferable.
• the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Is a compound.
• examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
• the preferable acid value of the radical cross-linking agent having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
• the acid value of the radical cross-linking agent is within the above range, it is excellent in manufacturing handleability and further excellent in developability. Moreover, the polymerizable property is good.
• the acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. The acid value is measured according to the description of JIS K 0070: 1992.
• thermosetting photosensitive composition of the present invention it is preferable to use bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film elasticity.
• the compound include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and PEG200 diacrylate (polyethylene glycol diacrylate having a formula of polyethylene glycol chain).
• a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent.
• the monofunctional radical cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth).
• the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the thermosetting photosensitive composition of the present invention.
• the lower limit is more preferably 5% by mass or more.
• the upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
• One type of radical cross-linking agent may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably in the above range.
• the thermosetting photosensitive composition of the present invention preferably contains a thermosetting agent.
• the thermal cross-linking agent is particularly limited as long as it is a compound having a plurality of groups in the molecule in which a reaction for forming a covalent bond with another compound in the composition or a reaction product thereof is promoted by the action of an acid.
• a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferable, and at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to a nitrogen atom.
• Compounds having a structure are more preferable.
• thermal cross-linking agent for example, an amino group-containing compound such as melamine, glycoluril, urea, alkyleneurea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is replaced with a methylol group or an alkoxymethyl group.
• an amino group-containing compound such as melamine, glycoluril, urea, alkyleneurea, or benzoguanamine
• formaldehyde or formaldehyde and alcohol examples thereof include compounds having the above-mentioned structure.
• the method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
• a thermal cross-linking agent using melamine is a melamine-based cross-linking agent
• a thermal cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent
• a thermal cross-linking agent using alkylene urea is an alkylene.
• Those using a urea-based cross-linking agent and benzoguanamine are called benzoguanamine-based cross-linking agents.
• thermosetting photosensitive composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and is preferably a glycoluril-based cross-linking agent described later. It is more preferable to contain at least one compound selected from the group consisting of the melamine-based cross-linking agent and the melamine-based cross-linking agent.
• melamine-based cross-linking agent examples include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutyl melamine and the like.
• urea-based cross-linking agent examples include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol uryl.
• Glycoluryl-based cross-linking agent such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, Monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethyl
• Ethyleneurea-based cross-linking agents such as ethyleneurea, monobutoxymethylated, or dibutoxymethylated ethyleneurea, Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethyl
• benzoguanamine-based cross-linking agent examples include monohydroxymethylated benzoguanamine and dihydroxymethylated benzoguanamine. Trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated Benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, Examples thereof include tetrabutoxymethylated benzogu
• a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring).
• a compound to which a group is directly bonded is also preferably used.
• Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylbenzoate hydroxymethylphenyl.
• thermal cross-linking agent Commercially available products may be used as the thermal cross-linking agent, and suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, etc.
• thermosetting photosensitive composition of the present invention preferably contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as a thermosetting agent.
• Epoxy compound (compound having an epoxy group)
• the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
• the epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the thermosetting photosensitive composition.
• the epoxy compound preferably contains a polyethylene oxide group.
• the polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.
• epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether. , Trimethylol propantriglycidyl ether and other alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl ether and other polyalkylene glycol type epoxy resins; polymethyl (glycidyloxypropyl) siloxane and other epoxy groups Examples include, but are not limited to, containing silicones.
• an epoxy resin containing a polyethylene oxide group is preferable because it is excellent in suppressing warpage and heat resistance.
• Epicron® EXA-4880, Epicron® EXA-4822, and Ricaresin® BEO-60E are preferred because they contain polyethylene oxide groups.
• oxetane compound compound having an oxetanyl group
• examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, and the like.
• examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like.
• the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone. Alternatively, two or more types may be mixed.
• benzoxazine compound examples include BA type benzoxazine, Bm type benzoxazine, Pd type benzoxazine, FA type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), poly.
• examples thereof include a benzoxazine adduct of a hydroxystyrene resin and a phenol novolac type dihydrobenzoxazine compound. These may be used alone or in combination of two or more.
• the content of the thermosetting agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the thermosetting photosensitive composition of the present invention. , 0.5 to 15% by mass is more preferable, and 1.0 to 10% by mass is particularly preferable. Only one type of thermal cross-linking agent may be contained, or two or more types may be contained. When two or more kinds of thermal cross-linking agents are contained, the total is preferably in the above range.
• thermosetting photosensitive composition of the present invention is selected from at least a group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure. It is preferable to further contain one compound.
• the sulfonamide structure is a structure represented by the following formula (S-1).
• R represents a hydrogen atom or an organic group
• R may be bonded to another structure to form a ring structure
• * may independently form a binding site with another structure.
• the R is preferably the same group as R 2 in the following formula (S-2).
• the compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but a compound having one sulfonamide structure is preferable.
• the compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2).
