CN116888217A - Resin composition, cured product, laminate, method for producing cured product, semiconductor device, and alkali generator - Google Patents

Resin composition, cured product, laminate, method for producing cured product, semiconductor device, and alkali generator Download PDF

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Publication number
CN116888217A
CN116888217A CN202280014903.8A CN202280014903A CN116888217A CN 116888217 A CN116888217 A CN 116888217A CN 202280014903 A CN202280014903 A CN 202280014903A CN 116888217 A CN116888217 A CN 116888217A
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group
formula
compound
acid
carbon atoms
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Inventor
浅川大辅
小泉孝德
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Fujifilm Corp
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Fujifilm Corp
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Priority claimed from PCT/JP2022/005364 external-priority patent/WO2022172996A1/en
Publication of CN116888217A publication Critical patent/CN116888217A/en
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Abstract

The present invention provides a resin composition comprising a resin and a base generator represented by the following formula (1-1), a cured product obtained by curing the resin composition, a laminate comprising the cured product, a method for producing the cured product, a semiconductor device comprising the cured product or the laminate, and a base generator.

Description

Resin composition, cured product, laminate, method for producing cured product, semiconductor device, and alkali generator
Technical Field
The present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, a semiconductor device, and a base generator.
Background
Cyclized resins such as polyimide are excellent in heat resistance, insulation properties, and the like, and therefore can be used for various applications. The use is not particularly limited, and examples of the use of the semiconductor device for mounting include use of a material or a protective film as an insulating film or a sealing material. Further, the film can be used as a base film, a cover film, or the like of a flexible substrate.
For example, in the above-mentioned applications, a cyclized resin such as polyimide is used in the form of a resin composition containing at least 1 kind of cyclized resin such as polyimide and a precursor of cyclized resin.
Such a resin composition is applied to a substrate to form a photosensitive film by coating or the like, and then exposed to light, developed, heated or the like as necessary, whereby a cured product can be formed on the substrate.
The precursor of the cyclized resin such as a polyimide precursor is cyclized by heating, for example, to form a cyclized resin such as polyimide in a cured product.
Since the resin composition can be applied by a known coating method or the like, the shape, size, application position and the like of the applied resin composition are highly flexible in design and the like when applied, and thus, it is said that the resin composition is excellent in manufacturing flexibility. In addition to the high performance of the cyclized resin such as polyimide, the expansion of the application of the resin composition in industry is expected from the viewpoint of excellent suitability for such production.
For example, patent document 1 describes a photosensitive resin composition having a polymer precursor and a specific structure that promote a reaction for producing a final product by an alkaline substance or by heating in the presence of an alkaline substance, and containing a base generator that generates a base by irradiation of electromagnetic waves and heating.
Patent document 2 describes a resin composition containing the following components (a) to (d).
(a) Polyimide precursor having specific structural unit
(b) Compounds for generating free radicals by irradiation with active light
(c) Compounds having specific structures
(d) Solvent(s)
Technical literature of the prior art
Patent literature
Patent document 1: japanese patent application laid-open No. 2011-121962
Patent document 2: japanese patent application laid-open No. 2014-201695
Disclosure of Invention
Technical problem to be solved by the invention
In a resin composition for obtaining a cured product, the obtained cured product is required to have excellent drug resistance.
The present invention provides a resin composition which can obtain a cured product having excellent drug resistance, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, a semiconductor device containing the cured product or the laminate, and a novel base generator.
Means for solving the technical problems
Examples of representative embodiments of the present invention are shown below.
<1> a resin composition comprising a resin and a base generator represented by the following formula (1-1),
[ chemical formula 1]
In the formula (1-1), R is independently a hydrogen atom or a 1-valent organic group, and when 2R are not present, 2R may be bonded to form a ring structure, OH in the formula (1-1) represents a hydroxyl group, L is a 2-valent organic group, and at least 1 heteroatom is present in the shortest path connecting adjacent oxygen atoms and carbon atoms.
<2> the resin composition according to <1>, wherein,
the hetero atom present in the shortest path linking chain contained in L of the formula (1-1) is any one of a nitrogen atom, an oxygen atom and a sulfur atom.
<3> the resin composition according to <1> or <2>, which comprises a compound represented by the following formula (1-2) as the above-mentioned base generator.
[ chemical formula 2]
In the formula (1-2), R is independently a hydrogen atom or an optional 1-valent organic group, and when 2R are hydrogen atoms, 2R can be connected to form a ring structure, L 1 Represents alkylene which may be substituted, Z represents-O-, -S-or-NR N -，R N Represents a hydrogen atom or a 1-valent organic group, R 1 R is R 2 Each independently represents a hydrogen atom or an organic group, 2R 1 R is R 2 At least 2 of the bonds may be bonded to form a ring structure, wherein the bond having the dotted line portion represents a single bond or a double bond, n represents 0 or 1, n is 1 when the bond having the dotted line portion is a double bond, and n is 0 when the bond having the dotted line portion is a single bond.
<4> the resin composition according to any one of <1> to <3>, which comprises a compound represented by the following formula (1-3) as the above-mentioned base generator.
[ chemical formula 3]
In the formula (1-3), R is independently a hydrogen atom or an optional 1-valent organic group, and when 2R are hydrogen atoms, 2R can be connected to form a ring structure, L 1 Represents alkylene which may be substituted, Z represents-O-, -S-or-NR N -，R N Represents a hydrogen atom or a 1-valent organic group, R 3 Each independently is a hydrogen atom or a 1-valent organic group, R 3 Can be joined to form a ring structure.
<5> the resin composition according to any one of <1> to <4>, which comprises a compound represented by the following formula (1-4) as the above-mentioned base generator.
[ chemical formula 4]
In the formula (1-4), R 2 R is R 4 Each independently represents a 1-valent organic group, 2R 2 Each other or R 2 And R is R 4 Can be connected to form a ring structure L 1 Represents alkylene which may be substituted, Z represents-O-, -S-or-NR N -，R N Represents a hydrogen atom or a 1-valent organic group, R 3 Each independently is a hydrogen atom or a 1-valent organic group, R 3 Can be joined to form a ring structure.
<6> the resin composition according to any one of <1> to <5>, wherein,
the resin is a precursor of the cyclized resin.
<7> the resin composition according to any one of <1> to <6>, further comprising a photopolymerization initiator.
<8> the resin composition according to any one of <1> to <7>, further comprising a polymerizable compound.
<9> the resin composition according to any one of <1> to <8>, which is used for forming an interlayer insulating film for a rewiring layer.
<10> a cured product obtained by curing the resin composition according to any one of <1> to <9 >.
<11> a laminate comprising 2 or more layers of the cured product of <10>, wherein any of the layers of the cured product comprises a metal layer between each other.
<12> a method for producing a cured product, comprising a film formation step of applying the resin composition according to any one of <1> to <9> to a substrate to form a film.
<13> the method for producing a cured product according to <12>, comprising:
an exposure step of selectively exposing the film; a kind of electronic device with high-pressure air-conditioning system
And a developing step of developing the film with a developer to form a pattern.
<14> the method for producing a cured product according to <12> or <13>, comprising a heating step of heating the film at 50 to 450 ℃.
<15> a semiconductor device comprising the cured product of <10> or the laminate of <11 >.
<16> a base generator represented by the following formula (1-1),
[ chemical formula 5]
In the formula (1-1), R is independently a hydrogen atom or a 1-valent organic group, and when 2R are not present, 2R may be bonded to form a ring structure, OH in the formula (1-1) represents a hydroxyl group, L is a 2-valent organic group, and at least 1 heteroatom is present in the shortest path connecting adjacent oxygen atoms and carbon atoms.
<17> the base generator according to <16>, which is represented by the following formula (1-2),
[ chemical formula 6]
In the formula (1-2), R is independently a hydrogen atom or an optional 1-valent organic group, and when 2R are hydrogen atoms, 2R can be connected to form a ring structure, L 1 Represents alkylene which may be substituted, Z represents-O-, -S-or-NR N -，R N Represents a hydrogen atom or a 1-valent organic group, R 1 R is R 2 Each independently represents a hydrogen atom or an organic group, 2R 1 R is R 2 At least 2 of them can be combined to form a ring structure, and a key sheet having a dotted line portionThe number "n" represents 0 or 1, and when the bond having the dotted line is a double bond, n is 1, and when the bond having the dotted line is a single bond, n is 0.
<18> the base generator according to <16> or <17>, which is represented by the following formula (1-3),
[ chemical formula 7]
In the formula (1-3), R is independently a hydrogen atom or an optional 1-valent organic group, and when 2R are hydrogen atoms, 2R can be connected to form a ring structure, L 1 Represents alkylene which may be substituted, Z represents-O-, -S-or-NR N -，R N Represents a hydrogen atom or a 1-valent organic group, R 3 Each independently is a hydrogen atom or a 1-valent organic group, R 3 Can be joined to form a ring structure.
<19> the base generator according to any one of <16> to <18>, which is represented by the following formula (1-4),
[ chemical formula 8]
In the formula (1-4), R 2 R is R 4 Each independently represents a 1-valent organic group, 2R 2 Each other or R 2 And R is R 4 Can be connected to form a ring structure L 1 Represents alkylene which may be substituted, Z represents-O-, -S-or-NR N -，R N Represents a hydrogen atom or a 1-valent organic group, R 3 Each independently is a hydrogen atom or a 1-valent organic group, R 3 Can be joined to form a ring structure.
Effects of the invention
According to the present invention, there are provided a resin composition which can give a cured product excellent in drug resistance, a cured product obtained by curing the resin composition, a laminate comprising the cured product, a method for producing the cured product, a semiconductor device comprising the cured product or the laminate, and a novel base generator.
Detailed Description
Hereinafter, a main embodiment of the present invention will be described. However, the present invention is not limited to the illustrated embodiments.
In the present specification, the numerical range indicated by the symbol "to" refers to a range in which numerical values before and after "to" are included as a lower limit value and an upper limit value, respectively.
In the present specification, the term "process" includes not only an independent process but also a process which cannot be clearly distinguished from other processes as long as the intended function of the process can be achieved.
In the labeling of groups (radicals) in the present specification, the label which is not labeled with a substituted or unsubstituted includes a group (radical) having no substituent and also includes a group (radical) having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, unless otherwise specified, "exposure" includes exposure using not only light but also particle beams such as electron beams and ion beams. Examples of the light used for exposure include an open line spectrum of a mercury lamp, an active ray such as extreme ultraviolet rays (EUV light), X-rays, and electron beams, and radiation, which are typified by excimer laser light.
In the present specification, "(meth) acrylate" means either or both of "acrylate" and "methacrylate", "(meth) acrylic" means either or both of "acrylic" and "methacrylic", and "(meth) acryl" means either or both of "acryl" and "methacryl".
In the present specification, me in the structural formula represents methyl, et represents ethyl, bu represents butyl, and Ph represents phenyl.
In the present specification, the total solid content refers to the total mass of all the components of the composition except the solvent. In the present specification, the solid content concentration is the mass percentage of the other components than the solvent with respect to the total mass of the composition.
In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by Gel Permeation Chromatography (GPC) and are defined as polystyrene equivalent values. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained by using HLC-8220GPC (manufactured by TOSOH CORPORATION) as a column, and using the protection columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION as above) in series. These molecular weights were measured using THF (tetrahydrofuran) as an eluent, unless otherwise specified. Among them, when THF is unsuitable as a solution, for example, when the solubility is low, NMP (N-methyl-2-pyrrolidone) can be used. Further, unless otherwise specified, a UV ray (ultraviolet ray) detector having a wavelength of 254nm was used for detection in GPC measurement.
In the present specification, when the positional relationship of each layer constituting the laminate is described as "up" or "down", it is sufficient that another layer exists above or below the layer serving as the reference among the layers concerned. That is, the 3 rd layer or the 3 rd element may be further interposed between the layer to be the reference and the other layer, and the layer to be the reference and the other layer do not need to be in contact. If not specifically described, the direction in which the base material layers are stacked is referred to as "up", or the direction from the base material toward the resin composition layer is referred to as "up", and the opposite direction is referred to as "down", when the resin composition layer is present. In addition, these vertical directions are set for convenience in the present specification, and in a practical embodiment, the "upper" direction in the present specification may be oriented differently from the vertical direction.
In the present specification, unless otherwise specified, each component contained in the composition may contain 2 or more compounds corresponding to the component. Unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, unless otherwise specified, the temperature was 23℃and the air pressure was 101,325Pa (1 air pressure), and the relative humidity was 50% RH.
In the present specification, a combination of preferred embodiments is a more preferred embodiment.
(resin composition)
The resin composition of the present invention comprises a resin and a base generator represented by the following formula (1-1) (hereinafter, also referred to as "specific base generator").
[ chemical formula 9]
In the formula (1-1), R is independently a hydrogen atom or a 1-valent organic group, and when 2R are each a hydrogen atom, 2R may be bonded to form a ring structure, and L is a 2-valent organic group having at least 1 hetero atom in the shortest-path bonding chain connecting adjacent oxygen atoms and carbon atoms.
The resin composition of the present invention is preferably used for forming a photosensitive film for exposure and development, and more preferably used for forming a film for exposure and development using a developer containing an organic solvent.
The resin composition of the present invention can be used for, for example, forming an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like, and is preferably used for forming an interlayer insulating film for a rewiring layer.
The resin composition of the present invention can be used for forming a positive-type photosensitive film for development, and can also be used for forming a negative-type photosensitive film for development.
In the present invention, negative development means development in which a non-exposed portion is removed by development during exposure and development, and positive development means development in which an exposed portion is removed by development.
As the exposure method, the developing solution, and the developing method, for example, the exposure method described in the exposure step described in the description of the method for producing a cured product, the developing solution described in the developing step, and the developing method described in the developing step can be used.
According to the resin composition of the present invention, a cured film excellent in drug resistance can be obtained.
The mechanism by which the above-described effects can be obtained is not clear, but is presumed to be as follows.
Conventionally, resin compositions containing resins, alkali generators, and the like have been used in various fields.
For example, a composition containing a precursor of a cyclized resin such as a polyimide precursor and a base generator is used, and the composition is heated to generate a base from the base generator, thereby obtaining a cured product containing a polyimide resin.
Further, a composition containing a polymerizable compound having an epoxy group and a base generating agent may be used, and the composition may be heated to generate a base from the base generating agent, thereby curing the polymerizable compound having an epoxy group to obtain a cured product.
Here, as a result of studies, the present inventors have found that the conventional alkali generator is inferior in drug resistance.
This is presumably because the structure of the base generator itself has low polarity and high solubility in an organic solvent.
The base generator represented by the formula (1-1) used in the present invention has at least 1 or more hetero atoms in the shortest path connecting adjacent oxygen atoms and carbon atoms. It is presumed that the polarity of the base generator is increased, and the decomposed product of the base generator or the unreacted base generator is less likely to be dissolved in the organic solvent, thereby improving the drug resistance of the film obtained from the resin composition. By improving the drug resistance, there are the following advantages: for example, when a pattern is formed by further adding another resin composition to the formed cured product, dissolution of the cured product by a solvent contained in the other resin composition is suppressed.
Further, it is considered that the presence of the hetero atom improves the mobility of the connecting chain, and thus, when the specific base generator is a base generator, the base generation efficiency is easily improved.
In particular, when a precursor of a cyclized resin is used as a resin, the alkali generation efficiency is improved, and the elongation at break of the cured film obtained therefrom is also improved.
It is further believed that by including heteroatoms in a particular base generator, the surface free energy of the molecule increases. Thus, it is considered that the alkali generator which is originally liable to be biased to the side different from the substrate side of the film is distributed in a more nearly uniform state in the depth direction of the film, and thus the generated alkali is liable to be uniformly distributed in the film.
The following are considered: when a precursor of the cyclized resin is used, if the base generator is biased to the surface of the film, cyclization is likely to proceed near the surface of the film on the side opposite to the substrate side, and cyclization is unlikely to proceed near the substrate side of the film (i.e., the deep side of the film). Here, film shrinkage occurs when the precursor of the cyclized resin cyclizes. Film shrinkage refers to the reduction (shrinkage) of the volume of a cured product (e.g., a cured film) obtained after curing compared to the composition before curing (e.g., a composition film before heating). For example, as described above, in the case where cyclization is easily performed near the surface of the film on the side opposite to the substrate side and cyclization is not easily performed near the substrate of the film, shrinkage of the film is easily caused on the side opposite to the substrate side, and the shape of the obtained cured product may be in a positive taper shape.
As described above, it is considered that the specific alkali generator used in the present invention is easily distributed in a more nearly uniform state in the depth direction of the film. In the present invention, it is considered that the structure exhibiting the property of generating alkali is distributed in a nearly uniform state throughout the film, and therefore, the difference in the shrinkage degree of the film due to the position is less likely to occur, and the rectangularity of the pattern is improved.
Here, patent documents 1 and 2 do not describe a specific alkali generator.
The components contained in the resin composition of the present invention will be described in detail below.
< resin >
The resin composition of the present invention comprises a resin.
The resin is not particularly limited, and examples thereof include resins used in conventional patterning compositions, preferably containing at least 1 resin (specific resin) selected from cyclized resins and precursors thereof, and more preferably containing precursors of cyclized resins.
The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.
In the present invention, the main chain means a relatively longest bonding chain in a resin molecule.
Examples of the cyclized resin include polyimide, polybenzoxazole, and polyamideimide.
The precursor of the cyclized resin is a resin whose chemical structure is changed by an external stimulus to form a cyclized resin, preferably a resin whose chemical structure is changed by heat to form a cyclized resin, and more preferably a resin whose chemical structure is changed by a ring-closure reaction by heat generation to form a ring structure.
Examples of the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor.
That is, the resin composition of the present invention preferably contains at least 1 resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor as the specific resin.
The resin composition of the present invention preferably contains polyimide or a polyimide precursor as a specific resin.
The specific resin preferably has a polymerizable group, and more preferably contains a radical polymerizable group.
When the specific resin has a radical polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator described later, more preferably contains a radical polymerization initiator described later and contains a radical crosslinking agent described later. The composition may further contain a sensitizer as required. Such a resin composition of the present invention forms, for example, a negative photosensitive film.
The specific resin may have a polar conversion group such as an acid-decomposable group.
When the specific resin has an acid-decomposable group, the resin composition of the present invention preferably contains a photoacid generator described later. For example, a positive photosensitive film or a negative photosensitive film as a chemically amplified film is formed from such a resin composition of the present invention.
[ polyimide precursor ]
The polyimide precursor used in the present invention is not particularly limited in kind and the like, but preferably contains a repeating unit represented by the following formula (2).
[ chemical formula 10]
In the formula (2), A 1 A is a 2 Each independently represents an oxygen atom or-NH-, R 111 Represents a 2-valent organic group, R 115 Represents a 4-valent organic group, R 113 R is R 114 Each independently represents a hydrogen atom or a 1-valent organic group.
A in formula (2) 1 A is a 2 Each independently represents an oxygen atom or-NH-, preferably an oxygen atom.
R in formula (2) 111 Represents a 2-valent organic group. Examples of the 2-valent organic group include a group containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, preferably a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group composed of a combination of these groups, and more preferably a group containing an aromatic group having 6 to 20 carbon atoms. The hydrocarbon group in the chain of the straight-chain or branched aliphatic group may be substituted with a heteroatom-containing group, and the hydrocarbon group of the cyclic aliphatic group and the aromatic group may be substituted with a heteroatom-containing group. As a preferred embodiment of the present invention, examples thereof include-Ar-and-Ar-a group represented by L-Ar-and a group represented by L-Ar, particularly preferred are groups represented by-Ar-L-Ar-. Wherein Ar is an aromatic group, L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -0-, -CO-, -S-, -SO 2 -or-NHCO-, or a group consisting of a combination of more than 2 of the above. The preferred ranges of these are as described above.
R 111 Preferably derived from diamines. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, and aromatic diamines. The diamine may be used in an amount of 1 or 2 or more.
Specifically, a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group composed of a combination of these is preferable, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. The hydrocarbon group in the chain of the straight-chain or branched aliphatic group may be substituted with a heteroatom-containing group, and the hydrocarbon group of the cyclic aliphatic group and the aromatic group may be substituted with a heteroatom-containing group. Examples of the group containing an aromatic group include the following groups.
[ chemical formula 11]
Wherein A represents a single bond or a 2-valent group, preferably a single bond or an aliphatic hydrocarbon group selected from the group consisting of C1-10 aliphatic hydrocarbon groups which may be substituted with fluorine atoms, -O-, -C (=O) -, -S-, -SO 2 -, -NHCO-or a combination of these, more preferably a single bond or an alkylene group selected from the group consisting of C1-3 which may be substituted with a fluorine atom, -O-, -C (=O) -, -S-or-SO 2 The radicals in (E) -are further preferably-CH 2 -、-O-、-S-、-SO 2 -、-C(CF 3 ) 2 -or-C (CH) 3 ) 2 -。
Wherein, represents the bonding site with other structures.
Specific examples of the diamine include a diamine selected from 1, 2-diaminoethane, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane and 1, 6-diaminohexane; 1, 2-or 1, 3-diaminocyclopentane, 1,2-, 1, 3-or 1, 4-diaminocyclohexane, 1,2-, 1, 3-or 1, 4-bis (aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4 '-diamino-3, 3' -dimethylcyclohexylmethane, isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4' -or 3,3' -diaminobiphenyl, 4' -diaminodiphenyl ether, 3-diaminodiphenyl ether, 4' -or 3,3' -diaminodiphenylmethane, 4' -or 3,3' -diaminodiphenylsulfone, 4,4' -or 3,3' -diaminodiphenyl sulfide, 4' -or 3,3' -diaminobenzophenone, 3' -dimethyl-4, 4' -diaminobiphenyl, 2' -dimethyl-4, 4' -diaminobiphenyl, 3' -dimethoxy-4, 4' -diaminobiphenyl, and 2, 2-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis (3-hydroxy-4-aminophenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4' -diamino p-diphenyl, 4' -bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] sulfone, bis [4- (2-aminophenoxy) phenyl ] sulfone, 1, 4-bis (4-aminophenoxy) benzene, 9, 10-bis (4-aminophenyl) anthracene, 3 '-dimethyl-4, 4' -diaminodiphenyl sulfone, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenyl) benzene, 3 '-diethyl-4, 4' -diaminodiphenyl methane 3,3 '-dimethyl-4, 4' -diaminodiphenylmethane, 4 '-diaminooctafluorobiphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 9-bis (4-aminophenyl) -10-hydroanthracene, 3',4,4 '-tetraminobiphenyl, 3',4 '-tetraminodiphenyl ether, 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 3-dihydroxy-4, 4' -diaminobiphenyl, 9 '-bis (4-aminophenyl) fluorene, 4' -dimethyl-3, 3 '-diaminodiphenyl sulfone, 3',5 '-tetramethyl-4, 4' -diaminodiphenyl methane, 2, 4-and 2, 5-diaminocumene, 2, 5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5, 6-tetramethyl-p-phenylenediamine, 2,4, 6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, 2, 7-diaminofluorene, 2, 5-diaminopyridine, 1, 2-bis (4-aminophenyl) ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1, 5-diaminonaphthalene, diaminobenzol, 1, 3-bis (4-aminophenyl) hexafluoropropane, 1, 4-bis (4-aminophenyl) octafluorobutane, 1, 5-bis (4-aminophenyl) decafluoropentane, 1, 7-bis (4-aminophenyl) tetradecanefluoroheptane, 2-bis [4- (3-aminophenyl) hexafiuorophenoxy ] propane, 2-5-diaminophenoxy ] hexafluoropropane, 2, 4-bis [ 2, 3-aminophenyl ] hexafluoropropane For bis (4-amino-2-trifluoromethylphenoxy) benzene, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4' -bis (4-amino-3-trifluoromethylphenoxy) biphenyl 4,4' -bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4' -bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl ] hexafluoropropane, 3', at least 1 diamine of 5,5' -tetramethyl-4, 4' -diaminobiphenyl, 4' -diamino-2, 2' -bis (trifluoromethyl) biphenyl, 2', 5', 6' -hexafluoro-biphenyl, and 4,4' -diaminotetrabiphenyl.
Further, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International publication No. 2017/038598 are also preferable.
Further, diamines having 2 or more alkylene glycol units in the main chain as described in paragraphs 0032 to 0034 of International publication No. 2017/038598 may be preferably used.
From the viewpoint of flexibility of the obtained organic film, R is preferable 111 Represented by-Ar-L-Ar-. Wherein Ar is each independently an aromatic group, L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 -or-NHCO-, or a group consisting of a combination of more than 2 of the above. Ar is preferably a phenylene group which is preferably a phenylene group, L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom-O-, -CO-, -S-or-SO 2 -. The aliphatic group hereThe hydrocarbyl group is preferably an alkylene group.
Moreover, from the viewpoint of the i-ray transmittance, R is preferable 111 Is a 2-valent organic group represented by the following formula (51) or (61). In particular, from the viewpoints of i-ray transmittance and availability, the 2-valent organic group represented by formula (61) is more preferable.
(51)
[ chemical formula 12]
In formula (51), R 50 ～R 57 Each independently is a hydrogen atom, a fluorine atom or a 1-valent organic group, R 50 ～R 57 At least 1 of which is a fluorine atom, a methyl group or a trifluoromethyl group, each independently represents a bonding site to a nitrogen atom in formula (2).
As R 50 ～R 57 Examples of the 1-valent organic group (1) include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).
[ chemical formula 13]
/>
In the formula (61), R 58 R is R 59 Each independently represents a fluorine atom, a methyl group or a trifluoromethyl group, and each independently represents a bonding site to a nitrogen atom in formula (2).
Examples of the diamine having the structure of formula (51) or (61) include 2,2 '-dimethylbenzidine, 2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 2' -bis (fluoro) -4,4 '-diaminobiphenyl, and 4,4' -diaminooctafluorobiphenyl. These may be used in 1 kind or in combination of 2 or more kinds.
R in formula (2) 115 Represents a 4-valent organic group. The 4-valent organic group is preferably an aromatic ring-containing 4-valent organic group, more preferably a group represented by the following formula (5) or formula [ ]6) A group represented by the formula (I).
In the formula (5) or (6), each independently represents a bonding site to another structure.
[ chemical formula 14]
In the formula (5), R 112 Is a single bond or a 2-valent linking group, preferably a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom-O-, -CO-, -S-, -SO 2 -and-NHCO-, and combinations thereof, more preferably a single bond, selected from the group consisting of alkylene groups having 1 to 3 carbon atoms which may be substituted with fluorine atoms, -O-, -CO-, -S-, and-SO 2 The radicals in are further preferably selected from the group consisting of-CH 2 -、-C(CF 3 ) 2 -、-C(CH 3 ) 2 -, -O-, -CO-; -S-and-SO 2 -a valence 2 group in (a).
Specifically, R 115 The tetracarboxylic acid residue remaining after the acid anhydride group is removed from the tetracarboxylic dianhydride may be mentioned. As equivalent to R 115 The polyimide precursor may contain only 1 tetracarboxylic dianhydride residue or may contain 2 or more types.
The tetracarboxylic dianhydride is preferably represented by the following formula (0).
[ chemical formula 15]
In formula (O), R 115 Represents a 4-valent organic group. R is R 115 R in the formula (2) 115 The meaning is the same, and the preferred ranges are also the same.
Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3',4' -biphenyl tetracarboxylic dianhydride, 3',4,4' -diphenyl sulfide tetracarboxylic dianhydride, 3',4' -diphenyl sulfone tetracarboxylic dianhydride, 3',4,4' -diphenyl sulfide tetracarboxylic dianhydride, 3',4,4' -diphenyl sulfone tetracarboxylic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 4' -oxydiphthalic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 1,4,5, 7-naphthalene tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride 2, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1, 3-diphenylhexafluoropropane-3, 4-tetracarboxylic dianhydride, 1,4,5, 6-naphthalene tetracarboxylic dianhydride, 2',3,3' -diphenyltetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, 1,2,4, 5-naphthalene tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 1,8,9, 10-phenanthrene tetracarboxylic dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1,2,3, 4-benzene tetracarboxylic dianhydride, and alkyl groups having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.
As a preferable example, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International publication No. 2017/038598 can be mentioned.
In formula (2), R may also be 111 R is R 115 Having OH groups. More specifically, as R 111， The residue of a bisaminophenol derivative may be mentioned.
R in formula (2) 113 R is R 114 Each independently represents a hydrogen atom or a 1-valent organic group. As the 1-valent organic group, a linear or branched alkyl group, a cyclic alkyl group, an aromatic group or a polyalkylene oxide group is preferably contained. Also, R is preferably 113 R is R 114 At least 1 of (a) comprises a polymerizable group, more preferably both comprise a polymerizable group. Also preferred is R 113 R is R 114 At least 1 of the (B) contains 2 or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, a radical, or the like, and is preferably a radical polymerizable group. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, alkoxymethyl group, hydroxymethyl group, acyloxymethyl group, epoxy group, oxetanyl group, benzoxazolyl group, and the like,Blocked isocyanate groups and amino groups. The radical polymerizable group of the polyimide precursor is preferably a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenic unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group or the like), (meth) acrylamide group, (meth) acryloyloxy group, a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.
