WO2020226052A1 - Photosensitive resin composition, resin film, and electronic device - Google Patents
Photosensitive resin composition, resin film, and electronic device Download PDFInfo
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- WO2020226052A1 WO2020226052A1 PCT/JP2020/017228 JP2020017228W WO2020226052A1 WO 2020226052 A1 WO2020226052 A1 WO 2020226052A1 JP 2020017228 W JP2020017228 W JP 2020017228W WO 2020226052 A1 WO2020226052 A1 WO 2020226052A1
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- resin composition
- photosensitive resin
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- 0 C*(C)C(C(*(C)C)C(O1)=O)C1=O Chemical compound C*(C)C(C(*(C)C)C(O1)=O)C1=O 0.000 description 2
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
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- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- 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
Definitions
- the present invention relates to a photosensitive resin composition, a resin film, and an electronic device. More specifically, the present invention relates to a photosensitive resin composition, a resin film made of a cured product of the photosensitive film-forming composition, and an electronic device including the resin film as a permanent film.
- Patent Document 1 describes a monomer having a cyclic hydrocarbon group, an unsaturated polybasic acid anhydride such as maleic anhydride, a copolymerizable monomer such as vinyl toluene, and a monomer having a hydroxyl group.
- a photosensitive resin composition containing a polymer and a color filter formed from a cured film of the resin composition are disclosed.
- the present inventors have found that by using a copolymer containing a specific structural unit as a base resin, a photosensitive resin composition in which the cured product has high transparency and excellent heat-resistant discoloration can be obtained.
- the present invention has been reached.
- l and m indicate the molar content of A and B in the copolymer, respectively.
- l + m 1
- X is hydrogen or an organic group having 1 or more and 30 or less carbon atoms.
- Y is ⁇ SR 5a
- S is a sulfur atom, and R 5a is an organic group having 1 or more and 30 or less carbon atoms.
- A includes a structural unit represented by the following formula (A1).
- B comprises at least one of the structural units represented by the formulas (B1)-(B6):
- R 1 , R 2 , R 3 and R 4 are each independently hydrogen or an organic group having 1 or more and 30 or less carbon atoms or an ethylenic double bond having 1 or more and 30 or less carbon atoms. It is an organic group, and n is 0, 1 or 2.
- R 5 is the number 1 to 30 of the organic group having a carbon having an organic group or ethylenic double bond of 1 to 30 carbon atoms.
- R 6 and R 7 are independent organic groups having 1 or more and 30 or less carbon atoms or organic groups having 1 or more and 30 or less carbon atoms having an ethylenic double bond.
- R 8 is an organic group having 1 to 30 carbon atoms or an organic group having an ethylenic double bond and having 1 to 30 carbon atoms.
- at least one of the structural unit represented by the formula (A1) and the structural unit represented by the formulas (B1) to (B6) contained in the formula (1) has an ethylenic double bond. It has 1 or more and 30 or less organic groups. ).
- a resin film made of a cured film of the above-mentioned photosensitive resin composition is provided.
- an electronic device provided with the above resin film is provided.
- an electronic device including a photosensitive resin composition in which the cured product has excellent transparency, a resin film made of the cured product of the photosensitive resin composition, and the resin film as a permanent film.
- electronic device refers to an element to which electronic engineering technology is applied, such as a semiconductor chip, a semiconductor element, a printed wiring board, an electric circuit display device, an information communication terminal, a light emitting diode, a physical battery, and a chemical battery. , Devices, final products, etc.
- the photosensitive resin composition of the present embodiment contains a copolymer represented by the general formula (1), a cross-linking agent, and a photosensitive agent.
- l and m indicate the molar content of A and B in the copolymer, respectively.
- l + m 1
- X is hydrogen or an organic group having 1 or more and 30 or less carbon atoms.
- Y is ⁇ SR 5a
- R 5a is an organic group having 1 or more and 30 or less carbon atoms.
- A includes a structural unit represented by the following formula (A1).
- B contains at least one of the structural units represented by the formulas (B1) to (B6).
- R 1 , R 2 , R 3 and R 4 are independently hydrogen or an organic group having 1 to 30 carbon atoms or an organic group having an ethylenic double bond having 1 to 30 carbon atoms.
- n is 0, 1 or 2.
- R 5 is 1 to 30 organic group having a carbon number having an organic group or ethylenic double bond of 1 to 30 carbon atoms.
- R 6 and R 7 are independent organic groups having 1 or more and 30 or less carbon atoms or organic groups having 1 or more and 30 or less carbon atoms having an ethylenic double bond.
- R 8 is an organic group having 1 to 30 carbon atoms or an organic group having an ethylenic double bond and having 1 to 30 carbon atoms.
- at least one of the structural unit represented by the formula (A1) included in the general formula (1) and the structural unit represented by the formulas (B1) to (B6) has an ethylenic double bond and has 1 carbon atom. It has more than 30 organic groups.
- the copolymer of the present embodiment contains a structural unit having an ethylenic double bond and having an organic group having 1 to 30 carbon atoms as an essential component.
- the photosensitive resin composition of the present embodiment has various properties required for the photosensitive resin composition such as adhesion to a support, resolution, and heat resistance, and also has various properties.
- the cured product has excellent transparency, and the transparency is maintained without coloring or clouding when used in a high temperature environment.
- a photosensitive resin composition applied to a photolithography method a composition containing a cyclic olefin monomer and a copolymer obtained by polymerizing a plurality of types of monomers including maleic anhydride has been known.
- a conventional photosensitive resin composition has functions as a photosensitive material such as alkali solubility, processability, and heat resistance, the resin film obtained by curing the composition is colored.
- the present inventor has found that the cause of coloring of the cured product is due to the structural unit derived from maleic anhydride in the copolymer.
- the copolymer used in the present embodiment contains a structural unit derived from norbornene monomer or maleic anhydride having an organic group having an ethylenic double bond and having 1 to 30 carbon atoms, and -SR 5a at the end thereof. It has a group (S represents a sulfur atom).
- a copolymer having such a structure it has functions as a photosensitive material such as alkali solubility, processability, and heat resistance, and the cured product has high transparency, and is subjected to heat treatment or a high temperature environment. It is possible to obtain a photosensitive resin composition having excellent heat-resistant discoloration property in which a decrease in transparency due to use in the above is reduced.
- the copolymer used in the photosensitive resin composition of the present embodiment has a structure represented by the general formula (1).
- l and m indicate the molar content of A and B in the copolymer, respectively.
- l + m 1
- X is hydrogen or an organic group having 1 or more and 30 or less carbon atoms.
- Y is ⁇ SR 5a
- S is a sulfur atom, and R 5a is an organic group having 1 or more and 30 or less carbon atoms.
- A includes a structural unit represented by the following formula (A1).
- B contains at least one of the structural units represented by the formulas (B1) to (B6).
- the arrangement of the structural units A and B in the above-mentioned copolymer is not limited, and may take the form of a random copolymer, a cross-polymer, a block copolymer, or a periodic copolymer.
- composition ratio of the structural unit A and the structural unit B in the above copolymer will be described.
- molar content (mol%) of the structural unit of A in the copolymer is l and the molar content (mol%) of the structural unit of B is m
- l + m 1, for example, a numerical value of l.
- the range is preferably 0.1 ⁇ l ⁇ 0.9.
- the numerical range of m is preferably 0.1 ⁇ m ⁇ 0.9.
- the structural unit A includes a structural unit derived from the norbornene monomer represented by the formula (A1).
- R 1 , R 2 , R 3 and R 4 are independently hydrogen or an organic group having 1 to 30 carbon atoms or an organic group having an ethylenic double bond having 1 to 30 carbon atoms.
- n is 0, 1 or 2.
- the organic groups having 1 to 30 carbon atoms or the organic groups having an ethylenic double bond and having 1 to 30 carbon atoms constituting R 1 to R 4 in the general formula (A1) are independent of each other.
- the structure may contain one or more atoms selected from O (oxygen atom), N (nitrogen atom), S (sulfur atom), P (phosphorus atom) and Si (silicon atom).
- none of the organic groups constituting R 1 , R 2 , R 3 and R 4 can have an acidic functional group. This makes it possible to easily control the acid value in the copolymer.
- R 1 to R 4 in the above formula (A1) are independently hydrogen, an organic group having 1 or more and 30 or less carbon atoms, or an organic group having an ethylenic double bond and having 1 or more and 30 carbon atoms or less. It is an organic group, preferably hydrogen or an organic group having 1 or more and 15 or less carbon atoms or an organic group having an ethylenic double bond having 1 or more and 15 or less carbon atoms, and hydrogen or an organic group having 1 or more and 10 or less carbon atoms. Alternatively, it is more preferably an organic group having an ethylenic double bond and having 1 or more and 10 or less carbon atoms.
- examples of the organic group having 1 or more and 30 or less carbon atoms include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkalil group, a cycloalkyl group, an alkoxy group and a heterocyclic group. Can be mentioned.
- alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group and heptyl group. , Octyl group, nonyl group, and decyl group.
- Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group.
- alkynyl group examples include an ethynyl group.
- alkylidene group examples include a methylidene group and an ethylidene group.
- Examples of the aryl group include a tolyl group, a xsilyl group, a phenyl group, a naphthyl group, and an anthrasenyl group.
- Examples of the aralkyl group include a benzyl group and a phenethyl group.
- Examples of the alkaline group include a tolyl group and a xylyl group.
- Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
- alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, an isobutoxy group and a t-butoxy group, an n-pentyloxy group and a neopentyloxy group.
- N-hexyloxy group examples include an epoxy group and an oxetanyl group.
- organic group having an ethylenic double bond having 1 to 30 carbon atoms include an allyl group, an acrylic group, a methacryl group, a maleimide group, a styryl group, an aromatic vinyl group such as an indenyl group, and the like. ..
- n in the above formula (A1) is 0, 1 or 2, and may be 0 or 1, or may be 0.
- the structural unit B includes at least one of the structural units represented by the formulas (B1) to (B6).
- R 5 is 1 to 30 organic group having a carbon number having an organic group or ethylenic double bond of 1 to 30 carbon atoms.
- R 6 and R 7 are independent organic groups having 1 or more and 30 or less carbon atoms or organic groups having 1 or more and 30 or less carbon atoms having an ethylenic double bond.
- R 8 is an organic group having 1 to 30 carbon atoms or an organic group having an ethylenic double bond and having 1 to 30 carbon atoms.
- the general formula (B1), the general formula (B2) and the general formula (B6) R 5 ⁇ having 1 or more carbon atoms with organic groups or ethylenic double bond of one to 30 carbon atoms constituting the R 8 in 30
- the following organic groups may contain one or more atoms selected from O, N, S, P and Si in their structure. Further, in the present embodiment, none of the organic groups constituting R 5 to R 8 can have an acidic functional group such as a carboxyl group. This makes it possible to easily control the acid value in the copolymer.
- R 5 to R 8 in the general formula (B1), the general formula (B2) and the general formula (B6) are independently organic groups having 1 or more and 30 or less carbon atoms or ethylenic di. It is preferably an organic group having a heavy bond having 1 or more and 30 or less carbon atoms, preferably an organic group having 1 or more and 15 carbon atoms or less, or an organic group having an ethylenic double bond and having 1 or more carbon atoms and 15 or less carbon atoms.
- the organic group has 1 or more and 10 or less or an ethylenic double bond and has 1 or more and 10 or less carbon atoms, and the organic group has 1 or more and 6 or less carbon atoms or an ethylenic double bond. It is more preferable that the number of organic groups is 1 or more and 6 or less.
- examples of the organic group constituting R 5 to R 8 in the above formula (B1), formula (B2) and formula (B6) include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group and an aryl group.
- examples include groups, aralkyl groups, alkaline groups, cycloalkyl groups, alkoxy groups and heterocyclic groups.
- alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group and heptyl group. , Octyl group, nonyl group, and decyl group.
- Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group.
- alkynyl group examples include an ethynyl group.
- alkylidene group examples include a methylidene group and an ethylidene group.
- Examples of the aryl group include a tolyl group, a xsilyl group, a phenyl group, a naphthyl group, and an anthrasenyl group.
- Examples of the aralkyl group include a benzyl group and a phenethyl group.
- Examples of the alkaline group include a tolyl group and a xylyl group.
- Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
- alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, an isobutoxy group, a t-butoxy group, an n-pentyloxy group and a neopentyloxy group.
- alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, an isobutoxy group, a t-butoxy group, an n-pentyloxy group and a neopentyloxy group.
- heterocyclic group examples include an epoxy group and an oxetanyl group.
- the above formula (B1), specific examples of the formula (B2) and the number 1 to 30 of the organic group having a carbon having an ethylenic double bond which constitutes the R 5 ⁇ R 8 in the formula (B6) examples include aromatic vinyl groups such as allyl group, acrylic group, methacryl group, maleimide group, styryl group and indenyl group.
- At least one of the structural units represented by the formula (A1) and the structural units represented by the formulas (B1) to (B6) contained in the formula (1) has an ethylenic double bond. It has an organic group having 1 or more and 30 or less carbon atoms.
- X is hydrogen or an organic group having 1 or more and 30 or less carbon atoms.
- the organic group having 1 or more and 30 or less carbon atoms is the same as the above-mentioned organic group having 1 or more and 30 or less carbon atoms constituting R 1 to R 4 or R 5 to R 8 .
- Y is a group represented by ⁇ SR 5a
- S is a sulfur atom
- R 5a is an organic group having 1 or more and 30 or less carbon atoms.
- the organic group having 1 or more and 30 or less carbon atoms may contain one or more atoms selected from O, N, S, P and Si.
- Examples of the organic group having 1 to 30 carbon atoms constituting R 5 include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkalil group, a cycloalkyl group, an alkoxy group and a heterocyclic group. Can be mentioned.
- alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group and heptyl group. , Octyl group, nonyl group, and decyl group.
- Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group.
- alkynyl group examples include an ethynyl group.
- alkylidene group examples include a methylidene group and an ethylidene group.
- Examples of the aryl group include a tolyl group, a xsilyl group, a phenyl group, a naphthyl group, and an anthrasenyl group.
- Examples of the aralkyl group include a benzyl group and a phenethyl group.
- Examples of the alkaline group include a tolyl group and a xylyl group.
- Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
- alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, an isobutoxy group, a t-butoxy group, an n-pentyloxy group and a neopentyloxy group.
- alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, an isobutoxy group, a t-butoxy group, an n-pentyloxy group and a neopentyloxy group.
- heterocyclic group examples include an epoxy group and an oxetanyl group.
- Y may include a structural unit derived from a radical polymerization initiator, hydrogen, or a structural unit derived from a chain transfer agent, and is derived from a structural unit derived from a radical polymerization initiator, hydrogen, or a chain transfer agent. It may be a structural unit. This is because when a radical polymerization initiator is used as the polymerization initiator when synthesizing the copolymer represented by the general formula (1), Y can be formed by the termination reaction of the radical chain reaction which is a polymerization reaction. Because.