• R 1 , R 2 and R 3 each independently represent a hydrogen atom or a monovalent organic group, and two or more of R 1 , R 2 and R 3 are bonded to each other. It may form a ring structure. It is preferable that R 1 , R 2 and R 3 are independently monovalent organic groups.
• R 1 , R 2 and R 3 include hydrogen atoms, or alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl groups, arylether groups, carboxy groups, Examples thereof include a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these are combined.
• the alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
• alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group and the like.
• a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable.
• examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
• an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable.
• Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentoxy group.
• As the alkoxysilyl group an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable.
• Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
• aryl group an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable.
• the aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and a naphthyl group.
• heterocyclic group examples include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isooxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring and a piperidine ring.
• R 1 is an aryl group and R 2 and R 3 are independently hydrogen atoms or alkyl groups are preferable.
• Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfanylamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1.
• the thiourea structure is a structure represented by the following formula (T-1).
• R 4 and R 5 each independently represent a hydrogen atom or a monovalent organic group, and R 4 and R 5 may be combined to form a ring structure, where R 4 is.
• the ring structure may be formed by combining with other structures to which * is bonded, R 5 may be combined with other structures to which * is bonded to form a ring structure, and * may be independently and others. Represents the site of connection with the structure of.
• R 4 and R 5 are independently hydrogen atoms.
• R 4 and R 5 include hydrogen atom, or alkyl group, cycloalkyl group, alkoxy group, alkyl ether group, alkylsilyl group, alkoxysilyl group, aryl group, arylether group, carboxy group, carbonyl group, Examples thereof include an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these are combined.
• the alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
• alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group and the like.
• a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable.
• examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
• an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable.
• Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentoxy group.
• As the alkoxysilyl group an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable.
• Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
• aryl group an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable.
• the aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and a naphthyl group.
• heterocyclic group examples include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isooxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring and a piperidine ring.
• the compound having a thiourea structure may be a compound having two or more thiourea structures, but is preferably a compound having one thiourea structure.
• the compound having a thiourea structure is preferably a compound represented by the following formula (T-2).
• R 4 to R 7 independently represent a hydrogen atom or a monovalent organic group, and at least two of R 4 to R 7 are bonded to each other to form a ring structure. You may.
• R 4 and R 5 have the same meanings as R 4 and R 5 in formula (T-1), a preferable embodiment thereof is also the same.
• R 6 and R 7 are independently monovalent organic groups.
• the preferred embodiment of the monovalent organic group in R 6 and R 7 is the same as the preferred embodiment of the monovalent organic group in R 4 and R 5 in the formula (T-1). ..
• Examples of compounds having a thiourea structure include N-acetylthiourea, N-allyl thiourea, N-allyl-N'-(2-hydroxyethyl) thiourea, 1-adamantyl thiourea, N-benzoyl thiourea, N, N'-.
• Diphenylthiourea 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1- (3- (trimethoxysilyl) propyl) -3-methylthiourea, trimethyl Examples thereof include thiourea, tetramethylthiourea, N, N-diphenylthiourea, ethylenethiourea (2-imidazolinthione), carbimazole, and 1,3-dimethyl-2-thiohydranthin.
• the total content of the compound having a sulfonamide structure and the compound having a thiourea structure is preferably 0.05 to 10% by mass, preferably 0.1 to 10% by mass, based on the total mass of the thermosetting photosensitive composition of the present invention. It is more preferably 5% by mass, and even more preferably 0.2 to 3% by mass.
• the thermosetting photosensitive composition of the present invention may contain only one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure, or may contain two or more compounds. When only one type is contained, the content of the compound is preferably within the above range, and when two or more types are contained, the total amount thereof is preferably within the above range.
• thermosetting photosensitive composition of the present invention preferably further contains a migration inhibitor.
• a migration inhibitor By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the thermosetting photosensitive composition layer.
• the migration inhibitor is not particularly limited, but heterocycles (pyrazole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc.
• triazole-based compounds such as 1,2,4-triazole and benzotriazole
• tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.
• an ion trap agent that traps anions such as halogen ions can also be used.
• Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656.
• the compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used.
• the migration inhibitor include the following compounds.
• the content of the migration inhibitor shall be 0.01 to 5.0% by mass with respect to the total solid content of the thermocurable photosensitive composition. Is more preferable, 0.05 to 2.0% by mass is more preferable, and 0.1 to 1.0% by mass is further preferable.
• the migration inhibitor may be only one type or two or more types. When there are two or more types of migration inhibitors, the total is preferably in the above range.
• thermosetting photosensitive composition of the present invention preferably contains a polymerization inhibitor.
• polymerization inhibitor examples include hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, and diphenyl-p-benzoquinone.
• the content of the polymerization inhibitor is, for example, 0.01 to 20 with respect to the total solid content of the thermosetting photosensitive composition of the present invention.
• An embodiment of 0.0% by mass is mentioned, preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and 0.05 to 2.5% by mass. Is more preferable.
• the embodiment of 0.02 to 15.0% by mass is also preferably raised, and in that case, 0.05 to 10.0% by mass is more preferable. Is.
• the polymerization inhibitor may be only one type or two or more types. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.