[ chemical formula 16]
In formula (III), R 200 Represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group.
In formula (III), the bonding sites to other structures are represented.
In formula (III), R 201 Represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH(OH)CH 2 -, cycloalkylene or polyalkoxyene groups.
R 201 Preferable examples of (C) include an alkylene group such as an ethenyl group, an propenyl group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, or a dodecamethylene group, a 1, 2-butanediyl group, a 1, 3-butanediyl group, and-CH 2 CH(OH)CH 2 -, polyalkoxylene, more preferably alkylene such as ethenyl or propenyl, -CH 2 CH(OH)CH 2 -, cyclohexyl, polyalkoxy, more preferably alkylene such as ethenyl, propenyl, or the like, or polyalkoxy.
In the present invention, the polyalkoxylene group means a group to which 2 or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkylene groups contained in the polyalkylene oxide groups may be the same or different, respectively.
When the polyalkylene group contains a plurality of alkylene groups having different alkylene groups, the arrangement of the alkylene groups in the polyalkylene group may be random, may have a block, or may have an alternating pattern.
The number of carbon atoms of the alkylene group (including the number of carbon atoms of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, still more preferably 2 to 6, still more preferably 2 to 5, still more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.
The alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, halogen atoms, and the like.
The number of alkyleneoxy groups (the number of repeating polyalkyleneoxy groups) contained in the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, and still more preferably 2 to 6.
The polyalkylene oxide group is preferably a polyethylene oxide group, a polypropylene oxide group, a polytrimethylene group, a polytetramethylene group, or a group in which a plurality of ethylene oxide groups are bonded to a plurality of propylene oxide groups, more preferably a polyethylene oxide group or a polypropylene oxide group, and still more preferably a polyethylene oxide group, from the viewpoints of solvent solubility and solvent resistance. Among the above groups in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, ethyleneoxy groups and propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in an alternating pattern. Preferred modes of repeating the number of ethyleneoxy groups and the like in these groups are as described above.
In formula (2), R is 113 In the case of hydrogen atoms or R 114 In the case of a hydrogen atom, the polyimide precursor may form a conjugate salt with a tertiary amine compound having an ethylenic unsaturated bond. Examples of such tertiary amine compounds having ethylenic unsaturation include N, N-dimethylaminopropyl methacrylate.
In formula (2), R 113 R is R 114 At least 1 of them may be a polar group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, but is preferably an acetal group, a ketal group, a silicon-based ether group, a tertiary alkyl ester group, or the like, and more preferably an acetal group or a ketal group from the viewpoint of sensitivity to exposure.
Specific examples of the acid-decomposable group include a t-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group (tetrahydropyranyl group), a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a t-butoxycarbonylmethyl group, and a trimethylsilyl ether group. Ethoxyethyl or tetrahydrofuranyl is preferred from the viewpoint of exposure sensitivity.
Furthermore, the polyimide precursor preferably has a fluorine atom in the structure. The fluorine atom content in the polyimide precursor is preferably 10 mass% or more, and more preferably 20 mass% or less.
In addition, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to the substrate. Specifically, as the diamine, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like can be mentioned.
The repeating unit represented by the formula (2) is preferably a repeating unit represented by the formula (2-A). That is, at least 1 of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by the formula (2-a). By including the repeating unit represented by the formula (2-a) in the polyimide precursor, the amplitude of the exposure latitude can be further increased.
(2-A)
[ chemical formula 17]
In the formula (2-A), A 1 A is a 2 Represents an oxygen atom, R 111 R is R 112 Each independently represents a 2-valent organic group, R 113 R is R 114 Each independently represents a hydrogen atom or a 1-valent organic group, R 113 R is R 114 At least 1 of (a) is a group containing a polymerizable group, and preferably both are groups containing a polymerizable group.
A 1 、A 2 、R 111、 R 113 R is R 114 Are respectively independentGround and A in formula (2) 1 、A 2 、R 111 、R 113 R is R 114 The meaning is the same, and the preferred ranges are also the same.
R 112 R in formula (5) 112 The meaning is the same, and the preferred ranges are also the same.
The polyimide precursor may contain 1 kind of repeating unit represented by the formula (2), or may contain 2 or more kinds. Further, a structural isomer of the repeating unit represented by formula (2) may be contained. It is also apparent that the polyimide precursor may contain other kinds of repeating units in addition to the repeating unit of the above formula (2).
As an embodiment of the polyimide precursor in the present invention, the content of the repeating unit represented by the formula (2) is 50 mol% or more based on the total repeating unit. The total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyimide precursor other than the terminal may be the repeating unit represented by the formula (2).
The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 ～ 100,000, more preferably 10,000 ～ 50,000, and even more preferably 15,000 ～ 40,000. The number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and still more preferably 4,000 to 20,000.
The molecular weight of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly limited, and is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.
In the present specification, the dispersity of the molecular weight is a value calculated from the weight average molecular weight/number average molecular weight.
When the resin composition contains a plurality of polyimide precursors as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight, and the dispersity of at least 1 polyimide precursor be within the above-mentioned ranges. Further, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated from the plurality of polyimide precursors as 1 resin are each within the above-mentioned ranges.
[ polyimide ]
The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer mainly containing an organic solvent.
In the present specification, the alkali-soluble polyimide means a polyimide in which 0.1g or more of polyimide is dissolved in 100g of a 2.38 mass% aqueous tetramethylammonium solution at 23 ℃, and from the viewpoint of pattern formability, a polyimide in which 0.5g or more of polyimide is dissolved is preferable, and a polyimide in which 1.0g or more of polyimide is more preferable. The upper limit of the amount of dissolution is not particularly limited, but is preferably 100g or less.
Further, from the viewpoints of film strength and insulation properties of the obtained organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.
In the present specification, "main chain" means a relatively longest bonding chain among molecules of a polymer compound constituting a resin, and "side chain" means a bonding chain other than the above.
Fluorine atom-
From the viewpoint of film strength of the obtained organic film, the polyimide also preferably has fluorine atoms.
The fluorine atom is preferably, for example, R contained in the repeating unit represented by the following formula (4) 132 Or R in the repeating unit represented by the following formula (4) 131 R contained as a fluorinated alkyl group in the repeating unit represented by the following formula (4) is more preferable 132 Or R in the repeating unit represented by the following formula (4) 131 。
The amount of fluorine atoms is preferably 5 mass% or more, and preferably 20 mass% or less, relative to the total mass of the polyimide.
Silicon atom-
From the viewpoint of film strength of the obtained organic film, the polyimide also preferably has silicon atoms.
Silicon atoms are preferably contained in examplesR in the repeating unit represented by the following formula (4) 131 R contained in the repeating unit represented by the following formula (4) is more preferable as the structure of the organomodified (poly) siloxane to be described later 131 。
Further, the silicon atom or the organic modified (poly) siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in a main chain of the polyimide.
The amount of silicon atoms is preferably 1 mass% or more, more preferably 20 mass% or less, relative to the total mass of the polyimide.
Ethylenic unsaturation
From the viewpoint of the film strength of the obtained organic film, polyimide preferably has ethylenic unsaturated bonds.
The polyimide may have an ethylenic unsaturated bond at the terminal of the main chain, or may have a side chain, and preferably has a side chain.
The ethylenically unsaturated bond preferably has radical polymerization.
The ethylenic unsaturated bond is preferably R contained in the repeating unit represented by the following formula (4) 132 Or R in the repeating unit represented by the following formula (4) 131 R contained in the repeating unit represented by the following formula (4) is more preferable as a group having an ethylenic unsaturated bond 132 Or R in the repeating unit represented by the following formula (4) 131 。
Among these, R in the repeating unit represented by the following formula (4) is preferably contained as an ethylenic unsaturated bond 131 R contained in the repeating unit represented by the following formula (4) is more preferable as a group having an ethylenic unsaturated bond 131 。
Examples of the group having an ethylenic unsaturated bond include a group having a vinyl group which may be substituted and directly bonded to an aromatic ring, such as a vinyl group, an allyl group, and a vinyl phenyl group, (meth) acrylamido group, (meth) acryloyloxy group, and a group represented by the following formula (IV).
[ chemical formula 18]
In formula (IV), R 20 Represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group.
In formula (IV), R 21 Represents an alkylene group having 2 to 12 carbon atoms, -O-CH 2 CH(OH)CH 2 -, -C (=O) O-, -O (C=O) NH-, a (poly) alkyleneoxy group having 2 to 30 carbon atoms (alkylene group having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 or 3 carbon atoms, a repetition number of preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3) or a combination of 2 or more of these.
The alkylene group having 2 to 12 carbon atoms may be any of a linear, branched, cyclic, or a combination thereof.
The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.
Among these, R 21 The group represented by any one of the following formulas (R1) to (R3) is preferable, and the group represented by the formula (R1) is more preferable.
[ chemical formula 19]
/>
In the formulae (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly) alkyleneoxy group having 2 to 30 carbon atoms, or a group obtained by bonding these groups together in an amount of 2 or more, X represents an oxygen atom or a sulfur atom, X represents a bonding site to another structure, and ∈ represents R in the formula (IV) 21 Bonding sites for the bonded oxygen atoms.
In the formulae (R1) to (R3), a preferable mode of the alkylene group having 2 to 12 carbon atoms or the (poly) alkyleneoxy group having 2 to 30 carbon atoms in L is the same as that of the above R 21 The preferred mode of the alkylene group having 2 to 12 carbon atoms or the (poly) alkyleneoxy group having 2 to 30 carbon atoms is the same.
In formula (R1), X is preferably an oxygen atom.
In the formulae (R1) to (R3), the meanings are the same as those in the formula (IV), and preferred modes are also the same.
The structure represented by the formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenic unsaturated bond (for example, 2-isocyanatoethyl methacrylate or the like).
The structure represented by the formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenic unsaturated bond (for example, 2-hydroxyethyl methacrylate or the like).
The structure represented by the formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenic unsaturated bond (for example, glycidyl methacrylate or the like).
In formula (IV), the bonding site to other structure is preferably a bonding site to the main chain of polyimide.
The amount of ethylenic unsaturation is preferably 0.0001 to 0.1mol/g, more preferably 0.0005 to 0.05mol/g, relative to the total mass of the polyimide.
Polymerizable groups other than those having ethylenic unsaturation
The polyimide may contain a polymerizable group other than the group having an ethylenic unsaturated bond.
Examples of the polymerizable group other than the group having an ethylenic unsaturated bond include a cyclic ether group such as an epoxy group and an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, a hydroxymethyl group, and the like.
For example, the polymerizable group other than the group having an ethylenic unsaturated bond is preferably R contained in the repeating unit represented by the following formula (4) 131 。
The amount of the polymerizable group other than the group having an ethylenic unsaturated bond is preferably 0.0001 to 0.1mol/g, more preferably 0.001 to 0.05mol/g, relative to the total mass of the polyimide.
Polarity-switching group-
The polyimide may have a polar conversion group such as an acid-decomposable group. Acid-decomposable groups in polyimide and R of the above formula (2) 113 R is R 114 The acid decomposable groups described in the above are the same, and the preferable modes are also the same.
The polarity-converting group is, for example, R contained in the repeating unit represented by the following formula (4) 131 、R 132 The ends of polyimide, and the like.
Acid number-
When the polyimide is used for alkali development, the acid value of the polyimide is preferably 3OmgKOH/g or more, more preferably 50mgKOH/g or more, and still more preferably 70mgKOH/g or more, from the viewpoint of improving the developability.
The acid value is preferably 500mgKOH/g or less, more preferably 400mgKOH/g or less, and still more preferably 200mgKOH/g or less.
When polyimide is used for development (for example, the "solvent development" described later) using a developer mainly composed of an organic solvent, the acid value of polyimide is preferably 1 to 35mgKOH/g, more preferably 2 to 30mgKOH/g, and still more preferably 5 to 20mgKOH/g.
The acid value is measured by a known method, for example, by the method described in JIS K0070: the method in 1992.
Further, as the acid group contained in the polyimide, an acid group having a pKa of 0 to 10 is preferable, and an acid group having a pKa of 3 to 8 is more preferable from the viewpoint of both storage stability and developability.
The pKa is expressed by its negative common logarithmic pKa taking into account the dissociation reaction of the hydrogen ions released by the acid. In the present specification, unless otherwise specified, pKa is set to a calculated value based on ACD/ChemSketch (registered trademark). Alternatively, reference may be made to the values described in the "reform 5 th edition chemical review base" by the japan chemical society.
In the case where the acid group is a polybasic acid such as phosphoric acid, the pKa is a first dissociation constant.
The polyimide preferably contains at least 1 selected from the group consisting of a carboxyl group and a phenolic hydroxyl group as such an acid group, and more preferably contains a phenolic hydroxyl group.
Phenolic hydroxyl radical-
From the viewpoint of making the development speed by the alkali developer appropriate, polyimide preferably has a phenolic hydroxyl group.
The polyimide may have a phenolic hydroxyl group at the terminal of the main chain or may have a side chain.
The phenolic hydroxyl group is preferably R contained in, for example, a repeating unit represented by the following formula (4) 132 Or R in the repeating unit represented by the following formula (4) 131 。
The amount of phenolic hydroxyl groups is preferably 0.1 to 30mol/g, more preferably 1 to 20mol/g, relative to the total mass of the polyimide.
The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, and preferably contains a repeating unit represented by the following formula (4).
[ chemical formula 20]
In formula (4), R 131 Represents a 2-valent organic group, R 132 Represents a 4-valent organic group.
When the polymerizable group is present, the polymerizable group may be located at R 131 R is R 132 At least 1 of these may be located at the terminal of polyimide as shown in the following formula (4-1) or formula (4-2).
(4-1)
[ chemical formula 21]
In the formula (4-1), R 133 The other groups are as defined for formula (4) and are polymerizable groups.
(4-2)
[ chemical formula 22]
R 134 R is R 135 At least 1 of them is a polymerizable group, and if not, an organic group, and the other groups have the same meaning as in formula (4).
Examples of the polymerizable group include a group containing the above-mentioned ethylenic unsaturated bond and a crosslinkable group other than the group containing the above-mentioned ethylenic unsaturated bond.
R 131 Represents a 2-valent organic group. As the 2-valent organic group, R in the formula (2) can be exemplified 111 The same groups, preferably the same ranges.
And as R 131 The diamine residue remaining after removal of the amino group of the diamine may be mentioned. Examples of the diamine include aliphatic, cyclic aliphatic and aromatic diamines. Specific examples thereof include R in formula (2) of polyimide precursor 111 Is an example of (a).
From the viewpoint of more effectively suppressing warpage generated during alkane formation, R 131 Diamine residues having at least 2 alkylene glycol units in the backbone are preferred. More preferably, the diamine contains 2 or more ethylene glycol chains, propylene glycol chains, or both of them in total in one molecule, and still more preferably, the diamine contains no aromatic ring at the same time.
As diamines containing 2 or more ethylene glycol chains, propylene glycol chains, or both in total, there may be mentioned JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by Huntsman Corporation), 1- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, and the like, but not limited thereto.
R 132 Represents a 4-valent organic group. As the 4-valent organic group, R in the formula (2) can be exemplified 115 The same groups, preferably the same ranges.
For example, as R 115 And the illustrated 4-valent organic compoundThe 4 bonding bonds of the group are bonded to 4-C (=o) -moieties in the above formula (4) to form a condensed ring.
And R is 132 The tetracarboxylic acid residue remaining after the acid anhydride group is removed from the tetracarboxylic dianhydride may be mentioned. Specific examples thereof include R in formula (2) of polyimide precursor 115 Is an example of (a). From the viewpoint of the strength of the organic film, R 132 Preferably an aromatic diamine residue having 1 to 4 aromatic rings.
Also preferred is where R 131 And R is 132 Having OH groups on at least 1 of them. More specifically, as R 131 Examples of the compounds include 2, 2-bis (3-hydroxy-4-aminophenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and the above-mentioned compounds (DA-1) to (DA-18) as R 132 The above-mentioned (DAA-1) to (DAA-5) are more preferable examples.
Furthermore, polyimide is also preferred to have fluorine atoms in the structure. The fluorine atom content in the polyimide precursor is preferably 10 mass% or more, and more preferably 20 mass% or less.
In addition, polyimide may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to a substrate. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like.
In order to improve the storage stability of the resin composition, it is preferable that the main chain end of the polyimide is blocked with a blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacyl chloride compound, or reactive monoester compound. Among these, monoamines are more preferably used, and preferable examples of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-dihydroxypyrimidine, 2-amino-4, 3-aminophenol, 4-aminophenol, and thiophenol. These may be used in an amount of 2 or more, and various terminal groups may be introduced by reacting various kinds of blocking agents.
Imidization ratio (ring closure ratio)
The imidization ratio (also referred to as "ring closure ratio") of the polyimide is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more from the viewpoints of film strength, insulation property, and the like of the obtained organic film.
The upper limit of the imidization ratio is not particularly limited, and may be 100% or less.
The imidization rate can be measured, for example, by the following method.
The infrared absorption spectrum of the polyimide was measured to obtain an absorption peak derived from the imide structure, namely 1377cm -1 A nearby peak intensity P1. Next, the polyimide was heat-treated at 350℃for 1 hour, and then the infrared absorption spectrum was measured again to obtain 1377cm -1 A nearby peak intensity P2. The imidization ratio of polyimide can be obtained by using the obtained peak intensities P1 and P2 according to the following formula.
Imidization ratio (%) = (peak intensity P1/peak intensity P2) ×100
The polyimide may have a polyimide composition containing all 1R 131 Or R is 132 The repeating unit represented by the above formula (4) may have a structure comprising at least 2R 131 Or R is 132 Is represented by the above formula (4). The polyimide may contain a repeating unit represented by the above formula (4) or another kind of repeating unit. Examples of the other types of repeating units include repeating units represented by the above formula (2).
For example, polyimide can be synthesized as follows: the polyimide precursor is obtained by a method in which a tetracarboxylic dianhydride is reacted with a diamine (a part of which is substituted with a monoamine, i.e., a capping agent) at a low temperature, a method in which a tetracarboxylic dianhydride is reacted with a diamine (a part of which is substituted with an acid anhydride or a monoacylchloride compound or an active monoester compound, i.e., a capping agent) at a low temperature, a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol and then reacted in the presence of a diamine (a part of which is substituted with a monoamine, i.e., a capping agent) and a condensing agent, a method in which a residual dicarboxylic acid is chlorinated and reacted with a diamine (a part of which is substituted with a monoamine, i.e., a capping agent) after a dicarboxylic anhydride and an alcohol are obtained, a method in which a part of an imide structure is introduced by a conventional imidization method is stopped or a method in which a part of an imide structure is introduced by further mixing a fully imidized polymer and a polyimide precursor thereof is used. Further, other known polyimide synthesis methods can be applied.
The polyimide preferably has a weight average molecular weight (Mw) of 5,000 ～ 100,000, more preferably 10,000 ～ 50,000, and even more preferably 15,000 ～ 40,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film excellent in mechanical properties (for example, elongation at break), the weight average molecular weight is particularly preferably 15,000 or more.
The number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
The molecular weight of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly limited, and is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.
When the resin composition contains a plurality of polyimides as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity of at least 1 polyimide be in the above-mentioned range. Further, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated for the plurality of kinds of polyimide as 1 kind of resin are each within the above-mentioned ranges.
[ polybenzoxazole precursor ]
The polybenzoxazole precursor used in the present invention is not particularly limited in its structure, and preferably contains a repeating unit represented by the following formula (3).
[ chemical formula 23]
In formula (3), R 121 Represents a 2-valent organic group, R 122 Represents a 4-valent organic group, R 123 R is R 124 Each independently represents a hydrogen atom or a 1-valent organic group.
In formula (3), R 123 R is R 124 Respectively with R in the formula (2) 113 The meaning is the same, and the preferred ranges are also the same. That is, at least 1 is preferably a polymerizable group.
In the formula (3), R 121 Represents a 2-valent organic group. The 2-valent organic group preferably contains at least 1 of an aliphatic group and an aromatic group. As the aliphatic group, a straight chain aliphatic group is preferable. R is R 121 Dicarboxylic acid residues are preferred. The dicarboxylic acid residues may be used in an amount of 1 or 2 or more.
The dicarboxylic acid residue is preferably a dicarboxylic acid residue containing an aliphatic group or a dicarboxylic acid residue containing an aromatic group, and more preferably a dicarboxylic acid residue containing an aromatic group.
The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, and more preferably a dicarboxylic acid composed of a linear or branched (preferably linear) aliphatic group and 2-COOH. The number of carbon atoms of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, still more preferably 3 to 20, still more preferably 4 to 15, and particularly preferably 5 to 10. The straight chain aliphatic group is preferably an alkylene group.
As the dicarboxylic acid comprising a straight-chain aliphatic group, examples thereof include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2-dimethylsuccinic acid, 2, 3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, and 2-methylglutaric acid, 3-methylglutaric acid, 2-dimethylglutaric acid, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoro-adipic acid, 3-methyladipic acid, pimelic acid, 2, 6-tetramethylpimelic acid, suberic acid, dodecafluoro-suberic acid, azelaic acid sebacic acid, hexadecanedioic acid, 1, 9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, ditridecanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, icosanedioic acid, triacontanedioic acid, tricosanedioic acid, diglycolic acid, dicarboxylic acids represented by the following formula, and the like.
[ chemical formula 24]
(wherein Z is a hydrocarbon group having 1 to 6 carbon atoms and n is an integer of 1 to 6.)
The dicarboxylic acid having an aromatic group is preferably a dicarboxylic acid having the following aromatic group, and more preferably a dicarboxylic acid consisting of only a group having the following aromatic group and 2-COOH.
[ chemical formula 25]
Wherein A represents a member selected from the group consisting of-CH 2 -、-O-、-S-、-SO 2 -、-CO-、-NHCO-、-C(CF 3 ) 2 -and-C (CH) 3 ) 2 The 2-valent groups in (a) are each independently represented by andbonding sites of other structures.
Specific examples of the dicarboxylic acid containing an aromatic group include 4,4 '-carbonyldibenzoic acid, 4' -dicarboxydiphenyl ether, and terephthalic acid.
In the formula (3), R 122 Represents a 4-valent organic group. R in the above formula (2) is used as a 4-valent organic group 115 The meaning is the same, and the preferred ranges are also the same.
And R is 122 Preferably a group derived from a bisaminophenol derivative, as a group derived from a bisaminophenol derivative, for example, examples thereof include 3,3 '-diamino-4, 4' -dihydroxybiphenyl, 4 '-diamino-3, 3' -dihydroxybiphenyl, 3 '-diamino-4, 4' -dihydroxydiphenylsulfone, 4 '-diamino-3, 3' -dihydroxydiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis- (4-amino-3-hydroxyphenyl) hexafluoropropane bis- (4-amino-3-hydroxyphenyl) methane, 2-bis- (4-amino-3-hydroxyphenyl) propane, 4 '-diamino-3, 3' -dihydroxybenzophenone, 3 '-diamino-4, 4' -dihydroxybenzophenone, 4 '-diamino-3, 3' -dihydroxydiphenyl ether, 3 '-diamino-4, 4' -dihydroxydiphenyl ether, 1, 4-diamino-2, 5-dihydroxybenzene, 1, 3-diamino-2, 4-dihydroxybenzene, 1, 3-diamino-4, 6-dihydroxybenzene, and the like. These bisaminophenols may be used alone or in combination.
Among the bisaminophenol derivatives, those having the following aromatic groups are preferable.
[ chemical formula 26]
Wherein X is 1 represents-O-, -S-, -C (CF) 3 ) 2 -、-CH 2 -、-SO 2 -, -NHCO-, and # each represent a bonding site to another structure. R represents a hydrogen atom or a 1-valent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferablyPreferably a hydrogen atom or an alkyl group. And R is 122 The structure represented by the above formula is also preferable. R is R 122 In the case of the structure represented by the above formula, a total of 4 are preferably any 2 of them are R in the formula (3) 122 The bonding site of the bonded nitrogen atom and the other 2 are R in the formula (3) 122 The bonding site of the bonded oxygen atom is more preferably 2 x is R in formula (3) 122 The bonding site of the bonded oxygen atom and 2# are R in formula (3) 122 The bonding site or 2 of the bonded nitrogen atoms is R in formula (3) 122 The bonding site of the bonded nitrogen atom and 2 # are R in formula (3) 122 The bonding site of the bonded oxygen atom is more preferably 2 x is R in formula (3) 122 The bonding site of the bonded oxygen atom and 2# are R in formula (3) 122 Bonding sites for the bonded nitrogen atoms.
The bisaminophenol derivative is also preferably a compound represented by the formula (A-s).
[ chemical formula 27]
In the formula (A-s), R 1 Is selected from hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO 2 -, -CO-, -NHCO-; a single bond or an organic group in the following formula (A-sc). R is R 2 The hydrogen atom, alkyl group, alkoxy group, acyloxy group, and cyclic alkyl group may be the same or different. R is R 3 Any of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group may be the same or different.
[ chemical formula 28]
(in the formula (A-sc): represents an aromatic ring bond with an aminophenol group of the bisaminophenol derivative represented by the formula (A-s))
It is considered that in the above formula (A-s), the amino group is located at the ortho position to the phenolic hydroxyl group, i.e., at R 3 The substituent is particularly preferable in that the distance between the carbonyl carbon of the amide bond and the hydroxyl group is closer and the effect of increasing the cyclization ratio at the time of curing at low temperature is further improved.
In the above formula (A-s), R 2 Is alkyl and R 3 In the case of an alkyl group, the effect of high transparency to i-rays and high cyclization ratio when cured at low temperature can be maintained, and thus is preferable.
In the above formula (A-s), R 1 Further preferred is an alkylene group or a substituted alkylene group. As R 1 Specific examples of the alkylene group and substituted alkylene group include straight-chain or branched alkyl groups having 1 to 8 carbon atoms, and among them, from the viewpoint of maintaining the effect of high transparency to i-rays and high cyclization ratio at the time of curing at low temperature, and having sufficient solubility in a solvent and being capable of obtaining a polybenzoxazole precursor excellent in balance, more preferably-CH 2 -、-CH(CH 3 )-、-C(CH 3 ) 2 -。
Examples of the production method of the bisaminophenol derivative represented by the formula (A-s) include paragraphs 0085 to 0094 and example 1 (0189 to 0190) of Japanese unexamined patent publication No. 2013-256506, which are incorporated herein by reference.
Specific examples of the structure of the bisaminophenol derivative represented by the formula (A-s) include those described in paragraphs 0070 to 0080 of Japanese patent application laid-open No. 2013-256506, which are incorporated herein by reference. Of course, not limited to these.
The polybenzoxazole precursor may contain other kinds of repeating units in addition to the repeating unit of the above formula (3).
From the viewpoint of being able to suppress warpage accompanying closed-loop bovine production, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another kind of repeating unit.
[ chemical formula 29]
In formula (SL), Z has a structure of a and b structure, R 1s Is hydrogen atom or hydrocarbon group with 1-10 carbon atoms, R 2s Is a hydrocarbon group of 1 to 10 carbon atoms, R 3s 、R 4s 、R 5s 、R 6s At least 1 of them is an aromatic group, and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and may be the same or different. The polymerization of the a and b structures may be block polymerization or random polymerization. Regarding the mole% of the Z moiety, the a structure is 5 to 95 mole%, the b structure is 95 to 5 mole%, and a+b is 100 mole%.
In the formula (SL), preferable Z is R in the b structure 5s R is R 6s Is phenyl. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight in the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be reduced more effectively, and the effect of suppressing warpage and the effect of improving solvent solubility can be achieved at the same time.
When the diamine residue represented by the formula (SL) is contained as another type of repeating unit, it is preferable that the diamine residue further contains a tetracarboxylic acid residue remaining after the acid anhydride group is removed from the tetracarboxylic acid dianhydride as a repeating unit. Examples of such tetracarboxylic acid residues include R in formula (2) 115 Is an example of (a).
For example, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 ～ 30,000, more preferably 20,000 ～ 29,000, and further preferably 22,000 ～ 28,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200.
The dispersion degree of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly limited, and is, for example, preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, still more preferably 2.3 or less, and still more preferably 2.2 or less.
When the resin composition contains a plurality of polybenzoxazole precursors as a specific resin, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity of at least 1 polybenzoxazole precursor are within the above-mentioned ranges. It is also preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated for the plurality of polybenzoxazole precursors as 1 resin are each within the above ranges.
[ polybenzoxazole ]
The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, and is preferably a compound represented by the following formula (X), more preferably a compound represented by the following formula (X) and having a polymerizable group. The polymerizable group is preferably a radical polymerizable group. Further, the compound may be a compound represented by the following formula (X) and having a polar conversion group such as an acid-decomposable group.
[ chemical formula 30]
In formula (X), R 133 Represents a 2-valent organic group, R 134 Represents a 4-valent organic group.