- Y derived from the chain transfer agent is -SR 5a .
- S represents a sulfur atom
- R 5a is a linear or branched hydrocarbon group having 1 to 15 carbon atoms or an organic group having 1 to 15 carbon atoms.
- -SR 5a is a compound represented by the formula (Y1-a) or the formula (Y2-a); alkanethiols such as 1-butanethiol, 1-octanethiol, 1-decanethiol; mercaptoacetic acid, 3-mercapto.
- Thiocarboxylic acids such as propionic acid; thiocarboxylic acid esters such as ethyl mercaptoacetate, 2-ethylhexyl mercaptoacetate, 2-ethylhexyl 3-mercaptopropionic acid; polyvalent thiols such as trimethylpropanthris (3-mercaptopropionate) It can be introduced into the copolymer of the formula (1) by using the above.
- Y in the formula (1) when a copolymer is prepared by using the compound represented by the above formula (Y1-a) as a chain transfer agent, Y in the formula (1) has a structure represented by the formula (Y1). Coalescence is obtained. Further, when a copolymer is prepared by using the compound represented by the above formula (Y2-a) as a chain transfer agent, Y in the formula (1) has a structure represented by the formula (Y2). Coalescence is obtained.
- the lower limit of Mw (weight average molecular weight) of the copolymer may be, for example, 1500 or more, 2000 or more, preferably 2500 or more, and preferably 3000 or more, from the viewpoint of forming an appropriate crosslinked structure. The above is more preferable.
- the upper limit of Mw of the copolymer may be, for example, 30,000 or less, preferably 25,000 or less, and more preferably 20,000 or less.
- the upper limit of the polydispersity of the copolymer according to the present embodiment makes the physical properties of each molecular chain of the copolymer uniform, and the shape of the resin film made of the photosensitive resin composition containing the copolymer is good.
- it is preferably 2.5 or less, preferably 2.2 or less, more preferably 2.0 or less, and even more preferably 1.5 or less.
- the lower limit value of the polydispersity of the copolymer is preferably 1.0 or more, for example.
- the degree of polydispersity is represented by Mw (weight average molecular weight) / Mn (number average molecular weight), and means the degree of dispersion indicating the width of the molecular weight distribution.
- Mw weight average molecular weight
- Mn number average molecular weight
- Mw / Mn molecular weight distribution
- PS standard polystyrene
- the peak area at a molecular weight of 1000 or less may be 1% or less of the whole.
- the ratio of the peak area of the molecular weight distribution curve obtained by GPC to the molecular weight of 1000 or less within the above range the pattern shape of the film made of the resin composition containing the copolymer can be improved. it can. Therefore, it is possible to improve the operation reliability of a liquid crystal display device and a solid-state image sensor having the film as a permanent film.
- the lower limit of the amount of the low molecular weight component in the copolymer is not limited.
- the copolymer according to the present embodiment allows a case where the peak area at a molecular weight of 1000 or less is 0.01% or more of the whole in the molecular weight distribution curve obtained by GPC.
- the amount of the low molecular weight component in the copolymer is calculated from the ratio of the total area of the components corresponding to the molecular weight of 1000 or less to the total area of the molecular weight distribution based on the data on the molecular weight obtained by, for example, GPC measurement. ..
- the alkali dissolution rate of the copolymer in this embodiment is, for example, 300 ⁇ / sec or more and 20,000 ⁇ / sec or less, more preferably 500 ⁇ / sec or more and 25,000 ⁇ / sec or less.
- the alkali dissolution rate of the copolymer in this embodiment is, for example, 20,000 ⁇ / sec or less.
- the alkali dissolution rate of the copolymer is, for example, a copolymer solution prepared by dissolving the copolymer in propylene glycol monomethyl ether acetate and adjusting the solid content to 20% by weight, and applying the copolymer solution on a silicon wafer by a spin method.
- the copolymer film obtained by soft-baking at 110 ° C. for 100 seconds is impregnated with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C., and the time until the copolymer film is visually erased is allowed. Calculated by measuring
- the alkali dissolution rate of the copolymer By setting the alkali dissolution rate of the copolymer to the above lower limit or higher, the throughput in the developing process using the alkaline developer can be improved. Further, by setting the alkali dissolution rate of the copolymer to the above upper limit or less, the residual film ratio after the development step with the alkaline developer can be improved. Therefore, it is possible to suppress film loss due to the lithography process.
- a monomer is polymerized by a polymerization step to prepare a copolymer, and then a low molecular weight component is removed by a low molecular weight component removing step, and the copolymer is the main component. It is prepared by the method of obtaining the copolymer. It will be described in detail below.
- a norbornene-type monomer (A) and one or more selected from the group consisting of maleic anhydride (B), maleimide (C), and maleimide derivative (D) are prepared. Further, one type of norbornene type monomer may be prepared, or two or more types may be prepared.
- the structural unit A is derived from the norbornene-type monomer (A)
- the structural unit B is maleic anhydride (B), maleimide (C) or maleimide derivative (D).
- norbornene-type monomer represented by the formula (A) include bicyclo [2.2.1] -hept-2-ene (common name: 2-norbornene), and more specifically, the norbornene type monomer.
- Alkenyl groups such as 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, etc. have an alkyl group.
- alkynyl group such as 5-allyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, etc.
- 5-Ethynyl-2-norbornene and the like having an aralkyl group include 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene and the like.
- the norbornene-type monomer an organic group having the above-mentioned ethylenic double bond and having 1 to 30 carbon atoms or less is used in the structure of the groups of R 1 , R 2 , R 3 , and R 4 of the formula (A). What you have can be adopted.
- the monomer represented by the formula (A) and the monomer represented by the formula (B), the monomer represented by the formula (C), or the monomer represented by the formula (D) are subjected to the above-mentioned chain transfer agent. Addition polymerization with.
- a copolymer of these monomers (copolymer 1) is formed by radical polymerization.
- the polymerization method for example, a method of polymerizing using a radical polymerization initiator and, if necessary, a molecular weight modifier is preferable.
- methods such as suspension polymerization, solution polymerization, dispersion polymerization, and emulsion polymerization can be used.
- solution polymerization is preferable.
- all the monomers may be charged in a batch, or a part thereof may be charged in a reaction vessel and the rest may be dropped.
- a monomer represented by the formula (A), a monomer represented by the formula (B), a monomer represented by the formula (C), and a monomer represented by the formula (D) are used as a solvent with a polymerization initiator.
- a polymerization initiator By dissolving and then heating for a predetermined time, the norbornene-type monomer represented by the formula (A), maleic anhydride, and maleimide are solution-polymerized.
- the heating temperature is, for example, 50 to 80 ° C., and the heating time is 10 to 20 hours.
- solvent used for the polymerization examples include diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, ethyl acetate and the like, and any one or more of these can be used.
- radical polymerization initiator examples include azo compounds and organic peroxides, and any one or more of these can be used.
- examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis (2-methylpropionate), and 1,1'-azobis (cyclohexanecarbonitrile) (ABCN). , Any one or more of these can be used.
- examples of the organic peroxide include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). Of these, any one or more can be used.
- the amount (number of moles) of the radical polymerization initiator is preferably 1 mol% to 10 mol% with respect to the total amount of the monomers used.
- the structural unit represented by the following formula (A1), the structural unit represented by the following formula (B3), the structural unit represented by the following formula (B5), and the following formula (B6) are represented.
- the copolymer 1 having the structural unit to be polymerized can be polymerized.
- R 1 having the structure of the formula (A1) is common to each repeating unit, but it may be different for each repeating unit. The same applies to R 2 ⁇ R 4, R 8 .
- n, R 1 ⁇ R 4 and R 8 are the same as defined above.
- the copolymer 1 may have the structural units (A1), (B3), (B5) and (B6) randomly arranged, or may be alternately arranged. .. Further, the structural units (A1), (B3), (B5) and (B6) may be block copolymerized.
- the copolymer 1 is preferably an alternating copolymer from the viewpoint of obtaining uniform solubility of the photosensitive resin composition.
- the copolymer By reducing the amount of low molecular weight components in the copolymer, it is possible to suppress the deformation of the pattern of the film formed by the copolymer at the time of curing, and the film made of a photosensitive resin composition containing the copolymer.
- the pattern shape of the above can be made good. It is possible to improve the operation reliability of a liquid crystal display device or a solid-state image sensor that includes the film as a permanent film.
- the repeating units derived from maleic anhydride of the copolymer 1 for example, it is preferable to open the ring of 60% or less of the repeating unit, and open the ring of 50% or less of the repeating unit. Is more preferable. Within the above range, it becomes easy to impart a sufficient alkaline developer to the copolymer 1 and to allow the cross-linking reaction by the photoradical generator to proceed more efficiently.
- an alcohol represented by R 5- OH (where R 5 is synonymous with the above) or water is allowed to act on the structural unit derived from maleic anhydride, and the above formula (2) is used.
- the maleic anhydride moiety of the indicated structural unit is opened to form a carboxyl group or a salt thereof in the precursor polymer.
- R 5 is 1 to 30 organic group having a carbon number having an organic group or ethylenic double bond of 1 to 30 carbon atoms.
- the structure represented by the formula (B2) may be formed.
- R 6 and R 7 are independent organic groups having 1 or more and 30 or less carbon atoms or organic groups having 1 or more and 30 or less carbon atoms having an ethylenic double bond.
- This step can be performed, for example, by adding a predetermined amount of alcohol or water to the solution containing the copolymer 1 and heating the solution.
- the alcohol can be R 5 OH, and the organic group R 5 can be the one described above.
- examples of the alcohol include allyl alcohol, metallic alcohol, 3-butene-1-ol, 3-methyl-3-butene-1-ol, 4-pentene-1-ol, 5-hexene-1-ol, 6 -Heptene-1-ol, 7-octen-1-ol, 8-nonen-1-ol, 9-decene-1-ol, 10-undecene-1-ol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate , Hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate, and 1,4-cyclohexanedimethanol monomethacrylate, any of these.
- One or more can be used.
- the solvent for dissolving the precursor polymer can be appropriately selected from those that do not inhibit the reaction, and the heating conditions can be set, for example, in the range of 50 to 100 ° C.
- the reaction time can be appropriately set while observing the degree of change in the chemical structure of the polymer.
- the solvent used in this step include diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, ethyl acetate and the like as highly versatile solvents, and any one or more of these can be used. ..
- a catalyst can be appropriately added from the viewpoint of accelerating the reaction, and for example, a base catalyst or an acid catalyst can be added.
- a base catalyst pyridine, alkylamines such as triethylamine, amine compounds such as dimethylaniline, urotropin and dimethylaminopyridine, and metal salts such as sodium acetate can be used.
- the acid catalyst mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as paratoluenesulfonic acid, and Lewis acids such as boron trifluoride etherate can be used.
- the copolymer obtained by the present embodiment can be preferably used for forming a photosensitive resin film because of the specificity of the chemical performance contained in this structural unit.
- the “photosensitive resin film” refers to a resin film that is subjected to an exposure process in the manufacturing process of an electronic device or the like.
- a negative type photosensitive resin in which a portion irradiated with light is cured, while a portion not irradiated is dissolved and removed in a developing solution.
- a developing solution for example, an alkaline solution
- the cross-linking agent is not limited as long as it is a compound containing a functional group that reacts with the active hydrogen of the copolymer.
- the functional group that reacts with the active hydrogen of the copolymer preferably contains, for example, one or more selected from the group consisting of a glycidyl group, an oxetanyl group, and a blocked isocyanate group, and includes a glycidyl group or an oxetanyl group. It is more preferable, and it is more preferable to contain a glycidyl group. Thereby, an appropriate crosslinked structure can be formed.
- the photosensitive resin composition one kind or two or more kinds selected from a compound having a blocked isocyanate group, an epoxy compound and an oxetane compound can be used in combination.
- Examples of the compound having a glycidyl group used as a cross-linking agent include allyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, and bisphenol A.
- glycidyl ether such as glycidyl ether, adipic acid diglycidyl ester, glycidyl ester such as o-phthalic acid diglycidyl ester, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, 3 , 4-epoxy-6-methylcyclohexylmethyl (3,4-epoxy-6-methylcyclohexane) carboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentanediene oxide, bis (2) , 3-Epoxycyclopentyl) Ether and alicyclic epoxy such as Celoxide 2021, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 8000, Epolide GT401, 2,2'-(((((1- (1-(1-) 4- (2- (4- (Oxylan-2-yl)
- Aromatic glycidyl ether, 1,1,3,3,5,5-hexamethyl-1,5-bis (3- (oxylan-2-ylmethoxy) propyl) trisiloxane (for example, DMS-E09 (manufactured by Gerest)) Etc. can be used.
- bisphenol A such as LX-01 (manufactured by Daiso), jER1001, 1002, 1003, 1004, 1007, 1009, 1010, 828, jER825 (trade name; manufactured by Mitsubishi Chemical Corporation).
- Type epoxy resin bisphenol F type epoxy resin such as jER807 (trade name; manufactured by Mitsubishi Chemical Co., Ltd.), jER152, 154 (trade name; manufactured by Mitsubishi Chemical Co., Ltd.), EPPN201, 202 (trade name; manufactured by Nippon Kayaku Co., Ltd.)
- Phenolic novolac type epoxy resin such as EOCN102, 103S, 104S, 1020, 1025, 1027 (trade name; manufactured by Nippon Kayaku Co., Ltd.), jER157S70 (trade name; manufactured by Mitsubishi Chemical Co., Ltd.)
- Araldite CY179, 184 (trade name; manufactured by Huntsman Advanced Materials), ERL-4206, 4221, 4234, 4299 (trade name; manufactured by Dow Chemical), Epicron 200,
- Examples of the compound having an oxetane group used as a cross-linking agent include 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene and bis [1-ethyl (3-oxetanyl)] methyl ether.
- the compound having a blocked isocyanate group used as a cross-linking agent is not limited, and examples thereof include a compound in which the isocyanate group of a polyfunctional isocyanate is protected by a blocking agent.
- the polyfunctional isocyanate is an organic compound having a plurality of isocyanate groups in one molecule.
- examples of the polyfunctional isocyanate include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4.
- the blocking agent examples include alcohol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, urea compounds, and oximes. Examples thereof include one or more selected from system compounds, amine compounds, imine compounds, heavy sulfites, pyridine compounds and the like.
- blocking agent examples include oxime, ethanol, propanol, butanol, 2-ethylhexanol, methylcellosolve, butylcellosolve, methylcarpitol, benzyl alcohol, cyclohexanol and the like.
