Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G10/00—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only
  • C08G10/02—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only of aldehydes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/022—Quinonediazides
• • 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
  • G03F7/22—Exposing sequentially with the same light pattern different positions of the same surface

Definitions

• the present disclosure relates to aralkyl resins, diluents for epoxy resins, curable resin compositions, photosensitive resin compositions, cured products, electronic devices, and methods for producing aralkyl resins.
• Patent Document 1 describes a composition for forming a resist upper layer film for lithography containing a fluorine-containing resin.
• Patent Document 2 describes a resin substrate for a circuit board containing a polymer having a fluorine atom.
• Patent Document 3 describes a resist underlayer film material containing a fluorine-containing resin.
• Patent Document 4 discloses a fluorine-containing resin that can be preferably used for manufacturing electronic devices.
• the resin described in Patent Document 4 is a novolac resin, and in particular, a resin containing a structure in which a monocyclic or polycyclic aromatic ring is directly substituted with an oxygen atom is disclosed.
• This novolak resin has also been required to have further improved properties.
• the present inventors conducted studies with one object being to provide a fluorine-containing aralkyl resin having excellent properties that can be used for the production of electronic devices.
• R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different.
• n is an integer of 0 to 2
• R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different.
• m and k are integers of 0 to 2
• m+k 3
• m+k is 4
• X is a single bond or a divalent substituent other than an oxygen atom.
• R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different.
• t is an integer of 0 to 2
• r is an integer of 1 or more
• s is an integer of 0 or more, provided that r + s ⁇ 4 when t is 0, r + s ⁇ 6 when t is 1,
• R 2 represents a hydrogen atom or a monovalent substituent, and when multiple R 2 are present, they may be the same or different.
• R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different.
• n is an integer of 0 to 2
• R 2 represents a hydrogen atom or a monovalent substituent, and when multiple R 2 are present, they may be the same or different, t is an integer of 0 to 2, r is 1 or more is an integer and s is an integer greater than or equal to 0, provided that r+s ⁇ 4 when t is 0, r+s ⁇ 6 when t is 1, and r+s ⁇ 8 when t is 2.
• R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different.
• m and k are integers of 0 to 2
• m+k 3
• m+k 4, it is an integer of p+q ⁇ 16
• X is a single bond or a divalent substituent other than an oxygen atom.
• R 2 represents a hydrogen atom or a monovalent substituent, and when multiple R 2 are present, they may be the same or different, t is an integer of 0 to 2, r is 1 or more is an integer and s is an integer greater than or equal to 0, provided that r+s ⁇ 4 when t is 0, r+s ⁇ 6 when t is 1, and r+s ⁇ 8 when t is 2.
• R3 represents a hydrogen atom or a monovalent organic group
• R4 represents a hydrogen atom, a methyl group, or a fluorine atom.
• a photosensitive resin composition comprising the aralkyl resin according to any one of [1] to [14] and a photosensitive agent.
• the photosensitive resin composition according to [19] which is a photoresist composition, a solder resist composition or an imprint composition.
• a method for producing an aralkyl resin comprising reacting an aromatic compound with fluoral in the presence of an acid catalyst to produce an aralkyl resin having a structural unit represented by the following general formula (1) or (2).
• R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different.
• n is an integer of 0 to 2
• R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different.
• m and k are integers of 0 to 2
• m+k 3
• m+k is 4
• X is a single bond or a divalent substituent other than an oxygen atom.
• a structure represented by the following general formula (4) or (5) by reacting an aromatic compound represented by the following general formula (11) or (12) with a phenolic compound in the presence of an acid catalyst A method for producing an aralkyl resin, comprising producing an aralkyl resin having units.
• R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different.
• n is an integer of 0 to 2
• a is an integer of 2 or more
• n is 2 is an integer of p+a ⁇ 10 when Z represents a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and when multiple Zs are present, they may be the same or different.
• R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when multiple R 1 are present, they may be the same or different.
• m and k are integers of 0 to 2
• a and b are integers of 1 or more
• Z represents a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and when multiple Zs are present, they may be the same or different.
• R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different.
• n is an integer of 0 to 2
• R 2 represents a hydrogen atom or a monovalent substituent, and when multiple R 2 are present, they may be the same or different, t is an integer of 0 to 2, r is 1 or more is an integer and s is an integer greater than or equal to 0, provided that r+s ⁇ 4 when t is 0, r+s ⁇ 6 when t is 1, and r+s ⁇ 8 when t is 2.
• R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different.
• m and k are integers of 0 to 2
• m+k 3
• m+k 4, it is an integer of p+q ⁇ 16
• X is a single bond or a divalent substituent other than an oxygen atom.
• R 2 represents a hydrogen atom or a monovalent substituent, and when multiple R 2 are present, they may be the same or different, t is an integer of 0 to 2, r is 1 or more is an integer and s is an integer greater than or equal to 0, provided that r+s ⁇ 4 when t is 0, r+s ⁇ 6 when t is 1, and r+s ⁇ 8 when t is 2.
• R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different.
• n is an integer of 0 to 2
• a is an integer of 2 or more, when n is 0, it is an integer of p + a ⁇ 6, when n is 1, it is an integer of p + a ⁇ 8, and n is 2 is an integer of p+a ⁇ 10 when
• R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different.
• m and k are integers of 0 to 2
• a and b are integers of 1 or more
• X is a single bond or excluding an oxygen atom It is a divalent substituent.
• X to Y in the description of numerical ranges means X or more and Y or less, unless otherwise specified.
• “1 to 5% by mass” means “1% by mass or more and 5% by mass or less”.
• alkyl group includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
• (meth)acryl used herein represents a concept that includes both acryl and methacryl. The same applies to similar notations such as "(meth)acrylate”.
• substituted means an atom or group of atoms having a bond.
• substituent refers to an atom or atomic group having one bond
• divalent substituent refers to an atom or atomic group having two bonds.
• organic group as used herein means an atomic group obtained by removing one or more hydrogen atoms from an organic compound, unless otherwise specified.
• monovalent organic group refers to an atomic group obtained by removing one hydrogen atom from any organic compound
• divalent organic group refers to two hydrogen atoms from any organic compound.
• the term “Me” represents a methyl group ( CH3 ).
• the term “fluoral” means trifluoroacetaldehyde.
• electronic device in this specification refers to semiconductor chips, semiconductor elements, printed wiring boards, electric circuits, display devices, information communication terminals, light emitting diodes, physical batteries, chemical batteries, etc., to which electronic engineering technology is applied. It is used in the sense of including elements, devices, final products, etc.
• Having a fluorine atom within a structural unit also provides advantages in, for example, imprint applications. Low adhesion to metal molds is expected as a property required for general imprinting resins. In the present disclosure, having a fluorine atom in a structural unit can reduce adhesion to a mold.
• the aralkyl resin in the present disclosure is an aralkyl resin having a structural unit represented by general formula (1) or (2) below.
• R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different.
• n is an integer of 0 to 2
• R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different.
• m and k are integers of 0 to 2
• m+k 3
• m+k is 4
• X is a single bond or a divalent substituent other than an oxygen atom.
• the aralkyl resin of the present disclosure has a structural unit represented by general formula (1) or (2) and a structural unit represented by general formulas (3), (4) and/or (5) below.
• R2 represents a hydrogen atom or a monovalent substituent, and when there are multiple R2s , they may be the same or different, and R1 is directly bonded to the aromatic ring.
• R 1 represents a monovalent substituent excluding those where the atom is an oxygen atom, and when there are multiple R 1s , they may be the same or different, t is an integer of 0 to 2, r is 1 and s is an integer greater than or equal to 0, provided that when t is 0, r+s ⁇ 4, when t is 1, r+s ⁇ 6, and when t is 2, r+s ⁇ 8.
• R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different.
• n is an integer of 0 to 2, when n is 0, it is an integer of p ⁇ 4, when n is 1, it is an integer of p ⁇ 6, and when n is 2, it is an integer of p ⁇ 8 .