When the polar group such as a polymerizable group or an acid-decomposable group is present, the polar group such as a polymerizable group or an acid-decomposable group may be present at R 133 R is R 134 At least 1 of the above may be located at the terminal of polybenzoxazole as shown by the following formula (X-1) or formula (X-2).
(X-1)
[ chemical formula 31]
In the formula (X-1), R 135 R is R 136 At least 1 of them is a polar group such as a polymerizable group or an acid-decomposable group, and is not a polar group such as a polymerizable group or an acid-decomposable groupIn the case of organic radicals, the other radicals having the same meaning as in formula (X).
(X-2)
[ chemical formula 32]
In the formula (C-2), R 137 The other groups are as defined for formula (X) and the rest are substituents which are polar inversion groups such as polymerizable groups or acid-decomposable groups.
The polar conversion group such as a polymerizable group or an acid-decomposable group is the same as the polymerizable group described in the polymerizable group of the polyimide precursor.
R 133 Represents a 2-valent organic group. Examples of the 2-valent organic group include an aliphatic group and an aromatic group. Specific examples thereof include R in formula (3) of a polybenzoxazole precursor 121 Is an example of (a). Further, the preferable examples and R 121 The meaning is the same.
R 134 Represents a 4-valent organic group. Examples of the 4-valent organic group include R in formula (3) of the polybenzoxazole precursor 122 Is an example of (a). Further, the preferable examples and R 122 The meaning is the same.
For example, as R 122 And 4 bonding bonds of the illustrated 4-valent organic group are bonded to the nitrogen atom and the oxygen atom in the above formula (X) to form a condensed ring. For example, R 134 In the case of the following organic group, the following structure is formed. In the following structures, the bonding sites with nitrogen or oxygen atoms in formula (X) are represented, respectively.
[ chemical formula 33]
The oxazolization ratio of the polybenzoxazole is preferably 85% or more, more preferably 90% or more. The upper limit is not particularly limited and may be 100%. By having an oxazolization ratio of 85% or more, film shrinkage due to closed loops (which occurs when oxazolized by heating) becomes small, and warpage can be effectively suppressed.
For example, the above-mentioned oxazolification rate can be measured by the following method.
The infrared absorption spectrum of polybenzoxazole was measured to obtain an absorption peak of 1650cm, which is an amide structure derived from the precursor -1 A nearby peak intensity Q1. Next, the film is used at 1490cm -1 The absorption intensity of the aromatic ring observed nearby was normalized. After the polybenzoxazole precursor was heat-treated at 350℃for 1 hour, the infrared absorption spectrum was measured again to obtain 1650cm -1 The peak intensity Q2 in the vicinity was measured at 1490cm -1 The absorption intensity of the aromatic ring observed nearby was normalized. Using the normalized values of the obtained peak intensities Q1, Q2, the oxazolization ratio of the polybenzoxazole can be obtained according to the following formula.
Oxazolification rate (%) = (normalized value of peak intensity Q1/normalized value of peak intensity Q2) ×100
Polybenzoxazole can have a structure containing all 1R 131 Or R is 132 The repeating unit of the above formula (X) may have at least 2R 131 Or R is 132 The repeating unit of formula (X) above. The polybenzoxazole may contain a repeating unit of other types in addition to the repeating unit of the above formula (X).
For example, polybenzoxazole can be obtained as follows: by reacting a bisaminophenol derivative with a compound containing R 133 The dicarboxylic acid or a compound selected from the dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acids is reacted to obtain a polybenzoxazole precursor, which is then oxazolized by a conventional oxazolization reaction method.
In the case of dicarboxylic acid, an active ester-type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1, 2, 3-benzotriazole or the like in advance may be used in order to improve the reaction yield or the like.
The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, still more preferably 10,000 ～ 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film excellent in mechanical characteristics, the weight average molecular weight is particularly preferably 20,000 or more. When the polybenzoxazole is contained in an amount of 2 or more, it is preferable that the weight average molecular weight of at least 1 polybenzoxazole is within the above range.
The number average molecular weight (Mn) of the polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200.
The molecular weight of the polybenzoxazole has a dispersity of preferably 1.4 or more, more preferably 1.5 or more, and still more preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of the polybenzoxazole is not particularly limited, and is, for example, preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, further preferably 2.3 or less, and further preferably 2.2 or less.
When the resin composition contains a plurality of polybenzoxazoles as a specific resin, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity of at least 1 polybenzoxazole be within the above-mentioned ranges. It is also preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated for the plurality of polybenzoxazoles as 1 resin are each within the above-mentioned ranges.
[ Polyamide imide precursor ]
The polyamideimide precursor preferably comprises a repeating unit represented by the following formula (PAI-2).
[ chemical formula 34]
In the formula (PAI-2), R 117 Represents a 3-valent organic group, R 111 Represents a 2-valent organic group, A 2 Represents an oxygen atom or-NH-, R 113 Represents a hydrogen atom or a 1-valent organic group.
In the formula (PA 1-2), R 117 Examples of the group include linear or branched aliphatic, cyclic aliphatic, aromatic, heteroaromatic, and groups obtained by connecting these groups by a single bond or a linking group for 2 or more, preferably linear chain having 2 to 20 carbon atomsAn aliphatic group, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining 2 or more of these groups by a single bond or a linking group, more preferably an aromatic group having 6 to 20 carbon atoms or a group obtained by combining 2 or more of aromatic groups having 6 to 20 carbon atoms by a single bond or a linking group.
As the above-mentioned linking group, preferably-O-, -S-; -C (=o) -, -S (=o) 2 -, alkylene halide, arylene, or a linking group obtained by bonding 2 or more of them, more preferably-O-, -S-, alkylene halide, arylene, or a linking group obtained by bonding 2 or more of these.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.
The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and still more preferably a halogenated alkylene group having 1 to 4 carbon atoms. The halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is preferable. The above-mentioned halogenated alkylene group may have a hydrogen atom and all the hydrogen atoms may be substituted with a halogen atom, preferably all the hydrogen atoms are substituted with a halogen atom. Examples of the preferred halogenated alkylene group include (bistrifluoromethyl) methylene.
The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1, 3-phenylene group or a 1, 4-phenylene group.
And R is 117 Preferably from tricarboxylic acid compounds in which at least 1 carboxyl group can be halogenated. As the above halogenation, chlorination is preferable.
In the present invention, a compound having 3 carboxyl groups is referred to as a tricarboxylic acid compound.
2 carboxyl groups among 3 carboxyl groups of the above-mentioned tricarboxylic acid compound may be anhydrated.
Examples of the tricarboxylic acid compound which may be halogenated for producing the polyamideimide precursor include branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds and the like.
Only 1 kind of these tricarboxylic acid compounds may be used, or 2 or more kinds may be used.
Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining 2 or more of these groups by a single bond or a linking group, more preferably an tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms or a group obtained by combining 2 or more of aromatic groups having 6 to 20 carbon atoms by a single bond or a linking group.
Further, specific examples of the tricarboxylic acid compound include 1,2, 3-propane tricarboxylic acid, 1,3, 5-pentane tricarboxylic acid, citric acid, trimellitic acid, 2,3, 6-naphthalene tricarboxylic acid, phthalic acid (or phthalic anhydride) and benzoic acid by a single bond, -O-, -CH 2 -、-C(CH 3 ) 2 -、-C(CF 3 ) 2 -、-SO 2 Or a compound in which phenylene groups are bonded.
These compounds may be those obtained by the anhydrization of 2 carboxyl groups (for example, trimellitic anhydride), or those obtained by the halogenation of at least 1 carboxyl group (for example, trimellitic anhydride chloride).
In the formula (PAI-2), R 111 、A 2 、R 113 Respectively with R in the above formula (2) 111 、A 2 、R 113 The meaning is the same, and the preferred mode is the same.
The polyamideimide precursor may further comprise other repeating units.
Examples of the other repeating unit include a repeating unit represented by the above formula (2), a repeating unit represented by the following formula (PAI-1), and the like.
[ chemical formula 35]
In the formula (PAI-1), R 116 Represents a 2-valent organic group, R 111 Represents a 2-valent organic group.
In the formula (PAI-1), R 116 Examples of the group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, and a group in which these groups are linked by a single bond or a linking group to 2 or more, preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and a group in which these groups are combined by a single bond or a linking group to 2 or more, more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group to 2 or more.
As the above-mentioned linking group, preferably-O-, -S-; -C (=o) -, -S (=o) 2 -, alkylene halide, arylene, or a linking group obtained by bonding 2 or more of them, more preferably-O-, -S-, alkylene halide, arylene, or a linking group obtained by bonding 2 or more of these.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.
The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and still more preferably a halogenated alkylene group having 1 to 4 carbon atoms. The halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is preferable. The above-mentioned halogenated alkylene group may have a hydrogen atom and all the hydrogen atoms may be substituted with a halogen atom, preferably all the hydrogen atoms are substituted with a halogen atom. Examples of the preferred halogenated alkylene group include (bistrifluoromethyl) methylene.
The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1, 3-phenylene group or a 1, 4-phenylene group.
And R is 116 Preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
In the present invention, a compound having 2 carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having 2 halogenated carboxyl groups is referred to as a dicarboxylic acid dihalide compound.
The carboxyl groups in the dicarboxylic acid dihalide compound may be halogenated, for example, preferably chlorinated. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
Examples of the dicarboxylic acid compound or dicarboxylic acid dihalide compound which may be halogenated for producing the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compound or dicarboxylic acid dihalide compound, and the like.
These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used in an amount of 1 or 2 or more.
Specifically, the dicarboxylic acid compound or dicarboxylic acid dihalide compound is preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining 2 or more of these groups by a single bond or a linking group, more preferably an aromatic group having 6 to 20 carbon atoms or a group obtained by combining 2 or more of aromatic groups having 6 to 20 carbon atoms by a single bond or a linking group.
Further, as a specific example of the dicarboxylic acid compound, examples thereof include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2-dimethylsuccinic acid, 2, 3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, and 2, 2-dimethylglutaric acid, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoro adipic acid, 3-methyladipic acid, pimelic acid, 2, 6-tetramethylpimelic acid, suberic acid, dodecafluoro suberic acid, azelaic acid, sebacic acid, hexadecyl sebacic acid, 1, 9-azelaic acid, dodecanedioic acid tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, icosanedioic acid, hencanedioic acid, docanedioic acid, ditridecanedioic acid, ditetradecanedioic acid, heptadecanedioic acid, octadecanedioic acid, icosanedioic acid, triacontanedioic acid, triamcinolone diacid, triacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4' -biphenylcarboxylic acid, 4' -dicarboxyl diphenyl ether, benzophenone-4, 4' -dicarboxylic acid, and the like.
Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which 2 carboxyl groups are halogenated among the above-mentioned specific examples of the dicarboxylic acid compound.
In the formula (PAI-1), R 111 R is the same as R in the above formula (2) 111 The meaning is the same, and the preferred mode is the same.
Furthermore, the polyamideimide precursor preferably also has a fluorine atom in the structure. The fluorine atom content in the polyamideimide precursor is preferably 10 mass% or more, and preferably 20 mass% or less.
In addition, the polyamideimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to a substrate. Specifically, as the diamine component, there can be mentioned a method using bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, or the like.
One embodiment of the polyamideimide precursor in the present invention includes a repeating unit represented by the formula (PAI-2), a repeating unit represented by the formula (PAI-1), and a repeating unit represented by the formula (2) in a total amount of 50 mol% or more based on the total repeating units. The total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyamideimide precursor other than the terminal may be any one of the repeating unit represented by the formula (PAI-2), the repeating unit represented by the formula (PAI-1) and the repeating unit represented by the formula (2).
In addition, another embodiment of the polyamideimide precursor in the present invention includes a structure in which the total content of the repeating unit represented by the formula (PAI-2) and the repeating unit represented by the formula (PAI-1) is 50 mol% or more of the total repeating units. The total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyamideimide precursor other than the terminal may be any of the repeating units represented by the formula (PAI-2) or the repeating units represented by the formula (PAI-1).
The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 ～ 500,000, more preferably 5,000 ～ 100,000, and even more preferably 10,000 ～ 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000.
The molecular weight of the polyamideimide precursor has a dispersity of preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersivity of the polyamideimide precursor is not particularly limited, and is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less. When the resin composition contains a plurality of polyamide-imide precursors as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight, and the dispersity of at least 1 polyamide-imide precursor are within the above-mentioned ranges. Further, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated as 1 resin of the plurality of polyamide-imide precursors are each within the above-mentioned ranges.
[ Polyamide imide ]
The polyamideimide used in the present invention may be an alkali-soluble polyamideimide or a polyamideimide which is soluble in a developer containing an organic solvent as a main component.
In the present specification, the alkali-soluble polyamideimide means a polyamideimide in which 0.1g or more, preferably 0.5g or more, more preferably 1.0g or more, of the polyamideimide is dissolved in 100g of a 2.38 mass% aqueous tetramethylammonium solution at 23 ℃. The upper limit of the amount of dissolution is not particularly limited, but is preferably 100g or less.
In addition, from the viewpoints of film strength and insulation properties of the obtained organic film, the polyamideimide is preferably a polyamideimide having a plurality of amide bonds and a plurality of imide structures in the main chain.
Fluorine atom-
From the viewpoint of film strength of the obtained organic film, the polyamideimide preferably has fluorine atoms.
The fluorine atom is preferably contained in R in the repeating unit represented by the following formula (PAI-3) 117 Or R is 111 R contained as the fluorinated alkyl group in the repeating unit represented by the following formula (PAI-3) is more preferable 117 Or R is 111 。
The amount of fluorine atoms is preferably 5 mass% or more, and preferably 20 mass% or less, relative to the total mass of the polyamideimide.
Ethylenic unsaturation
From the viewpoint of film strength of the obtained organic film, the polyamideimide may have an ethylenic unsaturated bond.
The polyamideimide may have an ethylenic unsaturated bond at the terminal of the main chain, or may have a side chain, preferably a side chain.
The ethylenically unsaturated bond preferably has radical polymerization.
The ethylenic unsaturation is preferably R contained in a repeating unit represented by the following formula (PAI-3) 117 Or R is 111 R contained in the repeating unit represented by the following formula (PAI-3) is more preferable as the group having an ethylenic unsaturated bond 117 Or R is 111 。
The preferred mode of the group having ethylenic unsaturation is the same as that of the group having ethylenic unsaturation in the above polyimide.
The amount of ethylenic unsaturation is preferably 0.0001 to 0.1mol/g, more preferably 0.001 to 0.05mol/g, relative to the total mass of the polyamideimide.
Polymerizable groups other than ethylenic unsaturation
The polyamideimide may have a polymerizable group other than an ethylenic unsaturated bond.
Examples of the polymerizable group other than an ethylenic unsaturated bond in the polyamideimide include the same groups as those of the polymerizable group other than an ethylenic unsaturated bond in the polyimide.
For example, the polymerizable group other than the ethylenic unsaturated bond is preferably R contained in a repeating unit represented by the following formula (PAI-3) 111 。
The amount of the polymerizable group other than the ethylenic unsaturated bond is preferably 0.05 to 10mol/g, more preferably 0.1 to 5mol/g, relative to the total mass of the polyamideimide.
Polarity-switching group-
The polyamideimide may have a polar conversion group such as an acid-decomposable group. Acid-decomposable groups in the polyamideimide and R of the above formula (2) 113 R is R 114 The acid decomposable groups described in the above are the same, and the preferable modes are also the same.
Acid number-
When the polyamideimide is used for alkali development, the acid value of the polyamideimide is preferably 30mgKOH/g or more, more preferably 50mgKOH/g or more, and still more preferably 70mgKOH/g or more from the viewpoint of improving the developability.
The acid value is preferably 500mgKOH/g or less, more preferably 400mgKOH/g or less, and still more preferably 200mgKOH/g or less.
When the polyamideimide is used for development (for example, the "solvent development" described later) using a developing solution containing an organic solvent as a main component, the acid value of the polyamideimide is preferably 2 to 35mgKOH/g, more preferably 3 to 30mgKOH/g, and still more preferably 5 to 20mgKOH/g.
The acid value is measured by a known method, for example, by the method described in JIS K0070: the method in 1992.
The acid groups contained in the polyamide-imide include the same groups as the acid groups contained in the polyimide, and the preferable embodiments are also the same.
Phenolic hydroxyl radical-
From the viewpoint of making the development speed by the alkali developer appropriate, the polyamideimide preferably has a phenolic hydroxyl group.
The polyamideimide may have a phenolic hydroxyl group at the terminal of the main chain or may have a side chain.
The phenolic hydroxyl group is preferably R contained in a repeating unit represented by, for example, the following formula (PAI-3) 117 Or R is 111 。
The amount of the phenolic hydroxyl groups is preferably 0.1 to 30mol/g, more preferably 1 to 20mol/g, relative to the total mass of the polyamideimide.
The polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, and preferably contains a repeating unit represented by the following formula (PAI-3).
[ chemical formula 36]
In the formula (PAI-3), R 111 R is R 117 Respectively with R in the formula (PAI-2) 111 R is R 117 The meaning is the same, and the preferred mode is the same.
When the polymerizable group is present, the polymerizable group may be located at R 111 R is R 117 May be located at the terminal of the polyamideimide.
In order to improve the storage stability of the resin composition, the main chain end of the polyamide-imide is preferably blocked with a blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacyl chloride compound, or an active monoester compound. The preferable mode of the blocking agent is the same as that of the blocking agent in the polyimide described above.
Imidization ratio (ring closure ratio)
The imidization rate (also referred to as "ring closure rate") of the polyamideimide is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more from the viewpoints of film strength, insulation property, and the like of the obtained organic film.
The upper limit of the imidization ratio is not particularly limited, and may be 100% or less.
The imidization ratio can be measured by the same method as the ring closure ratio of the polyimide.
The polyamideimide may have a composition comprising all 1R 111 Or R is 117 The repeating unit represented by the above formula (PAI-3) may further have a structure comprising at least 2 different kinds of R 131 Or R is 132 Is represented by the above formula (PAI-3). The polyamideimide may contain a repeating unit represented by the above formula (PAI-3) and other types of repeating units. Examples of the other type of repeating unit include a repeating unit represented by the above formula (PAI-1) or formula (PAI-2).
The polyamideimide can be synthesized, for example, as follows: the polyamide-imide precursor is obtained by a known method, and is synthesized by a method of completely imidizing the polyamide-imide precursor by a conventional imidization method, or a method of stopping the imidization reaction in the middle and introducing a part of the imide structure, and a method of introducing a part of the imide structure by further mixing the completely imidized polymer with the polyamide-imide precursor.
The weight average molecular weight (Mw) of the polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and further preferably 10,000 ～ 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film excellent in mechanical characteristics, the weight average molecular weight is particularly preferably 20,000 or more.
The number average molecular weight (Mn) of the polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
The molecular weight of the polyamideimide precursor has a dispersity of preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyamideimide is not particularly limited, and is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.
When the resin composition contains a plurality of polyamide-imides as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity of at least 1 polyamide-imide are within the above-mentioned ranges. Further, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated from the plurality of polyamide-imide as 1 resin are each within the above-mentioned ranges.
[ method for producing polyimide precursor and the like ]
For example, a polyimide precursor or the like can be obtained, for example, by the following method: a method of reacting a tetracarboxylic dianhydride with a diamine at a low temperature, a method of reacting a tetracarboxylic dianhydride with a diamine at a low temperature to obtain a polyamic acid and esterifying with a condensing agent or an alkylating agent, a method of reacting a diamine and a condensing agent with a tetracarboxylic dianhydride and an alcohol to obtain a diester, a method of halogenating the remaining dicarboxylic acid with a halogenating agent and reacting the same with a diamine after obtaining a diester with a tetracarboxylic dianhydride and an alcohol, and the like. Among the above production methods, more preferred is a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is halogenated with a halogenating agent and reacted with a diamine.
Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1, 2-dihydroxyquinoline, 1-carbonyldioxy-di-1, 2, 3-benzotriazole, N' -disuccinimide carbonate, and trifluoroacetic anhydride.
Examples of the alkylating agent include N, N-dimethylformamide dimethyl acetal, N-dimethylformamide diethyl acetal, N-dialkylformamide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate and the like.
Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphoryl chloride.
In the method for producing a polyimide precursor or the like, an organic solvent is preferably used in the reaction. The organic solvent may be 1 or 2 or more.
Examples of the organic solvent include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ -butyrolactone, which are appropriately determined according to the raw materials.
In the method for producing a polyimide precursor or the like, an alkali compound is preferably added at the time of the reaction. The number of the basic compounds may be 1 or 2 or more.
The basic compound can be appropriately determined depending on the starting materials, and triethylamine, diisopropylethylamine, pyridine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, N-dimethyl-4-aminopyridine, and the like can be exemplified.
Blocking agent-
In the production of a polyimide precursor or the like, in order to further improve the storage stability, a carboxylic acid anhydride, an acid anhydride derivative, or an amino group remaining at the end of a resin such as a polyimide precursor is preferably blocked. When the carboxylic acid anhydride and acid anhydride derivative remaining at the end of the resin are blocked, examples of the blocking agent include monoalcohols, phenols, thiols, thiophenols, monoamines, and the like, and from the viewpoints of reactivity and film stability, monoalcohols, phenols, and monoamines are more preferably used. Preferred examples of the monoalcohol include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol (dodecynylol), benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, secondary alcohols such as isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, tertiary alcohols such as butanol and adamantanol. Preferred examples of the phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Further, preferable examples of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4, 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminophenol, 3-aminophenol, thiophenol, and the like. These may be used in an amount of 2 or more, and various terminal groups may be introduced by reacting various kinds of blocking agents.
In addition, when the amino group at the end of the lipid is blocked, a compound having a functional group reactive with the amino group can be used for blocking. The preferable blocking agent for amino group is preferably carboxylic anhydride, carboxylic chloride, carboxylic bromide, sulfonic chloride, sulfonic anhydride, sulfonic carboxylic anhydride or the like, more preferably carboxylic anhydride or carboxylic chloride. Preferred examples of the carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2, 3-dicarboxylic anhydride. Preferred compounds of carboxylic acid chlorides include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, pivaloyl chloride, cyclohexanoyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearoyl chloride, and benzoyl chloride.
Solid precipitation-
The method for producing a polyimide precursor or the like may include a step of precipitating a solid. Specifically, the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction liquid is filtered as needed, and then the obtained polymer component is poured into a poor solvent such as water, aliphatic lower alcohol or a mixed liquid thereof, and the polymer component is precipitated, whereby the polymer component is precipitated as a solid and dried to obtain a polyimide precursor or the like. In order to improve the purification degree, operations such as redissolution, reprecipitation, precipitation, and drying may be repeated for the polyimide precursor or the like. The method may further comprise a step of removing ionic impurities using an ion exchange resin.
[ content ]
The content of the specific resin in the resin composition of the present invention is preferably 20 mass% or more, more preferably 30 mass% or more, still more preferably 40 mass% or more, and still more preferably 50 mass% or more, relative to the total solid content of the resin composition. The content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, still more preferably 97% by mass or less, and still more preferably 95% by mass or less, based on the total solid content of the resin composition.
The resin composition of the present invention may contain only 1 specific resin or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.
Furthermore, the resin composition of the present invention preferably further comprises at least 2 resins.
Specifically, the resin composition of the present invention may contain 2 or more types of specific resins and other resins described later in total, or may contain 2 or more types of specific resins, and preferably contains 2 or more types of specific resins.
When the resin composition of the present invention contains 2 or more specific resins, it preferably contains, for example, a structure derived from dianhydride (R in the above formula (2) 115 ) Different polyimide precursors of 2 or more types.
< other resins >
The resin composition of the present invention may contain other resins (hereinafter, also simply referred to as "other resins") different from the specific resins in addition to or instead of the specific resins.
Examples of the other resin include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth) acrylic resins, (meth) acrylamide resins, urethane resins, butyral resins, styrene resins, polyether resins, and polyester resins.
In particular, by using a (meth) acrylic resin having an acid-decomposable group, the resin composition can be used as a composition for forming an image. Examples of the (meth) acrylic resin having such an acid-decomposable group include the resin (B) described in paragraphs 0069 to 0170 of Japanese unexamined patent publication No. 2019-174549.
Further, for example, by further adding a (meth) acrylic resin, a resin composition excellent in coatability can be obtained, and a pattern (cured product) excellent in solvent resistance can be obtained.
For example, a resin composition having a weight average molecular weight of 20,000 or less and a high value of a polymerizable group (for example, a resin having a molar amount of a polymerizable group of 1X 10 in 1 g) is added in place of or in addition to a polymerizable compound to be described later -3 Molar ratio of (meth) acrylic resin of at least one molar ratio), the coatability of the resin composition, the solvent resistance of the pattern (cured product), and the like can be improved.
When the resin composition of the present invention contains another resin, the content of the other resin is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, further preferably 1 mass% or more, further preferably 2 mass% or more, further preferably 5 mass% or more, and further preferably 10 mass% or more, based on the total solid content of the resin composition.
The content of the other resin in the resin composition of the present invention is preferably 80 mass% or less, more preferably 75 mass% or less, still more preferably 70 mass% or less, still more preferably 60 mass% or less, and still more preferably 50 mass% or less, based on the total solid content of the resin composition.
In addition, as a preferable embodiment of the resin composition of the present invention, the content of other resins may be reduced. In the above aspect, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the content is not particularly limited, and may be 0 mass% or more.
The resin composition of the present invention may contain only 1 kind of other resin or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.
< specific alkali Generator >
The resin composition of the present invention contains a base generator (specific base generator) represented by the formula (1-1).
[ chemical formula 37]
In the formula (1-1), R is independently a hydrogen atom or a 1-valent organic group, and when 2R are not present, 2R may be bonded to form a ring structure, OH in the formula (1-1) represents a hydroxyl group, L is a 2-valent organic group, and at least 1 heteroatom is present in the shortest path connecting adjacent oxygen atoms and carbon atoms.
〔R〕
From the viewpoint of elongation at break of the cured product, in the formula (1-1), R preferably independently represents a 1-valent organic group.
R is preferably a hydrocarbon group, more preferably an alkyl group, an aromatic hydrocarbon group or a group represented by a combination of these, further preferably an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms or a group represented by a combination of these, and particularly preferably an alkyl group having 1 to 10 carbon atoms.
The alkyl group may be any of a linear, branched, and cyclic alkyl group, and a branched alkyl group (for example, isopropyl, isobutyl, 2-ethylhexyl, etc.) or a cyclic alkyl group (for example, cyclohexyl, etc.) is preferable from the viewpoint of increasing the elongation at break.
R may have a substituent, and examples of the substituent include a halogen atom, an alkoxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, a hydroxyl group, a group represented by the following formula (R-1), and the like.
[ chemical formula 38]
In the formula (R-1), R a Represents a 1-valent organic group, R b Represents a 2-valent organic group, n represents an integer of 1 or more, m represents 0 or 1, and a bonding site to another structure is represented.
In the formula (R-1), R a The alkyl group is preferably a hydrocarbon group, more preferably an alkyl group, and even more preferably an alkyl group having 1 to 10 carbon atoms.
In the formula (R-1), R b The hydrocarbon group is preferably a hydrocarbon group, more preferably an alkylene group, further preferably an alkylene group having 2 to 10 carbon atoms, particularly preferably an alkylene group having 2 to 4 carbon atoms, and most preferably an ethenyl group or an propenyl group. When n is 2 or more, n R are present in the formula (R-1) b The two may be the same or different.
In the formula (R-1), an integer of 1 to 10 is preferable.
In the formula (R-1), m is preferably 1.
Examples of the ring structure formed by bonding 2R groups in the formula (1-1) include a piperidine ring and a morpholine ring each having a nitrogen atom contained in the amide bond as a ring member. These ring structures may further have a substituent. Examples of the substituent include the same groups as those in the above-mentioned hydrocarbon groups.
In the formula (1-1), it is also preferable that at least 1 of R has a structure represented by the formula (R-2).
By virtue of at least 1 of R being a structure represented by the formula (R-2), the volume around the nitrogen atom of the amino group in the produced base becomes large, and therefore, the reaction with the resin in the film can be suppressed by steric hindrance (steric). Thus, the alkali is likely to diffuse more uniformly in the film. This is considered to easily suppress the occurrence of a difference in the shrinkage degree of the film between the surface side and the substrate side of the film, and thus the obtained pattern is further excellent in rectangularity.
[ chemical formula 39]
In the formula (R-2), R 2 R is R 4 Each independently represents a 1-valent organic group, 2R 2 Each other or R 2 The other R in formula (1-1) (i.e., one of 2R in formula (1-1) is represented by formula (R-2) and the other R.1R in formula (1-1) may be represented by formula (R-2)) may be bonded to each other to form a ring structure.
In the formula (R-2), R 2 The hydrocarbon group is preferably an alkyl group, an aromatic hydrocarbon group, or a group represented by a combination of these groups, more preferably an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a group represented by a combination of these groups, and particularly preferably an alkyl group having 1 to 10 carbon atoms.