- Alcor compounds such as phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, hydroxybenzoic acid ester; malonic acid Active methylene compounds such as dimethyl, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone; mercaptan compounds such as butyl mercaptan and dodecyl mercaptan; acetoanilide, acetate, ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam Oxime-based compounds such as; oxyimide-based compounds such as succinateimide and maleateimide; imidazole-based compounds such as imidazole and 2-methylimidazole; urea-based compounds such as urea, thiourea and ethyleneurea.
- malonic acid Active methylene compounds such as dimethyl, diethyl mal
- Oxime compounds such as formaldehyde, acetoaldoxime, acetooxime, methylethylketooxime, cyclohexanone oxime; amine compounds such as diphenylamine, aniline, and carbazole; imide compounds such as ethyleneimine and polyethyleneimine; Das and other heavy sulfites; pyridine compounds such as 2-hydroxypyridine and 2-hydroxyquinoline can be mentioned.
- Specific examples of the compound having a blocked isocyanate group used as a cross-linking agent include Barnock D-500 (tolylene diisocyanate blocked product) and Barnock D-550 (1,6) manufactured by Dainippon Ink and Chemicals. -Hexamethylene diisocyanate block), Vernock D-980K (1,6-hexamethylene diisocyanate block); Takenate B-830 (trilened isocyanate block) manufactured by Mitsui Takeda Chemical Co., Ltd.
- a photoactive compound can be used as the photosensitizer, and for example, a diazoquinone compound can be used.
- a diazoquinone compound can be used.
- any one or more of the following compounds can be used.
- N2 is an integer of 1 or more and 5 or less.
- Q is any of the structures shown below or a hydrogen atom.
- at least one of the Qs of each compound is any of the following.
- an o-naphthoquinonediazide sulfonic acid derivative having a Q of (a) or (b) is preferable from the viewpoint of transparency and dielectric constant of the photosensitive resin composition.
- the positive photosensitive resin composition may contain an acid generator that generates an acid by light or heat.
- an acid generator that generates an acid by light or heat.
- the cross-linking reaction of the cross-linking agent can be promoted by exposing and developing the photosensitive resin composition and then irradiating or heating with light.
- the amount of the acid generator is preferably 3 parts by mass or less with respect to 100 parts by mass of the cross-linking agent.
- the photoacid generator that generates acid by light those described later can be used.
- the content of the thermoacid generator is preferably 0.1% by mass or more and 5% by mass or less, for example, when the total solid content of the photosensitive resin composition is 100% by mass.
- the total solid content of the photosensitive resin composition means a component excluding the solvent.
- a photoacid generator can be used as the photosensitive agent.
- the photoacid generator may be any agent that absorbs the energy of light to produce blended acid or Lewis acid. For example, triphenylsulfonium trifluoromethanesulfonate and tris (4-t-butylphenyl) sulfonium-trifluo.
- Sulfonium salts such as lomethanesulfonate; diazonium salts such as p-nitrophenyldiazonium hexafluorophosphate; ammonium salts; phosphonium salts; diphenyliodonium trifluoromethanesulfonates, iodonium salts such as (tricmill) iodonium-tetrakis (pentafluorophenyl) borate; quinonediazide , Diazomethanes such as bis (phenylsulfonyl) diazomethane; sulfonic acid esters such as 1-phenyl-1- (4-methylphenyl) sulfonyloxy-1-benzoylmethane, N-hydroxynaphthalimide-trifluoromethanesulfonate; diphenyl Disulfons such as disulfones; tris (2,4,6-trichloromethyl) -s-triazin
- the second cross-linking agent may contain a material that cross-links the copolymer by the action of an acid.
- This second cross-linking agent cross-links the copolymer using the acid generated by the photo-acid generator as a catalyst, and is different from the compound used for the cross-linking agent.
- a melamine-based cross-linking agent, a urea-based cross-linking agent, and the like can be mentioned.
- Examples of the melamine-based cross-linking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutyl melamine and the like, and among them, hexamethoxymethylmelamine is preferable.
- Examples of the urea-based cross-linking agent include methylated urea resin, bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, and among them, methylated urea resin is preferable.
- Examples of commercially available methylated urea resins include MX-270, MX-280, and MX-290 (manufactured by Sanwa Chemical Co., Ltd.).
- the ratio of the second cross-linking agent in the negative type photosensitive resin composition is preferably 5% by mass or more and 40% by mass or less when the total solid content of the resin composition is 100% by mass, and the resolution is high. From the viewpoint, it is more preferably 5% by mass or more and 30% by mass or less, and further preferably 10 to 25% by mass.
- the ratio of each component is, for example, as follows.
- the total solid content of the photosensitive resin composition is 100% by mass, it is preferable that the above-mentioned copolymer is contained in an amount of, for example, 30% by mass or more and 70% by mass or less, and above all, 40% by mass or more and 60% by mass or less. It is preferable to contain it.
- the cross-linking agent is preferably contained, for example, 15% by mass or more and 50% by mass or less, and above all, 20% by mass or more and 50% by mass or less. Is preferable.
- the photoactive compound as a photosensitive agent is contained, for example, 5% by mass or more and 40% by mass or less, and 10% by mass or more and 30% by mass. It is more preferably contained in an amount of% by mass or less.
- the ratio of each component is as follows, for example.
- the above-mentioned copolymer is preferably contained in an amount of, for example, 30% by mass or more and 70% by mass, particularly 40% by mass or more and 60% by mass or less. It is preferable to do so.
- the total solid content of the photosensitive resin composition is 100% by mass, it is preferable to contain a cross-linking agent (excluding the second cross-linking agent), for example, 15% by mass or more and 50% by mass or less, and among them, 20. It is preferably contained in an amount of% by mass or more and 50% by mass or less.
- the amount of the photoacid generator is, for example, 0.1% by mass or more and 40% by mass or less, forming a high-resolution pattern film. It is more preferably 1% by mass or more and 30% by mass or less from the viewpoint that it can be used.
- Additives such as a solvent, an antioxidant, a surfactant, an adhesion aid, a dissolution accelerator, a filler, a sensitizer, and polyphenols may be further added to the photosensitive resin composition.
- a solvent such as a solvent, an antioxidant, a surfactant, an adhesion aid, a dissolution accelerator, a filler, a sensitizer, and polyphenols.
- solvent The photosensitive resin composition described in this embodiment can be used as a varnish by dissolving each of the above-mentioned components in a solvent.
- solvents include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, and dipropylene glycol.
- Monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, and methyl -3-methoxypropionate and the like can be mentioned.
- the photosensitive resin composition of the present embodiment contains a filler, a binder resin other than the above-mentioned polymer, a cross-linking agent, an acid generator, a heat resistance improver, a developing aid, a plasticizer, and the like, depending on the purpose and required characteristics of each application.
- Polymerizers, UV absorbers, antioxidants, matting agents, defoaming agents, leveling agents, antistatic agents, dispersants, slip agents, surface modifiers, rocking agents, rocking aids, surfactants , Silane-based, aluminum-based, titanium-based coupling agents, polyhydric phenol compounds, and other components other than the above essential components may be blended.
- the method for preparing the photosensitive resin composition in the present embodiment is not limited, and it can be prepared by using a conventionally known method.
- each of the above components can be prepared by mixing and dissolving in a solvent. Thereby, a photosensitive resin composition as a varnish can be obtained.
- the photosensitive resin composition of the present embodiment can be used as a cured product to obtain a resin film.
- a resin film can be used, for example, as a resist, and can also form, for example, a protective film for an electronic device, an interlayer film, or a permanent film such as a dam material.
- the photosensitive resin composition of the present embodiment preferably has a transmittance of 95% or more, more preferably 98% or more, as measured under the following conditions.
- (conditions) A photosensitive resin composition is applied onto a glass substrate, dried at 100 ° C. for 120 seconds, and exposed to an exposure amount of 300 mJ / cm 2 , and the resin film A having a thickness of 3 ⁇ m is exposed to light having a wavelength of 400 nm. the light transmittance was evaluated with a spectrophotometer, and the pre-heat resistance test transmittance T a%.
- the photosensitive resin composition of the present embodiment preferably has a heat-resistant discoloration property of the resin film of 95% or more, more preferably 96% or more, as measured under the following conditions.
- (conditions) A photosensitive resin composition is applied onto a glass substrate, dried at 100 ° C. for 120 seconds, and exposed to an exposure amount of 300 mJ / cm 2 , and the resin film A having a thickness of 3 ⁇ m is exposed to light having a wavelength of 400 nm. the light transmittance was evaluated with a spectrophotometer, and the pre-heat resistance test transmittance T a%.
- the permanent film obtained by curing the photosensitive resin composition of the present invention is a permanent film having excellent transmittance and heat-resistant discoloration. Therefore, it is not colored even when it is heated, especially in applications requiring transparency. It is preferable to apply it to a coloring pattern, a black matrix, an overcoat, a rib, and a spacer of an electronic device having various display devices such as a liquid crystal display device and an organic EL element.
- the solution after the reaction was poured into a large amount of methanol to precipitate a polymer.
- the polymer was then collected by filtration, washed with methanol, and vacuum dried at 120 ° C. for 16 hours.
- the yield of the polymer was 145.3 g, and the yield was 97%.
- the polymer had a weight average molecular weight Mw of 3,500 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.62.
- the yield of the polymer was 56.0 g and the yield was 64%.
- the polymer had a weight average molecular weight Mw of 4,500 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.59.
- the polymer was then collected by filtration, washed with methanol, and vacuum dried at 120 ° C. for 16 hours.
- the yield of the polymer was 92.5 g and the yield was 93%.
- the polymer had a weight average molecular weight Mw of 6,900 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.76.
- the polymer had a weight average molecular weight Mw of 7,600 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.88.
- the polymer had a weight average molecular weight Mw of 4,900 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 2.11. Table 1 shows the blending amounts of the components used in Synthesis Examples 1 to 5, and the weight average molecular weight and dispersity of the obtained precursor polymer.
- the obtained polymer was collected by filtration, washed with pure water, dissolved in PGMEA, and residual water was removed and concentrated under reduced pressure to obtain a polymer solution having a solid content of about 35%.
- the weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are as shown in Table 2.
- Synthesis Example 7 Synthesis of Polymer B-1) 20.0 g of the precursor polymer B synthesized in Synthesis Example 2 was dissolved in 30.0 g of MEK. Further, 11.6 g of 2-hydroxyethyl acrylate (HEA) and 2.0 g of triethylamine (TEA) were added, the temperature was raised to 70 ° C., and the reaction was carried out for 6 hours. The reaction mixture was then cooled to room temperature and neutralized with formic acid. The solution was poured into a large amount of pure water to precipitate the polymer.
- HOA 2-hydroxyethyl acrylate
- TEA triethylamine
- the obtained polymer was collected by filtration, washed with pure water, dissolved in PGMEA, and residual water was removed and concentrated under reduced pressure to obtain a polymer solution having a solid content of about 35%.
- the weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are as shown in Table 2.
- the obtained polymer was collected by filtration, washed with pure water, dissolved in PGMEA, and residual water was removed and concentrated under reduced pressure to obtain a polymer solution having a solid content of about 35%.
- the weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are as shown in Table 2.
- Synthesis Example 9 Synthesis of Polymer D-1) 20.0 g of the precursor polymer D synthesized in Synthesis Example 4 was dissolved in 30.0 g of MEK. Further, 9.0 g of 2-hydroxyethyl acrylate (HEA) and 2.0 g of triethylamine (TEA) were added, the temperature was raised to 70 ° C., and then the reaction was carried out for 6 hours. The reaction mixture was then cooled to room temperature and neutralized with formic acid. The solution was poured into a large amount of pure water to precipitate the polymer.
- HOA 2-hydroxyethyl acrylate
- TEA triethylamine
- the obtained polymer was collected by filtration, washed with pure water, dissolved in PGMEA, and residual water was removed and concentrated under reduced pressure to obtain a polymer solution having a solid content of about 35%.
- the weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are as shown in Table 2.
- Synthesis Example 10 Synthesis of Polymer E-1) 5.0 g of the precursor polymer D synthesized in Synthesis Example 5 was dissolved in 7.5 g of MEK. Further, 2.9 g of 2-hydroxyethyl acrylate (HEA) and 0.5 g of triethylamine (TEA) were added, the temperature was raised to 70 ° C., and the reaction was carried out for 6 hours. The reaction mixture was then cooled to room temperature and neutralized with formic acid. The solution was poured into a large amount of pure water to precipitate the polymer.
- HOA 2-hydroxyethyl acrylate
- TEA triethylamine
- the obtained polymer was collected by filtration, washed with pure water, dissolved in PGMEA, and residual water was removed and concentrated under reduced pressure to obtain a polymer solution having a solid content of about 35%.
- the weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are as shown in Table 2.
- the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw / Mn) are converted to polystyrene obtained from the calibration curve of standard polystyrene (PS) obtained by GPC measurement. Use the value.
- the measurement conditions are as follows. Equipment: Tosoh gel permeation chromatography equipment HLC-8320GPC Column: TSK-GEL Supermultipore HZ-M manufactured by Tosoh Corporation Detector: RI detector for liquid chromatogram Measurement temperature: 40 ° C Solvent: THF Sample concentration: 2.0 mg / ml
- the double bond equivalent of the polymer was measured by the following method. First, about 50 mg of the polymer which was dried under reduced pressure to remove the solvent and about 5 mg of dimethyl terephthalate as an internal standard substance were weighed and dissolved in DMSO-d6. This solution was measured by 1H-NMR using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL Ltd.). From the integral ratio of the signal derived from the (meth) acrylic group (5-7 ppm) of the obtained spectrum chart and the signal (4H, 8.1 ppm) of the phenyl group of the internal standard substance, the polymer weight per mole of the double bond ( g / mol, double bond equivalent) was calculated.
- ⁇ Preparation of photosensitive resin composition For each 100 parts by mass of the polymers obtained in Synthesis Examples 6 to 10, 50 parts by mass of dipentaerythritol hexaacrylate (crosslinking agent 1, DPHA) as a cross-linking agent and a photoradical initiator as a photosensitizer (manufactured by BASF). , Irgacure OXE01) 10 parts by mass, adhesion aid (3-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical Industry Co., Ltd., KBM-403) 1 part by mass, surfactant (DIC Co., Ltd., F556) 0.
- crosslinking agent 1 dipentaerythritol hexaacrylate
- photoradical initiator as a photosensitizer
- Crosslinking agent -Crosslinking agent 1: An acrylic crosslinking agent represented by the following formula (12) (DPHA manufactured by Daicel Cytec).
- Photosensitive agent Photosensitizer 1: A photoradical polymerization initiator (Irgaceure OXE02 manufactured by BASF) represented by the following formula (11) was used.