• R 2 represents a hydrogen atom or a monovalent substituent, and when multiple R 2 are present, they may be the same or different, t is an integer of 0 to 2, r is 1 or more is an integer and s is an integer greater than or equal to 0, provided that r+s ⁇ 4 when t is 0, r+s ⁇ 6 when t is 1, and r+s ⁇ 8 when t is 2.
• R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different.
• m and k are integers of 0 to 2
• m+k 3
• m+k 4, it is an integer of p+q ⁇ 16
• X is a single bond or a divalent substituent other than an oxygen atom.
• R 2 represents a hydrogen atom or a monovalent substituent, and when multiple R 2 are present, they may be the same or different, t is an integer of 0 to 2, r is 1 or more is an integer and s is an integer greater than or equal to 0, provided that r+s ⁇ 4 when t is 0, r+s ⁇ 6 when t is 1, and r+s ⁇ 8 when t is 2.
• R 1 is a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom
• examples of the monovalent substituent include an alkyl group, a cycloalkyl group, an aryl group and an alkenyl group. , an alkynyl group, a cyano group, and the like.
• Arbitrary carbon atoms of these groups may be substituted with any number and combination of substituents such as halogen atoms and haloalkoxy groups.
• the number of carbon atoms in the monovalent substituent is, for example, 1-20, preferably 1-10.
• R 1 directly bonded to the aromatic ring examples include hydrogen, fluorine, carbon, nitrogen, sulfur, silicon and phosphorus atoms. These atoms may be substituted with any number and any combination of substituents such as hydrogen atoms, alkyl groups, cycloalkyl groups and aryl groups. Furthermore, when the number of R 1 in general formula (1) is 2 or more, two or more R 1 are linked to form a saturated or unsaturated, monocyclic or polycyclic, C 3-6 A cyclic group may be formed.
• R 1 is preferably a hydrogen atom, a fluorine atom or an alkyl group.
• the alkyl group is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, among which n-butyl, s-butyl, isobutyl, t-butyl, n-propyl, i- A propyl group, an ethyl group and a methyl group are preferred, and an ethyl group and a methyl group are particularly preferred.
• n is an integer of 0 to 2; when n is 0, p ⁇ 4; when n is 1, p ⁇ 6; and when n is 2, p ⁇ 8.
• p is preferably an integer of 0 to 2 from the viewpoint of ease of preparation of raw materials and cost.
• Preferred embodiments of the structural unit of the aralkyl resin having the partial structure represented by general formula (1) include structural units represented by the following structural formulas.
• R 1 is the same as R 1 in general formula (1), and preferred forms thereof are also the same.
• X is a divalent substituent group excluding an oxygen atom, it is preferably a divalent organic group.
• the divalent organic group include a methylene group, an ethylene group, an ethylidene group, a propylene group and a propylidene group. , isopropylidene group, butylene group, hexafluoroisopropylidene group, 2,2,2-trifluoroethylidene group, carbonyl group, phenylene group, naphthalene-1,4-diyl group and the like.
• X is a divalent substituent excluding an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, or the like is substituted with, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or the like. It may be a divalent substituent substituted with any number of groups in any combination.
• X is preferably a single bond or a divalent substituent in which a methylene group, an ethylene group, a hexafluoroisopropylidene group, a 2,2,2-trifluoroethylidene group, a nitrogen atom or a sulfur atom is the bonding site of X. is.
• Examples of divalent substituents in which a nitrogen atom serves as a binding site for X include -N(Me)- and -N(C 6 H 5 )-.
• m and k may be integers from 0 to 2.
• n and k are integers of 0 to 2; when m+k is 0, p+q ⁇ 8; when m+k is 1, p+q ⁇ 10; when m+k is 2, p+q ⁇ 12; , m+k is an integer of p+q ⁇ 14 when m+k is 3, and an integer of p+q ⁇ 16 when m+k is 4.
• p+q is preferably an integer of 0 to 4 from the viewpoint of ease of preparation of raw materials and cost.
• Preferred embodiments of the structural unit of the aralkyl resin having the partial structure represented by general formula (2) include structural units represented by the following structural formulas.
• aralkyl resin in the present disclosure may contain structural units that fit general formula (1) or (2) and structural units that do not fit general formulas (1) and (2).
• an aralkyl resin having a structural unit represented by general formula (1) or (2) and a structural unit represented by general formula (3), (4) and/or (5) is also used in the manufacture of electronic devices. It can be preferably used for
• R 1 is the same as R 1 in general formula (1), and preferred forms thereof are also the same.
• R 2 is a monovalent substituent
• examples of the monovalent substituent include an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group, a cyano group, a glycidyl group, and a (meth)acryl group. etc. can be mentioned. Any number and any combination of substituents such as halogen atoms, alkoxy groups and haloalkoxy groups may be substituted on any carbon of these groups.
• R 2 is preferably a partial structure containing a hydrogen atom, an alkyl group, a glycidyl group, a polymerizable carbon-carbon double bond, or a partial structure represented by general formula (6) below.
• R3 represents a hydrogen atom or a monovalent organic group
• R4 represents a hydrogen atom, a methyl group, or a fluorine atom. Having this partial structure is preferable from a synthetic point of view.
• R3 in the partial structure represented by the general formula (6) is a monovalent organic group having a terminal carboxyl group.
• the presence of a carboxyl group at the end provides the effect of increasing developability.
• t is an integer of 0 to 2
• r is an integer of 1 or more
• s is an integer of 0 or more
• r+s is preferably 1 to 2 from the viewpoint of ease of preparation of raw materials and cost.
• R 1 is the same as R 1 in general formula (1), and preferred forms thereof are also the same.
• R 2 is the same as R 2 in general formula (3), and the same preferred forms are also included.
• n is an integer of 0 to 2; when n is 0, p ⁇ 4; when n is 1, p ⁇ 6; and when n is 2, p ⁇ 8.
• t is an integer of 0 to 2
• r is an integer of 1 or more
• s is an integer of 0 or more, provided that r + s ⁇ 4 when t is 0, r + s ⁇ 6 when t is 1, and t is When 2, r+s ⁇ 8.
• the structural unit represented by the general formula (4) means a structural unit in which the structural unit represented by the general formula (1) and the structural unit represented by the general formula (3) are combined, and the general formula In the structural unit represented by (4), the molar ratio of the structural unit represented by general formula (1) to the structural unit represented by general formula (3) is 1:1.
• R 1 is the same as R 1 in general formula (1), and preferred forms thereof are also the same.
• X is the same as X in general formula (2), and the same preferred forms are also included.
• R 2 is the same as R 2 in general formula (3), and the same preferred forms are also mentioned.
• m and k are integers of 0 to 2; when m+k is 0, p+q ⁇ 8; when m+k is 1, p+q ⁇ 10; when m+k is 2, p+q ⁇ 12; , m+k is an integer of p+q ⁇ 14 when m+k is 3, and an integer of p+q ⁇ 16 when m+k is 4.
• t is an integer of 0 to 2
• r is an integer of 1 or more
• s is an integer of 0 or more, provided that r + s ⁇ 4 when t is 0, r + s ⁇ 6 when t is 1, and t is When 2, r+s ⁇ 8.
• the structural unit represented by the general formula (5) means a structural unit in which the structural unit represented by the general formula (2) and the structural unit represented by the general formula (3) are combined, and the general formula In the structural unit represented by (5), the molar ratio of the structural unit represented by general formula (2) to the structural unit represented by general formula (3) is 1:1.
• the weight average molecular weight of the aralkyl resin in the present disclosure is preferably 300-500,000, more preferably 300-300,000, and even more preferably 300-200,000.
• the weight-average molecular weight it is possible to adjust alkali solubility, solvent solubility, physical properties when formed into a film, and the like. That is, by adjusting the weight-average molecular weight, the applicability of the aralkyl resin of the present disclosure to the manufacture of electronic devices can be further enhanced.
• the polydispersity (weight average molecular weight/number average molecular weight) of the aralkyl resin in the present disclosure is preferably 1-40, more preferably 1-20.