The alkyl group may be any of a linear, branched, and cyclic alkyl group, and a branched alkyl group (for example, isopropyl, isobutyl, 2-ethylhexyl, etc.) or a cyclic alkyl group (for example, cyclohexyl, etc.) is preferable from the viewpoint of increasing the elongation at break.
As 2R 2 Each other or R 2 Examples of the ring structure formed by bonding with the other R in the formula (1-1) include a piperidine ring and a morpholine ring each having a nitrogen atom contained in the amide bond as a ring member. These ring structures may further have a substituent. Examples of the substituent include the same groups as those in the above-mentioned hydrocarbon groups.
The following structure is given as an example of a preferred embodiment of R, but is not limited thereto. The nitrogen atom contained in the structure of the following specific example means a nitrogen atom contained in an amide bond in the formula (1-1). In the following specific examples, the bonding sites to carbonyl groups are shown.
[ chemical formula 40]
The dimethylpiperidine ring in the above structure may have both cis and trans forms. Here, the cis form is preferable from the viewpoint of elongation at break of the obtained cured product.
The volume around the nitrogen atom in the trans form becomes slightly larger than in the cis form. Thus, the matrix compound in the cis form is more easily accessible to the nitrogen atom of the active site, and the imidization promoting effect is improved. On the other hand, since the resin has a sufficiently large volume to the extent that the resin does not react, the rectangularity of the pattern can also be maintained. Therefore, the cis body is excellent in elongation at break while maintaining other properties as compared with the trans body.
〔L〕
In formula (1-1), L is a 2-valent organic group having at least 1 heteroatom in the shortest path linking chain connecting adjacent oxygen atoms (i.e., oxygen atoms in OH groups in formula (1-1)) and carbon atoms (i.e., carbon atoms in carbonyl groups in formula (1-1)).
Having at least 1 heteroatom in the shortest path of the linking chain means that the heteroatom is contained in the linking chain having the smallest number of atoms in the linking chain connecting the oxygen atom in the OH group in formula (1-1) and the carbon atom in the carbonyl group in formula (1-1).
L may have only 1 heteroatom or may have 2 or more heteroatoms. Further, L may have only 1 heteroatom or 2 or more heteroatoms in the shortest-path linking chain.
Examples of the hetero atom contained in the L of the formula (1-1) and present in the shortest path connecting chain include a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom and the like, and a nitrogen atom, an oxygen atom or a sulfur atom is preferable.
In particular, a nitrogen atom is preferable from the viewpoint of chemical resistance, and an oxygen atom or a sulfur atom is preferable from the viewpoint of elongation at break.
In the formula (1-1), L is preferably a mixture of more than 1 hydrocarbon group and a catalyst selected from the group consisting of-O-, -S-, -NR N -、-P(＝O)(OR P ) O-and-SiR P 2 The group represented by at least 1 bond of the structure in (E), more preferably a group represented by 1 or more hydrocarbon groups and selected from the group consisting of-0-, -S-and-NR N -a group represented by a bond of at least 1 structure in (a). R is R N Represents a hydrogen atom or a 1-valent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.
The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond of these.
The saturated aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and more preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms. In the present invention, any of the structures represented by a straight chain, branched chain, cyclic or a combination of these are included in the description of a saturated aliphatic hydrocarbon group, an alkyl group, an alkenyl group, an alkylene group, and the like, unless otherwise specified.
The unsaturated aliphatic hydrocarbon group is preferably an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms, and more preferably an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms.
The aromatic hydrocarbon group includes an aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably a group in which a plurality of hydrogen atoms are removed from a benzene ring or a naphthalene ring, and more preferably a group in which a plurality of hydrogen atoms are removed from a benzene ring.
From the viewpoints of elongation at break and chemical resistance of the cured product obtained, the linking group preferably contains an aliphatic hydrocarbon group or an aromatic hydrocarbon group as the hydrocarbon group, more preferably contains an aromatic hydrocarbon group, and still more preferably contains a group obtained by removing a plurality of hydrogen atoms from a benzene ring.
The aliphatic hydrocarbon ring group is not particularly limited, and examples thereof include a group obtained by removing a plurality of hydrogen atoms from a dicyclopentane ring, a cyclopentene ring, a bornene ring, an isobornene ring, or an adamantane ring.
The aromatic hydrocarbon group includes an aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably a group in which a plurality of hydrogen atoms are removed from a benzene ring or a naphthalene ring, and more preferably a group in which a plurality of hydrogen atoms are removed from a benzene ring.
The aromatic hydrocarbon group or the aliphatic hydrocarbon ring group may be condensed with another ring. Examples of such a scheme include groups obtained by removing a plurality of hydrogen atoms from an indole ring, a benzofuran ring, a benzothiophene ring, and a dihydrodicyclopentene ring.
From the viewpoints of elongation at break and chemical resistance of the cured product obtained, L is preferably an aromatic hydrocarbon group as the hydrocarbon group, and more preferably a group obtained by removing a plurality of hydrogen atoms from a benzene ring.
In addition, from the viewpoint of the efficiency of base generation, when L contains an aromatic hydrocarbon group, it is also preferable that the aromatic hydrocarbon group in L is directly bonded to-OH in formula (1-1). When the aromatic hydrocarbon group in L is directly bonded to-OH in the formula (1-1), it is preferable that the aromatic hydrocarbon groups in the above-mentioned-OH and L are present in the ortho position in the aromatic hydrocarbon group in L at the site where they are bonded to the amide bond directly or via the bonding group. Ortho refers to the position of the aromatic hydrocarbon group in which the ring member bonded to one substituent and the ring member bonded to the other substituent are adjacent ring members in the aromatic hydrocarbon group, and when the aromatic hydrocarbon group is a benzene ring, the ortho is referred to.
Further, the bonding site to-OH in the formula (1-1) in L is preferably a hydrocarbon group.
the-OH group in the formula (1-1) is a hydroxyl group. Moreover, the mode in which-OH in the formula (1-1) is a phenolic hydroxyl group is also a preferable mode of the present invention.
Furthermore, the shortest path linking chain connecting the heteroatom in L with the-OH in formula (1-1) is preferably formed of 2 carbon atoms.
For example, in the case of the following compound A-1, the shortest path connecting a hetero atom (oxygen atom) to-OH in the formula (1-1) is formed of 2 carbon atoms indicated by italics numerals 1 and 2.
[ chemical formula 41]
Furthermore, the shortest path linking chain connecting the heteroatom in L and the carbonyl group in formula (1-1) is preferably formed of 1 or 2 carbon atoms, more preferably 1 carbon atom. For example, the hetero atom in L and the carbonyl group in the formula (1-1) are preferably bonded via a methylene group or a vinyl group, more preferably via a methylene group.
Among these, L is preferably a group represented by a combination of an aromatic hydrocarbon group or an aliphatic hydrocarbon ring group and a linear aliphatic saturated hydrocarbon group.
When L is a group represented by an aromatic hydrocarbon group or a combination of an aliphatic hydrocarbon group and a linear aliphatic hydrocarbon group, it is preferable that the bond site with-OH in the formula (1-1) is present in the aromatic hydrocarbon group or the aliphatic hydrocarbon group, and the bond site with carbonyl in the formula (1-1) is present in the linear aliphatic saturated hydrocarbon group.
The preferred modes of the aromatic hydrocarbon group, the aliphatic hydrocarbon ring group and the aliphatic saturated hydrocarbon group are as described above.
Furthermore, L may further contain-OH within the structure, and may further contain an amide bond (-C (=O) NR) 2 ). R is as defined for R in formula (1-1).
In addition, from the viewpoint of further improving the rectangularity of the pattern, L preferably further contains a polymerizable group. The polymerizable group is preferably a radical polymerizable group, more preferably an ethylenically unsaturated group, and examples thereof include a group in which a vinyl group such as a vinylphenyl group is directly bonded to an aromatic ring, (meth) acryloyloxy group, (meth) acrylic amide group, maleimide group, vinyl group, allyl group, and the like, and more preferably a vinylphenyl group or (meth) acryloyloxy group.
Specific examples of L include, but are not limited to, the following bases. In the following structure, # represents a bonding site to OH in formula (1-1), and # represents a bonding site to carbonyl in formula (1-1).
[ chemical formula 42]
[ alkali-generating agent represented by the formula (1-2) ]
The composition of the present invention preferably contains a base generator represented by the formula (1-2) as a specific base generator.
[ chemical formula 43]
In the formula (1-2), R is respectively and independently hydrogen A sub or any 1-valent organic group, in which case 2R's are not all hydrogen atoms, 2R's may be linked to form a ring structure, L 1 Represents alkylene which may be substituted, Z represents-O-, -S-or-NR N -，R N Represents a hydrogen atom or a 1-valent organic group, R 1 R is R 2 Each independently represents a hydrogen atom or an organic group, 2R 1 R is R 2 At least 2 of the bonds may be bonded to form a ring structure, wherein the bond having the dotted line portion represents a single bond or a double bond, n represents 0 or 1, n is 1 when the bond having the dotted line portion is a double bond, and n is 0 when the bond having the dotted line portion is a single bond.
-R-
In the formula (1-2), R has the same meaning as R in the formula (1-1), and the preferable mode is the same.
-L 1 -
In the formula (1-2), L 1 The alkylene group which may be substituted is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, still more preferably an alkylene group having 2 to 4 carbon atoms, and still more preferably a vinyl group.
The alkylene group may be any of linear, branched, and cyclic, or may be a group represented by a combination of these, and is preferably linear or branched.
The substituent in the alkylene group is not particularly limited as long as the effect of the present invention can be obtained, and examples thereof include a carboxyl group, a halogen atom, and the like.
The unsubstituted alkylene group is also one of the preferable embodiments of the present invention.
-Z-
In the formula (1-2), Z represents-O-, -S-or-NR N From the viewpoint of chemical resistance, it is preferably-NR N From the viewpoint of elongation at break, it is preferably-O-or-S-.
-R 1 R is R 2 -
R 1 R is R 2 Each independently represents a hydrogen atom or an organic group, preferably at least 1 is an organic group.
As R 1 Preferably a hydrocarbon groupMore preferably a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group.
The saturated aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and more preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms. In the present invention, any of the structures represented by a straight chain, branched chain, cyclic or a combination of these are included in the description of a saturated aliphatic hydrocarbon group, an alkyl group, an alkenyl group, an alkylene group, and the like, unless otherwise specified.
The aromatic hydrocarbon group includes an aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably a group in which a plurality of hydrogen atoms are removed from a benzene ring or a naphthalene ring, and more preferably a group in which a plurality of hydrogen atoms are removed from a benzene ring.
And 2R 1 R is R 2 At least 2 of which may be bonded to form a ring structure, preferably 2R 1 Bonding to form a ring structure.
The ring structure to be formed may be an aromatic ring structure or an aliphatic ring structure, and is preferably an aromatic ring structure, more preferably an aromatic hydrocarbon ring structure, and particularly preferably a benzene ring structure.
For example, 2R 1 When bonded to form a ring structure, the bond having a dotted line in formula (1-1) is a double bond.
-n-
n represents 0 or 1, preferably 0. That is, the bond having a dotted line portion in the formula (1-1) preferably represents a double bond.
[ alkali-generating agent represented by the formula (1-3) ]
The composition of the present invention preferably contains a base generator represented by the formula (1-3) as a specific base generator.
[ chemical formula 44]
In the formula (1-3), R is independently a hydrogen atom or an optional 1-valent organic group, and when 2R are hydrogen atoms, 2R can be connected to form a ring structure, L 1 Represents alkylene which may be substituted, Zrepresents-O-, -S-or-NR N -，R N Represents a hydrogen atom or a 1-valent organic group, R 3 Each independently is a hydrogen atom or a 1-valent organic group, R 3 Can be joined to form a ring structure.
R, L in the formula (1-3) 1 And Z is preferably the same as R, L in the formula (1-2) 1 And Z are the same in the preferred manner.
In the formula (1-3), R 3 Preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.
And R is 3 The mode of being a polymerizable group such as vinyl group is also one of preferred modes of the present invention.
[ alkali-generating agent represented by the formula (1-4) ]
The composition of the present invention preferably contains a base generator represented by the formula (1-4) as a specific base generator. The base produced from the formulas (1-4) has a high volume around the nitrogen atom of the amino group, and thus can inhibit the reaction with the resin in the film by steric hindrance. Thus, the alkali is likely to diffuse more uniformly in the film. This is considered to easily suppress the occurrence of a difference in the shrinkage degree of the film between the surface side and the substrate side of the film, and thus the obtained pattern is further excellent in rectangularity.
[ chemical formula 45]
In the formula (1-4), R 2 R is R 4 Each independently represents a 1-valent organic group, 2R 2 Each other or R 2 And R is R 4 Can be connected to form a ring structure L 1 Represents alkylene which may be substituted, Z represents-O-, -S-or-NR N -，R N Represents a hydrogen atom or a 1-valent organic group, R 3 Each independently is a hydrogen atom or a 1-valent organic group, R 3 Can be joined to form a ring structure.
Z, L in the formula (1-4) 1 R is R 3 Z, L in the formulae (1-3) 1 R is R 3 The same is preferable.
R in the formula (1-4) 2 R in formula (1-1) 2 The same is preferable.
R in the formula (1-4) 4 The preferred mode of (2) is the same as that when R in the formula (1-1) is a 1-valent organic group.
[ alkali ]
The specific alkali generator preferably exhibits a property of generating alkali by heat.
That is, the specific alkali generator is preferably a thermal alkali generator.
Specifically, the specific alkali generator preferably generates alkali by heating at 250 ℃, more preferably generates alkali by heating at 220 ℃, further preferably exhibits the property of generating alkali by heating at 200 ℃, particularly preferably generates alkali by heating at 190 ℃, and most preferably generates alkali by heating at 180 ℃. The lower limit of the temperature at which the base is generated is not particularly limited, but is preferably 100℃or higher from the viewpoint of storage stability of the composition, for example.
It can be judged whether or not a specific alkali generator exhibits alkali generating properties at a certain temperature X c by the following method.
After 1 mole of a specific alkali generator was heated in a sealed container under 1 atmosphere at the above-mentioned condition of X ℃ for 3 hours, the amount of decomposition was quantified by means of NMR (nuclear magnetic resonance apparatus), HPLC (high performance liquid chromatography), GC (gas chromatography) or the like, and the case where 0.01 mole or more of alkali was generated was determined as "alkali generation". The amount of the base to be produced is preferably 0.1 mol or more, more preferably 1 mol or more. The upper limit of the amount of the base to be produced is not particularly limited, and may be 1000 moles or less, for example.
The molecular weight of the produced base is preferably 45 to 500, more preferably 70 to 400, and even more preferably 80 to 250.
The boiling point of the base produced is preferably 50 to 450 ℃, more preferably 60 to 400 ℃, still more preferably 80 to 350 ℃ under 1 atmosphere.
The specific base generator preferably exhibits a property of generating a base by cleavage of an amide bond described in formula (1-1).
Further, from the viewpoint of elongation at break and the like of the obtained cured product, the base generated from the specific base generator is preferably an amine, more preferably a secondary amine.
In addition, when the amine is produced from a specific resin, the amine may be an aliphatic amine or an aromatic amine.
The base to be produced is preferably a base having a pKa of 0 or more, more preferably 3 or more, and still more preferably 6 or more of the conjugate acid. The upper limit of the pKa of the conjugate acid is not particularly limited, but is preferably 30 or less.
The pKa is expressed by its negative common logarithmic pKa taking into account the dissociation reaction of the hydrogen ions released by the acid. In the present specification, unless otherwise specified, pKa is set to a calculated value based on ACD/ChemSketch (registered trademark).
When there are a plurality of pKa of the conjugate acid, it is preferable that at least 1 is within the above range.
Specific examples of the produced base include, but are not particularly limited to, bases having the following structures.
[ chemical formula 46]
The dimethylpiperidine ring in the above structure may have both cis and trans forms. Here, the cis form is preferable from the viewpoint of elongation at break of the obtained cured product.
The volume around the nitrogen atom in the trans form becomes slightly larger than in the cis form. Thus, the matrix compound in the cis form is more easily accessible to the nitrogen atom of the active site, and the imidization promoting effect is improved. On the other hand, since the resin has a sufficiently large volume to the extent that the resin does not react, the rectangularity of the pattern can also be maintained. Therefore, the cis body is excellent in elongation at break while maintaining other properties as compared with the trans body.
[ molecular weight ]
The molecular weight of the specific alkali generator is preferably 100 to 1,000, more preferably 100 to 800, and even more preferably 150 to 500.
When the molecular weight is not less than the lower limit, a cured film excellent in elongation at break can be easily obtained. Further, when the molecular weight is not more than the upper limit, film shrinkage of the cured film is easily suppressed.
[ synthetic method ]
For example, the specific alkali generator can be synthesized by the method described in the synthesis example in the examples described below. The synthesis may be performed by other known synthesis methods, and the synthesis method is not particularly limited.
Specific examples of the specific alkali generator are not particularly limited, and examples include A-1 to A-47 used in examples. Further, the compound may have the following structure.
[ chemical formula 47]
The content of the specific alkali generator is preferably 0.5 to 20% by mass based on the total solid content of the resin composition of the present invention. The lower limit is more preferably 1 mass% or more. The upper limit is more preferably 15 mass% or less, and still more preferably 10 mass% or less.
The specific alkali generator may be used alone or in combination of 1 or more than 2. When 2 or more kinds are used in combination, the total amount thereof is preferably within the above range.
When the resin composition of the present invention contains a specific alkali generator and an alkali generator to be described later, the total content of the specific alkali generator and the alkali generator is preferably 0.5 to 20% by mass. The lower limit is more preferably 1 mass% or more. The upper limit is more preferably 15 mass% or less, and still more preferably 10 mass% or less.
< organometallic Complex >
From the viewpoint of chemical resistance, the resin composition of the present invention may contain an organometallic complex.
The organometallic complex may be an organic complex compound containing a metal atom, and is preferably a complex compound containing a metal atom and an organic group, more preferably a compound in which an organic group is coordinated with a metal atom, and still more preferably a metallocene compound.
In the present invention, the metallocene compound means an organometallic complex containing 2 cyclopentadienyl anion derivatives which may have substituents as eta 5-ligands.
The organic group is not particularly limited, and is preferably a hydrocarbon group or a group composed of a combination of a hydrocarbon group and a heteroatom. The hetero atom is preferably an oxygen atom, a sulfur atom or a nitrogen atom.
In the present invention, it is preferable that at least 1 of the organic groups is a cyclic group, and more preferably at least 2 are cyclic groups.
The cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and more preferably a 5-membered cyclic group.
The cyclic group may be a hydrocarbon ring, or may be a heterocyclic ring, and is preferably a hydrocarbon ring.
As the cyclic group of the 5-membered ring, cyclopentadienyl is preferable.
The organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in 1 molecule.
The metal contained in the organometallic complex is not particularly limited, but is preferably a metal corresponding to a group 4 element, more preferably at least 1 metal selected from titanium, zirconium and hafnium, still more preferably at least 1 metal selected from titanium and zirconium, and particularly preferably titanium.
The organometallic complex may contain 2 or more metal atoms, or may contain only 1 metal atom, preferably only 1 metal atom. When the organometallic complex contains 2 or more metal atoms, the organometallic complex may contain only 1 metal atom or may contain 2 or more metal atoms.
The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound or a hafnocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnocene compound, still more preferably a titanocene compound or a zirconocene compound, particularly preferably a titanocene compound.
The manner in which the organometallic complex has the ability to initiate photoradical polymerization is also one of the preferred modes of the invention.
In the present invention, having a photoradical polymerization initiation capability means that radicals capable of initiating radical polymerization can be generated by irradiation of light. For example, when a composition containing a radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength region where the organometallic complex absorbs light and the radical crosslinking agent does not absorb light, it is possible to confirm that there is no free radical polymerization initiation ability by confirming whether the radical crosslinking agent is disappeared. When confirming whether or not to disappear, an appropriate method can be selected depending on the type of the radical crosslinking agent, and for example, confirmation may be performed by IR measurement (infrared spectroscopic measurement) or HPLC measurement (high performance liquid chromatography).
When the organometallic complex has a photoradical polymerization initiation ability, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnocene compound, further preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound.
When the organometallic complex does not have a photoradical polymerization initiation ability, the organometallic complex is preferably at least 1 compound selected from the group consisting of a titanocene compound, a tetraalkoxy titanium compound, an acylated titanium compound, a chelated titanium compound, a zirconocene compound, and a hafnocene compound, more preferably at least 1 compound selected from the group consisting of a titanocene compound, a zirconocene compound, and a hafnocene compound, still more preferably at least 1 compound selected from the group consisting of a titanocene compound and a zirconocene compound, and particularly preferably a titanocene compound.
The molecular weight of the organometallic complex is preferably 50 to 2,000, more preferably 100 to 1,000.
The organometallic complex is preferably a compound represented by the following formula (P).
[ chemical formula 48]
In the formula (P), M is a metal atom, and R is each independently a substituent.
R is preferably independently selected from an aromatic group, an alkyl group, a halogen atom and an alkylsulfonyloxy group.
In the formula (P), the metal atom represented by M is preferably an iron atom, a titanium atom, a zirconium atom or a hafnium atom, more preferably a titanium atom, a zirconium atom or a hafnium atom, still more preferably a titanium atom or a zirconium atom, and particularly preferably a titanium atom.
The aromatic group in R in the formula (P) may be an aromatic group having 6 to 20 carbon atoms, preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and the like.
The alkyl group in R in the formula (P) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, propyl, octyl, isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, and cyclopentyl.
Examples of the halogen atom in R include F, cl, br, I.
The alkyl group constituting the alkylsulfonyloxy group in the above R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, propyl, octyl, isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, and cyclopentyl.
The above R may further have a substituent. Examples of the substituent include a halogen atom (F, cl, br, I), a hydroxyl group, a carboxyl group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, and a diarylamino group.
Specific examples of the organometallic complex include, but are not particularly limited to, tetraisopropoxytitanium, tetra (2-ethylhexyloxy) titanium, diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetonato) titanium, bis (. Eta.5-2, 4-cyclopenta-en-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, pentamethylcyclopentadien trimethoxytitanium, bis (. Eta.5-2, 4-cyclopenta-1-yl) bis (2, 6-difluorophenyl) titanium, and the following compounds.
[ chemical formula 49]
Further, the compounds described in paragraphs 0078 to 0088 of International publication No. 2018/025738 can be used, but are not limited thereto.
The content of the organometallic complex is preferably 0.1 to 30% by mass relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 1.0 mass% or more, still more preferably 1.5 mass% or more, and particularly preferably 3.0 mass% or more. The upper limit is more preferably 25 mass% or less.
The organometallic complex can be used in an amount of 1 or 2 or more. When 2 or more kinds are used, the total amount is preferably within the above range.
< polymerizable Compound >
The resin composition of the present invention preferably contains a polymerizable compound.
Examples of the polymerizable compound include a free-radical crosslinking agent and other crosslinking agents.
[ free radical crosslinking agent ]
The resin composition of the present invention preferably contains a radical crosslinking agent.
The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenic unsaturated bond. Examples of the group containing an ethylenic unsaturated bond include a group having an ethylenic unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryl group, a maleimide group, and a (meth) acrylamide group.
Among these, the group containing an ethylenic unsaturated bond is preferably a (meth) acryloyl group, (meth) acrylamide group or vinylphenyl group, and more preferably a (meth) acryloyl group from the viewpoint of reactivity.
The radical crosslinking agent is preferably a compound having 1 or more ethylenic unsaturated bonds, more preferably a compound having 2 or more ethylenic unsaturated bonds. The radical crosslinking agent may have 3 or more ethylenic unsaturated bonds.
The compound having 2 or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and still more preferably a compound having 2 to 6 ethylenically unsaturated bonds.
Further, from the viewpoint of film strength of the obtained pattern (cured product), the resin composition of the present invention preferably further comprises a compound having 2 ethylenically unsaturated bonds and a compound having 3 or more ethylenically unsaturated bonds.
The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and further preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.
Specific examples of the radical polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters and amides thereof, and preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds and amides of unsaturated carboxylic acids and polyvalent amine compounds. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, a sulfanyl group, or the like with a monofunctional or polyfunctional isocyanate or epoxy, a dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid, or the like can be preferably used. The addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also preferable, and the substitution reaction product of an unsaturated carboxylic acid ester or amide having a releasable substituent such as a halogen group or a tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also preferable. Further, as another example, a compound group substituted with a vinyl benzene derivative such as unsaturated phosphonic acid or styrene, a vinyl ether, or an allyl ether may be used instead of the unsaturated carboxylic acid. For a specific example, reference is made to paragraphs 0113 to 0122 of Japanese patent application laid-open No. 2016-027357, which is incorporated herein by reference.
The radical crosslinking agent is preferably a compound having a boiling point of 100 ℃ or higher at normal pressure. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloxypropyl) ether, tri (acryloxyethyl) isocyanurate, a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then subjecting the resultant to (meth) acrylation, and polyfunctional acrylates such as epoxy acrylates described in Japanese patent application publication No. 48-041708, japanese patent application publication No. 50-006034, japanese patent application publication No. 51-037193, japanese patent application publication No. 48-064183, japanese patent application publication No. 49-043191, and Japanese patent application publication No. 52-030490; and mixtures of these. Furthermore, the compounds described in paragraphs 0254 to 0257 of JP-A2008-292970 are also preferred. Further, a polyfunctional (meth) acrylate obtained by reacting a compound having a cyclic ether group and an ethylenic unsaturated bond such as glycidyl (meth) acrylate with a polyfunctional carboxylic acid can also be mentioned.
Further, as a preferable radical crosslinking agent other than the above, a compound having a fluorene ring and containing 2 or more groups having ethylenic unsaturated bonds, and a cardo (cardo) resin described in japanese patent application laid-open publication No. 2010-160418, japanese patent application laid-open publication No. 2010-129825, japanese patent application laid-open publication No. 4364216, and the like can also be used.
Further, examples of the compounds include specific unsaturated compounds described in Japanese patent publication No. 46-043946, japanese patent publication No. 01-040337 and Japanese patent publication No. 01-040336, and vinyl phosphonic acid compounds described in Japanese patent publication No. 02-025493. Furthermore, a perfluoroalkyl group-containing compound described in Japanese patent application laid-open No. 61-022048 can also be used. Furthermore, the compounds described as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol.20, no.7,300 to 308 (1984) can also be used.
In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese patent application laid-open No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International publication No. 2015/199219, which are incorporated herein by reference, can be used.
Further, a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylating the resultant mixture as described in JP-A-10-062986 as the formula (1) and the formula (2) together with specific examples thereof can also be used as a radical crosslinking agent.
Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese patent application laid-open No. 2015-187211 can also be used as radical crosslinking agents, and these are incorporated herein.
The radical crosslinking agent is preferably dipentaerythritol triacrylate (commercially available as KAYARAD-330 (manufactured by Nippon Kayaku co., ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku co., ltd.)), a-TMMT (manufactured by Shin-Nakamura Chemic al co., ltd.)), dipentaerythritol penta (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku co., ltd.)), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku co., ltd.)), a-DPH (manufactured by Shin-Nakamura Chemical co., ltd.)) or a structure in which these (meth) acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.
As commercial products of the radical crosslinking agent, for example, SR-494, which is a 4-functional acrylate having 4 ethyleneoxy chains, manufactured by Sartomer Company, inc, which is a 2-functional methacrylate having 4 ethyleneoxy chains, which is Sartomer Company, inc, which is SR-209, 231, 239, nippon Kayaku Co., ltd., which is a 6-functional acrylate having 6 ethyleneoxy chains, which is DPCA-60, ltd., which is a 3-functional acrylate having 3 isobutyloxy chains, which is TPA-330, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD., ltd.), NK ESTER M-40G, NK ESTER M-9300, NK ESTER A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., ltd.), 3-functional acrylate having 3 isobutoxy chains, which is UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD., ltd., NK ESTER M-40G, NK ESTER M-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., ltd.) and so on, which is manufactured by PYTAR-600, LTD. Co., LTD. Manufactured by PORE, LTD. Co., LTD. R.R.600, etc., manufactured by POR. Co., LTR 6.
As the radical crosslinking agent, urethane acrylates described in Japanese patent publication No. 48-041708, japanese patent application laid-open No. 51-037193, japanese patent application laid-open No. 02-032293, and Japanese patent application laid-open No. 02-016765, urethane compounds having an ethylene oxide skeleton described in Japanese patent publication No. 58-049860, japanese patent publication No. 56-017654, japanese patent publication No. 62-039417, and Japanese patent publication No. 62-039418 are also preferred. Further, as the radical crosslinking agent, a compound having an amino structure or a thioether structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 can also be used.
The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxyl group or a phosphate group. Among the radical crosslinking agents having an acid group, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferable, and radical crosslinking agents having an acid group by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic acid anhydrides are more preferable. Particularly preferred is a radical crosslinking agent having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercial products include TOAGOSEI CO., LTD. Polyacid modified acrylic oligomers M-510 and M-520.