- Adhesion aid 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)
- Surfactant 1 Megafuck F-556 (manufactured by DIC Corporation)
- the obtained photosensitive resin composition was evaluated according to the following.
- Light transmittance T A For each Example and each Comparative Example, the light transmittance of the resin film A formed by using the photosensitive resin composition was measured as follows. First, the obtained photosensitive resin composition was applied to a glass substrate using a spin coater, and then baked on a hot plate at 110 ° C. for 110 seconds. As the glass substrate, a 1737 glass substrate manufactured by Corning Inc. having a size of 100 mm in length and 100 mm in width was used. Then, the entire photosensitive resin composition was exposed with g + h + i line mask aligner (PLA-501F) manufactured by Canon Inc. at 300 mJ / cm 2 . Then, of the resin film A, and measured for light transmittance T A (%) with respect to light having a wavelength of 400 nm. Light transmittance T A was measured using an ultraviolet-visible spectrophotometer. The results are shown in Table 3.
Abstract
Description
一般式(1)で表される共重合体と、
架橋剤と、
感光剤と
を含む、感光性樹脂組成物が提供される。 According to the present invention
With the copolymer represented by the general formula (1),
Crosslinker and
A photosensitive resin composition containing a photosensitive agent is provided.
lおよびmはそれぞれ、共重合体中における、AおよびBのモル含有率を示し、
l+m=1であり、
Xは、水素または炭素数1以上30以下の有機基であり、
Yは、-SR5aであり、Sは硫黄原子であり、R5aは、炭素数1以上30以下の有機基であり、
Aは、以下式(A1)で示される構造単位を含み、
Bは、式(B1)~(B6)により示される構造単位のうち少なくとも1つを含み:
l and m indicate the molar content of A and B in the copolymer, respectively.
l + m = 1
X is hydrogen or an organic group having 1 or more and 30 or less carbon atoms.
Y is −SR 5a , S is a sulfur atom, and R 5a is an organic group having 1 or more and 30 or less carbon atoms.
A includes a structural unit represented by the following formula (A1).
B comprises at least one of the structural units represented by the formulas (B1)-(B6):
ただし、前記式(1)に含まれる前記式(A1)で示される構造単位、および前記式(B1)~(B6)により示される構造単位の少なくとも1つが、エチレン性二重結合を有する炭素数1以上30以下の有機基を有する。)。
However, at least one of the structural unit represented by the formula (A1) and the structural unit represented by the formulas (B1) to (B6) contained in the formula (1) has an ethylenic double bond. It has 1 or more and 30 or less organic groups. ).
まず、本実施形態の感光性樹脂組成物について説明する。
本実施形態の感光性樹脂組成物は、一般式(1)で表される共重合体と、架橋剤と、感光剤とを含む。 (Photosensitive resin composition)
First, the photosensitive resin composition of the present embodiment will be described.
The photosensitive resin composition of the present embodiment contains a copolymer represented by the general formula (1), a cross-linking agent, and a photosensitive agent.
lおよびmはそれぞれ、共重合体中における、AおよびBのモル含有率を示し、
l+m=1であり、
Xは、水素または炭素数1以上30以下の有機基であり、
Yは、-SR5aであり、R5aは、炭素数1以上30以下の有機基であり、
Aは、以下式(A1)で示される構造単位を含み、
Bは、式(B1)~(B6)により示される構造単位のうち少なくとも1つを含む。
l and m indicate the molar content of A and B in the copolymer, respectively.
l + m = 1
X is hydrogen or an organic group having 1 or more and 30 or less carbon atoms.
Y is −SR 5a , and R 5a is an organic group having 1 or more and 30 or less carbon atoms.
A includes a structural unit represented by the following formula (A1).
B contains at least one of the structural units represented by the formulas (B1) to (B6).
ただし、一般式(1)に含まれる式(A1)で示される構造単位、および前記式(B1)~(B6)により示される構造単位の少なくとも1つが、エチレン性二重結合を有する炭素数1以上30以下の有機基を有する。換言すると、本実施形態の共重合体は、エチレン性二重結合を有する炭素数1以上30以下の有機基を有する構造単位を必須成分として含む。
However, at least one of the structural unit represented by the formula (A1) included in the general formula (1) and the structural unit represented by the formulas (B1) to (B6) has an ethylenic double bond and has 1 carbon atom. It has more than 30 organic groups. In other words, the copolymer of the present embodiment contains a structural unit having an ethylenic double bond and having an organic group having 1 to 30 carbon atoms as an essential component.
本実施形態の感光性樹脂組成物に用いられる共重合体は、一般式(1)で表される構造を有する。 <Copolymer>
The copolymer used in the photosensitive resin composition of the present embodiment has a structure represented by the general formula (1).
lおよびmはそれぞれ、共重合体中における、AおよびBのモル含有率を示し、
l+m=1であり、
Xは、水素または炭素数1以上30以下の有機基であり、
Yは、-SR5aであり、Sは硫黄原子を表し、R5aは、炭素数1以上30以下の有機基であり、
Aは、以下式(A1)で示される構造単位を含み、
Bは、式(B1)~(B6)により示される構造単位のうち少なくとも1つを含む。
l and m indicate the molar content of A and B in the copolymer, respectively.
l + m = 1
X is hydrogen or an organic group having 1 or more and 30 or less carbon atoms.
Y is −SR 5a , S is a sulfur atom, and R 5a is an organic group having 1 or more and 30 or less carbon atoms.
A includes a structural unit represented by the following formula (A1).
B contains at least one of the structural units represented by the formulas (B1) to (B6).
さらに本実施形態において、R1、R2、R3およびR4を構成する有機基は、いずれも酸性官能基を有しないものとすることができる。これにより、共重合体中における酸価の制御を容易にすることができる。 The organic groups having 1 to 30 carbon atoms or the organic groups having an ethylenic double bond and having 1 to 30 carbon atoms constituting R 1 to R 4 in the general formula (A1) are independent of each other. The structure may contain one or more atoms selected from O (oxygen atom), N (nitrogen atom), S (sulfur atom), P (phosphorus atom) and Si (silicon atom).
Further, in the present embodiment, none of the organic groups constituting R 1 , R 2 , R 3 and R 4 can have an acidic functional group. This makes it possible to easily control the acid value in the copolymer.
アルキル基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、およびデシル基が挙げられる。アルケニル基としては、例えば、アリル基、ペンテニル基、およびビニル基が挙げられる。アルキニル基としては、エチニル基が挙げられる。アルキリデン基としては、例えば、メチリデン基、およびエチリデン基が挙げられる。アリール基としては、例えば、トリル基、キシリル基、フェニル基、ナフチル基、およびアントラセニル基が挙げられる。アラルキル基としては、例えば、ベンジル基、およびフェネチル基が挙げられる。アルカリル基としては、例えば、トリル基、キシリル基が挙げられる。シクロアルキル基としては、例えば、アダマンチル基、シクロペンチル基、シクロヘキシル基、およびシクロオクチル基が挙げられる。アルコキシ基としては、例えば、メトキシ基、エトキシ基、n-プロポキシ基、イソプロポキシ基、n-ブトキシ基、s-ブトキシ基、イソブトキシ基およびt-ブトキシ基、n-ペンチルオキシ基、ネオペンチルオキシ基、n-ヘキシルオキシ基が挙げられる。ヘテロ環基としては、例えば、エポキシ基、およびオキセタニル基が挙げられる。 In the present embodiment, examples of the organic group having 1 or more and 30 or less carbon atoms include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkalil group, a cycloalkyl group, an alkoxy group and a heterocyclic group. Can be mentioned.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group and heptyl group. , Octyl group, nonyl group, and decyl group. Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group. Examples of the alkynyl group include an ethynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a tolyl group, a xsilyl group, a phenyl group, a naphthyl group, and an anthrasenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaline group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, an isobutoxy group and a t-butoxy group, an n-pentyloxy group and a neopentyloxy group. , N-hexyloxy group. Examples of the heterocyclic group include an epoxy group and an oxetanyl group.
さらに本実施形態において、R5~R8を構成する有機基は、いずれもカルボキシル基などの酸性官能基を有しないものとすることができる。これにより、共重合体中における酸価の制御を容易にすることができる。 The general formula (B1), the general formula (B2) and the general formula (B6) R 5 ~ having 1 or more carbon atoms with organic groups or ethylenic double bond of one to 30 carbon atoms constituting the R 8 in 30 The following organic groups may contain one or more atoms selected from O, N, S, P and Si in their structure.
Further, in the present embodiment, none of the organic groups constituting R 5 to R 8 can have an acidic functional group such as a carboxyl group. This makes it possible to easily control the acid value in the copolymer.
アルキル基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、およびデシル基が挙げられる。アルケニル基としては、例えば、アリル基、ペンテニル基、およびビニル基が挙げられる。アルキニル基としては、エチニル基が挙げられる。アルキリデン基としては、例えば、メチリデン基、およびエチリデン基が挙げられる。アリール基としては、例えば、トリル基、キシリル基、フェニル基、ナフチル基、およびアントラセニル基が挙げられる。アラルキル基としては、例えばベンジル基、およびフェネチル基が挙げられる。アルカリル基としては、例えば、トリル基、キシリル基が挙げられる。シクロアルキル基としては、例えば、アダマンチル基、シクロペンチル基、シクロヘキシル基、およびシクロオクチル基が挙げられる。アルコキシ基としては、例えば、メトキシ基、エトキシ基、n-プロポキシ基、イソプロポキシ基、n-ブトキシ基、s-ブトキシ基、イソブトキシ基、t-ブトキシ基、n-ペンチルオキシ基、ネオペンチルオキシ基、およびn-ヘキシルオキシ基が挙げられる。ヘテロ環基としては、例えば、エポキシ基、およびオキセタニル基が挙げられる。
本実施形態において、上記式(B1)、式(B2)および式(B6)中のR5~R8を構成するエチレン性二重結合を有する炭素数1以上30以下の有機基の具体例としては、アリル基、アクリル基、メタクリル基、マレイミド基、スチリル基、インデニル基のような芳香族ビニル基等が挙げられる。 In the present embodiment, examples of the organic group constituting R 5 to R 8 in the above formula (B1), formula (B2) and formula (B6) include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group and an aryl group. Examples include groups, aralkyl groups, alkaline groups, cycloalkyl groups, alkoxy groups and heterocyclic groups.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group and heptyl group. , Octyl group, nonyl group, and decyl group. Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group. Examples of the alkynyl group include an ethynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a tolyl group, a xsilyl group, a phenyl group, a naphthyl group, and an anthrasenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaline group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, an isobutoxy group, a t-butoxy group, an n-pentyloxy group and a neopentyloxy group. , And n-hexyloxy groups. Examples of the heterocyclic group include an epoxy group and an oxetanyl group.
In the present embodiment, the above formula (B1), specific examples of the formula (B2) and the number 1 to 30 of the organic group having a carbon having an ethylenic double bond which constitutes the R 5 ~ R 8 in the formula (B6) Examples include aromatic vinyl groups such as allyl group, acrylic group, methacryl group, maleimide group, styryl group and indenyl group.
アルキル基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、およびデシル基が挙げられる。アルケニル基としては、例えば、アリル基、ペンテニル基、およびビニル基が挙げられる。アルキニル基としては、エチニル基が挙げられる。アルキリデン基としては、例えば、メチリデン基、およびエチリデン基が挙げられる。アリール基としては、例えば、トリル基、キシリル基、フェニル基、ナフチル基、およびアントラセニル基が挙げられる。アラルキル基としては、例えば、ベンジル基、およびフェネチル基が挙げられる。アルカリル基としては、例えば、トリル基、キシリル基が挙げられる。シクロアルキル基としては、例えば、アダマンチル基、シクロペンチル基、シクロヘキシル基、およびシクロオクチル基が挙げられる。アルコキシ基としては、例えば、メトキシ基、エトキシ基、n-プロポキシ基、イソプロポキシ基、n-ブトキシ基、s-ブトキシ基、イソブトキシ基、t-ブトキシ基、n-ペンチルオキシ基、ネオペンチルオキシ基、およびn-ヘキシルオキシ基が挙げられる。ヘテロ環基としては、例えば、エポキシ基、およびオキセタニル基が挙げられる。 In the copolymer represented by the general formula (1), Y is a group represented by −SR 5a , S is a sulfur atom, and R 5a is an organic group having 1 or more and 30 or less carbon atoms. The organic group having 1 or more and 30 or less carbon atoms may contain one or more atoms selected from O, N, S, P and Si. Examples of the organic group having 1 to 30 carbon atoms constituting R 5 include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkalil group, a cycloalkyl group, an alkoxy group and a heterocyclic group. Can be mentioned.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group and heptyl group. , Octyl group, nonyl group, and decyl group. Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group. Examples of the alkynyl group include an ethynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a tolyl group, a xsilyl group, a phenyl group, a naphthyl group, and an anthrasenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaline group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, an isobutoxy group, a t-butoxy group, an n-pentyloxy group and a neopentyloxy group. , And n-hexyloxy groups. Examples of the heterocyclic group include an epoxy group and an oxetanyl group.
これは、上記一般式(1)によって示される共重合体を合成する際、重合開始剤としてラジカル重合開始剤を用いる場合、重合反応であるラジカル連鎖反応の停止反応によってYを形成することができるためである。 Y may include a structural unit derived from a radical polymerization initiator, hydrogen, or a structural unit derived from a chain transfer agent, and is derived from a structural unit derived from a radical polymerization initiator, hydrogen, or a chain transfer agent. It may be a structural unit.
This is because when a radical polymerization initiator is used as the polymerization initiator when synthesizing the copolymer represented by the general formula (1), Y can be formed by the termination reaction of the radical chain reaction which is a polymerization reaction. Because.
なお、多分散度はMw(重量平均分子量)/Mn(数平均分子量)によって表され、分子量分布の幅を示す分散度を意味する。 Further, the upper limit of the polydispersity of the copolymer according to the present embodiment makes the physical properties of each molecular chain of the copolymer uniform, and the shape of the resin film made of the photosensitive resin composition containing the copolymer is good. For example, it is preferably 2.5 or less, preferably 2.2 or less, more preferably 2.0 or less, and even more preferably 1.5 or less. Further, from the same viewpoint as the upper limit value, the lower limit value of the polydispersity of the copolymer is preferably 1.0 or more, for example.
The degree of polydispersity is represented by Mw (weight average molecular weight) / Mn (number average molecular weight), and means the degree of dispersion indicating the width of the molecular weight distribution.
装置:東ソー社製ゲルパーミエーションクロマトグラフィー装置HLC-8320GPC
カラム:東ソー社製TSK-GEL Supermultipore HZ-M
検出器:液体クロマトグラム用RI検出器
測定温度:40℃
溶媒:THF
試料濃度:2.0mg/ミリリットル For the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw / Mn), for example, polystyrene-equivalent values obtained from the calibration curve of standard polystyrene (PS) obtained by GPC measurement are used. .. The measurement conditions are as follows, for example.