• the thermosetting photosensitive composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
• a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
• the metal adhesion improver include silane coupling agents, aluminum-based adhesive aids, titanium-based adhesive aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, ⁇ -ketoester compounds, and amino compounds. And so on.
• silane coupling agent examples include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraphs of International Publication No. 2011/080992.
• Examples include the compounds described in paragraph 0055. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Further, it is also preferable to use the following compounds as the silane coupling agent.
• Et represents an ethyl group.
• silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glyceride.
• the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used. ..
• Aluminum-based adhesive aid examples include aluminum tris (ethylacetacetate), aluminumtris (acetylacetoneate), ethylacetacetate aluminum diisopropirate, and the like.
• the content of the metal adhesive improving agent is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0. It is in the range of 5 to 5 parts by mass.
• the metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.
• thermosetting photosensitive composition of the present invention can be used for various additives such as sensitizers such as N-phenyldiethanolamine, chain transfer agents, and higher fatty acids, if necessary, as long as the effects of the present invention can be obtained.
• sensitizers such as N-phenyldiethanolamine
• chain transfer agents such as N-phenyldiethanolamine
• higher fatty acids if necessary, as long as the effects of the present invention can be obtained.
• Derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, antiaggregating agents and the like can be blended.
• the total blending amount is preferably 3% by mass or less of the solid content of the thermosetting photosensitive composition.
• the thermosetting photosensitive composition of the present invention may contain a sensitizer.
• the sensitizer absorbs specific active radiation and enters an electron-excited state.
• the sensitizer in the electron-excited state comes into contact with the thermal radical polymerization initiator, the photoradical polymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur.
• the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids or bases.
• Examples of the sensitizer include sensitizers such as N-phenyldiethanolamine.
• benzophenone type Michler's ketone type, coumarin type, pyrazole azo type, anilino azo type, triphenylmethane type, anthracene type, anthracene type, anthrapyridone type, benzylidene type, oxonor type, pyrazole triazole azo type, pyridone azo type, Compounds such as cyanine-based, phenothiazine-based, pyrrolopyrazoleazomethine-based, xanthene-based, phthalocyanine-based, penzopyran-based, and indigo-based compounds can be used.
• sensitizing dye can be mentioned. Moreover, you may use a sensitizing dye as a sensitizer.
• sensitizing dye the description in paragraphs 0161 to 0163 of JP-A-2016-0273557 can be referred to, and this content is incorporated in the present specification.
• the content of the sensitizer is 0.01 to 20% by mass with respect to the total solid content of the heat-curable photosensitive composition of the present invention. , More preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass.
• the sensitizer may be used alone or in combination of two or more.
• the thermosetting photosensitive composition of the present invention may contain a chain transfer agent.
• Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684.
• Examples of the chain transfer agent include RAFT (Reversible Addition Fragmentation chain Transfer), which is a group of compounds having -S-S-, -SO 2 -S-, -NO-, SH, PH, SiH, and GeH in the molecule.
• Dithiobenzoate, trithiocarbonate, dithiocarbamate, xantate compound and the like having a thiocarbonylthio group used for polymerization are used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
• a thiol compound can be preferably used.
• the content of the chain transfer agent is 0.01 to 100 parts by mass with respect to 100 parts by mass of the total solid content of the thermosetting photosensitive composition of the present invention. 20 parts by mass is preferable, 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable.
• the chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.
• thermosetting photosensitive composition of the present invention is thermoset in the process of drying after application by adding a higher fatty acid derivative such as behenic acid or behenic acid amide in order to prevent polymerization inhibition due to oxygen. It may be unevenly distributed on the surface of the photosensitive composition.
• the content of the higher fatty acid derivative is 0.1 to 10 mass by mass with respect to the total solid content of the thermosetting photosensitive composition of the present invention. It is preferably%. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.
• thermosetting photosensitive composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coating surface properties.
• the metal content of the thermosetting photosensitive composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and further less than 0.5 mass ppm from the viewpoint of insulating properties.
• the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, it is preferable that the total of these metals is in the above range.
• thermosetting photosensitive composition of the present invention a raw material having a low metal content is used as a raw material constituting the thermosetting photosensitive composition of the present invention.
• the thermosetting photosensitive composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, from the viewpoint of wiring corrosiveness. More preferably less than 200 mass ppm.
• those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
• the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
• a conventionally known storage container can be used as the storage container for the thermosetting photosensitive composition of the present invention.
• a multi-layer bottle in which the inner wall of the container is composed of 6 types and 6 layers of resin and 6 types of resins are used for the purpose of suppressing impurities from being mixed into the raw materials and the thermosetting photosensitive composition. It is also preferable to use a bottle having a 7-layer structure. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
• thermosetting photosensitive composition of the present invention is a composition used for forming a thermosetting photosensitive layer, and is more preferably used for forming a thermosetting photosensitive layer by a slit coating method.
• the thermosetting photosensitive composition of the present invention is preferably applied to a non-uniform substrate.