The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300mgKOH/g, particularly preferably 1 to 100mgK0H/g. The acid value of the radical crosslinking agent is within the above range, and therefore, the production workability and further the developability are excellent. Furthermore, the polymerizability was good. The acid value was determined in accordance with JIS K0070: 1992, the measurement was performed.
From the viewpoints of resolution of the pattern and stretchability of the film, 2-functional methacrylate or acrylate is preferably used in the resin composition.
As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1, 5-pentanediol diacrylate, 1, 6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol a, EO adduct dimethacrylate of bisphenol a, PO adduct diacrylate of bisphenol a, PO adduct dimethacrylate of bisphenol a, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid E0 modified diacrylate, isocyanuric acid modified dimethacrylate, other 2-functional acrylates having urethane bonds, 2-functional methacrylates having urethane bonds can be used. These may be used in combination of 2 or more kinds as required.
For example, PEG200 diacrylate refers to a polyethylene glycol diacrylate having a formula weight of about 200 in polyethylene glycol chains.
The resin composition of the present invention can preferably use a monofunctional radical crosslinking agent as the radical crosslinking agent from the viewpoint of suppressing warpage accompanying control of the elastic modulus of a pattern (cured product). As the monofunctional radical crosslinking agent, there may be preferably used (meth) acrylic acid derivatives such as N-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, epoxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allyl glycidyl ether. As the monofunctional radical crosslinking agent, a compound having a boiling point of 100 ℃ or higher at normal pressure is also preferable in order to suppress volatilization before exposure.
Examples of the radical crosslinking agent having a function of 2 or more include allyl compounds such as diallyl phthalate and triallyl trimellitate.
When the radical crosslinking agent is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 5 mass% or more. The upper limit is more preferably 50 mass% or less, and still more preferably 30 mass% or less.
The radical crosslinking agent may be used alone or in combination of 1 or more than 2. When 2 or more kinds are used in combination, the total amount thereof is preferably within the above range.
[ other crosslinking Agents ]
The resin composition of the present invention preferably further comprises a crosslinking agent other than the radical crosslinking agent described above.
In the present invention, the other crosslinking agent is a crosslinking agent other than the radical crosslinking agent, and preferably a compound having a plurality of groups in the molecule which promote a reaction with other compounds in the composition or reaction products thereof by sensitization with a photoacid generator or a photobase generator, more preferably a compound having a plurality of groups in the molecule which promote a reaction with other compounds in the composition or reaction products thereof by the action of an acid or a base.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
As the other crosslinking agent, a compound having at least 1 group selected from the group consisting of an acyloxymethyl group, a hydroxymethyl group, and an alkoxymethyl group is preferable, and a compound having a structure in which at least 1 group selected from the group consisting of an acyloxymethyl group, a hydroxymethyl group, and an alkoxymethyl group is directly bonded to a nitrogen atom is more preferable.
Examples of the other crosslinking agent include compounds having a structure in which an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, benzoguanamine, or the like is reacted with formaldehyde or formaldehyde is reacted with an alcohol, and a hydrogen atom of the amino group is substituted with an acyloxymethyl group, a hydroxymethyl group, or an alkoxymethyl group. The method for producing these compounds is not particularly limited as long as they have the same structure as the compounds produced by the above method. Furthermore, the oligomer may be one in which methylol groups of these compounds are self-condensed with each other.
As the above amino group-containing compound, a crosslinking agent using melamine is referred to as a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea or alkylene urea is referred to as a urea-based crosslinking agent, a crosslinking agent using alkylene urea is referred to as an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is referred to as a benzoguanamine-based crosslinking agent.
Among these, the resin composition of the present invention preferably contains at least 1 compound selected from urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least 1 compound selected from glycoluril-based crosslinking agents and melamine-based crosslinking agents described later.
Examples of the compound containing at least 1 of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group or a nitrogen atom of the urea structure described below or on a triazine.
The alkoxymethyl group or acyloxymethyl group contained in the above-mentioned compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and still more preferably 2 carbon atoms.
The total number of alkoxymethyl groups and acyloxymethyl groups in the above-mentioned compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
The molecular weight of the above compound is preferably 1500 or less, and preferably 180 to 1200.
[ chemical formula 50]
R 100 Represents an alkyl group or an acyl group.
R 101 R is R 102 Each independently represents a 1-valent organic group, and may be bonded to each other to form a ring.
Examples of the compound in which the alkoxymethyl group or the acyloxymethyl group is directly substituted on the aromatic group include compounds represented by the following general formula.
[ chemical formula 51]
Wherein X represents a single bond or a 2-valent organic group, each R 104 Each independently represents an alkyl group or an acyl group, R 103 Represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group which is decomposed by the action of an acid and generates an alkali-soluble group (e.g., a group which is detached by the action of an acid, a group which is formed by-C (R 4 ) 2 COOR 5 A group (R) 4 R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms 5 Represents groups which are detached by the action of an acid. )).
R 105 Each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.
Regarding the groups which decompose and generate alkali-soluble groups by the action of an acid, the groups which are detached by the action of an acid are represented by-C (R 4 ) 2 COOR 2 R in the radicals represented 5 For example, there can be mentioned-C (R 36 )(R 37 )(R 38 )、-C(R 36 )(R 37 )(OR 39 )、-C(R 01 )(R 02 )(OR 39 ) Etc.
Wherein R is 36 ～R 39 Each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R is R 36 And R is R 37 Can be bonded to each other to form a ring.
The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.
The alkyl group may be either a straight chain or a branched chain.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms.
The cycloalkyl group may have a monocyclic structure or may have a polycyclic structure such as a condensed ring.
The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an alkyl group having 7 to 16 carbon atoms.
The aralkyl group refers to an aryl group substituted with an alkyl group, and the preferable modes of the alkyl group and the aryl group are the same as those of the alkyl group and the aryl group.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, more preferably an alkenyl group having 3 to 16 carbon atoms.
Further, these groups may further have a known substituent within a range to obtain the effect of the present invention.
R 01 R is R 02 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
The group which is decomposed by the action of an acid to form an alkali-soluble group or the group which is detached by the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group or the like. Further preferred is a tertiary alkyl ester group and an acetal group.
Specific examples of the compound having an alkoxymethyl group include the following structures. Examples of the compound having an acyloxymethyl group include compounds in which an alkoxymethyl group of the following compound is changed to an acyloxymethyl group. Examples of the compound having an alkoxymethyl group or an acyloxymethyl group in the molecule include, but are not limited to, the following compounds.
[ chemical formula 52]
[ chemical formula 53]
The compound containing at least 1 of an alkoxymethyl group and an acyloxymethyl group may be commercially available, or may be synthesized by a known method.
From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferable.
Specific examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.
Specific examples of urea-based crosslinking agents include glycoluril-based crosslinking agents such as mono-methylolated glycoluril, di-methylolated glycoluril, tri-methylolated glycoluril, tetra-methylolated glycoluril, mono-methoxymethylated glycoluril, di-methoxymethylated glycoluril, trimethoxymethylated glycoluril, tetra-methoxymethylated glycoluril, mono-ethoxymethylated glycoluril, di-ethoxymethylated glycoluril, triethoxymethyl glycoluril, tetra-ethoxymethylated glycoluril, monopropoxy methylated glycoluril, dipropoxy methylated glycoluril, tripropoxy methylated glycoluril, tetrapropoxy methylated glycoluril, monobutyloxy methylated glycoluril, dibutoxy methylated glycoluril, tributoxy methylated glycoluril, or tetrabutoxy methylated glycoluril;
Urea-based crosslinking agents such as dimethoxymethyl urea, diethoxymethyl urea, dipropoxymethyl urea and dibutoxymethyl urea,
Vinyl urea cross-linking agents such as mono-methylolated vinyl urea or di-methylolated vinyl urea, mono-methoxymethylated vinyl urea, di-methoxymethylated vinyl urea, mono-ethoxymethylated vinyl urea, di-ethoxymethylated vinyl urea, mono-propoxymethylated vinyl urea, di-propoxymethylated vinyl urea, mono-or di-butoxymethylated vinyl urea,
Propylene urea-based crosslinking agents such as monocrystaline propylene urea, dimethylol propylene urea, monomethoxy methylated propylene urea, dimethoxy methylated propylene urea, monoethoxy methylated propylene urea, diethoxy methylated propylene urea, monopropoxy methylated propylene urea, dipropoxy methylated propylene urea, monobutyl oxy methylated propylene urea or dibutoxy methylated propylene urea,
1, 3-bis (methoxymethyl) -4, 5-dihydroxy-2-imidazolidinone, 1, 3-bis (methoxymethyl) -4, 5-dimethoxy-2-imidazolidinone, and the like.
Specific examples of the benzoguanamine-based crosslinking agent include monomethylol benzoguanamine, dimethylol benzoguanamine, trimethylol benzoguanamine, tetramethylol benzoguanamine, monomethylol methylated benzoguanamine, dimethoxymethyl benzoguanamine, trimethoxy methylated benzoguanamine, tetramethoxymethyl benzoguanamine, monoethoxymethyl benzoguanamine, diethoxymethyl benzoguanamine, triethoxymethyl benzoguanamine, tetraethoxymethyl benzoguanamine, monopropoxymethyl benzoguanamine, dipropoxymethyl benzoguanamine, tripropoxymethyl benzoguanamine, tetrapropoxymethyl benzoguanamine, monobutyloxymethyl benzoguanamine, dibutoxymethyl benzoguanamine, tributoxymethyl benzoguanamine, tetrabutoxymethyl benzoguanamine, and tetrabutoxymethyl benzoguanamine.
As the compound having at least 1 group selected from the group consisting of hydroxymethyl and alkoxymethyl, a compound in which at least 1 group selected from the group consisting of hydroxymethyl and alkoxymethyl is directly bonded to an aromatic ring (preferably a benzene ring) can be preferably used.
Specific examples of such compounds include xylylene glycol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, hydroxymethyl benzene hydroxymethyl benzoate, bis (hydroxymethyl) biphenyl, dimethyl bis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) benzophenone, methoxymethyl benzene methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethyl bis (methoxymethyl) biphenyl, 4',4 "-ethylenetris [2, 6-bis (methoxymethyl) phenol ], 5' - [2, 2-trifluoro-1- (trifluoromethyl) ethylene ] bis [ 2-hydroxy-1, 3-benzenedimethanol ], 3', 5' -tetrakis (methoxymethyl) -1,1 '-biphenyl-4, 4' -diol, and the like.
As other crosslinking agents, commercially available products may be used, and preferable commercially available products include 46DMOC, 46DMOEP (manufactured by ASAHI YUKIZAI CORPORATION above), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisc-P, DMOM-PC, DMM-PTBP, DMM-MBPC, triML-P, triML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-AF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPOM-TMOM, TMOM-BPOM-Z, DML-BPC, DMLBOC-P, DMOM-PC, DMM-PTBP, TML-PtP, TML-HPL-HPP, HMP, PHOM-TPP, PHP; LTD), NIKALAC (registered trademark, the same as described below) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (SANWA CHEMICAL co., LTD, above), and the like.
Further, the resin composition of the present invention preferably further contains at least 1 compound selected from the group consisting of an epoxy compound, an oxetane compound and a benzoxazine compound as another crosslinking agent.
Epoxy compound (epoxy group-containing compound)
As the epoxy compound, a compound having 2 or more epoxy groups in one molecule is preferable. The epoxy group undergoes a crosslinking reaction at 200 ℃ or less and does not cause dehydration reaction due to crosslinking, and thus film shrinkage is less likely to occur. Therefore, by containing the epoxy compound, the low-temperature curing and warpage of the resin composition of the present invention can be effectively suppressed.
The epoxy compound preferably contains a polyethylene oxide group. Thereby, the elastic modulus is further reduced, and warpage can be suppressed. The polyethylene oxide group represents ethylene oxide having a repeating unit number of 2 or more, preferably having a repeating unit number of 2 to 15.
Examples of the epoxy compound include bisphenol a epoxy resins; bisphenol F type epoxy resin; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and the like, or polyhydric alcohol hydrocarbon type epoxy resins; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing polysilicones such as polymethylsiloxane (glycidoxypropyl) and the like, but are not limited thereto. Specifically, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON-665-EXP-S, EPICLON (registered trademark) N-740 (the above are trade names, DIC Corporation), RIKARESIN (registered trademark) BEO-20E, RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (trade name, new Japan Chemical Co., ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (trade name, ADEKA CORPORATION, CELLOXDE 2021P, CELLOXIDE (registered trademark) 2081, CELLOXDE 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (trade name, daicel Corporation, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (trade name, nippon Kayaku Co., ltd.) and the like. Furthermore, the following compounds may also be preferably used.
[ chemical formula 54]
Wherein n is an integer of 1 to 5, and m is an integer of 1 to 20.
In the above structure, n is preferably 1 to 2 and m is preferably 3 to 7 from the viewpoint of both heat resistance and improvement of elongation.
Oxetane compounds (compounds having oxetanyl groups)
Examples of oxetane compounds include compounds having 2 or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyl oxetane, 1, 4-bis { [ (3-ethyl-3-oxetanyl) methoxy ] methyl } benzene, 3-ethyl-3- (2-ethylhexyl methyl) oxetane, and 1, 4-benzenedicarboxylic acid-bis [ (3-ethyl-3-oxetanyl) methyl ] ester. Specifically, TOAGOSEI CO. LTD. ARON OXETANE series (for example, OXT-121, OXT-221) may be preferably used, and these may be used alone or 2 or more may be mixed.
Benzoxazine compound (compound having benzoxazolyl group)
The benzoxazine compound is preferable because it does not undergo deaeration during curing due to a crosslinking reaction caused by a ring-opening addition reaction, and further, it reduces heat shrinkage to suppress warpage.
Preferable examples of the benzoxazine compound include P-d type benzoxazine, F-a type benzoxazine (trade name, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and novolak type dihydrobenzoxazine compounds. These may be used alone, or 2 or more kinds may be mixed.
The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition of the present invention. The other crosslinking agent may be contained only in 1 kind, or may be contained in 2 or more kinds. When the amount of the other thermal crosslinking agent is 2 or more, the total amount is preferably within the above range.
[ polymerization initiator ]
The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. Particularly preferably, a photopolymerization initiator is contained.
The photopolymerization initiator is preferably a photo radical polymerization initiator. The photo radical polymerization initiator is not particularly limited, and may be appropriately selected from known photo radical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays ranging from the ultraviolet region to the visible region is preferable. Furthermore, active agents that generate reactive radicals for some interaction with photosensitizers that are excited by light may be used.
The photo radical polymerization initiator preferably contains at least 1 of a molecular absorbance of at least about 50 L.mol in the wavelength range of about 240 to 800nm (preferably 330 to 500 nm) -1 ·cm -1 Is a compound of (a). The molar absorptivity of the compound can be measured by a known method. For example, the measurement is carried out by means of an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Co., ltd.) preferably using an ethyl acetate solvent at a concentration of 0.01 g/L.
As the photo radical polymerization initiator, a known compound can be arbitrarily used. Examples thereof include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, and the like), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbisimidazole, oxime derivatives, and the like, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α -amino ketone compounds such as aminoacetophenone, α -hydroxy ketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For details of these, reference is made to paragraphs 0165 to 0182 of JP-A-201 delta-027357 and paragraphs 0138 to 0151 of International publication No. 2015/199219, which are incorporated herein by reference. Examples of the initiator include a compound described in JP-A-2014-130173 at the stage 0065-0111, JP-A-6301489, MATERIAL STAGE-60 p, vol.19, no.3, 2019, a peroxide-based photopolymerization initiator described in International publication No. 2018/221177, a photopolymerization initiator described in International publication No. 2018/110179, a photopolymerization initiator described in JP-A-2019-043864, a photopolymerization initiator described in JP-A-2019-044030, and a peroxide-based initiator described in JP-A-2019-167313, which are incorporated herein by reference.
Examples of the ketone compound include compounds described in paragraph 0087 of Japanese patent application laid-open No. 2015-087611, incorporated herein. Among the commercial products, KAYACURE DETX-S (Nippon Kayaku co., ltd.) may also be preferably used.
In one embodiment of the present invention, as the photo radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine oxide initiator described in JP-A-4225898 can be used, and the contents of these are incorporated in the present specification.
As the alpha-hydroxyketone initiator, omnirad 184, omnirad 1173, omnirad 2959, omnirad 127 (manufactured by IGM Resins B.V. above), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (manufactured by BASF corporation) can be used.
As the α -aminoketone initiator, omnirad 907, omnirad 369E, omnirad 379EG (manufactured by the above-mentioned IGM Resins B.V.), IRGACURE 907, IRGAC URE 369 and IRGACURE 379 (trade names: all manufactured by BASF corporation) can be used.
As the aminoacetophenone initiator, a compound described in japanese patent application laid-open No. 2009-191179, which matches a light source having a wavelength of 365nm or 405nm, etc., and the content of which is incorporated in the present specification, can also be used.
Examples of the acylphosphine oxide initiator include 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. As the catalyst, omnirad 819, omnirad TPO (manufactured by IGM Resins B.V. above), IRGACURE-819, IRGACURE-TPO (trade name: manufactured by BASF corporation) can be used.
Examples of the metallocene compound include IRGACURE-784, IRGACURE-784EG (all manufactured by BASF corporation), keycure VIS 813 (King Brother Chem Co., ltd.).
As the photo radical polymerization initiator, an oxime compound is more preferably exemplified. By using an oxime compound, the exposure latitude can be further effectively improved. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.
Specific examples of the oxime compound include a compound described in japanese patent application laid-open No. 2001-233846, a compound described in japanese patent application laid-open No. 2000-080068, a compound described in japanese patent application laid-open No. 2006-342166, a compound described in j.c.s.perkin II (1979, pages 1653-1660), a compound described in j.c.s.perkin II (1979, pages 156-162), a compound described in Journal of Photopolymer Science and Technology (1995, pages 202-232), a compound described in japanese patent application laid-open No. 2000-066385, a compound described in japanese patent application laid-open No. 2004-534797, a compound described in japanese patent application laid-open No. 6065596, a compound described in international publication No. 2015/152153, a compound described in international publication No. 2017/051680, a compound described in japanese patent application laid-open No. 2017-865, a compound described in international publication No. 2015-1675, a compound described in international publication No. 2015-2015, a publication No. 1648, and the like.
Examples of the preferable oxime compound include 3- (benzoyloxy (imino)) butan-2-one, 3- (acetoxy (imino)) butan-2-one, 3- (propionyloxy (imino)) butan-2-one, 2- (acetoxy (imino)) pentan-3-one, 2- (acetoxy (imino)) -1-phenylpropan-1-one, 2- (benzoyloxy (imino)) -1-phenylpropan-1-one, 3- ((4-toluenesulfonyloxy) imino) butan-2-one, and 2- (ethoxycarbonyloxy (imino)) -1-phenylpropan-1-one having the following structure. In the resin composition of the present invention, an oxime compound (oxime-based photo radical polymerization initiator) is particularly preferably used as the photo radical polymerization initiator. The oxime-based photo-radical polymerization initiator has a linking group > c=n-O-C (=o) -, in the molecule.
[ chemical formula 55]
Among the commercial products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF corporation as described above), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION), and photo radical polymerization initiator 2 described in Japanese patent application laid-open No. 2012-014052 may be preferably used. In addition, TR-PBG-304, TR-PBG-305 (Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (ADEKA CORPORATION). Further, DFI-091 (manufactured by Daito Chemix Corporation) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Furthermore, an oxime compound having the following structure can also be used.
[ chemical formula 56]
As the photo radical polymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include a compound described in japanese patent application laid-open No. 2014-137466 and a compound described in japanese patent No. 06636081, which are incorporated herein by reference.
As the photo radical polymerization initiator, an oxime compound having at least 1 benzene ring of carbazole ring as a skeleton of naphthalene ring can also be used. Specific examples of such oxime compounds include those described in international publication No. 2013/083505, which is incorporated herein by reference.
Oxime compounds having a fluorine atom can also be used. Specific examples of such oxime compounds include a compound described in JP 2010-26261028A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852A, and compound (C-3) described in paragraph 0101 of JP 2013-164471A, which are incorporated in the present specification.
As the photopolymerization initiator, an oxime compound having a nitro group can be used. Oxime compounds having a nitro group are also preferably dimers. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of Japanese patent application laid-open No. 2013-114249, 0008 to 0012 and 0070 to 0079 of Japanese patent application laid-open No. 2014-137466, and 0007 to 0025 of Japanese patent application laid-open No. 4223071, which are incorporated herein by reference. Further, as the oxime compound having a nitro group, ADEKA ARKLS NCI-831 (ADEKA CORPORATION).
As the photo radical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples thereof include 0E-01 to 0E-75 described in International publication No. 2015/036910.
As the photo radical polymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can also be used. Examples of such photopolymerization initiators include compounds described in International publication No. 2019/088055, which is incorporated herein by reference.
As the photopolymerization initiator, an aromatic ring group Ar having an electron withdrawing group introduced into an aromatic ring can also be used 0X1 Is also referred to as oxime compound OX below. Ar as the above aromatic ring group 0X1 Examples of the electron-withdrawing group include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a cyano group, preferably an acyl group and a nitro group, and can be easily formedFor reasons of the film having excellent light resistance, an acyl group is more preferable, and a benzoyl group is further preferable. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, cyano group, nitro group, hydroxyl group, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic oxy group, alkenyl group, alkylthio group, arylthio group, acyl group or amino group, more preferably an alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group or amino group, still more preferably an alkoxy group, alkylthio group or amino group.
The oxime compound OX is preferably at least 1 selected from the group consisting of a compound represented by the formula (OX 1) and a compound represented by the formula (OX 2), more preferably a compound represented by the formula (OX 2).
[ chemical formula 57]
Wherein R is X1 Represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, alkylsulfanyl, arylsulfanyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyl, acyloxy, amino, phosphono, carbamoyl or sulfamoyl,
R X2 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, alkylsulfanyl, arylsulfanyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyloxy or amino,
R X3 ～R X14 each independently represents a hydrogen atom or a substituent.
Wherein R is X10 ～R X14 At least 1 of which is an electron withdrawing group.
In the above formula, R is preferably X12 R is an electron withdrawing group X10 、R X11 、R X13 、R X14 Is a hydrogen atom.
Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of japanese patent No. 4600600, incorporated herein by reference.
Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in japanese patent application laid-open No. 2007-269779, an oxime compound having a thioaryl group shown in japanese patent application laid-open No. 2009-191061, and the like, which are incorporated herein by reference.
From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethyl ketal compounds, α -hydroxyketone compounds, α -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadienyl-benzene-iron complexes and salts thereof, halomethyl oxadiazole compounds, 3-aryl-substituted coumarin compounds.
More preferred photo radical polymerization initiator is a trihalomethyltriazine compound, an α -amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, an acetophenone compound, still more preferably at least 1 compound selected from the group consisting of trihalomethyltriazine compound, α -amino ketone compound, metallocene compound, oxime compound, triarylimidazole dimer, benzophenone compound, still more preferably a metallocene compound or oxime compound.
The photo radical polymerization initiator may be a benzophenone, an aromatic ketone such as N, N ' -tetramethyl-4, 4' -diaminobenzophenone (Michler's ketone), an aromatic ketone such as N, N ' -tetraalkyl-4, 4' -diaminobenzophenone (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-acetone-1, a benzoin compound such as alkylanthraquinone, a benzoin alkyl ether, a benzoin compound such as benzoin, an alkyl benzoin, a benzyl derivative such as benzyl dimethyl ketal, or the like. Furthermore, a compound represented by the following formula (I) can also be used.
[ chemical formula 58]
In formula (I), R I00 Is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by 1 or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, a phenyl group or a biphenyl group substituted by at least 1 of an alkyl group having 2 to 18 carbon atoms and an alkyl group having 1 to 4 carbon atoms interrupted by 1 or more oxygen atoms, R I01 Is a group represented by formula (II) or is associated with R I00 The same radicals R I02 ～R I04 Each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.
[ chemical formula 59]
Wherein R is I05 ～R I07 R is the same as the R of the formula (I) I02 ～R I04 The same applies.
The photo radical polymerization initiator may be any one of the compounds described in paragraphs 0048 to 0055 of International publication No. 2015/125469, incorporated herein by reference.
As the photo radical polymerization initiator, a 2-functional or 3-functional or more photo radical initiator can be used. By using such a photo radical polymerization initiator, 2 or more radicals are generated from one molecule of the photo radical polymerization initiator, and thus good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, crystallinity is reduced, solubility in a solvent or the like is increased, and deposition is less likely to occur with the passage of time, whereby the stability of the resin composition with time can be improved. Specific examples of the 2-functional or 3-functional or more photo-radical polymerization initiator include the photoinitiators of oxime esters described in Japanese patent application publication No. 2010-527339, japanese patent application publication No. 2011-524436, the photoinitiators described in Japanese patent application publication No. 0020-0033, the photoinitiators described in Japanese patent application publication No. 2017-0412, the dimers of oxime compounds described in Japanese patent application publication No. 0039-0055, the compounds (E) and (G) described in Japanese patent application publication No. 2013-522445, the Cmpd 1-7 described in Japanese patent application publication No. 2016/034963, the photoinitiators of oxime esters described in Japanese patent application publication No. 2017-523465, the photoinitiators described in Japanese patent application publication No. 0020-0033, the photoinitiators described in Japanese patent application publication No. 2017-151342, the photoinitiators described in paragraphs 0017-0026, the photoinitiators described in Japanese patent application publication No. 6469669, and the like.
When the photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and still more preferably 1.0 to 10% by mass, relative to the total solid content of the resin composition of the present invention. The photopolymerization initiator may be contained in an amount of 1 or 2 or more. When the photopolymerization initiator is contained in an amount of 2 or more, the total amount is preferably within the above range.
In addition, the photopolymerization initiator may also function as a thermal polymerization initiator, and thus crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.
[ sensitizer ]
The resin composition may contain a sensitizer. The sensitizer absorbs a specific active radiation to be in an electron-excited state. The sensitizer in an electron excited state is brought into contact with a thermal radical polymerization initiator, a photo radical polymerization initiator or the like to cause an electron transfer, an energy transfer, heat generation or the like. Thus, the thermal radical polymerization initiator and the photo radical polymerization initiator cause chemical changes to decompose and generate radicals, acids or bases.
As the sensitizer that can be used, compounds such as benzophenone-based, milone-based, coumarin-based, pyrazole azo-based, aniline azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based and the like can be used.
As the sensitizer, for example, examples thereof include midone, 4' -bis (diethylamino) benzophenone, 2, 5-bis (4 ' -diethylaminobenzylidene) cyclopentane, 2, 6-bis (4 ' -diethylaminobenzylidene) cyclohexanone, 2, 6-bis (4 ' -diethylaminobenzylidene) -4-methylcyclohexanone, 4' -bis (dimethylamino) chalcone, 4' -bis (diethylamino) chalcone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenyl biphenyl) -benzothiazole, 2- (p-dimethylaminophenyl vinylidene) benzothiazole, and 2- (p-dimethylaminophenylvinylene) isonaphthylthiazole, 1, 3-bis (4 ' -dimethylaminobenzylidene) acetone, 1, 3-bis (4 ' -diethylaminobenzylidene) acetone, 3' -carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7- (diethylamino) coumarin-3-carboxylic acid ethyl ester), and, N-phenyl-N ' -ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinylbenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyrene) benzoxazole, 2- (p-dimethylaminostyrene) benzothiazole, 2- (p-dimethylaminostyrene) naphthalene (1, 2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4' -dimethylacetanilide, and the like.
Furthermore, a sensitizing dye may be used.
For details of the sensitizing dye, reference is made to paragraphs 0161 to 0163 of Japanese patent application laid-open No. 2016-027357, which is incorporated herein by reference.
When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of 2 or more.
[ chain transfer agent ]
The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in pages 683-684 of the third edition of the Polymer dictionary (university of Polymer (The Society of Polymer Science, japan) eds., 2005). As the chain transfer agent, for example, a chain transfer agent having-S-, -SO within the molecule can be used 2 The group of compounds S-, -N-O-, SH, PH, siH and GeH, dithiobenzoate esters having thiocarbonylthio groups for RAFT (Reversible Addition Fragmentation chain Transfer: reversible addition fragmentation chain transfer) polymerization, trithiocarbonates, dithiocarbamates, xanthate compounds, etc. These are radicals generated by supplying hydrogen to the low-activity radicals, or radicals may be generated by deprotonation after oxidation. In particular, a thiol compound can be preferably used.
The chain transfer agent may be a compound described in paragraphs 0152 to 0153 of International publication No. 2015/199219, incorporated herein by reference.
When the resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the resin composition of the present invention. The chain transfer agent may be 1 or 2 or more. When the chain transfer agent is 2 or more, the total amount thereof is preferably within the above range.