• the weight average molecular weight and polydispersity can be determined by gel permeation chromatography (GPC) using polystyrene as a standard substance.
• the aralkyl resins of the present disclosure are preferably used as diluents for epoxy resins. Also disclosed herein are diluents for epoxy resins, including the aralkyl resins of the present disclosure. Hereinafter, diluents for epoxy resins, including the aralkyl resins of the present disclosure, are referred to as diluents of the present disclosure.
• a curable resin composition comprising an aralkyl resin of the present disclosure or a diluent of the present disclosure and an epoxy resin is expected to have a dielectric constant and/or dissipation factor suitable for electronic device manufacturing.
• the term "diluent” refers to a substance that has few or no reactive substituents with the substance to be diluted (epoxy resin), and is used in the resin composition. It is a substance that reduces the concentration of the substance to be diluted in.
• the substance to be diluted is an epoxy resin
• the aralkyl resin used for the diluent of the epoxy resin or the diluent of the present disclosure preferably has a hydroxyl equivalent weight of 130 g/equivalent or more. It is also preferred that the aralkyl resin used for the diluent of the epoxy resin or the diluent of the present disclosure does not contain hydroxyl groups.
• the aralkyl resin of the present disclosure has a lower melt viscosity than the resin having no aralkyl structure of the present disclosure, and is excellent in handleability when used as a resin composition and fine workability during extrusion molding.
• the aralkyl resin of the present disclosure has a slower alkali dissolution rate than the resin having no aralkyl structure of the present disclosure, and the alkali dissolution rate can be appropriately controlled, so that the developability and film reduction are improved. be able to.
• the aralkyl resin of the present disclosure has sufficient heat resistance to be used in electronic device applications.
• the aralkyl resin of the present disclosure can employ a production method using a fluoral-containing mixture as a raw material in order to provide the “—CHCF 3 —” structure on the right side of general formulas (1) and (2).
• This method provides a higher yield than using formaldehyde as a raw material to produce an aralkyl resin having a “—CH 2 —” structure. From this point of view as well, the aralkyl resin of the present disclosure having the structure “—CHCF 3 —” is excellent.
• aralkyl resin I-1 (synthesis method I-1)> An aralkyl resin having a structural unit represented by general formula (1) or (2) can be produced (synthesized) by reacting an aromatic compound with fluorol in the presence of an acid catalyst. Raw materials, reaction conditions, and the like are described below.
• aromatic compounds examples include alkylbenzenes such as benzene, toluene, ethylbenzene, propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene and tert-butylbenzene; xylenes such as o-xylene, m-xylene and p-xylene; trimethylbenzenes such as 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene and 1,3,5-trimethylbenzene; halogenated benzenes such as fluorobenzene, chlorobenzene, bromobenzene and iodobenzene; , biphenyl, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 1,2-dimethylnaphthalene, 1,3-dimethylnaphthalene, 1,4-dimethylnaphthalene
• Polycyclic aromatics may also be mentioned.
• Aromatic compounds having multiple aromatic rings in the molecule such as hexafluoro-2,2-diphenylpropane and trifluoro-2,2-diphenylethane, can also be mentioned.
• Aromatic amines such as diphenylamine, triphenylamine and carbazole; aromatic thiols such as thiophenol, toluenethiol and naphthalenethiol; aromatics such as thioanisole, diphenylsulfide, bis(p-tolyl)sulfide and dibenzothiophene. Sulfides may also be mentioned.
• fluororal For the preparation of fluororal, commercially available hydrates (products of Tokyo Chemical Industry Co., Ltd.) and hemiacetal of fluororal can be used as its equivalents. A hydrate of fluoral and a hemiacetal of fluoral can also be prepared by the method described in Japanese Patent Application Laid-Open No. 5-97757.
• Fluorals are low-boiling compounds, generally highly self-reactive, and difficult to handle.
• fluoral can be handled very stably in a hydrogen fluoride solution.
• 1,2,2,2-tetrafluoroethanol which is an adduct of fluoral and hydrogen fluoride, is produced as shown in the scheme below.
• 1,2,2,2-tetrafluoroethanol is in an equilibrium relationship between fluoral and hydrogen fluoride. It is presumed that when hydrogen fluoride is excessively present in the system, the equilibrium shifts toward the 1,2,2,2-tetrafluoroethanol side, and as a result, the decomposition of fluororal is suppressed. According to the findings of the present inventors, it has been confirmed that fluoral in hydrogen fluoride not only improves the stability of the compound but also raises the boiling point. It can be easily handled as an adduct of hydrogen.
• the amount of hydrogen fluoride to be added is usually 0.1 to 100 mol, preferably 1 to 75 mol, more preferably 2 to 50 mol, per 1 mol of the prepared fluororal. is.
• the amount of hydrogen fluoride to be added is determined from the viewpoint of sufficient stabilization effect and cost.
• the fluoral/hydrogen fluoride mixture may also contain excess hydrogen fluoride.
• hydrogen fluoride since hydrogen fluoride itself has a function as an acidic substance, hydrogen fluoride may act as an acid catalyst or a dehydrating agent, or act as an additive that accelerates the reaction. From these points, it can be said that there is an advantage in treating fluoral as a mixture of hydrogen fluoride.
• the synthesis can be carried out, for example, at -20 to 150°C for 1 to 30 hours.
• the pressure during synthesis can be carried out under conditions of 0.1 to 10 MPa in terms of absolute pressure.
• the pressure is preferably 0.1-5 MPa, more preferably 0.1-1 MPa.
• a solvent may be used in the synthesis.
• solvents include ketones such as acetone and methyl ethyl ketone, alcohols such as ethanol and butanol, esters such as ethyl acetate and butyl acetate, and ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, diisopropyl ether, and tert-butyl methyl ether.
• ether alcohols such as ethoxyethyl alcohol
• ether esters such as propylene glycol monomethyl ether acetate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylimidazolidinone, etc.
• Nitriles such as amides, acetonitrile, propionitrile, and benzonitrile, sulfoxides such as dimethylsulfoxide, cyclic sulfones such as sulfolane, nitro hydrocarbons such as nitromethane and nitroethane, and nitro aromatic hydrocarbons such as nitrobenzene types can be mentioned.
• Halogen-based solvents such as 1,2-dichloroethane, chloroform, methylene chloride, carbon tetrachloride, and trichloroethane are also preferably used, particularly when fluoral is used as in the present disclosure.
• the molar ratio of aromatic compound:fluoral during synthesis is preferably 2:1 to 1:3, more preferably 2:1 to 1:2, still more preferably 2:1 to 1:1. be.
• the fluorine atoms are efficiently introduced into the aralkyl resin, and the solvent solubility when used in photosensitive resist applications can be made more suitable, making it suitable for imprint applications. Adhesion to the mold when used can be made more suitable.
• Catalysts that can be used in the synthesis include inorganic acids such as hydrochloric acid, sulfuric acid, perchloric acid and phosphoric acid, organic acids such as formic acid, acetic acid, oxalic acid, trichloroacetic acid and p-toluenesulfonic acid, zinc acetate, zinc chloride. and divalent metal salts such as magnesium acetate. These may be used alone or in combination of two or more. Incidentally, as mentioned above, it is believed that when a fluoral/hydrogen fluoride mixture is used, the hydrogen fluoride acts as an acid catalyst.
• the amount of the acid catalyst is preferably 0.01 to 100 mol, more preferably 0.1 to 30 mol, still more preferably 0, per 1 mol of fluoral. .5 to 25 mol.
• aralkyl resin For the obtained aralkyl resin, unreacted substances and impurities are removed by combining a precipitation treatment by putting it in a poor solvent (typically water), a washing treatment with water or sodium bicarbonate water, and a liquid separation operation. preferably.
• a poor solvent typically water
• a washing treatment with water or sodium bicarbonate water preferably.
• a liquid separation operation preferably.
• the aralkyl resin of this embodiment may be in powder form.
• the above powder may be dissolved in any solvent and used as an aralkyl resin solution.
• the total reaction time is usually 1 to 30 hours.