• the non-uniform base material may be a base material in which the thickness of the thermosetting photosensitive layer is not uniform when the thermosetting photosensitive layer is formed on the base material. For example, there is a step on the surface.
• the surface of the base material is such that the physical shape of the surface of the base material is not uniform, such as a base material having Examples thereof include a base material having non-uniform chemical properties.
• the base material having a step is a base material having a step on the surface, and may be a base material having a non-flat surface.
• the base material having an inclination on the surface is a base material having an inclination on at least a part of the surface, and may be a base material having a non-flat surface.
• a base material in which the chemical properties of the surface of the base material are not uniform, such that only a part of the surface is difficult to be compatible with the composition for example, a base material having a different material on the surface of the base material or a part of the surface Even if the surface is flat, it may be a base material on which a thermosetting photosensitive layer having a uniform thickness is not formed.
• Examples of the base material in which a part of the material on the surface of the base material is different include the case where the surface of the base material has an insulating layer and conductor wiring.
• the difference in height between the rearmost part and the lowest part of a base material having a non-uniform physical shape on the surface of the base material (a base material having a non-uniform surface height) is the average thickness of the thermosetting photosensitive layer. On the other hand, it is preferably 5 to 90%, more preferably 10 to 80%, and even more preferably 12 to 60%.
• the physical shape of the surface of the base material is not particularly uniform.
• the surface aspect of the base material is not particularly limited, and is rectangular parallelepiped, cubic, columnar, hemispherical, pyramidal, cone-shaped, sloped, or ridge-shaped. , Valley-shaped or saddle-shaped, high or low in the thickness direction, or any other shape that forms a height difference in the thickness direction.
• the difference in height may be a difference due to the shape of the substrate, a difference formed by elements formed on the base material such as an electrode and an insulating film, and may be formed by anything. Is not limited.
• thermosetting photosensitive composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer. In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, and the like.
• thermosetting photosensitive composition of the present invention can be prepared by mixing each of the above components.
• the mixing method is not particularly limited, and a conventionally known method can be used.
• the filter pore diameter is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
• the filter pore diameter may be, for example, 5 ⁇ m or less, preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, still more preferably 0.1 ⁇ m or less.
• the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
• the filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel.
• filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressure to be pressurized is, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less. , 0.05 MPa or more and 0.3 MPa or less is more preferable. In addition to filtration using a filter, impurities may be removed using an adsorbent.
• Filter filtration and impurity removal treatment using an adsorbent may be combined.
• a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
• the cured film of the present invention is obtained by curing the thermosetting photosensitive composition of the present invention.
• the film thickness of the cured film of the present invention can be, for example, 0.5 ⁇ m or more, and can be 1 ⁇ m or more. Further, the upper limit value can be 100 ⁇ m or less, and can be 30 ⁇ m or less.
• the cured film of the present invention may be laminated in two or more layers, and further in three to seven layers to form a laminated body. It is preferable that the laminate of the present invention contains two or more cured films and includes a metal layer between any of the cured films. For example, a laminate containing at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order is preferable.
• the first cured film and the second cured film are both cured films of the present invention.
• both the first cured film and the second cured film are thermosetting the present invention.
• a preferred embodiment is a film formed by curing a photosensitive composition.
• thermosetting photosensitive composition of the present invention used for forming the first cured film and the thermosetting photosensitive composition of the present invention used for forming the second cured film have the same composition. It may be a composition of the above, or it may be a composition having a different composition.
• the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
• Examples of the applicable field of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like.
• a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above may be patterned by etching. For these applications, for example, Science & Technology Co., Ltd.
• the cured film in the present invention can also be used for manufacturing plate surfaces such as offset plate surfaces or screen plate surfaces, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, especially microelectronics.
• the method for producing a cured film of the present invention is a film forming step of applying the thermosetting photosensitive composition of the present invention to a substrate to form a film. It is preferable to include it.
• the method for producing a cured film of the present invention preferably includes the film forming step, an exposure step for exposing the film, and a developing step for developing the film. Further, it is more preferable that the method for producing a cured film of the present invention includes a heating step of heating the film. Specifically, it is also preferable to include the following steps (a) to (d).
• thermosetting photosensitive composition layer (thermosetting photosensitive composition layer)
• Heating step for heating the developed film
• the resin layer cured by exposure can be further cured.
• the above-mentioned thermal acid generator is decomposed, and the generated acid promotes the cross-linking of the thermal cross-linking agent, so that sufficient curability can be obtained.
• the method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention.
• the method for producing the laminated body of the present embodiment is the step (a), the steps (a) to (c), or (a) after the cured film is formed according to the above-mentioned method for producing the cured film. )-(D).
• a laminated body can be obtained.
• the production method includes a film forming step (layer forming step) in which a thermosetting photosensitive composition is applied to a substrate to form a film (layered).
• the type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film, There are no particular restrictions on magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (thin film) array substrates, and electrode plates of plasma display panels (PDPs).
• a semiconductor-made base material is particularly preferable, and a silicon base material and a molded resin base material are more preferable.
• the base material for example, a plate-shaped base material (board) is used.