< alkali Generator >
The resin composition of the present invention may contain a base generator. Herein, the base generator means a compound capable of generating a base by physical or chemical action. The alkali generator preferable for the resin composition of the present invention includes a thermal alkali generator and a photobase generator.
Among them, the alkali generator corresponding to the above specific alkali generator is not the alkali generator described in the present invention.
In particular, when the resin composition contains a precursor of the cyclized resin, the resin composition preferably contains a base generator. By containing the thermal base generator in the resin composition, for example, the cyclization reaction of the precursor is promoted by heating, and thus the mechanical properties and chemical resistance of the cured product are improved, for example, the performance of the interlayer insulating film for a re-wiring layer included in the semiconductor package is improved.
The alkali generator may be an ionic alkali generator or a nonionic alkali generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.
The alkali generator of the present invention is not particularly limited, and a known alkali generator can be used. As the known base generating agent, for example, a carbamoyl oxime compound, a carbamoyl hydroxylamine compound, a carbamic acid compound, a carboxamide compound, an acetamide compound, a carbamic acid ester compound, a benzyl carbamic acid ester compound, a nitrobenzyl carbamic acid ester compound, a sulfonamide compound, an imidazole derivative compound, an amine imide compound, a pyridine derivative compound, an α -aminoacetophenone derivative compound, a quaternary ammonium salt derivative compound, a pyridinium salt, an α -lactone ring derivative compound, an amine imide compound, a phthalimide derivative compound, an acyloxyimide compound, or the like can be used.
Specific examples of the nonionic base generator include compounds represented by the formula (B1), the formula (B2), and the formula (B3).
[ chemical formula 60]
In the formula (R1) and the formula (B2), rb 1 、Rb 2 Rb 3 Each independently is an organic group having no tertiary amine structure, a halogen atom, or a hydrogen atom. Wherein Rb 1 Rb 2 And not simultaneously become hydrogen atoms. Furthermore, rb 1 、Rb 2 Rb 3 None of them has a carboxyl group. In the present specification, the tertiary amine structure means a structure in which all of 3 bonds of a 3-valent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the bonded carbon atom is a carbonyl group-forming carbon atom, that is, when an amide group is formed together with a nitrogen atom, the present invention is not limited thereto.
In the formulae (B1) and (B2), rb is preferably 1 、Rb 2 Rb 3 At least 1 of which comprises a cyclic structure, more preferably at least 2 of which comprises a cyclic structure. The cyclic structure may be any of a single ring and a condensed ring, and a condensed ring formed by condensing a single ring or 2 single rings is preferable. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, and more preferably a cyclohexane ring.
More specifically, rb 1 Rb 2 Preferably, the compound is a hydrogen atom, an alkyl group (having a carbon number of preferably 1 to 24, more preferably 2 to 18, still more preferably 3 to 12), an alkenyl group (having a carbon number of preferably 2 to 24, more preferably 2 to 18, still more preferably 3 to 12), an aryl group (having a carbon number of preferably 6 to 22, more preferably 6 to 18, still more preferably 6 to 10), or an aralkyl group (having a carbon number of preferably 7 to 25, more preferably 7 to 19, still more preferably 7 to 12). These groups may have substituents within a range that exerts the effects of the present invention. Rb (Rb) 1 With Rb 2 Can be bonded to each other to form a ring. The ring to be formed is preferably a 4-to 7-membered nitrogen-containing heterocycle. In particular, rb 1 Rb 2 The substituent-containing linear, branched or cyclic alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) is preferable, the substituent-containing cycloalkyl group (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) is more preferable, and the substituent-containing cyclohexyl group is still more preferable.
As Rb 3 Examples thereof include an alkyl group (having preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (having preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), and an alkenyl group (having preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably2 to 6), an aralkyl group (having a carbon number of preferably 7 to 23, more preferably 7 to 19, further preferably 7 to 12), an aralkenyl group (having a carbon number of preferably 8 to 24, more preferably 8 to 20, further preferably 8 to 16), an alkoxy group (having a carbon number of preferably 1 to 24, more preferably 2 to 18, further preferably 3 to 12), an aryloxy group (having a carbon number of preferably 6 to 22, more preferably 6 to 18, further preferably 6 to 12), or an aralkoxy group (having a carbon number of preferably 7 to 23, more preferably 7 to 19, further preferably 7 to 12). Among them, cycloalkyl groups (having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), aralkenyl groups, and aralkoxy groups are preferable. Rb (Rb) 3 Further, the substituent may be present within a range that exerts the effects of the present invention.
The compound represented by the formula (R1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
[ chemical formula 61]
In the formula, rb 11 Rb 12 And Rb 31 Rb 32 Rbw and Rb in the formula (B1) 2 The meaning is the same.
Rb 13 The alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), the alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), the aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), the aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms) may have a substituent in a range that exerts the effect of the present invention. Wherein Rb 13 Aralkyl groups are preferred.
Rb 33 Rb 34 Each independently represents a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, still more preferably 2 to 3 carbon atoms), or an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to carbon atoms)18, more preferably 6 to 10), an aralkyl group (the number of carbon atoms is preferably 7 to 23, still more preferably 7 to 19, still more preferably 7 to 11), and a hydrogen atom is preferable.
Rb 35 The alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), the alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 3 to 8 carbon atoms), the aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), the aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms), and the aryl group are preferable.
The compound represented by the formula (B1-1) is also preferably a compound represented by the formula (B1-1 a).
[ chemical formula 62]
Rh 11 Rb 12 And Rb in formula (B1-1) 11 Rb 12 The meaning is the same.
Rb 15 Rb 16 The hydrogen atom, the alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), the alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 3 carbon atoms), the aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), the aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 11 carbon atoms), and the hydrogen atom or the methyl group are preferable.
Rb 17 The aryl group is preferably an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 3 to 8 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), an aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms).
[ chemical formula 63]
In the formula (B3), L is a 2-valent hydrocarbon group having a saturated hydrocarbon group on the path of the linking chain linking the adjacent oxygen atoms and carbon atoms, and represents a hydrocarbon group having 3 or more atoms on the path of the linking chain. And R is N1 R is R N2 Each independently represents a 1-valent organic group.
In the present specification, the term "link chain" refers to a chain in which the link objects are connected at the shortest (minimum number of atoms) distance among the atomic chains on the path connecting 2 atoms or groups of atoms of the link objects. For example, in a compound represented by the following formula, L is composed of styrene, a saturated hydrocarbon group is a vinyl group, a linking chain is composed of 4 carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or "linking chain length") is 4.
[ chemical formula 64]
The number of carbon atoms in L in the formula (B3) (including carbon atoms other than the carbon atoms in the connecting chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, still more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. The upper limit of the chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less, from the viewpoint of rapidly proceeding the intramolecular cyclization reaction. The chain length of the linkage of L is particularly preferably 4 or 5, most preferably 4. Specific examples of preferred compounds for the base generator include, for example, compounds described in paragraphs 0102 to 0168 of International publication No. 2020/066416 and compounds described in paragraphs 0143 to 0177 of International publication No. 2018/038002.
The base generator preferably further comprises a compound represented by the following formula (N1).
[ chemical formula 65]
In the formula (N1), R N1 R is R N2 Each independently represents a 1-valent organic group, R C1 Represents a hydrogen atom or a protecting group, and L represents a 2-valent linking group.
L is a 2-valent linking group, preferably a 2-valent organic group. The chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The chain length refers to the number of atoms present in the atomic arrangement that forms the shortest path between 2 carbonyl groups in the formula.
In the formula (N1), R N1 R is R N2 Each independently represents a 1-valent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), preferably a hydrocarbon group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms), specifically, an aliphatic hydrocarbon group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), preferably an aliphatic hydrocarbon group. As R N1 R is R N2 If an aliphatic hydrocarbon group is used, the alkali generated is preferably highly basic. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in an aliphatic hydrocarbon chain, an aromatic ring, or a substituent. In particular, the manner in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain can be exemplified.
As a constituent R N1 R is R N2 Examples of the aliphatic hydrocarbon group(s) include a linear or branched alkyl group, a cyclic alkyl group, a group related to a combination of a linear alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The number of carbon atoms of the linear or branched chain alkyl group is preferably 1 to 24, more preferably 2 to 18, and still more preferably 3 to 12. Examples of the linear or branched chain alkyl group include methyl, ethyl, propyl, butyl,Pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl and the like.
The number of carbon atoms of the cyclic alkyl group is preferably 3 to 12, more preferably 3 to 6. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.
The number of carbon atoms of the group involved in the combination of the chain alkyl group and the cyclic alkyl group is preferably 4 to 24, more preferably 4 to 18, and still more preferably 4 to 12. Examples of the group involved in the combination of the chain alkyl group and the cyclic alkyl group include cyclohexylmethyl group, cyclohexylethyl group, cyclohexylpropyl group, methylcyclohexylmethyl group, ethylcyclohexylethyl group, and the like.
The number of carbon atoms of the alkyl group having an oxygen atom in the chain is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be linear or cyclic, or may be linear or branched.
Wherein R is from the viewpoint of increasing the boiling point of a base formed by decomposition to be described later N1 R is R N2 Preferably an alkyl group having 5 to 12 carbon atoms. Among them, in the prescription in which adhesion is important when stacking with a metal (e.g., copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
R N1 R is R N2 Can be connected with each other to form a ring structure. When the cyclic structure is formed, an oxygen atom or the like may be present in the chain. And R is N1 R is R N2 The cyclic structure may be a single ring or a condensed ring, and is preferably a single ring. The cyclic structure to be formed is preferably a 5-or 6-membered ring containing a nitrogen atom in the formula (N1), and examples thereof include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring, and examples thereof include a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.
R C1 Represents a hydrogen atom or a protecting group, preferably a hydrogen atom.
The protecting group is preferably a protecting group which is decomposed by the action of an acid or a base, and the protecting group which is decomposed by an acid is preferably exemplified.
Specific examples of the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain. Examples of the chain or cyclic alkyl group include methyl, ethyl, isoendo, t-butyl, and cyclohexyl. The chain alkyl group having an oxygen atom in the chain includes, specifically, an alkoxyalkyl group, and more specifically, a methoxymethyl group (MOM), an ethoxyethyl group (EE), and the like. Examples of the cyclic alkyl group having an oxygen atom in the chain include an epoxy group, an epoxypropyl group, an oxetanyl group, a tetrahydrofuranyl group, and a Tetrahydropyran (THP) group.
The 2-valent linking group constituting L is not particularly limited, but is preferably a hydrocarbon group, and more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and may have a kind of atom other than a carbon atom in the hydrocarbon chain. More specifically, the group is preferably a 2-valent hydrocarbon linking group which may have an oxygen atom in the chain, more preferably a 2-valent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a 2-valent aromatic hydrocarbon group, or a group related to a combination of a 2-valent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a 2-valent aromatic hydrocarbon group, and further preferably a 2-valent aliphatic hydrocarbon group which may have an oxygen atom in the chain. These groups preferably do not have an oxygen atom.
The number of carbon atoms of the 2-valent hydrocarbon linking group is preferably 1 to 24, more preferably 2 to 12, and still more preferably 2 to 6. The number of carbon atoms of the 2-valent aliphatic hydrocarbon group is preferably 1 to 12, more preferably 2 to 6, and still more preferably 2 to 4. The number of carbon atoms of the 2-valent aromatic hydrocarbon group is preferably 6 to 22, more preferably 6 to 18, and still more preferably 6 to 10. The number of carbon atoms of the group (for example, an arylene alkyl group) involved in the combination of the 2-valent aliphatic hydrocarbon group and the 2-valent aromatic hydrocarbon group is preferably 7 to 22, more preferably 7 to 18, and still more preferably 7 to 10.
The linking group L is preferably a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylene group, or an arylene alkylene group.
The number of carbon atoms of the linear or branched chain alkylene group is preferably 1 to 12, more preferably 2 to 6, and still more preferably 2 to 4.
The number of carbon atoms of the cyclic alkylene group is preferably 3 to 12, more preferably 3 to 6.
The number of carbon atoms of the group involved in the combination of the chain alkylene group and the cyclic alkylene group is preferably 4 to 24, more preferably 4 to 12, and still more preferably 4 to 6.
The alkylene group having an oxygen atom in the chain may be linear or cyclic, or may be linear or branched. The number of carbon atoms of the alkylene group having an oxygen atom in the chain is preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 3.
The number of carbon atoms of the linear or branched alkenyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 3. The number of c=c bonds of the linear or branched chain alkenylene group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3.
The number of carbon atoms of the cyclic alkenylene group is preferably 3 to 12, more preferably 3 to 6. The number of c=c bonds of the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 2.
The number of carbon atoms of the arylene group is preferably 6 to 22, more preferably 6 to 18, and still more preferably 6 to 10.
The number of carbon atoms of the arylene alkylene is preferably 7 to 23, more preferably 7 to 19, and still more preferably 7 to 11.
Among them, preferred are chain alkylene groups, cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, chain alkenylene groups, arylene alkylene groups, more preferred are 1, 2-vinyl groups, propane diyl groups (especially 1, 3-propane diyl group), cyclohexane diyl groups (especially 1, 2-cyclohexane diyl group), ethylene groups (especially cis-ethylene groups), phenylene groups (1, 2-phenylene groups), phenylene methylene groups (especially 1, 2-phenylene methylene groups), ethyleneoxy vinyl groups (especially 1, 2-ethyleneoxy-1, 2-vinyl groups).
The following examples are given as examples of the alkali generator, but the present invention should not be construed as being limited thereto.
[ chemical formula 66]
The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more.
Specific examples of preferred compounds for the ionic base generator include compounds described in paragraphs 0148 to 0163 of International publication No. 2018/038002.
Specific examples of the ammonium salt include the following compounds, but the present invention is not limited thereto.
[ chemical formula 67]
Specific examples of the imide salt include the following compounds, but the present invention is not limited thereto.
[ chemical formula 68]
When the resin composition of the present invention contains the alkali generator, the content of the alkali generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and still more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less.
The alkali generator can be used in an amount of 1 or 2 or more. When 2 or more kinds are used, the total amount is preferably within the above range.
< solvent >
The resin composition of the present invention preferably contains a solvent.
The solvent may be any known solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, alcohols, and the like.
Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, ε -caprolactone, δ -valerolactone, alkyl alkoxyacetate (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-ethoxypropionate, ethyl 2-alkoxy-2-methyl propionate, and ethyl 2-alkoxypropionate, etc.), methyl 2-alkoxypropionate, methyl 2-ethoxypropionate, etc.), methyl 2-alkoxypropionate, etc. (e.g., methyl 2-ethoxypropionate, etc.), ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl caproate, ethyl heptanoate, dimethyl malonate, diethyl malonate, and the like.
Examples of the ethers include ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether, and the like.
Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-methylcyclohexanone, l-glucosone (levoglucosenone), and dihydro-l-glucosone.
Examples of the cyclic hydrocarbon include aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene.
As the sulfoxide, dimethyl sulfoxide is preferable, for example.
As the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, N-dimethylisobutyramide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like can be preferably used.
Preferred examples of the urea include N, N, N ', N' -tetramethylurea and 1, 3-dimethyl-2-imidazolidinone.
Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methyl benzyl alcohol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
The solvent is preferably mixed with 2 or more solvents from the viewpoint of improvement of the properties of the coated surface.
In the present invention, it is preferable that the solvent be 1 or a mixed solvent of 2 or more solvents selected from methyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether acetate, levoglucosone, and dihydro-levoglucosone. Particularly preferred are dimethyl sulfoxide and gamma-butyrolactone in combination or N-methyl-2-pyrrolidone and ethyl lactate in combination.
The solvent content is preferably 5 to 80% by mass, more preferably 5 to 75% by mass, still more preferably 10 to 70% by mass, and still more preferably 20 to 70% by mass of the total solid content concentration of the resin composition of the present invention from the viewpoint of coatability. The solvent content is adjusted according to the thickness and coating method required by the coating film.
The resin composition of the present invention may contain only 1 solvent, or may contain 2 or more solvents. When the solvent is contained in an amount of 2 or more, the total amount thereof is preferably within the above range.
< Metal adhesion improver >
The resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to a metal material used for an electrode, wiring, or the like. Examples of the metal adhesion improver include a silane coupling agent having an alkoxy silicon group, an aluminum-based adhesion promoter, a titanium-based adhesion promoter, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β -keto ester compound, an amino compound, and the like.
[ silane coupling agent ]
Examples of the silane coupling agent include a compound described in paragraph 0167 of Japanese patent application laid-open No. 2015/199219, a compound described in paragraphs 0062 to 0073 of Japanese patent application laid-open No. 2014-191002, a compound described in paragraphs 0063 to 0071 of International patent application laid-open No. 2011/080992, a compound described in paragraphs 0060 to 0061 of Japanese patent application laid-open No. 2014-191252, a compound described in paragraphs 0045 to 0052 of Japanese patent application laid-open No. 2014/097594, a compound described in paragraphs 2017 to 0078 of Japanese patent application laid-open No. 2018-173573, and the like. Further, as described in paragraphs 0050 to 0058 of JP 2011-128358, it is also preferable to use 2 or more different silane coupling agents. Furthermore, the following compounds are also preferably used as the silane coupling agent. In the following formula, me represents methyl group, and Et represents ethyl group.
[ chemical formula 69]
Examples of the other silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidenepropylamine, N-phenyl-3-aminopropyltrimethoxysilane, triethoxypropylsilyl-3- (trimethoxypropyl) isocyanurate, 3-mercaptopropyl silane, and mercapto-propylmercapto-3-propylmercapto-silane, 3-trimethoxysilylpropyl succinic anhydride. These can be used singly or in combination of 1 or more than 2.
[ aluminum series adhesive auxiliary agent ]
Examples of the aluminum-based adhesive auxiliary agent include aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), aluminum ethylacetoacetate diisopropyl ester, and the like.
Further, as other metal adhesion improvers, compounds described in paragraphs 0046 to 0049 of JP-A2014-186186 and thioether compounds described in paragraphs 0032 to 0043 of JP-A2013-072935 can be used, and these are incorporated herein.
The content of the metal adhesion improver is preferably in the range of 0.01 to 30 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, and even more preferably in the range of 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By setting the lower limit value or more, adhesion between the pattern and the metal layer is improved, and by setting the upper limit value or less, heat resistance and mechanical properties of the pattern are improved. The metal adhesion improver may be 1 or 2 or more. When 2 or more kinds are used, the total thereof is preferably within the above range.
< migration inhibitor >
The resin composition of the present invention preferably further comprises a migration inhibitor. By including the migration inhibitor, transfer of metal ions originating from the metal layer (metal wiring) into the film can be effectively suppressed.
The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), compounds having thiourea and sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2, 4-triazole, benzotriazole, 3-amino-1, 2, 4-triazole, and 3, 5-diamino-1, 2, 4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.
Alternatively, an ion scavenger that traps anions such as halogen ions can also be used.
As other migration inhibitors, rust inhibitors described in paragraph 0094 of japanese patent application laid-open publication No. 2013-015701, compounds described in paragraphs 0073-0076 of japanese patent application laid-open publication No. 2009-283711, compounds described in paragraph 0052 of japanese patent application laid-open publication No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of japanese patent application laid-open publication No. 2012-194520, compounds described in paragraph 0166 of international publication No. 2015/199219, and the like can be used, and these are incorporated into the present specification.
Specific examples of migration inhibitors include the following compounds.
[ chemical formula 70]
When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass% relative to the total solid content of the resin composition of the present invention.
The migration inhibitor may be 1 or 2 or more. When the migration inhibitor is 2 or more, the total thereof is preferably within the above range.
< polymerization inhibitor >
The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenol compounds, quinone compounds, amino compounds, N-oxygen radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.
As specific compounds of the polymerization inhibitor, hydroquinone, catechol, o-methoxyphenol, p-methoxyphenol, di-t-butyl-p-cresol, gallphenol, p-t-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenyl-hydroxylamine cerium salt, N-nitroso-N-phenyl-hydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenyl-naphthylamine, ethylenediamine tetraacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2, 6-di-t-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthalene) hydroxylamine ammonium salt, bis (4-hydroxy-3, 5-phenyl-methane, 1, 2-cyclohexanediamine tetraacetic acid, 2, 6-di-t-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-sulfopropylamino) phenol, N-nitroso-N- (1-naphthalene) hydroxylamine, bis (4-hydroxy-3, 5-hydroxy-phenyl) -3, 3H-methyl-3, 3H-tri-4-hydroxy-4-methyl-3-6-hydroxy-3H-tri-phenyl ketone, 2, 6-tetramethylpiperidine 1-oxyl, 2, 6-tetramethylpiperidine 1-oxyl, phenothiazine, phenoxazine, 1-diphenyl-2-picrylhydrazine, copper (II) dibutyldithiocarbamate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, and the like. Further, a polymerization inhibitor described in paragraph 0060 of Japanese patent application laid-open No. 2015-127817 and a compound described in paragraphs 0031 to 0046 of International publication No. 2015/125469, which are incorporated herein by reference, can also be used.
When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition of the present invention.
The polymerization inhibitor may be 1 or 2 or more. When the polymerization inhibitor is 2 or more, the total amount thereof is preferably within the above range.
< other additives >
The resin composition of the present invention can be blended with various additives as needed within the range where the effects of the present invention are obtained, for example, photoacid generators, surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, anticoagulants, phenolic compounds, other polymer compounds, plasticizers, other auxiliaries (e.g., defoamers, flame retardants, etc.) and the like which are well known in the art. By properly containing these components, properties such as film properties can be adjusted. For these components, for example, reference can be made to the descriptions of paragraphs 0183 and later of Japanese patent application laid-open No. 2012-003225 (paragraph 0237 of the specification of corresponding U.S. patent application publication No. 2013/0034812), and the descriptions of paragraphs 0101 to 0104 and 0107 to 0109 of Japanese patent application laid-open No. 2008-250074, and the like, which are incorporated herein by reference. When these additives are blended, the total blending amount is preferably 3 mass% or less of the solid content of the resin composition of the present invention.
[ surfactant ]
As the surfactant, various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
By adding the surfactant to the photosensitive resin composition of the present invention, the liquid properties (particularly fluidity) when the composition is prepared into a coating liquid can be further improved, and uniformity of the coating thickness and liquid saving can be further improved. That is, when a film is formed using a composition containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, thereby improving the wettability to the surface to be coated and improving the coatability to the surface to be coated. Therefore, a film having a uniform thickness with small thickness unevenness can be further preferably formed.
Examples of the fluorine-based surfactant include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (manufactured by DIC Corporation above), fluoro FC430, fluoro FC431, fluoro FC171, novec FC4430, novec FC4432 (manufactured by 3M Japan Limited above), surflon S-382, surflon SC-101, surflon SC-103, surflon SC-104, surflon SC-105, surflon SC-1068, surflon SC-381, surflon SC-383, surflon S-40 (manufactured by DIC Corporation above), surfon FC431, fluold FC171, novelon FC4430 (manufactured by 3M Japanese Limited above), surflon SC-105, surflon SC-381, surfon SC-383, surfon S-40 (manufactured by Urfon, UF 656, PF) and PF 20, PF656 manufactured by NOF. The fluorine-based surfactant may be any of the compounds described in paragraphs 0015 to 0158 of Japanese patent application laid-open No. 2015-117327 and the compounds described in paragraphs 0117 to 0132 of Japanese patent application laid-open No. 2011-132503, which are incorporated herein by reference. As the fluorine-based surfactant, a block polymer can be used, and specific examples thereof include compounds described in japanese patent application laid-open publication No. 2011-89090, which are incorporated herein.
The fluorine-containing polymer compound (including a repeating unit derived from a (meth) acrylate compound having a fluorine atom and a repeating unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group)) can also be preferably used as the fluorine-containing surfactant used in the present invention.
[ chemical formula 71]
The weight average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used. Specific examples thereof include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A2010-164965, incorporated by reference herein. Examples of commercial products include MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC corporation.
The fluorine content of the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorine-containing surfactant having a fluorine content within this range is effective in uniformity of thickness of the coating film and liquid saving property, and has good solubility in the composition.
Examples of silicone surfactants include Toray Silicone DC PA, toray Silicone SH PA, toray Silicone DC PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH8400 (manufactured by ltd. Above), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials inc. Above), KP-341, KF6001, KF6002 (manufactured by Shin-Etsu Chemical co. Above, ltd. Above), BYK307, BYK323, BYK330 (manufactured by BYK Chemie GmbH) above, and the like.
Examples of hydrocarbon surfactants include PIONIN A-76, NEWKALGEN FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, PIONIN P-4050-T (TAKEMOTO OIL & FAT CO, LTD).
Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerin propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, and the like. Examples of the commercial products include PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF corporation), tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF corporation), solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL & FAT CO., manufactured by LTD), OLFIN E1010, surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry CO., ltd.), and the like.
Specific examples of the cationic surfactant include organosiloxane polymers KP-341 (Shin-Etsu Chemical Co., ltd.), and (meth) acrylic (co) polymers POLYFLOW No.75, no.77, no.90, no.95 (Kyoeisha Chemical Co., ltd.), W001 (Yusho Co., ltd.), and the like.
Specific examples of the anionic surfactant include W004, W005, W017 (Yusho co., ltd.), and saldet BL (manufactured by SANYO KASEI co.ltd.).
The surfactant may be used in an amount of 1 or 2 or more.
The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.
[ higher fatty acid derivative ]
In order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenamide may be added to the resin composition of the present invention so as to be biased to the surface of the resin composition of the present invention during drying after coating.
The higher fatty acid derivative may be a compound described in paragraph 0155 of International publication No. 2015/199219, which is incorporated herein by reference.
When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. The number of the higher fatty acid derivatives may be 1 or 2 or more. When the number of higher fatty acid derivatives is 2 or more, the total thereof is preferably within the above range.
[ thermal polymerization initiator ]
The resin composition of the present invention may contain a thermal polymerization initiator, and in particular, may contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound which generates radicals by thermal energy and starts or promotes the polymerization reaction of a compound having polymerizability. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be advanced, and therefore the solvent resistance can be further improved. The photopolymerization initiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese patent application laid-open No. 2008-063254, the contents of which are incorporated herein by reference.
When the thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass, relative to the total solid content of the resin composition of the present invention. The thermal polymerization initiator may be contained in an amount of 1 or 2 or more. When the thermal polymerization initiator is contained in an amount of 2 or more, the total amount is preferably within the above range.
[ inorganic particles ]
The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.
The average particle diameter of the inorganic particles is preferably 0.01 to 2.0. Mu.m, more preferably 0.02 to 1.5. Mu.m, still more preferably 0.03 to 1.0. Mu.m, particularly preferably 0.04 to 0.5. Mu.m.
The average particle diameter of the inorganic particles is a primary particle diameter and is a volume average particle diameter. The volume average particle size can be measured by a dynamic light scattering method of Nanotrac WAVE II EX-150 (NIKKISO co., ltd.).
If the measurement is difficult, the measurement can be performed by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction/scattering method.
[ ultraviolet absorber ]
The compositions of the present invention may comprise an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, and other ultraviolet absorbers can be used.
Examples of the salicylate-based ultraviolet light absorber include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate, and examples of the benzophenone-based ultraviolet light absorber include 2,2' -dihydroxy-4-methoxybenzophenone, 2' -dihydroxy-4, 4' -dimethoxybenzophenone, 2', 4' -tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone. Examples of the benzotriazole-based ultraviolet absorber include 2- (2 '-hydroxy-3', 5 '-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 '-t-butyl-5' -methylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3' -t-amyl-5 '-isobutylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 '-isobutyl-5' -methylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3' -isobutyl-5 '-propylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -di-t-butylphenyl) benzotriazole, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, and 2- [2 '-hydroxy-5' - (1, 3-tetramethyl) phenyl ] benzotriazole.
Examples of the substituted acrylonitrile ultraviolet absorber include ethyl 2-cyano-3, 3-diphenylacrylate and 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate. Further, examples of the triazine-based ultraviolet light absorber include mono (hydroxyphenyl) triazine compounds such as 2- [4- [ (2-hydroxy-3-dodecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [4- [ (2-hydroxy-3-tridecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, and 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine; bis (hydroxyphenyl) triazine compounds such as 2, 4-bis (2-hydroxy-4-propoxyphenyl) -6- (2, 4-dimethylphenyl) -1,3, 5-triazine, 2, 4-bis (2-hydroxy-3-methyl-4-propoxyphenyl) -6- (4-methylphenyl) -1,3, 5-triazine, and 2, 4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6- (2, 4-dimethylphenyl) -1,3, 5-triazine; tris (hydroxyphenyl) triazine compounds such as 2, 4-bis (2-hydroxy-4-butoxyphenyl) -6- (2, 4-dibutoxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-4-octyloxyphenyl) -1,3, 5-triazine, and 2,4, 6-tris [ 2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl ] -1,3, 5-triazine.
In the present invention, 1 kind of the above-mentioned various ultraviolet absorbers may be used alone, or 2 or more kinds may be used in combination.