• analytical instruments such as nuclear magnetic resonance (NMR), gas chromatography (GC), liquid chromatography (LC), and gel permeation chromatography (GPC) are used, and the reaction conversion rate reaches a predetermined value.
• the reaction is preferably terminated when it is confirmed that it has been reached.
• ⁇ Manufacturing method I-2 of aralkyl resin (synthesis method I-2)> By reacting an aromatic compound, a phenolic compound, and a fluoral in the presence of an acid catalyst, in addition to the structural unit represented by general formula (1) or (2), general formula (3), ( An aralkyl resin having structural units represented by 4) and/or (5) and having phenolic hydroxyl groups and/or alkoxy groups in the molecular chain can be produced (synthesized). Raw materials, reaction conditions, and the like are described below.
• aromatic compound The aromatic compound is the same as the aromatic compound in ⁇ Aralkyl resin production method I-1 (synthesis method I-1)>.
• phenolic compounds examples include phenol, cresols such as o-cresol, m-cresol and p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3 xylenols such as ,4-xylenol and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol; o-isopropylphenol, m-isopropylphenol, p-isopropylphenol, etc.
• polycyclic phenols such as 1-naphthol, 2-naphthol and 2-hydroxyanthracene, and dihydroxybenzenes such as hydroquinone, resorcinol and catechol.
• bisphenols such as bisphenol A, bisphenol F, bisphenol E, bisphenol S, bisphenol AF, bisphenol M, bisphenol P, bisphenol Z, 1,1,1-trifluoro-2,2-bis(4-hydroxyphenyl)ethane types can also be mentioned.
• alkoxybenzenes such as methoxybenzene, ethoxybenzene and propoxybenzene
• alkoxynaphthalenes such as 1-methoxynaphthalene and 2-methoxynaphthalene
• 1,2-dimethoxybenzene, 1,3-dimethoxybenzene and 1,4-dimethoxybenzene dialkoxybenzenes such as 1,2-dimethoxynaphthalene, 1,3-dimethoxynaphthalene, 1,4-dimethoxynaphthalene, 2,3-dimethoxynaphthalene, 2,4-dimethoxynaphthalene and other dialkoxynaphthalenes
• fluoroanisole chloroanisole, bromoanisole, iodoanisole, and other halogenated anisoles
• phenolic compounds having both a phenolic hydroxyl group and an alkoxy group on the aromatic ring, such as methoxyphenol and methoxynap
• fluoral is the same as the fluoral in ⁇ Aralkyl resin production method I-1 (synthesis method I-1)>.
• the synthesis can be carried out, for example, at -20 to 150°C for 1 to 30 hours.
• the pressure during synthesis can be carried out under conditions of 0.1 to 10 MPa in terms of absolute pressure.
• the pressure is preferably 0.1-5 MPa, more preferably 0.1-1 MPa.
• a solvent may be used in the synthesis.
• the solvent is the same as the solvent in the above ⁇ Aralkyl resin production method I-1 (synthesis method I-1)>.
• the molar ratio of aromatic compound to phenolic compound during synthesis is preferably from 99:1 to 1:99, more preferably from 95:5 to 5:95.
• the phenolic hydroxyl group and/or alkoxy group are efficiently introduced into the aralkyl resin, and the alkali solubility and solvent solubility are more suitable when used for photosensitive resist applications.
• the molar ratio of the sum of the aromatic compound and the phenolic compound to the fluoral during the synthesis is preferably from 2:1 to 1:3, more preferably from 2:1 to 1:2, still more preferably 2: 1 to 1:1.
• fluorine atoms are efficiently introduced into the aralkyl resin, and alkali solubility and solvent solubility can be made more suitable when used for photosensitive resist applications. Adhesion to a mold when used for imprinting can be made more suitable.
• the catalyst that can be used in the synthesis is the same as the catalyst in ⁇ Aralkyl resin production method I-1 (synthesis method I-1)>.
• the amount of the acid catalyst is the same as the amount of the catalyst in ⁇ Aralkyl resin production method I-1 (synthesis method I-1)>.
• aralkyl resin For the obtained aralkyl resin, unreacted substances and impurities are removed by combining a precipitation treatment by putting it in a poor solvent (typically water), a washing treatment with water or sodium bicarbonate water, and a liquid separation operation. preferably.
• a poor solvent typically water
• a washing treatment with water or sodium bicarbonate water preferably.
• a liquid separation operation preferably.
• the aralkyl resin of this embodiment may be in powder form.
• the above powder may be dissolved in any solvent and used as an aralkyl resin solution.
• the obtained aralkyl resin having a phenolic hydroxyl group can be used as an epoxy resin by, for example, reacting epichlorohydrin.
• the obtained epoxy resin can be reacted with a carboxylic acid such as (meth)acrylic acid and used as an epoxy (meth)acrylate resin.
• the resulting epoxy (meth)acrylate resin can be reacted with an acid anhydride or the like to be used as an acid-modified epoxy (meth)acrylate resin.
• the acid anhydride to be reacted may be a compound having a polymerizable carbon-carbon unsaturated bond.
• the total reaction time is usually 1 to 30 hours.
• analytical instruments such as nuclear magnetic resonance (NMR), gas chromatography (GC), liquid chromatography (LC), and gel permeation chromatography (GPC) are used, and the reaction conversion rate reaches a predetermined value.
• the reaction is preferably terminated when it is confirmed that it has been reached.
• n is an integer of 0 to 2
• a is an integer of 2 or more, when n is 0, it is an integer of p + a ⁇ 6, when n is 1, it is an integer of p + a ⁇ 8, and when n is 2 It is an integer of p+a ⁇ 10.
• Z represents a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and when multiple Zs are present, they may be the same or different.
• R 1 is the same as R 1 in general formula (1), and preferred forms thereof are also the same.
• X is the same as X in general formula (2), and the same preferred forms are also included.
• n and k are integers of 0 to 2
• a and b are integers of 1 or more
• m + k is an integer of p+q+a+b ⁇ 14 when is 2
• an integer of p+q+a+b ⁇ 16 when m+k is 3, and an integer of p+q+a+b ⁇ 18 when m+k is 4.
• Z is preferably a hydroxyl group from the viewpoints of ease of preparation of raw materials and cost.
• Z can be prepared by methods described in the literature, such as Journal of Polymer Science (Hoboken, NJ, United States) (2020), 58(16), 2197-2210.
• An aromatic compound having a structure represented by general formula (11), wherein Z is a hydroxyl group, is represented by general formula (13) below.
• An aralkyl resin having a structural unit represented by general formula (4) can be produced by reacting an aromatic compound represented by general formula (13) with a phenolic compound in the presence of an acid catalyst.
• R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different.
• n is an integer of 0 to 2
• a is an integer of 2 or more, when n is 0, it is an integer of p + a ⁇ 6, when n is 1, it is an integer of p + a ⁇ 8, and n is 2 is an integer of p+a ⁇ 10 when
• Z is preferably a hydroxyl group from the viewpoint of ease of preparation of raw materials and cost.
• Z can be prepared by methods described in literature such as Chinese Journal of Chemistry (2020), 38(9), 952-958.
• An aromatic compound having a structure represented by general formula (12), wherein Z is a hydroxyl group, is represented by general formula (14) below.
• An aralkyl resin having a structural unit represented by general formula (5) can be produced by reacting an aromatic compound represented by general formula (14) with a phenolic compound in the presence of an acid catalyst. preferable.
• R 1 represents a monovalent substituent excluding those in which the atom directly bonded to the aromatic ring is an oxygen atom, and when there are multiple R 1s , they may be the same or different.
• m and k are integers of 0 to 2
• a and b are integers of 1 or more
• p + q + a + b ⁇ 18 when m + k is 4
• X is a single bond or excluding an oxygen atom It is a divalent substituent.
• the synthesis can be carried out, for example, at -20 to 150°C for 2 to 30 hours.
• the pressure during synthesis can be carried out under conditions of 0.1 to 10 MPa in terms of absolute pressure.
• the pressure is preferably 0.1-5 MPa, more preferably 0.1-1 MPa.