• thermosetting photosensitive composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a base material.
• Coating is preferable as a means for applying the thermosetting photosensitive composition to the base material.
• the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method.
• the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the thermosetting photosensitive composition layer, the spin coating method, the slit coating method, the spray coating method, and the inkjet method are more preferable, and from the viewpoint that the effect of the present invention can be easily obtained, the effect of the present invention can be easily obtained.
• the slit coating method is preferable.
• a resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method.
• the coating method can be appropriately selected depending on the shape of the base material.
• a circular base material such as a wafer
• a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular base material, a slit coating method or a spray coating method is used.
• the method, the inkjet method and the like are preferable.
• the spin coating method for example, it may be applied at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds, and it may be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. it can.
• a plurality of rotation speeds can be combined and applied. Further, it is also possible to apply a method of transferring a coating film previously formed on a temporary support by the above-mentioned application method onto a substrate. Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 096 to 0108 of JP-A-2006-047592 can be preferably used in the present invention.
• the production method of the present invention may include a step of forming the film (thermosetting photosensitive composition layer), followed by a film forming step (layer forming step), and then drying to remove the solvent.
• the preferred drying temperature is 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C.
• the drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes. If the amount of solvent in the photosensitive resin composition solution is large, vacuum drying and heat drying can be combined.
• a hot plate, a hot air oven, or the like is used for heat drying, and the heating and drying is not particularly limited.
• the production method of the present invention may include an exposure step of exposing the film (thermosetting photosensitive composition layer).
• the amount of exposure is not particularly determined as long as the thermosetting photosensitive composition can be cured, but for example, it is preferable to irradiate 100 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, 200 to 8, It is more preferable to irradiate at 000 mJ / cm 2 .
• the exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
• the exposure wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h.
• Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Examples include a laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beam, etc., (7) a second harmonic of a YAG laser of 532 nm and a third harmonic of 355 nm.
• thermosetting photosensitive composition of the present invention exposure with a high-pressure mercury lamp is particularly preferable, and exposure with i-ray is particularly preferable. As a result, particularly high exposure sensitivity can be obtained. From the viewpoint of handling and productivity, a broad (three wavelengths of g, h, and i rays) light source of a high-pressure mercury lamp and a semiconductor laser of 405 nm are also suitable.
• the production method of the present invention may include a developing step of developing (developing the above-mentioned film) the exposed film (heat-curable photosensitive composition layer).
• a developing step of developing developing the above-mentioned film
• the exposed film heat-curable photosensitive composition layer
• an unexposed portion non-exposed portion
• the developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted.
• development is performed using a developing solution.
• the developing solution can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed.
• alkaline development the case where an alkaline developer is used as the developer
• solvent development the case where a developer containing 50% by mass or more of an organic solvent is used as the developer.
• the developer preferably has an organic solvent content of 10% by mass or less based on the total mass of the developing solution, more preferably 5% by mass or less, and 1% by mass or less. Is more preferable, and a developer containing no organic solvent is particularly preferable.
• the developing solution in alkaline development is more preferably an aqueous solution having a pH of 10 to 15.
• Examples of the alkaline compound contained in the developing solution in alkaline development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, and metasilicate. Examples include potassium silicate, ammonia or amine.
• amines examples include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, and tetramethylammonium hydroxide. (TMAH) or tetraethylammonium hydroxide and the like.
• TMAH tetraethylammonium hydroxide
• an alkaline compound containing no metal is preferable, and an ammonium compound is more preferable.
• the alkaline compound may be only one kind or two or more kinds. When there are two or more alkaline compounds, the total is preferably in the above range.
• the developer contains 90% by mass or more of an organic solvent.
• the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3.
• the ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
• Organic solvents include, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone.
• alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate, etc.)
• 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
• Ke Tons include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and cyclic hydrocarbons include, for example, aromatics such as toluene, xylene and anisole.
• Dimethylsulfoxide is preferably mentioned as the sulfoxides such as hydrocarbons and cyclic terpenes such as limonene.
• cyclopentanone and ⁇ -butyrolactone are particularly preferable, and cyclopentanone is more preferable.
• the developing solution may contain a surfactant.
• the development time is preferably 10 seconds to 5 minutes.
• the temperature of the developing solution at the time of development is not particularly specified, but is usually 20 to 40 ° C.
• rinsing After the treatment with the developing solution, further rinsing may be performed.
• solvent development it is preferable to rinse with an organic solvent different from the developing solution.
• organic solvent for example, propylene glycol monomethyl ether acetate can be mentioned.
• the rinsing time is preferably 5 seconds to 5 minutes.
• a step of applying both a developer and a rinse solution may be included between the development and the rinse.
• the time of the above step is preferably 1 second to 5 minutes.
• rinsing is preferably performed using pure water.
• the rinsing time is preferably 5 seconds to 1 minute.
• the production method of the present invention preferably includes a step (heating step) of heating the developed film.
• the heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step.