The composition of the present invention may or may not contain an ultraviolet absorber, but when contained, the content of the ultraviolet absorber is preferably 0.001 mass% or more and 1 mass% or less, more preferably 0.01 mass% or more and 0.1 mass% or less, relative to the total solid content mass of the composition of the present invention.
[ organic titanium Compound ]
The resin composition of the present embodiment may contain an organic titanium compound. By containing the organic titanium compound in the resin composition, a resin layer excellent in chemical resistance can be formed even when cured at a low temperature.
Examples of the usable organic titanium compound include compounds in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organic titanium compound are shown in the following I) to VII).
I) Chelating titanium compound: among them, a chelate titanium compound having 2 or more alkoxy groups is more preferable in view of excellent storage stability of the resin composition and obtaining a good cured pattern. Specific examples are titanium bis (triethanolamine) diisopropoxide, titanium bis (n-butoxy) bis (2, 4-glutarate) diisopropoxide bis (2, 4-glutarate) titanium, titanium diisopropoxide bis (tetramethylheptanedioate) titanium, titanium diisopropoxide bis (ethylacetoacetate), and the like.
II) a titanium tetraalkoxide compound: examples of the titanium include tetra (n-butoxy) titanium, tetraethoxy titanium, tetra (2-ethylhexyl) titanium, tetraisobutoxy titanium, tetraisopropoxy titanium, tetramethoxy titanium, tetramethoxypropoxy titanium, tetramethylphenoxy titanium, tetra (n-nonoxy) titanium, tetra (n-propoxy) titanium, tetrastearoxy titanium, and tetra [ bis {2,2- (allyloxymethyl) propoxy } ] titanium.
III) titanocene compound: for example, pentamethylcyclopentadienyl trimethoxytitanium, bis (. Eta.5-2, 4-cyclopenta-1-yl) bis (2, 6-difluorophenyl) titanium, bis (. Eta.5-2, 4-cyclopenta-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, and the like.
IV) monoalkoxytitanium compounds: for example, titanium isopropoxide, such as dioctyl phosphate, and titanium isopropoxide, such as dodecylbenzenesulfonate.
V) titanium oxide compound: examples of the compound include titanium oxide bis (glutarate), titanium oxide bis (tetramethylpimelate), and titanium oxide phthalocyanine.
VI) titanium tetra acetylacetonate compound: for example, titanium tetraacetylacetonate.
VII) titanate coupling agent: for example, isopropyl tridecyl benzene sulfonyl titanate, etc.
Among them, the organic titanium compound is preferably at least 1 compound selected from the group consisting of the above-mentioned I) chelate titanium compound, II) tetraalkoxy titanium compound and III) titanocene compound, from the viewpoint of exhibiting more excellent chemical resistance. Particularly preferred are diisopropoxybis (ethylacetoacetate) titanium, tetra (n-butoxy) titanium and bis (. Eta.5-2, 4-cyclopenta-n-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium.
When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the blending amount is 0.05 parts by mass or more, the obtained cured pattern more effectively exhibits good heat resistance and chemical resistance, while when 10 parts by mass or less, the composition is more excellent in storage stability.
[ antioxidant ]
The composition of the present invention may comprise an antioxidant. By containing an antioxidant as an additive, the tensile properties of the cured film and the adhesion to a metal material can be improved. Examples of the antioxidant include phenol compounds, phosphite compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. Preferred examples of the phenol compound include hindered phenol compounds. Compounds having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) are preferred. The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. Furthermore, the antioxidant is preferably a compound having a phenol group and a phosphite group in the same molecule. Further, the antioxidant can also preferably be a phosphorus-based antioxidant. Examples of the phosphorus antioxidant include tris [2- [ [2,4,8, 10-tetrakis (1, 1-dimethylethyl) dibenzo [ d, f ] [1,3,2] dioxaphosphepin-6-yl ] oxy ] ethyl ] amine, tris [2- [ (4, 6,9, 11-tetra-t-butyldibenzo [ d, f ] [1,3,2] dioxaphosphepin-2-yl) oxy ] ethyl ] amine, bis (2, 4-di-t-butyl-6-methylphenyl) ethyl phosphite, and the like. Examples of the commercially available antioxidants include ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50F, ADEKA STAB AO-60G, ADEKA STAB AO-80, ADEKA STAB AO-330 (manufactured by ADEKA CORPORATION). The antioxidant may be a compound described in paragraphs 0023 to 0048 of Japanese patent No. 6268967, incorporated herein by reference. Furthermore, the compositions of the present invention may contain latent antioxidants as desired. Examples of the latent antioxidant include a compound in which a site functioning as an antioxidant is protected with a protecting group, and in the compound, the protecting group is released by heating at 100 to 250 ℃ or heating at 80 to 200 ℃ in the presence of an acid/base catalyst, thereby functioning as an antioxidant. Examples of the potential antioxidant include compounds described in International publication No. 2014/021023, international publication No. 2017/030005, and Japanese patent application laid-open No. 2017-008219, which are incorporated herein by reference. Examples of commercial products of the latent antioxidant include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION).
Examples of the preferable antioxidant include 2, 2-thiobis (4-methyl-6-t-butylphenol), 2, 6-di-t-butylphenol, and a compound represented by formula (3).
[ chemical formula 72]
In the general formula (3), R 5 Represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), R 6 An alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). R is R 7 Represents a 1-to 4-valent organic group containing at least any one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom and a nitrogen atom. k represents an integer of 1 to 4.
The compound represented by formula (3) inhibits oxidative degradation of the aliphatic group and the phenolic hydroxyl group of the resin. Further, by the rust prevention effect on the metal material, oxidation of the metal can be suppressed.
In order to be able to act on both the resin and the metal material, k is more preferably an integer of 2 to 4. As R 7 Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silicon group, an alkoxy silicon group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, and a group obtained by combining these groups. Among them, alkyl ether and-NH-are preferable from the viewpoints of solubility in a developer and metal adhesion, and-NH-is more preferable from the viewpoints of interaction with a resin and metal adhesion due to metal complexation.
The compounds represented by the general formula (3) are exemplified by the following compounds, but are not limited to the following structures.
[ chemical formula 73]
[ chemical formula 74]
[ chemical formula 75]
[ chemical formula 76]
The amount of the antioxidant to be added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on the resin. By setting the addition amount to 0.1 part by mass or more, the effect of improving the adhesion to a metal material can be easily obtained by the tensile property even under a high-temperature and high-humidity environment, and by setting the addition amount to 10 parts by mass or less, for example, the sensitivity of the resin composition can be improved by the interaction with a sensitizer. The antioxidant may be used in an amount of 1 or 2 or more. When 2 or more kinds are used, the total amount of these is preferably within the above range.
[ anti-coagulant ]
The resin composition of the present embodiment may contain an anti-coagulant as necessary. Examples of the anti-caking agent include sodium polyacrylate.
In the present invention, 1 anticoagulant may be used alone, or 2 or more anticoagulants may be used in combination.
The composition of the present invention may or may not contain an anticoagulant, but when contained, the content of the anticoagulant is preferably 0.01 mass% or more and 10 mass% or less, more preferably 0.02 mass% or more and 5 mass% or less, relative to the total solid content mass of the composition of the present invention.
[ phenol-based Compound ]
The resin composition of the present embodiment may contain a phenolic compound as necessary. Examples of the phenolic compound include Bis-Z, bisP-EZ, tekP-4HBPA, trisP-HAP, trisP-PA, bisOCHP-Z, bisP-MZ, bisP-PZ, bisP-IPZ, bisOCP-IPZ, bisP-CP, bisRS-2P, bisRS-3P, bisP-OCHP, methyl Tris-FR-CR, bisRS-26X (trade name, honshuChemical Industry Co., ltd.), BIP-PC, BIR-PTBP, BIR-BIPC-F (trade name, ASAHI YUKIZAI CORPORATION).
In the present invention, 1 kind of phenolic compound may be used alone, or 2 or more kinds may be used in combination.
The composition of the present invention may or may not contain a phenolic compound, but when contained, the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less, relative to the total solid content mass of the composition of the present invention.
[ other Polymer Compounds ]
Examples of the other polymer compound include a silicone resin, a (meth) acrylic polymer copolymerized with (meth) acrylic acid, a novolak resin, a resol resin, a polyhydroxystyrene resin, and a copolymer of these. The other polymer compound may be a modified product obtained by introducing a crosslinking group such as a hydroxymethyl group, an alkoxymethyl group, or an epoxy group.
In the present invention, 1 or 2 or more other polymer compounds may be used alone or in combination.
The composition of the present invention may or may not contain other polymer compounds, but when contained, the content of other polymer compounds is preferably 0.01 mass% or more and 30 mass% or less, more preferably 0.02 mass% or more and 20 mass% or less, relative to the total solid content mass of the composition of the present invention.
< Properties of resin composition >
The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, it is preferably 1,000mm 2 /s～12,000mm 2 S, more preferably 2,000mm 2 /s～10,000mm 2 S, more preferably 2,500mm 2 /s～8,000mm 2 And/s. When the amount is within the above range, a coating film having high uniformity can be easily obtained. For example, if it is 1,000mm 2 At least/s, the film thickness required for the insulating film for re-wiring is easily applied, and the thickness is 12,000mm 2 A coating film having an excellent coating surface shape can be obtained.
< restriction of substances contained in resin composition >
The water content of the resin composition of the present invention is preferably less than 2.0 mass%, more preferably less than 1.5 mass%, and even more preferably less than 1.0 mass%. If less than 2.0%, the storage stability of the resin composition is improved.
Examples of the method for maintaining the water content include humidity adjustment under storage conditions, and reduction in porosity of the storage container during storage.
From the viewpoint of insulation properties, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million (parts per million)), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, and the like, except for metals contained as a complex of an organic compound and a metal. When a plurality of metals are contained, the total of these metals is preferably within the above range.
Further, as a method for reducing metal impurities accidentally contained in the resin composition of the present invention, the following method can be mentioned: the raw materials having a small metal content are selected as the raw materials constituting the resin composition of the present invention, the raw materials constituting the resin composition of the present invention are filtered by a filter, the inside of the apparatus is lined with polytetrafluoroethylene or the like, and distillation or the like is performed under a condition that contamination is suppressed as much as possible.
Regarding the resin composition of the present invention, when the use as a semiconductor material is considered, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the viewpoint of wiring corrosiveness. Among them, the content in the state of halogen ion is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, further preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of the chlorine atom and the bromine atom or the chlorine ion and the bromine ion is preferably within the above range.
As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferable.
As the container for containing the resin composition of the present invention, a conventionally known container can be used. In addition, as the storage container, a multilayer bottle having 6 kinds of 6 layers of resins constituting the inner wall of the container or a bottle having 6 kinds of resins in a 7-layer structure is preferably used for the purpose of suppressing the mixing of impurities into the raw material or the resin composition of the present invention. Examples of such a container include those described in Japanese patent application laid-open No. 2015-123351.
< cured product of resin composition >
By curing the resin composition of the present invention, a cured product of the resin composition can be obtained,
the cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
The curing of the resin composition is preferably performed by heating, and the heating temperature is more preferably in the range of 120 to 400 ℃, still more preferably in the range of 140 to 380 ℃, and particularly preferably in the range of 170 to 350 ℃. The form of the cured product of the resin composition is not particularly limited, and may be selected from films, rods, spheres, pellets, and the like according to the application. In the present invention, the cured product is preferably in the form of a film. Further, the shape of the cured product can be selected according to the use of patterning the resin composition, such as forming a protective film on the wall surface, forming a through hole for conduction, adjusting impedance, electrostatic capacitance, or internal stress, and imparting a heat dissipation function. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less.
The shrinkage of the resin composition of the present invention upon curing is preferably 50% or less, more preferably 45% or less, and still more preferably 40% or less. The shrinkage ratio herein refers to the percentage of the volume change of the resin composition before and after curing, and can be calculated from the following formula.
Shrinkage [% ] =100- (volume after curing ≡volume before curing) ×100
< Property of cured product of resin composition >
The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. If the content is 70% or more, a cured product having excellent mechanical properties may be obtained.
The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180℃or higher, more preferably 210℃or higher, and still more preferably 230℃or higher.
< preparation of resin composition >
The resin composition of the present invention can be prepared by mixing the above-described components. The mixing method is not particularly limited, and may be performed by a conventionally known method.
Mixing by stirring blades, mixing by a ball mill, mixing by rotating a tank itself, or the like can be employed for the mixing.
The temperature during mixing is preferably 10 to 30 ℃, more preferably 15 to 25 ℃.
In order to remove foreign matters such as dust and particles in the resin composition of the present invention, it is preferable to filter the resin composition by using a filter. The filter pore size is, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The filter is made of polytetrafluoroethylene, preferably polyethylene or nylon. When the filter is made of polyethylene, HDPE (high density polyethylene) is more preferable. The filter may be a filter previously washed with an organic solvent. In the filtration step of the filter, a plurality of filters may be connected in series or in parallel. When a plurality of filters are used, filters having different pore diameters or different materials may be used in combination. Examples of the connection method include the following: HDPE filters with a pore size of 1 μm were used as the first stage, HDPE filters with a pore size of 0.2 μm were used as the second stage, and the two were connected in series. Moreover, various materials may be filtered multiple times. When the filtration is performed a plurality of times, the filtration may be a cyclic filtration. Moreover, pressure filtration may be performed. When the pressure filtration is performed, for example, the pressure applied is 0.01MPa or more and 1.0MPa or less, preferably 0.03MPa or more and 0.9MPa or less, more preferably 0.05MPa or more and 0.7MPa or less, and still more preferably 0.05MPa or more and 0.5MPa or less.
In addition to filtration using a filter, impurity removal treatment may be performed using an adsorbent. It is also possible to combine filter filtration with impurity removal treatment using an adsorbent material. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
After filtration with the filter, the resin composition filled in the bottle may be further subjected to a step of deaeration by placing the resin composition under reduced pressure.
(method for producing cured product)
The method for producing a cured product of the present invention preferably includes a film formation step of applying a resin composition to a substrate to form a film.
The method for producing a cured product of the present invention further preferably includes the film formation step, an exposure step of selectively exposing the film formed in the film formation step, and a development step of developing the film exposed in the exposure step with a developer to form a pattern.
The method for producing a cured product according to the present invention particularly preferably includes at least 1 of the film forming step, the exposing step, the developing step, and a heating step of heating the pattern obtained in the developing step and a post-developing exposing step of exposing the pattern obtained in the developing step.
The production method of the present invention preferably further includes the film forming step and the step of heating the film.
The details of each step will be described below.
< film Forming Process >
The resin composition of the present invention can be used in a film forming step of forming a film by applying the composition to a substrate.
The method for producing a cured product of the present invention preferably includes a film formation step of applying a resin composition to a substrate to form a film.
[ substrate ]
The type of the substrate may be appropriately determined according to the application, and examples thereof include a substrate for semiconductor production such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, a metal substrate such as quartz, glass, an optical film, a ceramic material, a deposited film, a magnetic film, a reflective film, and Ni, cu, cr, fe (for example, any of a substrate formed of a metal and a substrate formed with a metal layer by plating, deposition, and the like), paper, SOG (Spin On Glass), a TFT (thin film transistor) array substrate, a mold substrate, and an electrode plate of a Plasma Display Panel (PDP), and the like, without being particularly limited. In the present invention, a substrate for semiconductor production is particularly preferable, and a silicon substrate, a Cu substrate, and a mold substrate are more preferable.
Further, a layer such as an adhesion layer or an oxide layer formed of Hexamethyldisilazane (HMDS) or the like may be provided on the surface of the base material.
The shape of the base material is not particularly limited, and may be circular or rectangular.
The size of the base material is, for example, 100 to 450mm, preferably 200 to 450mm, in the case of a circular shape. In the case of rectangular shape, the length of the short side is, for example, 100 to 1000mm, preferably 200 to 700mm.
As the base material, for example, a plate-like base material (substrate) is preferably used.
When a resin composition is applied to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer to form a film, the resin layer or the metal layer serves as a base material.
As a method for applying the resin composition of the present invention to a substrate, coating is preferable.
Specific examples of the application method include dip coating, air knife coating, curtain coating, bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. The spin coating method, the slit coating method, the spray coating method, or the inkjet method is more preferable from the viewpoint of uniformity of the film thickness, and the spin coating method and the slit coating method are preferable from the viewpoint of uniformity of the film thickness and productivity. By adjusting the solid content concentration and the coating conditions of the resin composition according to the method, a film having a desired thickness can be obtained. The coating method may be appropriately selected according to the shape of the substrate, and in the case of a circular substrate such as a wafer, spin coating, spray coating, or ink jet method is preferable, and in the case of a rectangular substrate, slit coating, spray coating, or ink jet method is preferable. In the case of spin coating, for example, a spin speed of 500 to 3,500rpm can be applied for about 10 seconds to 3 minutes.
Further, a method of transferring a coating film formed by the above-described application method onto a temporary support in advance onto a substrate can also be applied.
As the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of japanese patent application laid-open publication No. 2006-023696 or 0096 to 0108 of japanese patent application laid-open publication No. 2006-047592 can be preferably used in the present invention.
Further, a step of removing an excess film at the end of the base material may be performed. Examples of such a process include Edge Bead Ring (EBR) and back surface cleaning.
Furthermore, the following pre-wetting process may be employed: before the resin composition is applied to the substrate, various solvents are applied to the substrate to improve wettability of the substrate, and then the resin composition is applied.
< drying Process >
The film may be subjected to a step (drying step) of drying the formed film (layer) after the film forming step (layer forming step) to remove the solvent.
That is, the method for producing a cured product of the present invention may include a step of drying the film formed by the film forming step.
The drying step is preferably performed after the film formation step and before the exposure step.
The drying temperature of the film in the drying step is preferably 50 to 150 ℃, more preferably 70 to 130 ℃, and even more preferably 90 to 110 ℃. Further, drying may be performed by decompression. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.
< Exposure procedure >
The film can be used in an exposure process for selectively exposing the film.
That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed by the film forming step.
Selective exposure refers to exposing a portion of the film. Further, by selective exposure, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film.
The exposure amount is not particularly limited as long as the resin composition of the present invention can be cured, and is preferably 50 to 10,000mJ/cm, for example, in terms of an exposure energy conversion at a wavelength of 365nm 2 More preferably 200 to 8,000mJ/cm 2 。
The exposure wavelength can be appropriately determined in the range of 190 to 1,000nm, preferably 240 to 550nm.
As the exposure wavelength, there may be mentioned (1) a semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) a metal halide lamp, (3) a high-pressure mercury lamp, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), broadband (g, h, 3 wavelengths of i-rays), (4) an excimer laser, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), F 2 Excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, (7) second harmonic 532nm, third harmonic 355nm of YAG laser, etc. For the resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferable, and among them, exposure based on i-rays is preferable. Thus, particularly high exposure sensitivity can be obtained.
The method of exposure is not particularly limited as long as at least a part of the film composed of the resin composition of the present invention is exposed, and examples thereof include exposure using a photomask, exposure by a laser direct imaging method, and the like.
< post-exposure heating Process >
The film may be used in a heating step (post-exposure heating step) after exposure.
That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step.
The post-exposure heating step may be performed after the exposure step and before the development step.
The heating temperature in the post-exposure heating step is preferably 50 to 140 ℃, more preferably 60 to 120 ℃.
The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
The heating rate in the post-exposure heating step is preferably 1 to 12 ℃/min, more preferably 2 to 10 ℃/min, and even more preferably 3 to 10 ℃/min, from the temperature at the start of heating to the maximum heating temperature.
The temperature rise rate may be changed as appropriate during the heating process.
The heating method in the post-exposure heating step is not particularly limited, and a known heating plate, oven, infrared heater, or the like can be used.
In addition, the heating is preferably performed in an atmosphere of low oxygen concentration by passing an inert gas such as nitrogen, helium, or argon.
< developing Process >
The film after exposure can be used in a development step of developing with a developer to form a pattern.
That is, the method for producing a cured product of the present invention may include a developing step of developing the film exposed in the exposing step with a developer to form a pattern. By performing development, one of the exposed portion and the non-exposed portion of the film is removed, thereby forming a pattern.
Here, the development of the non-exposed portion of the film removed by the development step is referred to as negative development, and the development of the exposed portion of the film removed by the development step is referred to as positive development.
[ developer solution ]
As the developer used in the developing step, an aqueous alkali solution or a developer containing an organic solvent is exemplified.
When the developer is an aqueous alkali solution, examples of the basic compound that can be contained in the aqueous alkali solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, preferably TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methylttripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethyl bis (2-hydroxyethyl) ammonium hydroxide, trimethylphenylammonium, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, and more preferably TMAH. For example, when TMAH is used, the content of the alkaline compound in the developer is preferably 0.01 to 10 mass%, more preferably 0.1 to 5 mass%, and even more preferably 0.3 to 3 mass% based on the total amount of the developer.
When the developer contains an organic solvent, examples of the esters include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, epsilon-caprolactone, delta-valerolactone, and alkyl alkoxyacetate (for example: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate, and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), ethyl 2-alkoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol Monomethyl Ether (PGME), propylene Glycol Monomethyl Ether Acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like, and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, and the like, and as sulfoxides, for example, dimethyl sulfoxide, and as alcohols, methanol, ethanol, isopropanol, propanol, octanol, diethylene glycol, methyl octanol, N-butyl glycol, methyl pyrrolidone, N-methyl pyrrolidone, and the like, and as methyl amide, and the like, and as cyclic hydrocarbons, for example, methyl sulfoxide, and the like, are preferable.
When the developer contains an organic solvent, 1 or 2 or more organic solvents can be used in combination. In the present invention, a developer containing at least 1 selected from cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferable, a developer containing at least 1 selected from cyclopentanone, γ -butyrolactone, and dimethyl sulfoxide is more preferable, and a developer containing cyclopentanone is most preferable.
When the developing solution contains an organic solvent, the content of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the developing solution. The content may be 100% by mass.
The developer may further contain other components.
Examples of the other components include a known surfactant and a known defoaming agent.
[ method for supplying developer ]
The method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and there are the following methods: a method of immersing a substrate on which a film is formed in a developer, a spin-on immersion developing method of supplying a developer to a film formed on a substrate by a nozzle, or a method of continuously supplying a developer. The type of the nozzle is not particularly limited, and examples thereof include a direct current nozzle, a shower nozzle, a spray nozzle, and the like.
The method of supplying the developer by the direct-current nozzle or the method of continuously supplying the developer by the spray nozzle is preferable from the viewpoints of the permeability of the developer, the removability of the non-image portion, and the manufacturing efficiency, and the method of supplying the developer by the spray nozzle is more preferable from the viewpoints of the permeability of the developer to the image portion.
The process of continuously supplying the developer through the dc nozzle, then rotating the substrate to remove the developer from the substrate, after spin-drying, continuously supplying the developer through the dc nozzle again, and then rotating the substrate to remove the developer from the substrate may be employed, or the process may be repeated a plurality of times.
As a method for supplying the developer in the developing step, a step of continuously supplying the developer to the substrate, a step of holding the developer on the substrate in a substantially stationary state, a step of vibrating the developer on the substrate by ultrasonic waves or the like, a step of combining these, and the like can be used.
The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly limited, and can be preferably 10 to 45 ℃, more preferably 18 to 30 ℃.
In the developing step, the pattern cleaning (rinsing) by the rinse solution may be further performed after the treatment with the developer. Further, a method of supplying a rinse solution or the like before the developer in contact with the pattern is not completely dried may be employed.
[ flushing liquid ]
When the developer is an aqueous alkali solution, water can be used as the rinse liquid, for example. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water or an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.
When the rinse liquid contains an organic solvent, examples of the esters include ethyl acetate, n-butyl acetate, pentyl formate, isopentyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, ε -caprolactone, δ -valerolactone, alkyl alkoxyacetate (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc.), alkyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, methyl 2-methoxypropionate, methyl 2-ethoxypropionate, methyl 2-alkoxymethyl 2-alkoxypropionate, methyl 2-alkoxymethyl 2-ethoxypropionate, methyl 2-ethoxymethyl 2-ethoxypropionate, etc.), and the like (e.g., methyl 2-ethoxymethyl 2-alkoxypropionate, etc.), and the like, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol Monomethyl Ether (PGME), propylene glycol monomethyl ether acetate (PGMFA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like, and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, and the like, and as sulfoxides, for example, dimethyl sulfoxide, and as alcohols, methanol, ethanol, isopropanol, propanol, octanol, diethylene glycol, methyl octanol, N-butyl glycol, methyl pyrrolidone, N-methyl pyrrolidone, and the like, and as methyl amide, and the like, and as cyclic hydrocarbons, for example, methyl sulfoxide, and the like, are preferable.
When the rinse liquid contains an organic solvent, the organic solvent may be used in an amount of 1 or 2 or more kinds thereof may be used in combination. In the present invention, cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferable, cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferable, and cyclohexanone and PGMEA are further preferable.
When the rinse liquid contains an organic solvent, it is preferable that 50 mass% or more of the rinse liquid is an organic solvent, more preferably 70 mass% or more is an organic solvent, and still more preferably 90 mass% or more is an organic solvent. The rinse solution may be 100% by mass of the organic solvent.
The rinse solution may further comprise other ingredients.
Examples of the other components include a known surfactant and a known defoaming agent.
[ method for supplying rinse solution ]
The method of supplying the rinse liquid is not particularly limited as long as the desired pattern can be formed, and there are the following methods: a method of immersing a substrate in a rinse solution, a method of supplying a rinse solution to a substrate by spin-coating immersion, a method of supplying a rinse solution to a substrate by a shower head, and a method of continuously supplying a rinse solution to a substrate by a mechanism such as a direct-current nozzle.
From the viewpoints of the permeability of the rinse liquid, the removability of the non-image portion, and the production efficiency, a method of supplying the rinse liquid by using a spray nozzle, a direct-current nozzle, a spray nozzle, or the like is preferable, and a method of continuously supplying the rinse liquid by using a spray nozzle is more preferable from the viewpoint of the permeability of the rinse liquid to the image portion. The type of the nozzle is not particularly limited, and examples thereof include a direct current nozzle, a shower nozzle, a spray nozzle, and the like.
That is, the rinsing step is preferably a step of supplying or continuously supplying a rinsing liquid to the exposed film by a direct-current nozzle, and more preferably a step of supplying a rinsing liquid by a spray nozzle.
As a method for supplying the rinse liquid in the rinsing step, a step of continuously supplying the rinse liquid to the substrate, a step of holding the rinse liquid on the substrate in a substantially stationary state, a step of vibrating the rinse liquid on the substrate by ultrasonic waves or the like, a step of combining these, and the like can be used.
The flushing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinse liquid during rinsing is not particularly limited, and may be preferably 10 to 45 ℃, more preferably 18 to 30 ℃.
< heating Process >
The pattern obtained by the development process (the pattern after the rinsing process in the case of performing the rinsing process) may be used for a heating process of heating the pattern obtained by the development described above.
That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained by the developing step.
The method for producing a cured product of the present invention may further include a heating step of heating the pattern obtained by other methods without performing the developing step or the film obtained by the film forming step.
In the heating step, the resin such as polyimide precursor is cyclized into the resin such as polyimide.
Further, crosslinking of unreacted crosslinkable groups in the specific resin or the crosslinking agent other than the specific resin is also performed.
The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450 ℃, more preferably 150 to 350 ℃, still more preferably 150 to 250 ℃, still more preferably 160 to 250 ℃, and particularly preferably 160 to 230 ℃.
The heating step is preferably a step of accelerating the cyclization reaction of the polyimide precursor in the pattern by the action of a base or the like generated from the base generator by heating.
The heating in the heating step is preferably performed at a heating rate of 1 to 12 ℃/min from the temperature at the start of heating to the maximum heating temperature. The temperature rise rate is more preferably 2 to 10℃per minute, and still more preferably 3 to 10℃per minute. The temperature rise rate is set to 1 ℃/min or more, whereby excessive volatilization of the acid or solvent can be prevented while ensuring productivity, and the residual stress of the cured product can be relaxed by setting the temperature rise rate to 12 ℃/min or less.
In the case of an oven capable of rapid heating, the heating is preferably performed at a heating rate of 1 to 8 ℃/sec, more preferably 2 to 7 ℃/sec, and still more preferably 3 to 6 ℃/sec, from the temperature at the start of heating to the highest heating temperature.
The temperature at the start of heating is preferably 20 to 150 ℃, more preferably 20 to 130 ℃, still more preferably 25 to 120 ℃. The temperature at the start of heating means the temperature at the start of the step of heating to the highest heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature of the film (layer) after drying is preferably increased from a temperature lower by 30 to 200 ℃ than the boiling point of the solvent contained in the resin composition of the present invention.
The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, still more preferably 15 to 240 minutes.
In particular, when forming a multilayer laminate, the heating temperature is preferably 30 ℃ or higher, more preferably 80 ℃ or higher, still more preferably 100 ℃ or higher, and particularly preferably 120 ℃ or higher, from the viewpoint of interlayer adhesiveness.