• a solvent may be used in the synthesis.
• solvents include ketones such as acetone and methyl ethyl ketone, alcohols such as ethanol and butanol, esters such as ethyl acetate and butyl acetate, and ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, diisopropyl ether, and tert-butyl methyl ether.
• ether alcohols such as ethoxyethyl alcohol, ether esters such as propylene glycol monomethyl ether acetate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylimidazolidinone, etc.
• Nitriles such as amides, acetonitrile, propionitrile, and benzonitrile, sulfoxides such as dimethylsulfoxide, cyclic sulfones such as sulfolane, nitro hydrocarbons such as nitromethane and nitroethane, and nitro aromatic hydrocarbons such as nitrobenzene types can be mentioned.
• Halogen solvents such as 1,2-dichloroethane, chloroform, methylene chloride, carbon tetrachloride and trichloroethane are also preferably used.
• the molar ratio of the aromatic compound represented by the general formula (11) or (12) to the phenol compound during synthesis is preferably 1:5 to 2:1, more preferably 1:3 to 1: 1.
• fluorine atoms are efficiently introduced into the aralkyl resin, and alkali solubility and solvent solubility can be made more suitable when used for photosensitive resist applications. Adhesion to a mold when used for imprinting can be made more suitable.
• Catalysts that can be used in the synthesis include inorganic acids such as hydrochloric acid, sulfuric acid, hydrogen fluoride, perchloric acid and phosphoric acid; Organic acids, divalent metal salts such as zinc acetate, zinc chloride and magnesium acetate, and the like. These may be used alone or in combination of two or more.
• the amount of the acid catalyst is preferably 0.01 to 100 mol per 1 mol of the aromatic compound represented by the general formula (11) or (12). It is preferably 0.01 to 30 mol.
• aralkyl resin For the obtained aralkyl resin, unreacted substances and impurities are removed by combining a precipitation treatment by putting it in a poor solvent (typically water), a washing treatment with water or sodium bicarbonate water, and a liquid separation operation. preferably.
• a poor solvent typically water
• a washing treatment with water or sodium bicarbonate water preferably.
• a liquid separation operation preferably.
• the aralkyl resin of this embodiment may be in powder form.
• the above powder may be dissolved in any solvent and used as an aralkyl resin solution.
• the obtained aralkyl resin having a phenolic hydroxyl group can be used as an epoxy resin by, for example, reacting epichlorohydrin.
• the obtained epoxy resin can be reacted with a carboxylic acid such as (meth)acrylic acid and used as an epoxy (meth)acrylate resin.
• the resulting epoxy (meth)acrylate resin can be reacted with an acid anhydride or the like to be used as an acid-modified epoxy (meth)acrylate resin.
• the acid anhydride to be reacted may be a compound having a polymerizable carbon-carbon bond.
• the total reaction time is usually 1 to 30 hours.
• analytical instruments such as nuclear magnetic resonance (NMR), gas chromatography (GC), liquid chromatography (LC), and gel permeation chromatography (GPC) are used, and the reaction conversion rate reaches a predetermined value.
• the reaction is preferably terminated when it is confirmed that it has been reached.
• the aralkyl resin in the present disclosure can be used as a resin composition by mixing with each component different from the aralkyl resin in the present disclosure.
• a curable resin composition in the present disclosure can be mentioned as an application destination of the aralkyl resin in the present disclosure and the diluent in the present disclosure.
• a curable resin composition can be produced by using an aralkyl resin in the present disclosure in combination with an epoxy resin.
• the aralkyl resin in the present disclosure may act as a curing agent or a diluent for the epoxy resin.
• the aralkyl resin in the present disclosure has a substituent, such as a hydroxyl group, that exhibits reactivity with the epoxy resin, the aralkyl resin in the present disclosure acts as a curing agent for the epoxy resin.
• the aralkyl resin of the present disclosure When the aralkyl resin of the present disclosure does not have substituents, such as hydroxyl groups, that are reactive with the epoxy resin, the aralkyl resin of the present disclosure acts as a diluent for the epoxy resin.
• Aralkyl resins in the present disclosure contain fluorine atoms. Therefore, a cured product formed from a curable resin composition containing an aralkyl resin in the present disclosure is expected to have a dielectric constant and/or dielectric loss tangent suitable for electronic device manufacture.
• Epoxy resin The epoxy resin to be combined with the aralkyl resin in the present disclosure is not particularly limited, and known epoxy resins may be used.
• Known epoxy resins include bifunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, bisphenol AD type epoxy resin, hydrogenated bisphenol A type epoxy resin, and hydrogenated bisphenol.
• polyfunctional epoxy resins include phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A novolak epoxy resin, bisphenol AF novolak epoxy resin, dicyclopentadiene phenol epoxy resin, and terpene phenol epoxy resin. , phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol novolak type epoxy resin, polyhydric phenol resin obtained by condensation reaction with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, fluoral, petroleum heavy Epoxy resins, triglycidyl isocyanurates, etc. produced from various aromatic compounds such as modified phenolic resins obtained by polycondensing oils or pitches, formaldehyde polymers and phenols in the presence of acid catalysts, and epihalohydrin. can be mentioned.
• epoxy resins produced from various amine compounds such as diaminodiphenylmethane, aminophenol and xylenediamine and epihalohydrin
• epoxy resins produced from various carboxylic acids such as methylhexahydroxyphthalic acid and dimer acid and epihalohydrin Resins
• diluents for epoxy resins such as glycidyl ethers of aliphatic alcohols, alicyclic epoxy resins represented by 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, and the like are also included.
• the amount ratio of the aralkyl resin and the epoxy resin in the present disclosure may be appropriately designed based on the epoxy equivalent of the epoxy resin. Typically, the mass ratio of aralkyl resin to epoxy resin in the present disclosure is about 1:10 to 10:1.
• the curable resin composition in the present disclosure may contain curing agents other than the aralkyl resin in the present disclosure.
• the type of curing agent is not particularly limited. Examples of curing agents include amine-based curing agents, acid anhydride-based curing agents, and phenol-based curing agents.
• the amine curing agent includes diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N-aminoethylpiperazine, isophoronediamine, bis(4-aminocyclohexyl)methane, bis(aminomethyl)cyclohexane, m-xyl Aliphatic and alicyclic amines such as diamine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraspiro[5,5]undecane, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenyl aromatic amines such as sulfone, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo-(5,4,0)-undecene-7,1,5-diazabicyclo- Tertiary amines such as (4,3,0)-n
• the acid anhydride curing agent includes aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride.
• aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride
• tetrahydrophthalic anhydride methyltetrahydrophthalic anhydride
• hexahydrophthalic anhydride alicyclic acid anhydrides
• acids such as acids, methylhexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, and the like.
• phenolic curing agents include catechol, resorcinol, hydroquinone, bisphenol F, bisphenol A, bisphenol AF, bisphenol S, biphenol, 1,1,1-trifluoro-2,2-bis(4-hydroxyphenyl ) dihydric phenols such as ethane, phenol novolacs, cresol novolaks, bisphenol A novolaks, trishydroxyphenylmethanes, aralkylpolyphenols, and various aldehydes and phenols such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, and fluoral polyhydric phenol resin obtained by condensation reaction with bisphenol-based compounds, modified phenol resin obtained by polycondensation of heavy petroleum oil or pitches, formaldehyde polymer and phenols in the presence of an acid catalyst, etc.
• phenolic compounds and the like can be mentioned.
• curing agents include imidazole compounds and their salts, amine BF3 complex compounds, aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts and Bronsted acid salts such as phosphonium salts, dicyandiamide, adipic acid dihydrazide and phthalate. Also included are organic acid hydrazides such as acid dihydrazides, adipic acid, sebacic acid, terephthalic acid, trimellitic acid, and polycarboxylic acids such as carboxyl group-containing polyesters.
• the curable resin composition in the present disclosure may contain only one curing agent, or may contain curing agents with two or more different chemical structures.