Equipment: Tosoh gel permeation chromatography equipment HLC-8320GPC
Column: TSK-GEL Supermultipore HZ-M manufactured by Tosoh Corporation
Detector: RI detector for liquid chromatogram Measurement temperature: 40 ° C
Solvent: THF
Sample concentration: 2.0 mg / ml
このように、GPCにより得られる分子量分布曲線の分子量1000以下におけるピーク面積の比率を上記範囲とすることにより、共重合体を含む樹脂組成物からなる膜のパターン形状を良好なものとすることができる。そのため、当該膜を永久膜として備える液晶表示装置、固体撮像素子については、その動作信頼性を向上させることが可能となる。
なお、共重合体における低分子量成分の量の下限は、限定されない。しかし、本実施形態に係る共重合体は、GPCにより得られる分子量分布曲線において分子量1000以下におけるピーク面積が全体の0.01%以上である場合を許容するものである。
なお、共重合体中における低分子量成分量は、例えばGPC測定により得られた分子量に関するデータに基づき、分子量分布全体の面積に占める、分子量1000以下に該当する成分の面積総和の割合から算出される。 In the copolymer according to the present embodiment, for example, in the molecular weight distribution curve obtained by GPC (Gel Permeation Chromatography), the peak area at a molecular weight of 1000 or less may be 1% or less of the whole.
As described above, by setting the ratio of the peak area of the molecular weight distribution curve obtained by GPC to the molecular weight of 1000 or less within the above range, the pattern shape of the film made of the resin composition containing the copolymer can be improved. it can. Therefore, it is possible to improve the operation reliability of a liquid crystal display device and a solid-state image sensor having the film as a permanent film.
The lower limit of the amount of the low molecular weight component in the copolymer is not limited. However, the copolymer according to the present embodiment allows a case where the peak area at a molecular weight of 1000 or less is 0.01% or more of the whole in the molecular weight distribution curve obtained by GPC.
The amount of the low molecular weight component in the copolymer is calculated from the ratio of the total area of the components corresponding to the molecular weight of 1000 or less to the total area of the molecular weight distribution based on the data on the molecular weight obtained by, for example, GPC measurement. ..
本実施形態に係る共重合体は、例えば、重合工程によって、モノマーを重合して共重合体を作製し、次いで、低分子量成分除去工程によって、低分子量成分を除去し、共重合体を主成分とする共重合体を得る方法により調製される。以下に詳述する。 (Method for producing copolymer)
In the copolymer according to the present embodiment, for example, a monomer is polymerized by a polymerization step to prepare a copolymer, and then a low molecular weight component is removed by a low molecular weight component removing step, and the copolymer is the main component. It is prepared by the method of obtaining the copolymer. It will be described in detail below.
ノルボルネン型モノマー(A)と、無水マレイン酸(B)、マレイミド(C)、およびマレイミド誘導体(D)からなる群より選択される1種以上と、を用意する。また、ノルボルネン型モノマーは1種を用意してもよいし、2種以上を用意してもよい。
上記一般式(1)で示される共重合体において、構造単位Aは、ノルボルネン型モノマー(A)由来であり、構造単位Bは、無水マレイン酸(B)、マレイミド(C)またはマレイミド誘導体(D)に由来する。
A norbornene-type monomer (A) and one or more selected from the group consisting of maleic anhydride (B), maleimide (C), and maleimide derivative (D) are prepared. Further, one type of norbornene type monomer may be prepared, or two or more types may be prepared.
In the copolymer represented by the general formula (1), the structural unit A is derived from the norbornene-type monomer (A), and the structural unit B is maleic anhydride (B), maleimide (C) or maleimide derivative (D). ).
その他、ノルボルネン型モノマーとしては、式(A)のR1、R2、R3、R4の基の構造中に、上述のエチレン性二重結合を有する炭素数1~30以下の有機基を有するものを採用することができる。 Specific examples of the norbornene-type monomer represented by the formula (A) include bicyclo [2.2.1] -hept-2-ene (common name: 2-norbornene), and more specifically, the norbornene type monomer. Alkenyl groups such as 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, etc. have an alkyl group. Those having an alkynyl group such as 5-allyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, etc. , 5-Ethynyl-2-norbornene and the like having an aralkyl group include 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene and the like.
In addition, as the norbornene-type monomer, an organic group having the above-mentioned ethylenic double bond and having 1 to 30 carbon atoms or less is used in the structure of the groups of R 1 , R 2 , R 3 , and R 4 of the formula (A). What you have can be adopted.
アゾ化合物としては、例えば、アゾビスイソブチロニトリル(AIBN)、ジメチル2,2'-アゾビス(2-メチルプロピオネート)、1,1'-アゾビス(シクロヘキサンカルボニトリル)(ABCN)が挙げられ、これらのうち、いずれか1種以上を使用できる。
また、有機過酸化物としては、例えば、過酸化水素、ジターシャリブチルパーオキサイド(DTBP)、過酸化ベンゾイル(ベンゾイルパーオキサイド,BPO)および、メチルエチルケトンパーオキサイド(MEKP)を挙げることができ、これらのうち、いずれか1種以上を使用できる。 Examples of the radical polymerization initiator include azo compounds and organic peroxides, and any one or more of these can be used.
Examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis (2-methylpropionate), and 1,1'-azobis (cyclohexanecarbonitrile) (ABCN). , Any one or more of these can be used.
Examples of the organic peroxide include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). Of these, any one or more can be used.
ただし、共重合体1において、式(A1)の構造のR1は、各繰り返し単位において共通であることが好ましいが、それぞれの繰り返し単位ごとに異なっていてもよい。R2~R4、R8においても同様である。 By this polymerization step, the structural unit represented by the following formula (A1), the structural unit represented by the following formula (B3), the structural unit represented by the following formula (B5), and the following formula (B6) are represented. The copolymer 1 having the structural unit to be polymerized can be polymerized.
However, in the copolymer 1, it is preferable that R 1 having the structure of the formula (A1) is common to each repeating unit, but it may be different for each repeating unit. The same applies to R 2 ~ R 4, R 8 .
共重合体1は感光性樹脂組成物の均一な溶解性を得るという観点から、交互共重合体が好ましい。 The copolymer 1 may have the structural units (A1), (B3), (B5) and (B6) randomly arranged, or may be alternately arranged. .. Further, the structural units (A1), (B3), (B5) and (B6) may be block copolymerized.
The copolymer 1 is preferably an alternating copolymer from the viewpoint of obtaining uniform solubility of the photosensitive resin composition.
次に、共重合体1と、残留モノマーおよびオリゴマー等の低分子量成分とが含まれた有機層に対して、大量の貧溶媒、例えば、ヘキサンやメタノールに加えて、共重合体1を含む反応混合物を凝固沈殿させる。ここで、低分子量成分としては、残留モノマー、オリゴマー、さらには、重合開始剤等が含まれる。次いで、ろ過を行い、得られた凝固物を、乾燥させる。これにより、低分子量成分が除去された共重合体1を主成分(主生成物)とする生成物を得ることができる。 (Low molecular weight component removal process)
Next, a reaction involving the copolymer 1 and the organic layer containing a low molecular weight component such as a residual monomer and an oligomer in addition to a large amount of a poor solvent such as hexane or methanol. The mixture is solidified and precipitated. Here, the low molecular weight component includes a residual monomer, an oligomer, a polymerization initiator and the like. Then, filtration is performed and the obtained coagulated product is dried. As a result, a product containing the copolymer 1 from which the low molecular weight component has been removed as the main component (main product) can be obtained.
次に、得られた共重合体1の無水マレイン酸に由来する構造単位(B3)のうち、一部の構造単位を閉環した状態としながら、残りの繰り返し単位を開環することができる。これにより、共重合体1中におけるカルボキシル基の量を調整するともにラジカル重合性基を導入することができる。
本実施形態においては、共重合体1の無水マレイン酸由来の構造単位(B3)のうち、例えば、10%以上の繰り返し単位を開環させることが好ましい。中でも、共重合体1の無水マレイン酸由来の環状構造の繰り返し単位の全個数のうち、15%以上の繰り返し単位を開環することが好ましい。また、本実施形態においては、共重合体1の無水マレイン酸由来の繰り返し単位のうち、例えば、60%以下の繰り返し単位を開環させることが好ましく、50%以下の繰り返し単位を開環させることがより好ましい。上記範囲とすることにより、共重合体1に十分なアルカリ現像液を付与するとともに、光ラジカル発生剤による架橋反応をより効率的に進行させることが容易となる。 (Ring-opening process)
Next, among the structural units (B3) derived from maleic anhydride of the obtained copolymer 1, some of the structural units can be ring-closed and the remaining repeating units can be opened. Thereby, the amount of the carboxyl group in the copolymer 1 can be adjusted and the radical polymerizable group can be introduced.
In the present embodiment, it is preferable to open the ring of, for example, 10% or more of the structural units (B3) derived from maleic anhydride of the copolymer 1. Above all, it is preferable to open 15% or more of the repeating units of the cyclic structure derived from maleic anhydride of the copolymer 1 by ring-opening. Further, in the present embodiment, among the repeating units derived from maleic anhydride of the copolymer 1, for example, it is preferable to open the ring of 60% or less of the repeating unit, and open the ring of 50% or less of the repeating unit. Is more preferable. Within the above range, it becomes easy to impart a sufficient alkaline developer to the copolymer 1 and to allow the cross-linking reaction by the photoradical generator to proceed more efficiently.
また、式(B2)で示す構造体が形成されることもある。
In addition, the structure represented by the formula (B2) may be formed.
アルコールとしては、例えば、アリルアルコール、メタリルアルコール、3-ブテン-1-オール、3-メチル-3-ブテン-1-オール、4-ペンテン-1-オール、5-ヘキセン-1-オール、6-ヘプテン-1-オール、7-オクテン-1-オール、8-ノネン-1-オール、9-デセン-1-オール、10-ウンデセン-1-オール、2-ヒドロキシエチルアクリレート、2-ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、4-ヒドロキシブチルアクリレート、4-ヒドロキシブチルメタクリレート、1,4-シクロヘキサンジメタノールモノアクリレート、および1,4-シクロヘキサンジメタノールモノメタクリレートが挙げられ、これらのうちいずれか1以上使用することができる。 As the alcohol, monohydric alcohol is preferable. The alcohol can be R 5 OH, and the organic group R 5 can be the one described above.
Examples of the alcohol include allyl alcohol, metallic alcohol, 3-butene-1-ol, 3-methyl-3-butene-1-ol, 4-pentene-1-ol, 5-hexene-1-ol, 6 -Heptene-1-ol, 7-octen-1-ol, 8-nonen-1-ol, 9-decene-1-ol, 10-undecene-1-ol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate , Hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate, and 1,4-cyclohexanedimethanol monomethacrylate, any of these. One or more can be used.
なお、本工程に用いられる溶媒として、例えば、汎用性の高い溶媒として、ジエチルエーテル、テトラヒドロフラン、トルエン、メチルエチルケトン、酢酸エチル等が挙げられ、これらのうち、いずれか1種以上を使用することができる。 The solvent for dissolving the precursor polymer can be appropriately selected from those that do not inhibit the reaction, and the heating conditions can be set, for example, in the range of 50 to 100 ° C. The reaction time can be appropriately set while observing the degree of change in the chemical structure of the polymer.
Examples of the solvent used in this step include diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, ethyl acetate and the like as highly versatile solvents, and any one or more of these can be used. ..
塩基触媒としては、ピリジンや、トリエチルアミンなどのアルキルアミン、ジメチルアニリン、ウロトロピン、ジメチルアミノピリジンなどのアミン化合物、酢酸ナトリウム等の金属塩を用いることができる。
また、酸触媒としては、硫酸や塩酸などの鉱酸、パラトルエンスルホン酸などの有機酸、三フッ化ホウ素エーテラートなどのルイス酸などを用いることができる。 In this heating, a catalyst can be appropriately added from the viewpoint of accelerating the reaction, and for example, a base catalyst or an acid catalyst can be added.
As the base catalyst, pyridine, alkylamines such as triethylamine, amine compounds such as dimethylaniline, urotropin and dimethylaminopyridine, and metal salts such as sodium acetate can be used.
Further, as the acid catalyst, mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as paratoluenesulfonic acid, and Lewis acids such as boron trifluoride etherate can be used.
なお、本明細書中において「感光性樹脂膜」とは、電子装置等の作製過程において、露光工程に供される樹脂膜を指す。例えば、「感光性樹脂膜」は、光が照射された部位が硬化し、一方、照射されない部位は現像工程で現像液(例えばアルカリ溶液)に溶解して除去される、ネガ型の感光性樹脂膜を指す。 The copolymer obtained by the present embodiment can be preferably used for forming a photosensitive resin film because of the specificity of the chemical performance contained in this structural unit.
In the present specification, the “photosensitive resin film” refers to a resin film that is subjected to an exposure process in the manufacturing process of an electronic device or the like. For example, in the "photosensitive resin film", a negative type photosensitive resin in which a portion irradiated with light is cured, while a portion not irradiated is dissolved and removed in a developing solution (for example, an alkaline solution) in a developing process. Refers to the membrane.
本実施形態において、架橋剤は、共重合体の活性水素と反応する官能基を含む化合物であれば限定されるものでない。
上記共重合体の活性水素と反応する官能基としては、例えば、グリシジル基、オキセタニル基、およびブロックイソシアネート基からなる群より選択される1種以上を含むことが好ましく、グリシジル基またはオキセタニル基を含むことがより好ましく、グリシジル基を含むことが一層好ましい。これにより、適切な架橋構造を形成することができる。
また、感光性樹脂組成物は、ブロックイソシアネート基を有する化合物、エポキシ化合物およびオキセタン化合物から選択される1種または2種以上を併用することもできる。 <Crosslinking agent>
In the present embodiment, the cross-linking agent is not limited as long as it is a compound containing a functional group that reacts with the active hydrogen of the copolymer.
The functional group that reacts with the active hydrogen of the copolymer preferably contains, for example, one or more selected from the group consisting of a glycidyl group, an oxetanyl group, and a blocked isocyanate group, and includes a glycidyl group or an oxetanyl group. It is more preferable, and it is more preferable to contain a glycidyl group. Thereby, an appropriate crosslinked structure can be formed.
Further, as the photosensitive resin composition, one kind or two or more kinds selected from a compound having a blocked isocyanate group, an epoxy compound and an oxetane compound can be used in combination.