• the heating step for example, cyclization of a polyimide precursor or a polybenzoxazole precursor, cross-linking of an unreacted radical cross-linking agent, cross-linking of an unreacted thermal cross-linking agent, and the like can proceed.
• the heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher.
• the upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.
• the heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
• a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
• the temperature at the start of heating is preferably 20 ° C. to 150 ° C., more preferably 20 ° C. to 130 ° C., and even more preferably 25 ° C. to 120 ° C.
• the temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started.
• the thermosetting photosensitive composition when applied onto a substrate and then dried, it is the temperature of the film (layer) after drying, for example, the temperature of the solvent contained in the thermosetting photosensitive composition. It is preferable to gradually raise the temperature from a temperature 30 to 200 ° C. lower than the boiling point.
• the heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.
• the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C. from the viewpoint of adhesion between layers of the cured film. The reason is not clear, but it is considered that the ethynyl groups of the specific resin between the layers are undergoing a cross-linking reaction at this temperature.
• Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed.
• the heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547.
• the pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
• the pretreatment may be performed in two or more steps.
• the pretreatment step 1 may be performed in the range of 100 to 150 ° C.
• the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
• cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
• the heating step is preferably performed in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by performing the heating step in a vacuum, in order to prevent decomposition of the specific resin.
• the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
• the production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (thermosetting photosensitive composition layer).
• metal layer existing metal types can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, copper and aluminum are more preferable, and copper is preferable. More preferred.
• the method for forming the metal layer is not particularly limited, and an existing method can be applied.
• the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used.
• photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining these can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.
• the thickness of the metal layer is preferably 0.1 to 50 ⁇ m, more preferably 1 to 10 ⁇ m in the thickest portion.
• the production method of the present invention preferably further includes a laminating step.
• the laminating step means that (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, and (d) a heating step are performed again on the surface of the cured film (resin layer) or the metal layer. , A series of steps including performing in this order. However, the mode may be such that only the film forming step (a) is repeated. Further, (d) the heating step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated thermosetting photosensitive composition layers all at once. ..
• the (c) developing step may be followed by the (e) metal layer forming step, and even if the heating is performed each time (d), the steps of (d) are collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, the laminating step may further include the above-mentioned drying step, heating step, and the like as appropriate.
• the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step.
• An example of the surface activation treatment is plasma treatment.
• the laminating step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
• the resin layer is 3 or more and 7 or less, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and 3 or more and 5 or less are more preferable.
• thermosetting photosensitive composition layer of the thermosetting photosensitive composition so as to cover the metal layer after providing the metal layer.
• Examples thereof include an embodiment in which the steps, (b) exposure steps, (c) development steps, and (e) metal layer forming steps are repeated in this order, and (d) heating steps are collectively provided at the end or in the middle.
• the present invention also discloses a semiconductor device containing the cured film or laminate of the present invention.
• Specific examples of the semiconductor device in which the thermosetting photosensitive composition of the present invention is used to form the interlayer insulating film for the rewiring layer are described in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-0273557. These contents are incorporated herein by reference.
• PIP-1 Polyimide precursor PIP from oxydiphthalic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate Synthesis of -1] 10.00 g (32.3 mmol) of oxydiphthalic dianhydride (dried at 140 ° C. for 12 hours) and 9.48 g (32.3 mmol) of 3,3', 4,4'-biphenyltetracarboxylic acid Dianoxide (dried at 140 ° C.
• polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred at a rate of 5,000 rpm for 15 minutes.
• the polyimide precursor was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor was dried under reduced pressure at 45 ° C. for 3 days to obtain a polyimide precursor PIP-1.
• PIP-2 Synthesis of polyimide precursor PIP-2 from oxydiphthalic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate
• PIP-1 10.00 g (32.3 mmol) of oxydiphthalic dianhydride and 9.48 g (32.3 mmol) of 3,3', 4,4'-biphenyl.
• the polyimide precursor PIP-2 was prepared by the same method as for the synthesis of the polyimide precursor PIP-1, except that the tetracarboxylic dianhydride was changed to 20.01 g (64.5 mmol) of oxydiphthalic acid dianhydride. Synthesized.
• PI-1 oxydiphthalic acid dianhydride, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 2-isocyanato Synthesis of Polyimide PI-1 from Ethyl Methacrylate] 65.56 g (179 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane while removing water in a drying reactor equipped with a flat bottom joint equipped with a stirrer, condenser and internal thermometer.
• the precipitated polyimide resin was obtained by filtering, washed with 1.5 liters of water, mixed with 2 liters of methanol, stirred again for 30 minutes, and filtered again to obtain a polyimide.
• the obtained polyimide was dried under reduced pressure at 40 ° C. for 1 day to obtain PI-1.
• PI-2 Polyimide from oxydiphthalic dianhydride, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and 1,3-bis (3-aminopropyl) tetramethyldisiloxane] Synthesis of PI-2]
• polyimide PI-1 "After cooling the above reaction solution to 25 ° C., 0.005 g of p-methoxyphenol was added and dissolved. In this solution, 24.82 g (160 mmol) of 2-isocyanatoethyl methacrylate was added. The mixture was added dropwise, stirred at 25 ° C.