• the amount thereof may be appropriately adjusted based on the epoxy equivalent of the epoxy resin and the like. Typically, when a curing agent is used, its amount is about 0.1 to 1,000 parts by weight with respect to 100 parts by weight of the epoxy resin.
• the curable resin composition in the present disclosure may contain a curing accelerator.
• curing accelerators for general epoxy resins such as tertiary amines, imidazoles, organic phosphine compounds or their salts, metal soaps such as zinc octylate and tin octylate can be used. can.
• the curable resin composition in the present disclosure may contain only one curing accelerator, or may contain two or more curing accelerators with different chemical structures.
• the amount may be adjusted as appropriate. Typically, when a curing accelerator is used, its amount is about 0.001 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin.
• the curable resin composition in the present disclosure can contain one or more optional components in addition to the above components.
• Optional components include antioxidants, fillers, colorants, resins other than aralkyl resins, curable monomers, oligomers, and organic solvents.
• antioxidants examples include phenol-based, sulfur-based, and phosphorus-based antioxidants. When an antioxidant is used, its amount is usually 0.005 to 5 parts by weight, preferably 0.01 to 1 part by weight, per 100 parts by weight of the aralkyl resin.
• Fillers include metal oxides such as aluminum oxide and magnesium oxide, silicon compounds such as fine powder silica, fused silica and crystalline silica, glass beads, metal hydroxides such as aluminum hydroxide, gold, silver, Metals such as copper and aluminum, fluororesin powders such as polytetrafluoroethylene particles, carbon, rubbers, kaolin, mica, quartz powder, graphite, molybdenum disulfide, and boron nitride can be used.
• a filler its amount is, for example, 1,500 parts by mass or less, preferably 0.1 to 1,500 parts by mass, based on 100 parts by mass of the aralkyl resin.
• coloring agent examples include inorganic pigments such as titanium dioxide, molybdenum red, Prussian blue, ultramarine blue, cadmium yellow, and cadmium red, organic pigments, carbon black, phosphors, and the like.
• inorganic pigments such as titanium dioxide, molybdenum red, Prussian blue, ultramarine blue, cadmium yellow, and cadmium red
• organic pigments carbon black, phosphors, and the like.
• a coloring agent When a coloring agent is used, its amount is usually 0.01 to 30 parts by weight per 100 parts by weight of the aralkyl resin.
• flame retardants examples include antimony trioxide, bromine compounds, phosphorus compounds, and the like. When a flame retardant is used, its amount is usually 0.01 to 30 parts by weight per 100 parts by weight of the aralkyl resin.
• resins other than epoxy resins include (meth)acrylate resins, epoxy (meth)acrylate resins, styrene resins, polyimide resins, polyamide resins, polyamic acid resins, active ester resins, and the like.
• the amount thereof is usually 0.01 to 30 parts by mass with respect to 100 parts by mass of the solid content of the resin composition.
• curable monomers and oligomers examples include benzoxazine compounds and maleimide compounds.
• the amount thereof is usually 0.01 to 30 parts by mass with respect to 100 parts by mass of the solid content of the resin composition.
• organic solvents examples include ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate, butyl acetate and amyl acetate; ethers such as ethylene glycol monomethyl ether; One or more of amides such as formamide and N,N-dimethylacetamide, alcohols such as methanol and ethanol, and hydrocarbons such as toluene and xylene can be used.
• the curable resin composition of the present embodiment may contain a solvent, and may be solid or varnish-like.
• a cured product of a curable resin composition containing the aralkyl resin of the present disclosure has sufficient heat resistance to be used for electronic devices. Moreover, the curable resin composition containing the aralkyl resin of the present disclosure has a lower water absorption rate of the cured product than the curable resin composition containing the resin having no aralkyl structure of the present disclosure. The low water absorption of the cured product is effective when used in electronic devices from the viewpoint of dielectric properties and insulation reliability.
• a photosensitive resin composition can be preferably mentioned as an application destination of the aralkyl resin in the present disclosure.
• a photosensitive resin composition can be prepared by mixing the aralkyl resin of the present disclosure with at least a photosensitive agent.
• aralkyl resins tend to have good transparency to certain light and/or alkali solubility.
• a photosensitive resin composition having good performance can be prepared.
• the photosensitive resin composition herein can be patterned by exposure using a photoresist composition, ie, a photomask, followed by development, and selectively protects the substrate surface from processing such as etching in the manufacture of electronic devices. It is useful as a composition capable of protecting against This is due to the specific light transmittance, alkali solubility, and etching resistance of the aromatic ring contained in the aralkyl resin.
• the above-mentioned photosensitive resin composition can be patterned by a solder resist composition or an imprint composition, that is, by light, and can selectively protect the substrate surface from processing such as etching in the manufacture of electronic devices. It is also useful as a possible composition. This is due to the specific light transmittance described above and the etching resistance of the aromatic ring contained in the aralkyl resin.
• the amount of the aralkyl resin in the present disclosure is, for example, 20 to 99% by weight, preferably 50 to 98% by weight, based on the total non-volatile components of the photosensitive resin composition.
• a quinonediazide compound is typically used as the photosensitive agent.
• a quinonediazide compound is particularly preferably used when preparing a positive photosensitive resin composition. There are no particular restrictions on the quinonediazide compounds that can be used.
• Examples of the quinonediazide compound include those in which the sulfonic acid of quinonediazide is bonded to a polyhydroxy compound via an ester bond, the sulfonic acid of quinonediazide to a polyamino compound in a sulfonamide bond, and the sulfonic acid of quinonediazide to a polyhydroxypolyamino compound in an ester bond and/or a sulfone bond. Examples thereof include those with an amide bond. It is preferable that 50 mol % or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.
• both a 5-naphthoquinonediazidesulfonyl group and a 4-naphthoquinonediazidesulfonyl group are preferably used.
• a 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region and is suitable for i-line exposure.
• a 5-naphthoquinonediazide sulfonyl ester compound has absorption extending to the g-line region and is suitable for g-line exposure.
• a 4-naphthoquinonediazide sulfonyl ester compound or a 5-naphthoquinone diazidesulfonyl ester compound depending on the wavelength of exposure.
• a naphthoquinonediazide sulfonyl ester compound having a 4-naphthoquinonediazidesulfonyl group and a 5-naphthoquinonediazidesulfonyl group in the same molecule may be contained, and a 4-naphthoquinonediazide sulfonyl ester compound and a 5-naphthoquinonediazide sulfonyl ester compound may be contained. It may contain both.
• a photoinitiator is preferably used for preparing a negative photosensitive resin composition, particularly when the above-described aralkyl resin contains a polymerizable carbon-carbon double bond.
• the photopolymerization initiator is not particularly limited as long as it can generate active species such as radicals and polymerize polymerizable carbon-carbon double bonds upon irradiation with high-energy light such as ultraviolet rays. Specific examples include photoradical polymerization initiators.
• Radical photopolymerization initiators include intramolecular cleavage type that generates radicals by cleaving intramolecular bonds, and hydrogen abstraction type that generates radicals by using hydrogen donors such as tertiary amines and ethers together. . Either can be used in the first embodiment.
• 2-hydroxy-2-methyl-1-phenylpropan-1-one which is intramolecularly cleaved, generates radicals by cleaving the carbon-carbon bond upon exposure to light.
• Hydrogen-abstraction types include benzophenone, methyl orthobenzoin benzoate, 4-benzoyl-4'-methyldiphenyl sulfide, and the like.
• the radical photopolymerization generator is not particularly limited as long as it is a compound that generates radicals by absorbing light, and commercially available radical photopolymerization initiators can be used.
• a photoradical polymerization initiator can be purchased, for example, from BASF.
• the amount of the photosensitive agent is typically 1 to 90% by weight, preferably 1 to 50% by weight, based on the total non-volatile components in the photosensitive resin composition.
• the photosensitizer is a photopolymerization initiator, its proportion is preferably in the range of 0.1 to 7% by mass based on the total mass of non-volatile components in the photosensitive resin composition.
• the photosensitive resin composition preferably contains a solvent.