感光性樹脂組成物は、上記において例示したエポキシ化合物を1種または2種以上含むことが可能である。 Further, for example, bisphenol A such as LX-01 (manufactured by Daiso), jER1001, 1002, 1003, 1004, 1007, 1009, 1010, 828, jER825 (trade name; manufactured by Mitsubishi Chemical Corporation). Type epoxy resin, bisphenol F type epoxy resin such as jER807 (trade name; manufactured by Mitsubishi Chemical Co., Ltd.), jER152, 154 (trade name; manufactured by Mitsubishi Chemical Co., Ltd.), EPPN201, 202 (trade name; manufactured by Nippon Kayaku Co., Ltd.) Phenolic novolac type epoxy resin such as EOCN102, 103S, 104S, 1020, 1025, 1027 (trade name; manufactured by Nippon Kayaku Co., Ltd.), jER157S70 (trade name; manufactured by Mitsubishi Chemical Co., Ltd.) Araldite CY179, 184 (trade name; manufactured by Huntsman Advanced Materials), ERL-4206, 4221, 4234, 4299 (trade name; manufactured by Dow Chemical), Epicron 200, 400 (trade name; manufactured by DIC), jER871 , 872 (trade name; manufactured by Mitsubishi Chemical Co., Ltd.), Poly [(2-oxyranyl) -1,2-cyclohexanediol] 2-ethyl-2- (hydroxymethyl) -1,3-propanediol ether A polyfunctional alicyclic epoxy resin such as (3: 1), EHPE-3150 (manufactured by Daicel) can also be used.
The photosensitive resin composition may contain one or more of the epoxy compounds exemplified above.
感光性樹脂組成物は、上記において例示したオキセタン化合物を1種または2種以上含むことが可能である。 Examples of the compound having an oxetane group used as a cross-linking agent include 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene and bis [1-ethyl (3-oxetanyl)] methyl ether. , 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 4,4'-bis (3-ethyl-3-oxetanylmethoxy) biphenyl, ethylene glycol bis (3-ethyl-3-3) Oxetanylmethyl) ether, diethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) diphenoate, trimethylpropanthris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol Tetrax (3-ethyl-3-oxetanylmethyl) ether, poly [[3-[(3-ethyl-3-oxetanyl) methoxy] propyl] silaseskioxane] derivative, oxetanyl silicate, phenol novolac-type oxetane, 1,3- Examples thereof include oxetane compounds such as bis [(3-ethyloxetane-3-yl) methoxy] benzene.
The photosensitive resin composition can contain one or more of the oxetane compounds exemplified above.
感光性樹脂組成物がポジ型である場合には、感光剤として、光活性化合物を使用でき、例えば、ジアゾキノン化合物を使用することができる。
例えば、以下のいずれか1種以上の化合物を使用することができる。 (Photosensitive agent)
When the photosensitive resin composition is of the positive type, a photoactive compound can be used as the photosensitizer, and for example, a diazoquinone compound can be used.
For example, any one or more of the following compounds can be used.
中でも、感光性樹脂組成物の透明性、誘電率の観点から、Qが(a)あるいは(b)であるo-ナフトキノンジアジドスルホン酸誘導体が好ましい。 In each of the above compounds, Q is any of the structures shown below or a hydrogen atom. However, at least one of the Qs of each compound is any of the following.
Of these, an o-naphthoquinonediazide sulfonic acid derivative having a Q of (a) or (b) is preferable from the viewpoint of transparency and dielectric constant of the photosensitive resin composition.
この場合には、酸発生剤は、架橋剤100質量部に対して、3質量部以下であることが好ましい。
光により酸を発生する光酸発生剤としては、後述するものを使用できる。
熱により酸を発生する熱酸発生剤としては、SI-45L、SI-60L、SI-80L、SI-100L、SI-110L、SI-150L(三新化学工業社製)等の芳香族スルホニウム塩が使用できる。
熱酸発生剤の含有量は、例えば、感光性樹脂組成物の全固形分を100質量%としたとき、0.1質量%以上5質量%以下であることが好ましい。
なお、本実施形態において、感光性樹脂組成物の全固形分とは、溶媒を除く成分のことを示す。 In addition to the above-mentioned photoactive compound, the positive photosensitive resin composition may contain an acid generator that generates an acid by light or heat. By including such an acid generator, the cross-linking reaction of the cross-linking agent can be promoted by exposing and developing the photosensitive resin composition and then irradiating or heating with light.
In this case, the amount of the acid generator is preferably 3 parts by mass or less with respect to 100 parts by mass of the cross-linking agent.
As the photoacid generator that generates acid by light, those described later can be used.
Examples of the thermoacid generator that generates an acid by heat include aromatic sulfonium salts such as SI-45L, SI-60L, SI-80L, SI-100L, SI-110L, and SI-150L (manufactured by Sanshin Chemical Industry Co., Ltd.). Can be used.
The content of the thermoacid generator is preferably 0.1% by mass or more and 5% by mass or less, for example, when the total solid content of the photosensitive resin composition is 100% by mass.
In the present embodiment, the total solid content of the photosensitive resin composition means a component excluding the solvent.
例えば、メラミン系架橋剤、尿素系架橋剤などが挙げられる。
メラミン系架橋剤としては、例えば、ヘキサメトキシメチルメラミン、ヘキサエトキシメチルメラミン、ヘキサプロポキシメチルメラミン、ヘキサブトキシブチルメラミン等が挙げられ、中でも、ヘキサメトキシメチルメラミンが好ましい。
尿素系架橋剤としては、例えば、メチル化尿素樹脂、ビスメトキシメチル尿素、ビスエトキシメチル尿素、ビスプロポキシメチル尿素、ビスブトキシメチル尿素等が挙げられ、中でも、メチル化尿素樹脂が好ましい。
メチル化尿素樹脂の市販品として、例えば、MX-270、MX-280、MX-290(三和ケミカル社製)などが挙げられる。 When the photosensitive resin composition is a negative type, the second cross-linking agent may contain a material that cross-links the copolymer by the action of an acid. This second cross-linking agent cross-links the copolymer using the acid generated by the photo-acid generator as a catalyst, and is different from the compound used for the cross-linking agent.
For example, a melamine-based cross-linking agent, a urea-based cross-linking agent, and the like can be mentioned.
Examples of the melamine-based cross-linking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutyl melamine and the like, and among them, hexamethoxymethylmelamine is preferable.
Examples of the urea-based cross-linking agent include methylated urea resin, bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, and among them, methylated urea resin is preferable.
Examples of commercially available methylated urea resins include MX-270, MX-280, and MX-290 (manufactured by Sanwa Chemical Co., Ltd.).
感光性樹脂組成物の全固形分を100質量%としたとき、前述した共重合体を、例えば、30質量%以上70質量%以下含有することが好ましく、中でも、40質量%以上60質量%以下含有することが好ましい。
また、感光性樹脂組成物の全固形分を100質量%としたとき架橋剤を、例えば、15質量%以上50質量%以下含有することが好ましく、中でも、20質量%以上50質量%以下含有することが好ましい。
さらには、感光性樹脂組成物の全固形分を100質量%としたとき、感光剤である光活性化合物を、例えば、5質量%以上40質量%以下含有することが好ましく、10質量%以上30質量%以下含有することがさらに好ましい。 In the above photosensitive resin composition, when the photosensitive resin composition is a positive type, the ratio of each component is, for example, as follows.
When the total solid content of the photosensitive resin composition is 100% by mass, it is preferable that the above-mentioned copolymer is contained in an amount of, for example, 30% by mass or more and 70% by mass or less, and above all, 40% by mass or more and 60% by mass or less. It is preferable to contain it.
Further, when the total solid content of the photosensitive resin composition is 100% by mass, the cross-linking agent is preferably contained, for example, 15% by mass or more and 50% by mass or less, and above all, 20% by mass or more and 50% by mass or less. Is preferable.
Furthermore, when the total solid content of the photosensitive resin composition is 100% by mass, it is preferable that the photoactive compound as a photosensitive agent is contained, for example, 5% by mass or more and 40% by mass or less, and 10% by mass or more and 30% by mass. It is more preferably contained in an amount of% by mass or less.
感光性樹脂組成物の全固形分を100質量%としたとき、前述した共重合体を、例えば、30質量%以上70質量%含有することが好ましく、中でも、40質量%以上60質量%以下含有することが好ましい。
また、感光性樹脂組成物の全固形分100質量%としたとき架橋剤(第二の架橋剤をのぞく。)を、例えば、15質量%以上50質量%以下含有することが好ましく、中でも、20質量%以上50質量%以下含有することが好ましい。
さらには、感光性樹脂組成物の全固形分を100質量%としたとき、光酸発生剤の量は、例えば、0.1質量%以上40質量%以下であり、高解像度のパターン膜を形成することができる点から、より好ましくは1質量%以上30質量%以下である。 When the photosensitive resin composition is of the negative type, the ratio of each component is as follows, for example.
When the total solid content of the photosensitive resin composition is 100% by mass, the above-mentioned copolymer is preferably contained in an amount of, for example, 30% by mass or more and 70% by mass, particularly 40% by mass or more and 60% by mass or less. It is preferable to do so.
Further, when the total solid content of the photosensitive resin composition is 100% by mass, it is preferable to contain a cross-linking agent (excluding the second cross-linking agent), for example, 15% by mass or more and 50% by mass or less, and among them, 20. It is preferably contained in an amount of% by mass or more and 50% by mass or less.
Furthermore, when the total solid content of the photosensitive resin composition is 100% by mass, the amount of the photoacid generator is, for example, 0.1% by mass or more and 40% by mass or less, forming a high-resolution pattern film. It is more preferably 1% by mass or more and 30% by mass or less from the viewpoint that it can be used.
以下に、代表成分について、詳細を説明する。 Additives such as a solvent, an antioxidant, a surfactant, an adhesion aid, a dissolution accelerator, a filler, a sensitizer, and polyphenols may be further added to the photosensitive resin composition.
The details of the representative components will be described below.
本実施形態に記載の感光性樹脂組成物は、上述の各成分を溶媒に溶解することで、ワニス状として使用することができる。
このような溶媒の例としては、N-メチル-2-ピロリドン、γ-ブチロラクトン、N,N-ジメチルアセトアミド、ジメチルスルホキシド、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、乳酸メチル、乳酸エチル、乳酸ブチル、メチル-1,3-ブチレングリコールアセテート、1,3-ブチレングリコール-3-モノメチルエーテル、ピルビン酸メチル、ピルビン酸エチル、およびメチル-3-メトキシプロピオネート等が挙げられる。 (solvent)
The photosensitive resin composition described in this embodiment can be used as a varnish by dissolving each of the above-mentioned components in a solvent.
Examples of such solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, and dipropylene glycol. Monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, and methyl -3-methoxypropionate and the like can be mentioned.
本実施形態における感光性樹脂組成物を調製する方法は限定されず、従来公知の方法を用いて調製することができる。
例えば、上記各成分を、溶媒に混合して溶解することにより調製することができる。これにより、ワニスとした感光性樹脂組成物を得ることができる。 (Preparation of photosensitive resin composition)
The method for preparing the photosensitive resin composition in the present embodiment is not limited, and it can be prepared by using a conventionally known method.
For example, each of the above components can be prepared by mixing and dissolving in a solvent. Thereby, a photosensitive resin composition as a varnish can be obtained.
このような樹脂膜は、例えば、レジストとしての用途として用いることができ、また、例えば、電子装置用の保護膜、層間膜、またはダム材等の永久膜を構成することもできる。 The photosensitive resin composition of the present embodiment can be used as a cured product to obtain a resin film.
Such a resin film can be used, for example, as a resist, and can also form, for example, a protective film for an electronic device, an interlayer film, or a permanent film such as a dam material.
(条件)
感光性樹脂組成物をガラス基板上に塗布し、100℃、120秒間の条件で乾燥し、300mJ/cm2の露光量で露光して得られる厚み3μmの樹脂膜Aについて、波長400nmの光の光線透過率を分光光度計で評価し、耐熱試験前透過率TA%とした。 The photosensitive resin composition of the present embodiment preferably has a transmittance of 95% or more, more preferably 98% or more, as measured under the following conditions.
(conditions)
A photosensitive resin composition is applied onto a glass substrate, dried at 100 ° C. for 120 seconds, and exposed to an exposure amount of 300 mJ / cm 2 , and the resin film A having a thickness of 3 μm is exposed to light having a wavelength of 400 nm. the light transmittance was evaluated with a spectrophotometer, and the pre-heat resistance test transmittance T a%.
(条件)
感光性樹脂組成物をガラス基板上に塗布し、100℃、120秒間の条件で乾燥し、300mJ/cm2の露光量で露光して得られる厚み3μmの樹脂膜Aについて、波長400nmの光の光線透過率を分光光度計で評価し、耐熱試験前透過率TA%とした。樹脂膜Aを大気雰囲気下、250℃、1時間加熱して得られる樹脂膜Bについて、波長400nmの光の光線透過率を分光光度計で評価し、耐熱試験後透過率TB%とした。TB/TA×100を耐熱変色性%とした。
本発明の感光性樹脂組成物を硬化させて得られる永久膜は、透過率、耐熱変色性に優れた永久膜となるため、特に、透明性が要求される用途、特に加熱されても着色しないことが要求される、例えば、液晶表示装置や有機EL素子等の各種表示装置有する電子装置の着色パターン、ブラックマトリクス、オーバーコート、リブ、およびスペーサーに適用することが好ましい。 The photosensitive resin composition of the present embodiment preferably has a heat-resistant discoloration property of the resin film of 95% or more, more preferably 96% or more, as measured under the following conditions.
(conditions)
A photosensitive resin composition is applied onto a glass substrate, dried at 100 ° C. for 120 seconds, and exposed to an exposure amount of 300 mJ / cm 2 , and the resin film A having a thickness of 3 μm is exposed to light having a wavelength of 400 nm. the light transmittance was evaluated with a spectrophotometer, and the pre-heat resistance test transmittance T a%. The resin film A under an air atmosphere, 250 ° C., the resin film B obtained by heating 1 hour, the transmittance of light with a wavelength of 400nm was evaluated by spectrophotometer and after the heat resistance test transmittance T B%. The T B / T A × 100 was heat discoloration resistance%.
The permanent film obtained by curing the photosensitive resin composition of the present invention is a permanent film having excellent transmittance and heat-resistant discoloration. Therefore, it is not colored even when it is heated, especially in applications requiring transparency. It is preferable to apply it to a coloring pattern, a black matrix, an overcoat, a rib, and a spacer of an electronic device having various display devices such as a liquid crystal display device and an organic EL element.