• Polyimide PI-2 was synthesized by the same method as the synthesis of polyimide PI-1.
• the precipitated polybenzoxazole was obtained by filtration, washed with 1.5 liters of water, mixed with 2 liters of methanol, stirred again for 30 minutes, and filtered again to obtain polybenzoxazole.
• the obtained polybenzoxazole was dried under reduced pressure at 40 ° C. for 1 day to obtain polybenzoxazole PB-1.
• Examples and Comparative Examples> the components shown in Table 1, Table 2 or Table 3 below were mixed to obtain each thermosetting photosensitive composition. Further, in each comparative example, the components shown in Table 2 below were mixed to obtain each comparative composition. Specifically, the content of the component shown in Table 1, Table 2 or Table 3 was the amount shown in "Mass part” of Table 1, Table 2 or Table 3. Further, in each composition, the solvent content was adjusted so that the solid content concentration of the composition was the value shown in Table 1, Table 2 or Table 3. The description in the column of "metal concentration" in Table 1, Table 2 or Table 3 represents the metal content (mass ppm) with respect to the total mass of the composition.
• thermosetting photosensitive composition and comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 ⁇ m. Further, in Table 1, Table 2 or Table 3, the description of "-" indicates that the composition does not contain the corresponding component.
• [Radical cross-linking agent] -B-1 Tetraethylene glycol dimethacrylate-B-2: Dipentaerythritol hexaacrylate-B-3: Light ester BP-6EM (manufactured by Kyoei Kagaku Co., Ltd.)
• D-1 IRGACURE OXE 01 (manufactured by BASF)
• D-2 ADEKA NCI-930 (manufactured by ADEKA Corporation)
• D-3 Compounds with the following structures (2: 1 description represents the molar ratio of each structure) The above D-3 was synthesized according to the synthesis method described in International Publication No. 2017/217292.
• ⁇ Silane coupling agent ⁇ -F-1 N- (3- (triethoxysilyl) propyl) phthalamic acid-F-2: IM-1000 (manufactured by JX Nippon Mining & Metals Co., Ltd.)
• F-3 Benzophenone-3,3'-bis (N- (3-triethoxysilyl) propylamide) -4,4'-dicarboxylic acid
• G-1 A compound having the following structure
• thermosetting photosensitive composition or the comparative composition was applied to a flat 4-inch silicon wafer by a slit coating method, respectively, and on a hot plate.
• the thermosetting photosensitive layer A having a film thickness of 150% of the thickness shown in the “Film thickness ( ⁇ m)” column of Table 1, Table 2 or Table 3 and the table after drying at 80 ° C. for 5 minutes. 1.
• a thermosetting photosensitive layer B having a film thickness of 50% of the thickness described in the “Film thickness ( ⁇ m)” column of Table 2 or Table 3 was formed.
• thermosetting photosensitive layer A was heated at 250 ° C. for 120 minutes to prepare a cured film A. Then, the contact angle of water of the cured film A and the contact angle of diiodomethane were measured, and the surface free energy A (mJ / m 2 ) was calculated from these contact angles using the formula (1). In each of the Examples and Comparative Examples, the surface free energy B (mJ / m 2 ) was calculated for the thermosetting photosensitive layer B by the same method as the surface free energy A.
• a pattern consisting of OFPR is formed by forming a repeating pattern in which one step is arranged every 50 ⁇ m in both the vertical direction and the horizontal direction, and this pattern is dry-etched using an etching device (RIE-10N manufactured by SAMCO) as a mask.
• thermosetting photosensitive composition or a comparative composition was applied onto the stepped substrate by a slit coating method to form a resin layer 1.
• the thermosetting photosensitive composition was applied onto the stepped substrate by the spin coating method to form the resin layer 1, respectively.
• the stepped substrate to which the obtained resin layer 1 was applied was dried on a hot plate at 80 ° C. for 5 minutes, and the average thickness was "film thickness ( ⁇ m)) of Table 1, Table 2 or Table 3 on the stepped substrate.
• the thermosetting photosensitive layer 1 having the thickness described in the column of "" was obtained.
• thermosetting photosensitive layer 1 was exposed to i-rays with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C).
• the stepped substrate on which the thermosetting photosensitive layer 1 was formed after exposure was heated at 100 ° C. for 5 minutes on a hot plate.
• the exposed thermosetting photosensitive layer 1 was heated at a heating rate of 10 ° C./min under a nitrogen atmosphere to reach the temperature described in the “Cure temperature” column of Table 1, Table 2 or Table 3. After that, during the "cure time” of Table 1, Table 2 or Table 3, the temperature was maintained at the temperature described in the "Cure temperature” column and heated to obtain a cured film 1.
• thermosetting photosensitive composition used for forming the resin layer 1 or the same composition as the comparative composition was applied again to the surface of the obtained cured film 1 by the slit coating method to form the resin layer 2. ..