• the photosensitive resin composition preferably has components such as the aralkyl resin and the photosensitizer of the present disclosure dissolved or dispersed in a solvent.
• solvents include aprotic polar solvents such as N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide and dimethylsulfoxide;
• Examples include ethers, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone and diacetone alcohol, esters such as ethyl acetate, propylene glycol monomethyl ether acetate and ethyl lactate, and aromatic hydrocarbons such as toluene and xylene.
• the solvent may be a single solvent or a mixed solvent.
• the amount of the solvent to be used may be appropriately adjusted according to the thickness of the film to be formed using the photosensitive resin composition.
• the amount of solvent used is such that the concentration of non-volatile components in the photosensitive resin composition is 1 to 95% by mass.
• the photosensitive resin composition may contain optional components for performance adjustment in addition to the aralkyl resin, photosensitizer and solvent in the present disclosure.
• optional components include surfactants, antioxidants, sensitizers, resins other than aralkyl resins, fillers, colorants, curable monomers, oligomers, and the like.
• a good pattern can be formed by using the photosensitive resin composition, for example, in the following procedure.
• a film forming step of applying a photosensitive resin composition on a substrate to form a photosensitive film (2)
• An exposure step of exposing the photosensitive film (3)
• the substrate to which the photosensitive resin composition is applied is not particularly limited. Substrates made of silicon wafers, metals, glasses, ceramics and plastics can be mentioned. Alternatively, the photosensitive resin composition may be applied onto a substrate that has been previously coated with another polymer. As the coating method, known coating methods such as spin coating, dip coating, spray coating, bar coating, applicator, ink jet, and roll coater can be applied without any particular limitation.
• the base material coated with the photosensitive resin composition is heated, for example, at 80 to 120° C. for about 30 seconds to 30 minutes to dry the solvent.
• a photosensitive film can be obtained by carrying out like this.
• Exposure process The photosensitive film obtained in the film formation process is usually irradiated with light through a photomask for forming a desired pattern.
• a known method and apparatus can be used for the exposure.
• a light source having a light source wavelength in the range of 100 to 600 nm can be used. Specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, KrF excimer lasers (wavelength: 248 nm), UV-LED lamps, and the like.
• the exposure dose is usually about 1 to 10,000 mJ/cm 2 , preferably about 10 to 5,000 mJ/cm 2 .
• post-exposure heating may be performed before or after the development step, if necessary.
• the post-exposure heating temperature is 60 to 180° C.
• the post-exposure heating time is usually 0.1 to 60 minutes, preferably 0.5 to 10 minutes.
• Developing process A patterned film is produced by developing the exposed photosensitive film obtained in the exposure process. By using an alkaline aqueous solution as a developer, the exposed portion is dissolved to form a pattern.
• the developer is not particularly limited as long as it can remove the photosensitive film in the exposed area.
• alkaline aqueous solutions in which inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, quaternary ammonium salts, mixtures thereof, and the like are dissolved. More specifically, alkaline aqueous solutions such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide (abbreviation: TMAH) can be mentioned. Among them, it is preferable to use a TMAH aqueous solution, and it is particularly preferable to use a 0.1 to 5% by mass TMAH aqueous solution.
• a known method such as an immersion method, a puddle method, or a spray method can be used.
• the development time is usually 0.1 to 120 minutes, preferably 0.5 to 60 minutes. After that, washing, rinsing, drying, etc. are performed as necessary. In this way a pattern can be formed on the substrate.
• the photosensitive resin composition containing the aralkyl resin of the present disclosure can be used as a photosensitive resin composition used in the manufacture of electronic devices such as photoresists, and used to form patterns on silicon wafers. can do.
• a cured product can be obtained by curing the curable resin composition. Curing can be done by light and/or heat. More specifically, the curable resin composition is usually heated at 100-200° C. for 0.1-20 minutes. Thereby, a cured product can be obtained. In order to improve the curing performance, "post-curing" may be performed at 70 to 200° C. for 0.1 to 10 hours.
• the cured product may be in the form of a molded product, a cast product, a laminate having a cured film formed on one or both sides of a base material, a film, a base resin for biomaterials, and the like.
• a cured product obtained by curing the curable resin composition has good transparency. From the viewpoint of this transparency, it is preferable to manufacture an optical member using the curable resin composition (manufacture an optical member comprising a cured product of the curable resin composition).
• the curable resin composition can be used as a transparent material for sealing optical elements such as optical sensors and imaging elements.
• the curable resin composition can also be used for the production of microlenses and as an optical adhesive.
• An electronic device may be manufactured using the curable resin composition. That is, you may manufacture an electronic device provided with the said hardened
• the curable resin composition can be used as a sealing material for electronic parts. That is, by encapsulating an electronic component with a melted product obtained by heating a curable resin composition, an electronic device in which the electronic component is encapsulated with the cured product can be produced.
• a substrate preferably a fiber substrate
• a curable resin composition such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, paper, etc.
• curable materials can be produced.
• This curable material for lamination can be suitably used for manufacturing printed wiring boards such as multilayer electrical laminates, build-up laminates, and flexible laminates.
• an insulating film can be provided by applying a varnish-like curable resin composition to a circuit-formed substrate to form a resin film and curing the resin film.
• the weight average molecular weight Mw and number average molecular weight Mn were measured using gel permeation chromatography (GPC, HLC-8320 manufactured by Tosoh Corporation). Tetrahydrofuran (THF) was used as the mobile phase, and TSKgel SuperHZ (3000 ⁇ 1+2000 ⁇ 2)/(6.0 mm ID ⁇ 15 cm ⁇ 3) columns were used.
• the hydroxyl equivalent was calculated from the hydroxyl value measured based on JIS K 0070:1992.
• the epoxy equivalent was measured based on JIS K 7236:2009.
• the solid content acid value was calculated by measuring the acid value of the solution based on JIS K 0070:1992 and calculating the solid content acid value from the solid content concentration.
• the solid content concentration is calculated by dividing the mass of the residue after depressurizing distillation of the solvent in the solution containing the solvent by the total mass of the solution containing the solvent, or dividing the mass of the reaction substrate excluding the solvent into the solution containing the solvent. Calculated by dividing by the total mass.
• the gas flowing out of the reactor was collected over 18 hours in a SUS304 cylinder with a blowing tube cooled with a -15°C refrigerant.
• the hydrogen fluoride content, the hydrogen chloride content, and the organic substance content were calculated by titration for 484.8 g of the collected liquid containing fluororal obtained here.
• hydrogen fluoride was 40% by mass
• hydrogen chloride was 11% by mass
• the organic matter content was 49% by mass.
• part of the recovered organic matter was collected in a resin NMR tube and the degree of fluorination was confirmed by 19F-NMR, almost no low-order fluorinated substances were detected, and the fluorination progressed quantitatively.
• the fluoral-containing mixture (hydrogen fluoride: 44 mass% , hydrogen chloride: 1% by mass, organic matter: 55% by mass) 14.6 g (fluoral: 82 mmol, hydrogen fluoride: 0.321 mol), hydrogen fluoride 8.3 g (0.416 mol), benzene 1.3 g ( 16 mmol) and 10.0 g (0.106 mol) of phenol were added. Then, the reaction was carried out at 25° C. and an absolute pressure of 0.2 MPa for 20 hours. Thereafter, the same operation as in Synthesis Example 1 was performed, and the organic layer was recovered.
• the fluoral-containing mixture (hydrogen fluoride: 44 mass% , hydrogen chloride: 1% by mass, organic matter: 55% by mass) 14.6 g (fluoral: 82 mmol, hydrogen fluoride: 0.321 mol), hydrogen fluoride 8.3 g (0.416 mol), biphenyl 2.5 g ( 16 mmol) and 10.0 g (0.106 mol) of phenol were added. Then, the reaction was carried out at 25° C. and an absolute pressure of 0.2 MPa for 20 hours. Thereafter, the same operation as in Synthesis Example 1 was performed, and the organic layer was recovered.