還流冷却管および滴下漏斗を備えた反応容器内に、2-ノルボルネンの75%トルエン溶液(NB、98.1g、2-ノルボルネン換算73.6g、0.782mol)、無水マレイン酸(MAN、76.7g、0.782mol)およびメチルエチルケトン(MEK)371.6gを加え、撹拌・溶解させた。次いで、窒素バブリングにより系内の溶存酸素を除去したのち、加温し、内温が80℃に到達したところで、2,2'-アゾビスイソ酪酸ジメチル(和光純薬工業製,商品名:V-601、7.20g、0.031mol)およびペンタエリスリトールテトラキス(3-メルカプトプロピオネート)(PEMP、15.3g、0.029mol)をMEK31.5gに溶解させた溶液を1時間かけて添加した。その後、さらに80℃で7時間反応させた。次いで、反応混合物を室温まで冷却した。反応後の溶液を大量のメタノールに注ぎ、ポリマーを析出させた。次いでポリマーを濾取し、さらにメタノールで洗浄した後、120℃、16時間真空乾燥させた。ポリマーの収量は145.3g、収率は97%であった。また、ポリマーは、重量平均分子量Mwが3,500であり、分散度(重量平均分子量Mw/数平均分子量Mn)が1.62であった。 (Synthesis Example 1: Synthesis of precursor polymer A)
In a reaction vessel equipped with a reflux condenser and a dropping funnel, a 75% toluene solution of 2-norbornene (NB, 98.1 g, 2-norbornene equivalent 73.6 g, 0.782 mol), maleic anhydride (MAN, 76. 7 g, 0.782 mol) and 371.6 g of methyl ethyl ketone (MEK) were added, and the mixture was stirred and dissolved. Then, after removing the dissolved oxygen in the system by nitrogen bubbling, it was heated, and when the internal temperature reached 80 ° C., dimethyl 2,2'-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-601). , 7.20 g, 0.031 mol) and pentaerythritol tetrakis (3-mercaptopropionate) (PEMP, 15.3 g, 0.029 mol) dissolved in 31.5 g of MEK were added over 1 hour. Then, the reaction was further carried out at 80 ° C. for 7 hours. The reaction mixture was then cooled to room temperature. The solution after the reaction was poured into a large amount of methanol to precipitate a polymer. The polymer was then collected by filtration, washed with methanol, and vacuum dried at 120 ° C. for 16 hours. The yield of the polymer was 145.3 g, and the yield was 97%. The polymer had a weight average molecular weight Mw of 3,500 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.62.
還流冷却管および滴下漏斗を備えた反応容器内に、2-ノルボルネンの75%トルエン溶液(54.8g、2-ノルボルネン換算41.1g、0.436mol)、V-601(4.0g、0.017mol)およびMEK26.5gを加え、撹拌・溶解させた。次いで、窒素バブリングにより系内の溶存酸素を除去したのち、加温し、内温が60℃に到達したところで、N-シクロヘキシルマレイミド(CMI、7.8g、0.044mol)、無水マレイン酸(38.5g、0.393mol)および3-メルカプトプロピルトリメトキシシラン(商品名:KBM-803、信越化学工業株式会社製、8.6g、0.044mol)をMEK109.8gに溶解させた溶液を3時間かけて添加した。その後、80℃に昇温しさらに6時間反応させた。次いで、反応混合物を室温まで冷却し、MEK83.3gを添加し希釈した。希釈後の溶液を大量のメタノールに注ぎ、ポリマーを析出させた。次いでポリマーを濾取し、さらにメタノールで洗浄した後、120℃、16時間真空乾燥させた。ポリマーの収量は56.0g、収率は64%であった。また、ポリマーは、重量平均分子量Mwが4,500であり、分散度(重量平均分子量Mw/数平均分子量Mn)が1.59であった。 (Synthesis Example 2: Synthesis of precursor polymer B)
In a reaction vessel equipped with a reflux condenser and a dropping funnel, a 75% toluene solution of 2-norbornene (54.8 g, 2-norbornene equivalent 41.1 g, 0.436 mol), V-601 (4.0 g, 0. 017 mol) and 26.5 g of MEK were added, and the mixture was stirred and dissolved. Then, after removing the dissolved oxygen in the system by nitrogen bubbling, it was heated, and when the internal temperature reached 60 ° C., N-cyclohexylmaleimide (CMI, 7.8 g, 0.044 mol) and maleic anhydride (38). .5 g, 0.393 mol) and 3-mercaptopropyltrimethoxysilane (trade name: KBM-803, manufactured by Shin-Etsu Chemical Industry Co., Ltd., 8.6 g, 0.044 mol) dissolved in MEK 109.8 g for 3 hours. It was added over. Then, the temperature was raised to 80 ° C. and the reaction was carried out for another 6 hours. The reaction mixture was then cooled to room temperature and 83.3 g of MEK was added and diluted. The diluted solution was poured into a large amount of methanol to precipitate the polymer. The polymer was then collected by filtration, washed with methanol, and vacuum dried at 120 ° C. for 16 hours. The yield of the polymer was 56.0 g and the yield was 64%. The polymer had a weight average molecular weight Mw of 4,500 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.59.
還流冷却管および滴下漏斗を備えた反応容器内に、2-ノルボルネンの75%トルエン溶液(62.3g、2-ノルボルネン換算46.7g、0.496mol)、V-601(4.6g,0.020mol)およびMEK45.9gを加え、撹拌・溶解させた。次いで、窒素バブリングにより系内の溶存酸素を除去したのち、加温し、内温が60℃に到達したところで、無水マレイン酸(48.7g、0.496mol)をMEK88.5gに溶解させた溶液を3時間かけて添加した。その後、80℃に昇温しさらに6時間反応させた。次いで、反応混合物を室温まで冷却し、MEK83.3gを添加し希釈した。希釈後の溶液を大量のメタノールに注ぎ、ポリマーを析出させた。次いでポリマーを濾取し、さらにメタノールで洗浄した後、120℃、16時間真空乾燥させた。ポリマーの収量は92.5g、収率は93%であった。また、ポリマーは、重量平均分子量Mwが6,900であり、分散度(重量平均分子量Mw/数平均分子量Mn)が1.76であった。 (Synthesis Example 3: Synthesis of Precursor Polymer C)
In a reaction vessel equipped with a reflux condenser and a dropping funnel, a 75% toluene solution of 2-norbornene (62.3 g, 2-norbornene equivalent 46.7 g, 0.496 mol), V-601 (4.6 g, 0. 020 mol) and 45.9 g of MEK were added, and the mixture was stirred and dissolved. Then, after removing the dissolved oxygen in the system by nitrogen bubbling, it was heated, and when the internal temperature reached 60 ° C., a solution in which maleic anhydride (48.7 g, 0.496 mol) was dissolved in MEK 88.5 g. Was added over 3 hours. Then, the temperature was raised to 80 ° C. and the reaction was carried out for another 6 hours. The reaction mixture was then cooled to room temperature and 83.3 g of MEK was added and diluted. The diluted solution was poured into a large amount of methanol to precipitate the polymer. The polymer was then collected by filtration, washed with methanol, and vacuum dried at 120 ° C. for 16 hours. The yield of the polymer was 92.5 g and the yield was 93%. The polymer had a weight average molecular weight Mw of 6,900 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.76.
還流冷却管および滴下漏斗を備えた反応容器内に、2-ノルボルネン(NB)の75%トルエン溶液(179.7g、2-ノルボルネン換算134.8g、1.43mol)、V-601(13.2g,0.057mol)およびMEK101.0gを加え、撹拌・溶解させた。次いで、窒素バブリングにより系内の溶存酸素を除去したのち、加温し、内温が60℃に到達したところで、N-シクロヘキシルマレイミド(25.7g、0.14mol)および無水マレイン酸(126.4g、1.29mol)をMEK304.0gに溶解させた溶液を3時間かけて添加した。その後、80℃に昇温しさらに6時間反応させた。次いで、反応混合物を室温まで冷却し、MEK250gを添加し希釈した。希釈後の溶液を大量のメタノールに注ぎ、ポリマーを析出させた。次いでポリマーを濾取し、さらにメタノールで洗浄した後、120℃、16時間真空乾燥させた。ポリマーの収量は250.0g、収率は83%であった。また、ポリマーは、重量平均分子量Mwが7,600であり、分散度(重量平均分子量Mw/数平均分子量Mn)が1.88であった。 (Synthesis Example 4: Synthesis of Precursor Polymer D)
A 75% toluene solution of 2-norbornene (NB) (179.7 g, 2-norbornene equivalent 134.8 g, 1.43 mol), V-601 (13.2 g) in a reaction vessel equipped with a reflux condenser and a dropping funnel. , 0.057 mol) and 101.0 g of MEK were added, and the mixture was stirred and dissolved. Then, after removing the dissolved oxygen in the system by nitrogen bubbling, the mixture was heated, and when the internal temperature reached 60 ° C., N-cyclohexylmaleimide (25.7 g, 0.14 mol) and maleic anhydride (126.4 g) were used. , 1.29 mol) was dissolved in 304.0 g of MEK and added over 3 hours. Then, the temperature was raised to 80 ° C. and the reaction was carried out for another 6 hours. The reaction mixture was then cooled to room temperature and 250 g of MEK was added and diluted. The diluted solution was poured into a large amount of methanol to precipitate the polymer. The polymer was then collected by filtration, washed with methanol, and vacuum dried at 120 ° C. for 16 hours. The yield of the polymer was 250.0 g and the yield was 83%. The polymer had a weight average molecular weight Mw of 7,600 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.88.
還流冷却管および滴下漏斗を備えた反応容器内に、2-ノルボルネン(NB)の75%トルエン溶液(18.8g、2-ノルボルネン換算14.1g、0.15mol)、MAN(14.7g、0.15mol)、V-601(1.4g,6mmol)、α-メチルスチレンダイマー(α-MSD、1.4g、6mmol)およびMEK21.3gを加え、撹拌・溶解させた。次いで、窒素バブリングにより系内の溶存酸素を除去したのち、加温し、内温が60℃で16時間反応させた。次いで、反応混合物を室温まで冷却し、大量のメタノールに注ぎポリマーを析出させた。次いでポリマーを濾取し、さらにメタノールで洗浄した後、120℃、16時間真空乾燥させた。ポリマーの収量は6.7g、収率は23%であった。また、ポリマーは、重量平均分子量Mwが4,900であり、分散度(重量平均分子量Mw/数平均分子量Mn)が2.11であった。
合成例1~5で使用した成分の配合量、ならびに得られた前駆体ポリマーの重量平均分子量および分散度を、表1に示す。 (Synthesis Example 5: Synthesis of Precursor Polymer E)
A 75% toluene solution of 2-norbornene (NB) (18.8 g, 2-norbornene equivalent 14.1 g, 0.15 mol), MAN (14.7 g, 0) in a reaction vessel equipped with a reflux condenser and a dropping funnel. .15 mol), V-601 (1.4 g, 6 mmol), α-methylstyrene dimer (α-MSD, 1.4 g, 6 mmol) and 21.3 g of MEK were added, and the mixture was stirred and dissolved. Then, after removing the dissolved oxygen in the system by nitrogen bubbling, the mixture was heated and reacted at an internal temperature of 60 ° C. for 16 hours. The reaction mixture was then cooled to room temperature and poured into a large amount of methanol to precipitate the polymer. The polymer was then collected by filtration, washed with methanol, and vacuum dried at 120 ° C. for 16 hours. The yield of the polymer was 6.7 g and the yield was 23%. The polymer had a weight average molecular weight Mw of 4,900 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 2.11.
Table 1 shows the blending amounts of the components used in Synthesis Examples 1 to 5, and the weight average molecular weight and dispersity of the obtained precursor polymer.
合成例1で合成した前駆体ポリマーA20.0gをMEK30.0gに溶解させた。さらに2-ヒドロキシエチルメタクリレート(HEMA)8.5gとトリエチルアミン(TEA)2.0gを添加し、70℃に昇温した後6時間反応させた。次いで、系中にメタクリル酸グリシジル(GMA)4.4gを追加し70℃でさらに4時間反応させた。反応混合液を室温に冷却し、ギ酸にて中和した。溶液を大量の純水に注ぎ、ポリマーを析出させた。得られたポリマーを濾取し、さらに純水で洗浄した後、PGMEAに溶解させ、減圧下で残留水分の除去・濃縮を行って固形分約35%のポリマー溶液を得た。このようにして得られたポリマーの重量平均分子量(Mw)、分子量分布、アルカリ溶解速度、二重結合当量は、表2に記載の通りであった。 (Synthesis Example 6: Synthesis of Polymer A-1)
20.0 g of the precursor polymer A synthesized in Synthesis Example 1 was dissolved in 30.0 g of MEK. Further, 8.5 g of 2-hydroxyethyl methacrylate (HEMA) and 2.0 g of triethylamine (TEA) were added, the temperature was raised to 70 ° C., and the reaction was carried out for 6 hours. Then, 4.4 g of glycidyl methacrylate (GMA) was added to the system and reacted at 70 ° C. for another 4 hours. The reaction mixture was cooled to room temperature and neutralized with formic acid. The solution was poured into a large amount of pure water to precipitate the polymer. The obtained polymer was collected by filtration, washed with pure water, dissolved in PGMEA, and residual water was removed and concentrated under reduced pressure to obtain a polymer solution having a solid content of about 35%. The weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are as shown in Table 2.
合成例2で合成した前駆体ポリマーB20.0gをMEK30.0gに溶解させた。さらに2-ヒドロキシエチルアクリレート(HEA)11.6gとトリエチルアミン(TEA)2.0gを添加し、70℃に昇温した後6時間反応させた。次いで、反応混合液を室温に冷却し、ギ酸にて中和した。溶液を大量の純水に注ぎ、ポリマーを析出させた。得られたポリマーを濾取し、さらに純水で洗浄した後、PGMEAに溶解させ、減圧下で残留水分の除去・濃縮を行って固形分約35%のポリマー溶液を得た。
このようにして得られたポリマーの重量平均分子量(Mw)、分子量分布、アルカリ溶解速度、二重結合当量は、表2に記載の通りであった。 (Synthesis Example 7: Synthesis of Polymer B-1)
20.0 g of the precursor polymer B synthesized in Synthesis Example 2 was dissolved in 30.0 g of MEK. Further, 11.6 g of 2-hydroxyethyl acrylate (HEA) and 2.0 g of triethylamine (TEA) were added, the temperature was raised to 70 ° C., and the reaction was carried out for 6 hours. The reaction mixture was then cooled to room temperature and neutralized with formic acid. The solution was poured into a large amount of pure water to precipitate the polymer. The obtained polymer was collected by filtration, washed with pure water, dissolved in PGMEA, and residual water was removed and concentrated under reduced pressure to obtain a polymer solution having a solid content of about 35%.
The weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are as shown in Table 2.