• the stepped substrate to which the obtained resin layer 2 is applied is dried on a hot plate at 80 ° C. for 5 minutes, and described on the stepped substrate in the “Film thickness ( ⁇ m)” column of Table 1, Table 2 or Table 3.
• a thermosetting photosensitive layer 2 having an average thickness of 2 was obtained.
• the thermosetting photosensitive layer 2 was subjected to i-ray exposure and heating in the same manner as the thermosetting photosensitive layer 1 to obtain a cured film 2.
• the surface roughness Ra of the cured film 2 was 50 ⁇ m ⁇ 50 ⁇ m of the surface including the portion having a step and the portion having no step in the vertical direction of the cured film 2 using an atomic force microscope Dimension FastScan AFM (manufactured by Bruker). It was obtained by measuring the range of.
• the evaluation results are described in the column of "Substrate step suitability" in Table 1, Table 2 or Table 3. It can be said that the less the occurrence of striations and the smaller the surface roughness Ra, the more the occurrence of coating defects is suppressed.
• thermosetting photosensitive composition or a comparative composition was applied onto the stepped substrate by a slit coating method to form a resin layer 1.
• thermosetting photosensitive composition was applied onto the stepped substrate by the spin coating method to form the resin layer 1, respectively.
• the stepped substrate on which the resin layer was formed was dried on a hot plate at 80 ° C. for 5 minutes, and the average thickness described in the “Film thickness ( ⁇ m)” column of Table 1, Table 2 or Table 3 on the stepped substrate.
• the thermosetting photosensitive layer 1 was formed.
• thermosetting photosensitive layer 1 was exposed to i-rays with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C).
• the stepped substrate on which the thermosetting photosensitive layer 1 was formed after exposure was heated at 100 ° C. for 5 minutes on a hot plate.
• the exposed thermosetting photosensitive layer 1 was heated at a heating rate of 10 ° C./min under a nitrogen atmosphere to reach the temperature described in the “Cure temperature” column of Table 1, Table 2 or Table 3. After that, during the "cure time” of Table 1, Table 2 or Table 3, the temperature was maintained at the temperature described in the "Cure temperature” column and heated to obtain a cured film 1.
• thermosetting photosensitive composition used for forming the resin layer 1 or the same composition as the comparative composition was applied again to the surface of the obtained cured film 1 by the slit coating method to form the resin layer 2. ..
• the stepped substrate to which the obtained resin layer 2 is applied is dried on a hot plate at 80 ° C. for 5 minutes, and described on the stepped substrate in the “Film thickness ( ⁇ m)” column of Table 1, Table 2 or Table 3.
• a thermosetting photosensitive layer 2 having an average thickness of 2 was obtained.
• the thermosetting photosensitive layer 2 was exposed to light using a stepper (Nikon NSR 2005 i9C) to obtain a thermosetting photosensitive layer after exposure.
• the exposure was performed using i-rays, and the exposure amount at a wavelength of 365 nm was 400 mJ / cm 2 .
• a photomask having a 1: 1 line-and-space pattern with a line width of 10 ⁇ m was used.
• the exposure was performed so that the line and space pattern crossed the stepped portion.
• the stepped substrate on which the thermosetting photosensitive layer 2 was formed after exposure was heated at 100 ° C. for 5 minutes on a hot plate.
• cyclopentanone was used for 60 seconds.
• a cured film containing at least one resin, photosensitizer, surfactant and solvent selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor according to the present invention Absolute difference between the surface free energy of the cured film A and the surface free energy of the cured film B calculated using the equation (1) from the contact angle of water and the contact angle of diiodomethane with respect to the surface of A and the surface of the cured film B, respectively.
• thermosetting photosensitive composition whose value is 30% or less of the surface free energy of the cured film A
• a cured film is prepared by applying it to a non-uniform substrate, and the cured film is formed on the obtained cured film. It can be seen that the occurrence of defects in the other layers is suppressed even when the other layers are further formed.
• the thermosetting photosensitive composition according to Comparative Example 1 and Comparative Example 2 does not contain a surfactant.
• the absolute value of the difference between the surface free energy of the cured film A and the surface free energy of the cured film B exceeds 30% of the surface free energy of the cured film A.
• thermosetting photosensitive compositions according to Comparative Examples 1 to 3 are applied to a non-uniform substrate to prepare a cured film, and another layer is further formed on the obtained cured film. In this case, it can be seen that the occurrence of defects in the other layers is not suppressed.
• thermosetting photosensitive composition used in Example 1 was applied in layers to the surface of the copper thin layer of the resin substrate having the copper thin layer formed on the surface by a spin coating method, and dried at 80 ° C. for 5 minutes. Then, a thermosetting photosensitive composition layer having a thickness of 30 ⁇ m was formed, and then exposed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed at a wavelength of 365 nm via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m). After exposure, it was developed with cyclopentanone for 60 seconds and rinsed with PGMEA for 20 seconds to obtain a layer pattern.
• the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 180 ° C., the temperature was maintained at 180 ° C. for 120 minutes to form an interlayer insulating film for the rewiring layer.
• the interlayer insulating film for the rewiring layer was excellent in insulating property. Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

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