• the fluoral-containing mixture (hydrogen fluoride: 44 mass% , hydrogen chloride: 1% by mass, organic matter: 55% by mass), 14.6 g (fluoral: 82 mmol, hydrogen fluoride: 0.321 mol), hydrogen fluoride 8.3 g (0.416 mol), meta-xylene 1.7 g (16 mmol) and 10.0 g (0.106 mol) of phenol were added. Then, the reaction was carried out at 60° C. and an absolute pressure of 0.4 MPa for 20 hours. Thereafter, the same operation as in Synthesis Example 1 was performed, and the organic layer was recovered.
• the fluoral-containing mixture (hydrogen fluoride: 44 mass% , hydrogen chloride: 1% by mass, organic matter: 55% by mass), 104.7 g (fluoral: 664 mmol, hydrogen fluoride: 2.99 mol), hydrogen fluoride 60.0 g (3.00 mol), biphenyl 18.1 g ( 118 mmol) and 62.5 g (664 mmol) of phenol were added. Then, the reaction was carried out at 25° C. and an absolute pressure of 0.2 MPa for 20 hours.
• the fluoral-containing mixture (hydrogen fluoride: 44 mass% , hydrogen chloride: 1% by mass, organic matter: 55% by mass), 104.7 g (fluoral: 664 mmol, hydrogen fluoride: 2.99 mol), hydrogen fluoride 60.0 g (3.00 mol), meta-xylene 12.5 g (118 mmol) and 62.5 g (664 mmol) of phenol were added. Then, the reaction was carried out at 25° C. and an absolute pressure of 0.2 MPa for 20 hours.
• aralkyl resin solution II (acid-modified epoxy acrylate resin solution)
• aralkyl resin solution II epoxy resin solution
• 30.0 g of the aralkyl resin solution I epoxy resin solution obtained above ( Epoxy equivalent (298 g/equivalent)
• 3.5 g (48 mmol) of acrylic acid, 29 mg of 4-methoxyphenol, and 72 mg of triphenylphosphine were charged, and the internal temperature was raised to 110° C. while introducing dry air and allowed to react for 15 hours. rice field.
• aralkyl resin solution IV (acid-modified epoxy acrylate resin solution)
• aralkyl resin solution III epoxy resin solution obtained above ( Epoxy equivalent: 274 g/equivalent)
• 4.1 g (48 mmol) of acrylic acid, 31 mg of 4-methoxyphenol, and 77 mg of triphenylphosphine were charged, and the temperature was raised to 110° C. while introducing dry air, and the mixture was reacted for 15 hours.
• the fluoral-containing mixture (hydrogen fluoride: 44 mass% , hydrogen chloride: 1% by mass, organic matter: 55% by mass), 18 g (fluoral: 103 mmol, hydrogen fluoride: 0.40 mol), hydrogen fluoride 10 g (0.50 mol), biphenyl 1.6 g (10 mmol), 2 - 10 g (92 mmol) of cresol and 40 g of chloroform were added. Then, the reaction was carried out at 70° C. and an absolute pressure of 0.4 MPa for 18 hours.
• the fluoral-containing mixture (hydrogen fluoride: 44 mass% , hydrogen chloride: 1% by mass, organic matter: 55% by mass), 18 g (fluoral: 103 mmol, hydrogen fluoride: 0.40 mol), hydrogen fluoride 10 g (0.50 mol), meta-xylene 1.1 g (10 mmol), 10 g (92 mmol) of 2-cresol and 40 g of chloroform were added. Then, the reaction was carried out at 70° C. and an absolute pressure of 0.4 MPa for 18 hours.
• the hydroxyl equivalent weight was 175 g/equivalent.
• Curable Resin Composition (Containing Epoxy Resin)> A curable resin composition having the composition shown in Table 1 was prepared, and the glass transition temperature and 5% heat weight loss temperature of each cured product were measured.
• epoxy resins and curing accelerators are as follows.
• Curing accelerator triphenylphosphine (0.4% by mass relative to the epoxy resin)
• the glass transition temperature was measured using a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Co., Ltd., model name: DSC7000) at a heating rate of 10°C/min.
• thermogravimetric loss temperature was measured using a differential thermal/thermogravimetric simultaneous measurement device (manufactured by Hitachi High-Tech Science Co., Ltd., model name STA7200) under conditions of a temperature increase rate of 10° C./min in a nitrogen atmosphere.
• the cured product of the curable resin composition containing the aralkyl resin of the present embodiment has sufficient heat resistance for use in electronic devices.
• Table 2 shows the above measurement/evaluation results.
• the aralkyl resin of the present embodiment having an aralkyl structure is a resin having no aralkyl structure (Patent Document 4 (equivalent to the novolac resin described in 1.), and has a relatively low melt viscosity, and is excellent in handleability when used as a resin composition and fine workability during extrusion molding.
• epoxy resins and curing accelerators are as follows.
• Curing accelerator triphenylphosphine (0.4% by mass relative to the epoxy resin)
• the cured product of the curable resin composition comprising the aralkyl resin of the present embodiment is the resin having no aralkyl structure of the present disclosure (the novolak described in Patent Document 4 It is understood that the water absorption rate is lower than that of a cured product of a curable resin composition composed of (corresponding to resin).
• the low water absorption of the cured product is effective when used in electronic devices from the viewpoint of dielectric properties and insulation reliability.
• the glass transition temperature was measured using a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Co., Ltd., model name: DSC7000) at a heating rate of 10°C/min.
• thermogravimetric loss temperature was measured using a differential thermal/thermogravimetric simultaneous measurement device (manufactured by Hitachi High-Tech Science Co., Ltd., model name STA7200) under conditions of a temperature increase rate of 10° C./min in a nitrogen atmosphere.
• the aralkyl resin of the present embodiment is the resin having no aralkyl structure of the present disclosure (Patent Document 4), the heat resistance is equivalent.
• the alkali dissolution rate of the resin was evaluated by the following procedure.
• PGMEA propylene glycol monomethyl ether acetate
• a resin composition was applied by spin coating to the surface of a silicon wafer that had been subjected to HMDS treatment, and the PGMEA was dried using a hot plate. Thus, a resin film was formed on the surface of the silicon wafer.
• the details of the spin coating conditions are as follows.
• the alkali dissolution rate of the aralkyl resin of the present disclosure is higher than that of the resin having no aralkyl structure of the present disclosure (corresponding to the novolac resin described in Patent Document 4). It is understood that by using the aralkyl resin of the present disclosure, it is possible to appropriately control the alkali dissolution rate and improve developability and film reduction.
• a photosensitive resin composition (photoresist composition) was prepared and evaluated by the following procedures. (1) 75 parts by mass of the aralkyl resin obtained in Synthesis Example 12 and 25 parts by mass of a quinone diazide photosensitizer (NT200, manufactured by Toyo Gosei Co., Ltd.) were dissolved in 500 parts by mass of PGMEA (propylene glycol monomethyl ether acetate), Then, it was filtered through a filter with a pore size of 0.2 ⁇ m. By carrying out like this, the photosensitive resin composition (photoresist composition) was prepared.
• a photosensitive resin composition (photoresist composition) was applied to the surface of the HMDS-treated silicon wafer by spin coating, and the PGMEA was dried using a hot plate. Thus, a photosensitive resin film (photoresist film) was formed on the surface of the silicon wafer.
• ⁇ Spin coating conditions slope 10 s, 1,000 rpm, 60 s ⁇ Drying conditions: 110°C, 60s ⁇ Dry film thickness: 1 ⁇ m
• a photomask having a line/space pattern of various widths is placed on the photosensitive resin film (photoresist film) formed in (2) above, and a g h line lamp (g and h lines are 200 mJ/cm 2 of h-line converted light was irradiated with a device that emits light at the same time.
• the light-irradiated photosensitive resin film (photoresist film) was developed together with the silicon wafer by immersing it in a developer (2.38% by mass tetramethylammonium hydroxide aqueous solution) for 30 seconds.
• the aralkyl resin of the present disclosure is preferably applied to photosensitive resin compositions such as photoresists used in the manufacture of electronic devices.

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• 2022
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