合成例3で合成した前駆体ポリマーC20.0gをMEK30.0gに溶解させた。さらに2-ヒドロキシエチルメタクリレート(HEMA)8.5gとトリエチルアミン(TEA)2.0gを添加し、70℃に昇温した後6時間反応させた。次いで、系中にメタクリル酸グリシジル(GMA)4.4gを追加し70℃でさらに4時間反応させた。反応混合液を室温に冷却し、ギ酸にて中和した。溶液を大量の純水に注ぎ、ポリマーを析出させた。得られたポリマーを濾取し、さらに純水で洗浄した後、PGMEAに溶解させ、減圧下で残留水分の除去・濃縮を行って固形分約35%のポリマー溶液を得た。このようにして得られたポリマーの重量平均分子量(Mw)、分子量分布、アルカリ溶解速度、二重結合当量は、表2に記載の通りであった。 (Synthesis Example 8: Synthesis of Polymer C-1)
20.0 g of the precursor polymer C synthesized in Synthesis Example 3 was dissolved in 30.0 g of MEK. Further, 8.5 g of 2-hydroxyethyl methacrylate (HEMA) and 2.0 g of triethylamine (TEA) were added, the temperature was raised to 70 ° C., and the reaction was carried out for 6 hours. Then, 4.4 g of glycidyl methacrylate (GMA) was added to the system and reacted at 70 ° C. for another 4 hours. The reaction mixture was cooled to room temperature and neutralized with formic acid. The solution was poured into a large amount of pure water to precipitate the polymer. The obtained polymer was collected by filtration, washed with pure water, dissolved in PGMEA, and residual water was removed and concentrated under reduced pressure to obtain a polymer solution having a solid content of about 35%. The weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are as shown in Table 2.
合成例4で合成した前駆体ポリマーD20.0gをMEK30.0gに溶解させた。さらに2-ヒドロキシエチルアクリレート(HEA)9.0gとトリエチルアミン(TEA)2.0gを添加し、70℃に昇温した後6時間反応させた。次いで、反応混合液を室温に冷却し、ギ酸にて中和した。溶液を大量の純水に注ぎ、ポリマーを析出させた。得られたポリマーを濾取し、さらに純水で洗浄した後、PGMEAに溶解させ、減圧下で残留水分の除去・濃縮を行って固形分約35%のポリマー溶液を得た。
このようにして得られたポリマーの重量平均分子量(Mw)、分子量分布、アルカリ溶解速度、二重結合当量は、表2に記載の通りであった。 (Synthesis Example 9: Synthesis of Polymer D-1)
20.0 g of the precursor polymer D synthesized in Synthesis Example 4 was dissolved in 30.0 g of MEK. Further, 9.0 g of 2-hydroxyethyl acrylate (HEA) and 2.0 g of triethylamine (TEA) were added, the temperature was raised to 70 ° C., and then the reaction was carried out for 6 hours. The reaction mixture was then cooled to room temperature and neutralized with formic acid. The solution was poured into a large amount of pure water to precipitate the polymer. The obtained polymer was collected by filtration, washed with pure water, dissolved in PGMEA, and residual water was removed and concentrated under reduced pressure to obtain a polymer solution having a solid content of about 35%.
The weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are as shown in Table 2.
合成例5で合成した前駆体ポリマーD5.0gをMEK7.5gに溶解させた。さらに2-ヒドロキシエチルアクリレート(HEA)2.9gとトリエチルアミン(TEA)0.5gを添加し、70℃に昇温した後6時間反応させた。次いで、反応混合液を室温に冷却し、ギ酸にて中和した。溶液を大量の純水に注ぎ、ポリマーを析出させた。得られたポリマーを濾取し、さらに純水で洗浄した後、PGMEAに溶解させ、減圧下で残留水分の除去・濃縮を行って固形分約35%のポリマー溶液を得た。
このようにして得られたポリマーの重量平均分子量(Mw)、分子量分布、アルカリ溶解速度、二重結合当量は、表2に記載の通りであった。 (Synthesis Example 10: Synthesis of Polymer E-1)
5.0 g of the precursor polymer D synthesized in Synthesis Example 5 was dissolved in 7.5 g of MEK. Further, 2.9 g of 2-hydroxyethyl acrylate (HEA) and 0.5 g of triethylamine (TEA) were added, the temperature was raised to 70 ° C., and the reaction was carried out for 6 hours. The reaction mixture was then cooled to room temperature and neutralized with formic acid. The solution was poured into a large amount of pure water to precipitate the polymer. The obtained polymer was collected by filtration, washed with pure water, dissolved in PGMEA, and residual water was removed and concentrated under reduced pressure to obtain a polymer solution having a solid content of about 35%.
The weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are as shown in Table 2.
なお、本明細書において、重量平均分子量(Mw)、数平均分子量(Mn)、および分子量分布(Mw/Mn)は、GPC測定により得られる標準ポリスチレン(PS)の検量線から求めた、ポリスチレン換算値を用いる。測定条件は、以下の通りである。
装置:東ソー社製ゲルパーミエーションクロマトグラフィー装置HLC-8320GPC
カラム:東ソー社製TSK-GEL Supermultipore HZ-M
検出器:液体クロマトグラム用RI検出器
測定温度:40℃
溶媒:THF
試料濃度:2.0mg/ミリリットル (Weight average molecular weight / molecular weight distribution)
In the present specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw / Mn) are converted to polystyrene obtained from the calibration curve of standard polystyrene (PS) obtained by GPC measurement. Use the value. The measurement conditions are as follows.
Equipment: Tosoh gel permeation chromatography equipment HLC-8320GPC
Column: TSK-GEL Supermultipore HZ-M manufactured by Tosoh Corporation
Detector: RI detector for liquid chromatogram Measurement temperature: 40 ° C
Solvent: THF
Sample concentration: 2.0 mg / ml
ポリマーの二重結合当量は以下の方法で測定した。まず、減圧乾燥して溶媒を除去したポリマー約50mgおよび内部標準物質としてテレフタル酸ジメチル約5mgを計量し、DMSO-d6に溶解させた。この溶液について、核磁気共鳴分光装置JNM-AL300(JEOL社製)を用いて1H-NMRの測定を行った。得られたスペクトルチャートの(メタ)アクリル基に由来するシグナル(5-7ppm)と内部標準物質のフェニル基のシグナル(4H、8.1ppm)の積分比から二重結合1モル当たりのポリマー重量(g/mol、二重結合当量)を算出した。 (Double bond equivalent)
The double bond equivalent of the polymer was measured by the following method. First, about 50 mg of the polymer which was dried under reduced pressure to remove the solvent and about 5 mg of dimethyl terephthalate as an internal standard substance were weighed and dissolved in DMSO-d6. This solution was measured by 1H-NMR using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL Ltd.). From the integral ratio of the signal derived from the (meth) acrylic group (5-7 ppm) of the obtained spectrum chart and the signal (4H, 8.1 ppm) of the phenyl group of the internal standard substance, the polymer weight per mole of the double bond ( g / mol, double bond equivalent) was calculated.
上記合成例6~10で得られたポリマー各100質量部に対し、架橋剤であるジペンタエリスリトールヘキサアクリレート(架橋剤1、DPHA)50質量部、感光剤としての光ラジカル開始剤(BASF社製、イルガキュアOXE01)10質量部、密着助剤(3-グリシドキシプロピルトリメトキシシラン、信越化学工業株式会社製、KBM-403)1質量部、界面活性剤(DIC株式会社製、F556)0.1質量部をプロピレングリコールモノメチルエーテルアセテートにて溶解し、固形分30%の溶液とした。その後孔径0.2μmのメンブランフィルターでろ過し、感光性樹脂組成物を調製した。
表3に各成分の配合量を示す。 <Preparation of photosensitive resin composition>
For each 100 parts by mass of the polymers obtained in Synthesis Examples 6 to 10, 50 parts by mass of dipentaerythritol hexaacrylate (crosslinking agent 1, DPHA) as a cross-linking agent and a photoradical initiator as a photosensitizer (manufactured by BASF). , Irgacure OXE01) 10 parts by mass, adhesion aid (3-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical Industry Co., Ltd., KBM-403) 1 part by mass, surfactant (DIC Co., Ltd., F556) 0. 1 part by mass was dissolved with propylene glycol monomethyl ether acetate to prepare a solution having a solid content of 30%. Then, it was filtered through a membrane filter having a pore size of 0.2 μm to prepare a photosensitive resin composition.
Table 3 shows the blending amount of each component.
・架橋剤1:以下の式(12)で示されるアクリル系架橋剤(ダイセルサイテック社製 DPHA)。 (Crosslinking agent)
-Crosslinking agent 1: An acrylic crosslinking agent represented by the following formula (12) (DPHA manufactured by Daicel Cytec).
・感光剤1:以下の式(11)で示される光ラジカル重合開始剤(BASF社製 Irgacure OXE02)を用いた。 (Photosensitive agent)
Photosensitizer 1: A photoradical polymerization initiator (Irgaceure OXE02 manufactured by BASF) represented by the following formula (11) was used.
・密着助剤1:3-グリシドキシプロピルトリメトキシシラン(信越化学工業社製 KBM-403) (Adhesion aid)
・ Adhesion aid 1: 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)
界面活性剤1:メガファックF-556(DIC株式会社製) (Surfactant)
Surfactant 1: Megafuck F-556 (manufactured by DIC Corporation)
(光線透過率 TA)
各実施例および各比較例について、以下のようにして感光性樹脂組成物を用いて形成される樹脂膜Aの光線透過率を測定した。まず、得られた感光性樹脂組成物をガラス基板にスピンコーターを用いて塗布した後、110℃、110秒間ホットプレートにてベークした。ガラス基板としては、縦100mm、横100mmサイズのコーニング社製1737ガラス基板を用いた。その後、感光性樹脂組成物全体にキヤノン社製g+h+i線マスクアライナー(PLA-501F)にて、g+h+i線を300mJ/cm2で露光した。次いで、該樹脂膜Aの、波長400nmの光線に対する光線透過率TA(%)を測定した。光線透過率TAは、紫外可視分光光度計を用いて測定した。結果を表3に示す。 Moreover, the obtained photosensitive resin composition was evaluated according to the following.
(Light transmittance T A)
For each Example and each Comparative Example, the light transmittance of the resin film A formed by using the photosensitive resin composition was measured as follows. First, the obtained photosensitive resin composition was applied to a glass substrate using a spin coater, and then baked on a hot plate at 110 ° C. for 110 seconds. As the glass substrate, a 1737 glass substrate manufactured by Corning Inc. having a size of 100 mm in length and 100 mm in width was used. Then, the entire photosensitive resin composition was exposed with g + h + i line mask aligner (PLA-501F) manufactured by Canon Inc. at 300 mJ / cm 2 . Then, of the resin film A, and measured for light transmittance T A (%) with respect to light having a wavelength of 400 nm. Light transmittance T A was measured using an ultraviolet-visible spectrophotometer. The results are shown in Table 3.
上記光線透過率TAに記載の方法で得た樹脂膜Aを、大気雰囲気下、250℃、1時間加熱し樹脂膜Bを得た。その後樹脂膜Bの波長400nmの光の光線透過率TBを評価した。TB/TA×100を耐熱変色性%とした。結果を表3に示す。 (Heat discoloration resistance T B / T A × 100)
The resin film A obtained by the method of light transmittance T A, an air atmosphere, 250 ° C., to obtain a heated 1 hour the resin film B. It was then evaluated for light transmittance T B of the light of wavelength 400nm of the resin film B. The T B / T A × 100 was heat discoloration resistance%. The results are shown in Table 3.
Claims (5)
- 一般式(1)で表される共重合体と、
架橋剤と、
感光剤と
を含む、感光性樹脂組成物。
lおよびmはそれぞれ、共重合体中における、AおよびBのモル含有率を示し、
l+m=1であり、
Xは、水素または炭素数1以上30以下の有機基であり、
Yは、-SR5aであり、Sは硫黄原子であり、R5aは、炭素数1以上30以下の有機基であり、
Aは、以下式(A1)で示される構造単位を含み、
Bは、式(B1)~(B6)により示される構造単位のうち少なくとも1つを含み、
ただし、前記式(1)に含まれる前記式(A1)で示される構造単位、および前記式(B1)~(B6)により示される構造単位の少なくとも1つが、エチレン性二重結合を有する炭素数1以上30以下の有機基を有する。)。 With the copolymer represented by the general formula (1),
Crosslinker and
A photosensitive resin composition containing a photosensitive agent.
l and m indicate the molar content of A and B in the copolymer, respectively.
l + m = 1
X is hydrogen or an organic group having 1 or more and 30 or less carbon atoms.
Y is −SR 5a , S is a sulfur atom, and R 5a is an organic group having 1 or more and 30 or less carbon atoms.
A includes a structural unit represented by the following formula (A1).
B contains at least one of the structural units represented by the formulas (B1) to (B6).
However, at least one of the structural unit represented by the formula (A1) and the structural unit represented by the formulas (B1) to (B6) contained in the formula (1) has an ethylenic double bond. It has 1 or more and 30 or less organic groups. ). - 当該感光性樹脂組成物の、以下の条件で測定したときの耐熱変色性が95%以上である、請求項1に記載の感光性樹脂組成物。
(条件)
感光性樹脂組成物をガラス基板上に塗布し、100℃、120秒間の条件で乾燥し、300mJ/cm2の露光量で露光して得られる厚み3μmの樹脂膜Aについて、波長400nmの光の光線透過率を分光光度計で評価し、耐熱試験前透過率TA%とした。樹脂膜Aを大気雰囲気下、250℃、1時間加熱して得られる樹脂膜Bについて、波長400nmの光の光線透過率を分光光度計で評価し、耐熱試験後透過率TB%とした。TB/TA×100を耐熱変色性%とした。 The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition has a heat-resistant discoloration property of 95% or more when measured under the following conditions.
(conditions)
A photosensitive resin composition is applied onto a glass substrate, dried at 100 ° C. for 120 seconds, and exposed to an exposure amount of 300 mJ / cm 2 , and the resin film A having a thickness of 3 μm is exposed to light having a wavelength of 400 nm. the light transmittance was evaluated with a spectrophotometer, and the pre-heat resistance test transmittance T a%. The resin film A under an air atmosphere, 250 ° C., the resin film B obtained by heating 1 hour, the transmittance of light with a wavelength of 400nm was evaluated by spectrophotometer and after the heat resistance test transmittance T B%. The T B / T A × 100 was heat discoloration resistance%. - 前記共重合体の重量平均分子量が1500以上30000以下である、請求項1または2に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1 or 2, wherein the weight average molecular weight of the copolymer is 1500 or more and 30,000 or less.
- 請求項1~3のいずれかに記載の感光性樹脂組成物の硬化物からなる樹脂膜。 A resin film made of a cured product of the photosensitive resin composition according to any one of claims 1 to 3.
- 請求項4に記載の樹脂膜を備える電子装置。 An electronic device including the resin film according to claim 4.
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