The upper limit of the temperature is preferably 350℃or lower, more preferably 250℃or lower, and still more preferably 240℃or lower.
The heating may be performed in stages. As an example, a process of raising the temperature from 25 ℃ to 120 ℃ at 3 ℃/min and holding at 120 ℃ for 60 minutes, and a process of raising the temperature from 120 ℃ to 180 ℃ at 2 ℃/min and holding at 180 ℃ for 120 minutes may be performed. Further, as described in U.S. Pat. No. 9159547, it is also preferable to perform the treatment while irradiating ultraviolet rays. Such a pretreatment step can improve the film characteristics. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be performed in 2 stages or more, for example, the pretreatment in stage 1 may be performed at 100 to 150 ℃ and the pretreatment in stage 2 may be performed at 150 to 200 ℃.
Further, the cooling may be performed after the heating, and the cooling rate at this time is preferably 1 to 5 ℃/min.
The heating step is preferably performed in an atmosphere of low oxygen concentration by passing an inert gas such as nitrogen, helium, or argon under reduced pressure, or the like, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50ppm (volume ratio) or less, more preferably 20ppm (volume ratio) or less.
The heating method in the heating step is not particularly limited, and examples thereof include a heating plate, an infrared oven, an electrothermal oven, a hot air oven, an infrared oven, and the like.
< post-development exposure Process >
The pattern obtained by the development step (the pattern after the rinsing step in the case of performing the rinsing step) may be used in the post-development exposure step of exposing the pattern after the development step instead of or in addition to the heating step.
That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
In the post-development exposure step, for example, a reaction of cyclizing a polyimide precursor or the like by the light-sensitive action of a photo-alkali generator, a reaction of releasing an acid-decomposable group by the light-sensitive action of a photo-acid generator, or the like can be promoted.
In the post-development exposure step, only at least a part of the pattern obtained in the development step may be exposed, but it is preferable that all of the pattern is exposed.
Having a photosensitive compoundThe exposure energy conversion meter at the wavelength of sensitivity, the exposure amount in the post-development exposure process is preferably 50 to 20,000mJ/cm 2 More preferably 100 to 15,000mJ/cm 2 。
The post-development exposure step can be performed using, for example, the light source in the exposure step, and preferably using broadband light.
< Metal layer Forming Process >
The pattern obtained by the development process (preferably, at least 1 of the heating process and the post-development exposure process is performed) may be used for a metal layer forming process of forming a metal layer on the pattern.
That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on a pattern obtained by a developing step (preferably, at least 1 step of heating step and post-developing exposure step is performed).
The metal layer is not particularly limited, and conventional metal species can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, more preferably copper and aluminum, and still more preferably copper.
The method for forming the metal layer is not particularly limited, and a conventional method can be applied. For example, the methods described in Japanese patent application laid-open No. 2007-157879, japanese patent application laid-open No. 2001-521288, japanese patent application laid-open No. 2004-214501, japanese patent application laid-open No. 2004-101850, U.S. Pat. No. 7888181B2, and U.S. Pat. No. 9177926B2 can be used. For example, photolithography, PVD (physical deposition), CVD (chemical vapor deposition), lift off (lift off), electrolytic plating, electroless plating, etching, printing, a method of combining these, and the like can be considered. More specifically, a patterning method in which sputtering, photolithography, and etching are combined, and a patterning method in which photolithography and electrolytic plating are combined can be cited. A preferable embodiment of the plating includes electrolytic plating using a copper sulfate plating solution or a copper cyanide plating solution.
The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, in terms of the thickest part.
< use >
Examples of the field to which the method for producing a cured product of the present invention or the cured product of the present invention can be applied include an insulating film for an electronic device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. In addition, a sealing film, a substrate material (a base film or a cover film of a flexible printed circuit board, an interlayer insulating film), a pattern formed on the insulating film for mounting by etching, or the like can be given. For these uses, for example, reference can be made to Science & Technology co., ltd, "high functionalization of polyimide and application Technology of application", release of polyimide material base and development "11 th 2011", release of polyimide material base and application "NTS, 8 th 2010, etc., of the kaki ben yan min/prison, CMC technical library.
The method for producing a cured product of the present invention and the cured product of the present invention can also be used for producing a plate surface such as an offset plate surface or a screen plate surface, for etching a molded part, for producing a protective paint and a dielectric layer for electronics, particularly microelectronics, and the like.
(laminate and method for producing laminate)
The laminate of the present invention is a structure having a plurality of layers made of the cured product of the present invention.
The laminate of the present invention may be a laminate comprising 2 or more layers of cured products, or may be a laminate comprising 3 or more layers.
Of the layers of the cured product of 2 or more layers contained in the laminate, at least 1 layer is a layer of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product, deformation of the cured product accompanying the shrinkage, and the like, it is also preferable that all of the layers of the cured product contained in the laminate are layers of the cured product of the present invention.
That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes the step of repeating the method for producing a cured product of the present invention a plurality of times.
The laminate of the present invention preferably includes 2 or more layers of the cured product, and preferably includes a metal layer between any of the layers of the cured product. The metal layer is preferably formed by the metal layer forming step.
That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on a layer made of a cured product between the methods for producing a cured product that are carried out a plurality of times. The preferable mode of the metal layer forming step is as described above.
As the laminate, for example, a laminate having a layer structure in which at least 3 layers of a layer composed of a first cured product, a metal layer, and a layer composed of a second cured product are laminated in this order is preferable.
The layer composed of the first cured product and the layer composed of the second cured product are preferably both layers composed of the cured product of the present invention. The resin composition of the present invention for forming a layer composed of the first cured product and the resin composition of the present invention for forming a layer composed of the second cured product may be the same composition or may be different in composition. The metal layer in the laminate of the present invention can be preferably used as a metal wiring of a rewiring layer or the like.
< lamination Process >
The method for producing a laminate of the present invention preferably includes a lamination step.
The lamination step is a series of steps including at least 1 step of (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, (d) a heating step, and a post-development exposure step, in this order again, on the surface of the pattern (resin layer) or the metal layer. In this case, at least 1 of the film forming step (a) and the heating step (d) and the post-development exposure step may be repeated. Further, the metal layer forming step (e) may be included after at least 1 of the heating step (d) and the post-development exposure step. The lamination step may obviously further include the above-described drying step or the like as appropriate.
When the lamination step is further performed after the lamination step, a surface activation treatment step may be further performed after the exposure step, after the heating step, or after the metal layer formation step. As the surface activation treatment, a plasma treatment is exemplified. Details of the surface activation treatment will be described later.
The lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
For example, the resin layer is preferably 2 or more and 20 or less layers, more preferably 2 or more and 9 or less layers, such as the resin layer/metal layer/resin layer/metal layer.
The composition, shape, film thickness, etc. of the layers may be the same or different.
In the present invention, it is particularly preferable that after the metal layer is provided, the cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer. Specifically, the method includes a method in which (a) at least 1 of the film forming step, (b) the exposing step, (c) the developing step, (d) the heating step and the post-developing exposing step, and (e) the metal layer forming step are repeated in this order, or a method in which (a) at least 1 of the film forming step, (d) the heating step and the post-developing exposing step, and (e) the metal layer forming step are repeated in this order. The resin composition layer (resin layer) and the metal layer of the present invention can be alternately laminated by alternately performing the lamination step of laminating the resin composition layer (resin layer) and the metal layer formation step of the present invention.
(surface activation treatment Process)
The method for producing a laminate of the present invention preferably includes a surface activation treatment step of surface-activating at least a part of the metal layer and the resin composition layer.
The surface activation treatment step is usually performed after the metal layer formation step, but the metal layer formation step may be performed after the surface activation treatment step is performed on the resin composition layer after the development step (preferably after at least 1 step out of the heating step and the post-development exposure step).
The surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the resin composition layer after exposure, and may be performed on at least a part of both the metal layer and the resin composition layer after exposure. The surface activation treatment is preferably performed on at least a part of the metal layer, and more preferably, a part or the whole of the region of the metal layer where the resin composition layer is formed on the surface is subjected to the surface activation treatment. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin composition layer (film) provided on the surface thereof can be improved.
The surface activation treatment is preferably performed on a part or the whole of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, adhesion with the metal layer or the resin layer provided on the surface subjected to the surface activation treatment can be improved. In particular, in the case of performing negative development or the like, when the resin composition layer is cured, the resin composition layer is less likely to be damaged by the surface treatment, and adhesion is easily improved.
As the surface activation treatment, specifically, there may be mentioned a treatment such as plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, CF-based treatment, etc 4 /O 2 、NF 3 /O 2 、SF 6 、NF 3 、NF 3 /O 2 The etching treatment, the surface treatment by Ultraviolet (UV) ozone method, the treatment of immersing in an aqueous hydrochloric acid solution to remove an oxide film and then immersing in an organic surface treating agent containing a compound having at least 1 of an amino group and a thiol group, and the mechanical roughening treatment using a brush are selected, and plasma treatment is preferable, and oxygen plasma treatment using oxygen as a source gas is particularly preferable. In the case of corona discharge treatment, the energy is preferably 500 to 200,000J/m 2 More preferably 1000 to 100,000J/m 2 Most preferably from 10,000 to 50,000J/m 2 。
(method for manufacturing semiconductor device)
The present invention also discloses a semiconductor device comprising the cured product of the present invention or the laminate of the present invention.
The present invention also discloses a method for manufacturing a semiconductor device including the method for manufacturing a cured product of the present invention or the method for manufacturing a laminate of the present invention. As a specific example of a semiconductor device in which the resin composition of the present invention is used for forming an interlayer insulating film for a re-wiring layer, reference is made to the descriptions in paragraphs 0213 to 0218 and the description in fig. 1 of japanese patent application laid-open publication 2016-027357, which are incorporated herein by reference.
(alkali-generating agent)
The base generator of the present invention is represented by the following formula (1-1).
[ chemical formula 77]
In the formula (1-1), R is independently a hydrogen atom or a 1-valent organic group, and when 2R are not present, 2R may be bonded to form a ring structure, OH in the formula (1-1) represents a hydroxyl group, L is a 2-valent organic group, and at least 1 heteroatom is present in the shortest path connecting adjacent oxygen atoms and carbon atoms.
The base generator of the present invention has the same meaning as the specific base generator used in the resin composition of the present invention, and the preferred embodiment is the same.
Examples
The present invention will be described in further detail with reference to examples. The materials, amounts used, proportions, treatment contents, treatment orders and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are mass references.
< method for producing precursor of cyclized resin >
Synthesis example 1: synthesis of a precursor of a cyclized resin (resin 1)
23.48g of 4,4' -Oxybisphthalic Dianhydride (ODPA) and 22.27g of diphthalic dianhydride (BPDA) were placed in a separate flask, 39.69g of 2-hydroxyethyl methacrylate (HEMA) and 136.83g of tetrahydrofuran were added and stirred at room temperature (25 ℃ C.), and 24.66g of pyridine was added while stirring, thereby obtaining a reaction mixture. After the completion of the heat generation by the reaction, the reaction mixture was naturally cooled to room temperature and left for 16 hours.
Then, a solution of 62.46g of Dicyclohexylcarbodiimide (DCC) dissolved in 61.57g of tetrahydrofuran was added to the reaction mixture over 40 minutes while stirring under ice-cooling, and then a suspension of 27.42g of 4,4' -diaminodiphenyl ether (DADPE) suspended in 119.73g of tetrahydrofuran was added over 60 minutes while stirring. After stirring for 2 hours at room temperature, 7.17g of ethanol was added and stirred for 1 hour, and then 136.83g of tetrahydrofuran was added. The precipitate formed in the reaction mixture was removed by filtration, whereby a reaction solution was obtained.
The obtained reaction solution was added to 716.21g of ethanol, whereby a precipitate composed of a crude polymer was formed. The crude polymer thus obtained was collected by filtration and dissolved in 403.49g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26g of water to precipitate a polymer, and after the obtained precipitate was collected by filtration, vacuum drying was performed, whereby 80.3g of resin 1 was obtained in the form of powder. As a result of measuring the molecular weight of the resin 1 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000. The structure of the resin 1 is assumed to be represented by the following formula (P-1). Further, by appropriately adjusting the equivalent weight of 4,4' -diaminodiphenyl ether, resin 1 having an Mw of 10,000 and resin 1 having an Mw of 30,000 were also synthesized, respectively.
[ Synthesis example 2: synthesis of a precursor of a cyclized resin (resin 2)
21.2g of 4,4 '-oxybisphthalic anhydride, 18.0g of 2-hydroxyethyl methacrylate, 23.9g of pyridine and 250mL of diglyme (diglyme) were mixed and stirred at 60℃for 4 hours to synthesize a diester of 4,4' -oxybisphthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to-10℃and 17.0g of thionyl chloride was added over 60 minutes while maintaining the temperature at-10.+ -. 5 ℃. After dilution with 50mL of N-methylpyrrolidone, a solution of 12.6g of 4,4' -diaminodiphenyl ether dissolved in 100mL of N-methylpyrrolidone was added dropwise to the reaction mixture at-10.+ -. 5 ℃ for 60 minutes, and the mixture was stirred at room temperature for 2 hours. After that, 10.0g of ethanol was added thereto, and the mixture was stirred at room temperature for 1 hour.
Next, 6000g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid of polyimide precursor) was collected by filtration and dissolved in 500g of tetrahydrofuran. 6000g of water (poor solvent) was added to the obtained solution to precipitate a polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid of polyimide precursor) was again filtered and dried under reduced pressure at 45 ℃ for 3 days.
After 46.6g of the dried powder was dissolved in 419.6g of tetrahydrofuran, 2.3g of triethylamine was added thereto and the mixture was stirred at room temperature for 35 minutes. After that, 3000g of ethanol was added, and the precipitate was collected by filtration. The obtained precipitate was dissolved in 281.8g of tetrahydrofuran. 17.1g of water and 46.6g of ion exchange resin UP6040 (manufactured by Ambertech Limited) were added thereto, and the mixture was stirred for 4 hours. Thereafter, the ion exchange resin was filtered off by filtration, and the obtained polymer solution was added to a mixed solution of 4500g of heptane and 500g of ethyl acetate to obtain a precipitate. The precipitate was collected by filtration and dried at 45℃under reduced pressure for 24 hours, whereby 45.1g of resin 2 was obtained.
The structure of the resin 2 is assumed to be represented by the following formula (P-2). As a result of measuring the molecular weight of the resin 2 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000.
[ Synthesis examples 3 to 8: synthesis of precursors of cyclized resins (resins 3 to 8)
Resins 3 to 8 having structures represented by any of the following formulas (P-3) to (P-8) were synthesized in the same manner as in synthesis example 2, except that the compound used was changed appropriately.
The Mw of resin 3 was 20,000, the Mw of resin 4 was 20,000, the Mw of resin 5 was 20,000, the Mw of resin 6 was 20,000, the Mw of resin 7 was 20,000, and the Mw of resin 8 was 20,000.
[ chemical formula 78]
[ chemical formula 79]
[ Synthesis example 9: synthesis of resin 9
Cyclohexanone 30.78 parts by mass was heated to 80 ℃ under a nitrogen stream. While stirring the liquid, a mixed solution of 10.21 parts by mass of 2-oxotetrahydrofuran-3-yl methacrylate, 11.78 parts by mass of 1-diisopropylcyclopentyl methacrylate, 57.17 parts by mass of cyclohexanone, and 0.44 parts by mass of dimethyl 2,2' -azobisisobutyrate [ manufactured by V-601,FUJIFILM Wako Pure Chemical Corporation ] was added dropwise thereto over 6 hours. After the completion of the dropwise addition, stirring was further carried out at 80℃for 2 hours. After the reaction solution was naturally cooled, reprecipitation was performed with a large amount of methanol/water (mass ratio 9:1), filtration was performed, and the obtained solid was dried in vacuo, whereby 18.69 parts by mass of an acid-decomposable resin, namely, resin 9 was obtained.
The structure of the resin 9 is assumed to be represented by the following formula (P-9). As a result of measuring the molecular weight of the resin 9 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000.
[ Synthesis example 10: synthesis of resin 10
40.24 parts by mass of cyclohexanone are heated to 80℃under a nitrogen stream. While stirring the liquid, a mixed solution of 11.56 parts by mass of 2-oxohexahydro-2H-3, 5-methanocyclopentane [ b ] furan-6-yl methacrylate, 17.18 parts by mass of 1- (1-methoxy-2, 2-dimethylpropoxy) -4-vinylbenzene, 74.73 parts by mass of cyclohexanone, and 0.42 part by mass of dimethyl 2,2' -azobisisobutyrate [ manufactured by V-601,FUJIFILM Wako Pure Chemical Corporation ] was added dropwise thereto over 6 hours. After the completion of the dropwise addition, stirring was further carried out at 80℃for 2 hours. After the reaction solution was naturally cooled, the obtained solid was subjected to reprecipitation with a large amount of methanol/water (mass ratio 9:1), filtration and vacuum drying, whereby 26.15 parts by mass of an acid-decomposable resin, namely, resin 9 was obtained. The structure of the resin 10 is assumed to be represented by the following formula (P-10). As a result of measuring the molecular weight of the resin 10 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000.
In the following formula, the subscript between brackets indicates the content ratio (molar ratio) of each repeating unit.
[ chemical formula 80]
[ Synthesis example 11: synthesis of resin 11
In a flask equipped with a condenser and a stirrer, 18.0g (40.5 mmol) of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (Tokyo Chemical Industry co., ltd.) was dissolved in 80.0g of N-methylpyrrolidone (NMP) while removing water. Then, 7.95g (39.7 mmol) of 4,4' -diaminodiphenyl ether (Tokyo Chemical Industry co., ltd.) was added, and the mixture was stirred at 25℃for 3 hours and further at 45℃for 3 hours. Then, 12.8g (160 mmol) of pyridine, 10.3g (101 mmol) of acetic anhydride and 40.0g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80℃for 3 hours, and 50g of N-methylpyrrolidone (NMP) was added and diluted.
The reaction solution was precipitated in 1 liter of methanol and stirred at 3000rpm for 15 minutes. The resin was obtained by filtration, stirred in 1 liter of methanol for 30 minutes again and filtered again. The obtained resin was dried at 40℃under reduced pressure for 1 day to obtain a resin 11. As a result of measuring the molecular weight of the resin 11 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000. The structure of the resin 11 is assumed to be represented by the following formula (P-11).
[ chemical formula 81]
(P-11)
[ Synthesis example 12: synthesis of resin 12
Resin 12 was obtained in the same manner as in Synthesis example 11, except that in Synthesis example 11, 4'- (hexafluoroisopropylidene) diphthalic anhydride was changed to an equimolar amount of 4,4' -Oxydiphthalic Dianhydride (ODPA) and 4,4 '-diaminodiphenyl ether was changed to an equimolar amount of 2,2' -bis (trifluoromethyl) benzidine. As a result of measuring the molecular weight of the resin 12 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000. The structure of the resin 12 is assumed to be represented by the following formula (P-12).
[ chemical formula 82]
(P-12)
< examples and comparative examples >
In each example, the components described in the following table were mixed to obtain each resin composition. Further, the components described in the following table were mixed with each comparative example to obtain each comparative composition.
Specifically, the content (blending amount) of each component described in the table is set to the amount (part by mass) described in the column "part by mass" of each column in the table.
The obtained resin composition and comparative composition were subjected to pressure filtration using a polytetrafluoroethylene filter having a pore width of 0.8. Mu.m.
In the table, "-" indicates that the composition does not contain any corresponding components.
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TABLE 9
The details of the components described in the table are as follows.
[ resin ]
Resin 1 to resin 10: resins 1 to 10 obtained by the above synthesis examples
[ monomer (polymerizable Compound) ]
M-1: the compound of the following structure, the subscript of the brackets, indicates the number of repetitions.
[ chemical formula 83]
[ polymerization initiator or photoacid generator ]
I-1 to I-5: compounds of the structure
[ chemical formula 84]
[ specific alkali-generating agent or alkali-generating agent ]
A-1 to A-47: a compound of the structure. A-1 to A-47 are compounds conforming to the above specific alkali generator.
AX-1: a compound of the structure. AX-1 is a compound which does not conform to the above specific alkali generator.
RA-1: the compound RA-1 having the following structure is a compound which does not conform to the above-mentioned specific base generator.
[ chemical formula 85]
Wherein, the dimethyl piperidine ring contained in the structure of A-15 exists in cis-form and trans-form. A-15 is a mixture of cis/trans=1:1 (molar ratio).
[ chemical formula 86]
[ chemical formula 87]
Almost 100 mol% of all the dimethylpiperidine rings contained in the structures of A-46 and A-47 are cis-forms.
[ Synthesis example 13: synthesis of Compound A-12
[ chemical formula 88]
In a flask, catechol 20.0g was dissolved in dichloromethane 241.0 g. 36.8g of triethylamine was added dropwise thereto, and the reaction solution was cooled to 0℃to 5℃in an ice bath. 22.6g of 2-chloroacetyl chloride was added dropwise to the reaction mixture, and the mixture was heated to 40℃and refluxed. After confirming the disappearance of the starting material after 3 hours, the reaction solution was poured into 200mL of stirred water, and further stirred for 10 minutes after the addition. Thereafter, the collected organic layer was further washed 2 times with 100mL of water. The organic layer was dried over sodium sulfate, and the filtrate was concentrated under reduced pressure, thereby obtaining an oily crude product. 50.0g of diisopropyl ether was added thereto and stirred, whereby a solid was precipitated. The solid was collected by filtration, rinsed with diisopropyl ether and then air-dried with a buchner funnel, whereby 9.9g of compound a-12-I1 was obtained (yield 36%). The following shows 1 H-NMR data.
1 H-NMR，400MHz，δ((DMSO-d6)ppm：4.90(6H，s)，7.05-7.21(4H，m)。
In a flask, 4.0g of A-12-I1 was stirred in 23.2g of toluene, and 6.9g of 4-piperidineethanol was added thereto. The reaction solution was heated to 75℃to 80℃and stirred for 2 hours. After that, the reaction solution was cooled to room temperature, and concentrated under reduced pressure with heating, whereby toluene was distilled off. The oily reaction was dissolved by adding 150.0g of methylene chloride thereto, and washed 2 times with 100mL of 1N (1 mol/L) hydrochloric acid. After that, the organic layer was washed 2 times with 100mL of water, dried over sodium sulfate, and the filtered solution was concentrated under reduced pressure with heating, whereby a crude product was obtained. Further, purification was performed by silica gel column chromatography (the target product was purified by developing solvent: hexane/ethyl acetate=1/2 (volume ratio) →ethyl acetate, hexane/ethyl acetate=1/2 (volume ratio), rf=0.09), whereby 5.5g of compound a-12 was obtained (colorless transparent oil) (yield 74%). The following shows 1 H-NMR data.
1 H-NMR，400MHz，δ((DMSO-d6)ppm：0.89-1.15(2H，m)，1.35(2H，dd，J＝12，8)，1.55-1.72(3H，m)，2.59(1H，t，J＝12)，2.97(1H，t，12)，3.43(2H，dd，J＝12，8)，3.77(1H，d，J＝12)，4.31(1H，d，J＝12)，4.37(1H，t，J＝4)，4.78(2H，dd，J＝20，15)，6.69-6.91(4H，m)，9.44(1H，s)。
Synthesis example 14: synthesis of Compound A-28
[ chemical formula 89]
To 261.9g of methylene chloride, 20.0g of diisopropylamine and 24.0g of triethylamine were stirred. After the reaction mixture was cooled to 0℃to 5℃with an ice bath, 43.9g of 2-bromoacetyl bromide was added dropwise. After the dropwise addition, the temperature was raised to room temperature and stirred for 1 hour. Thereafter, the reaction solution was poured into 1000mL of water and stirred for a further 15 minutes. After the organic layer was extracted, the aqueous layer was extracted 1 time with 100g of methylene chloride, and the organic layer was collected. The organic layer was washed 3 times with 200mL portions of water, dried over sodium sulfate, and the filtrate was concentrated under heating and reduced pressure, whereby 29.5g of Compound A-28-I1 was obtained (yield 67%). The following shows 1 H-NMR data.
1 H-NMR，400MHz，δ((CDCl 3 )ppm：1.26(6H，d，J＝8)，1.39(6H，d，J＝8)，3.39-3.50(1H，m)，3.81(2H，s)，3.91-4.01(1H，m)。
In the flask, 10.0g of isovanillin, 52.0g of acetone and 10.0g of calcium carbonate were stirred at room temperature. 13.1g of A-28-I1 was added thereto, and the mixture was stirred at room temperature for 3 hours after the addition. After that, the solid was collected by filtration, and the filtrate was concentrated under reduced pressure with heating to distill off acetone. After 200.0g of ethyl acetate was added and dissolved, the mixture was washed 2 times with 200mL of a saturated aqueous sodium hydrogencarbonate solution and 1 time with 200mL of water, dried over sodium sulfate, and the filtrate was concentrated under reduced pressure and heated, whereby a solid crude product was obtained. 100.0g of hexane was added, and after stirring for 30 minutes, a solid was collected by filtration, whereby 16.8g of the objective product A-28-I2 was obtained (yield 9) 2%). The following shows 1 H-NMR data.
1 H-NMR，400MHz，δ((DMSO-d6)ppm：1.18(6H，d，J＝8)，1.28(6H，d，J＝8)，3.42-3.52(1H，m)，3.89(3H，s)，3.94-4.04(1H，m)，4.79(2H，s)。7.19(1H，d，J＝8)，7.29(1H，d，J＝2)，7.56(1H，dd，J＝8，2)，9.80(1H，s)
In the flask, 4.0g of A-28-12, 90.3g of methylene chloride were stirred. After the reaction mixture was cooled to-60 ℃, 68mL of a boron tribromide (1 mol/L) methylene chloride solution was added dropwise. After the dropwise addition, the reaction solution was warmed to room temperature and stirred for 2 hours. After that, the reaction solution was poured into 300mL of water, and after further stirring at room temperature for 30 minutes, the organic layer was collected by separation, dried over sodium sulfate, and the filtrate was concentrated under reduced pressure with heating, whereby a crude product was obtained. 1.76g of the desired product A-28-I3 (yield 46%) was obtained by silica gel column chromatography (developing solvent: hexane/ethyl acetate=3/1 (volume ratio) →2/1 (volume ratio)). The following shows 1 H-NMR data. 1 H-NMR，400MHz，δ((DMSO-d6)ppm：1.17(6H，d，J＝8)，1.30(6H，d，J＝8)，3.45-3.55(1H，m)，3.91-4.01(1H，m)，4.83(2H，s)，5.70(1H，bs)，7.00(1H，d，J＝8)，7.37(1H，s)，7.47(1H，dd，J＝8)，9.75(1H，s)
5.0g of methyltriphenylphosphine bromide and 81.0g of tetrahydrofuran were stirred in a flask under nitrogen atmosphere, and the reaction solution was cooled to-60 ℃. 9.0mL of a hexane solution of 1.6mol/L n-butyllithium was added dropwise thereto. After heating to-40℃the mixture was stirred for 1 hour. Thereafter, 1.3g of A-28-I3 was added thereto, and after warming to room temperature, the mixture was stirred for 1 hour. To the reaction mixture was added 100mL of a saturated aqueous ammonium chloride solution, and the mixture was stirred at room temperature for 15 minutes. Then, an organic layer was collected from a filtrate obtained by filtering the reaction liquid, and an aqueous layer was extracted 1 time with 100mL of methylene chloride, and then combined with the organic layer, dried over sodium sulfate, and the filtrate was concentrated under reduced pressure with heating, whereby a crude product was obtained. Purification of the target product by silica gel chromatography (developing solvent: hexane/ethyl acetate=5/1 (volume ratio) →1/1 (volume ratio)) gave 0.86g of target product a-28 (white solid) by purification with hexane/ethyl acetate=4/1, rf=0.39 ) (67% yield). The following shows 1 H-NMR data.
1 H-NMR，400MHz，δ((DMSO-d6)ppm：1.15(6H，d，J＝8)，1.30(6H，d，J＝8)，3.45-3.54(1H，m)，3.88-3.98(1H，m)，4.75(2H，s)，5.06(1H，dd，J＝12，1)，5.56(1H，dd，J＝12，1)，6.57(1H，dd，J＝16，12)，6.75(1H，d，J＝8)，6.92(1H，dd，J＝8，2)，7.05(1H，d，J＝2)，9.70(1H，s)
[ Synthesis example 15: synthesis of Compound A-37
[ chemical formula 90]
In a flask, 35.9g of dicyclohexylamine and 131.0g of methylene chloride were stirred, and the solution was cooled to 0℃to 5℃under an ice bath. After 20.0g of 2-bromoacetyl bromide was added dropwise, the reaction solution was warmed to room temperature and stirred for further 1 hour. Thereafter, the reaction solution was poured into 300mL of water and stirred for 15 minutes. The solid precipitate was removed by filtration, and the organic layer was extracted from the filtrate. The aqueous layer was extracted 1 time with 100.0g of methylene chloride, and after the organic layer was collected, it was washed with 100mL of water by pipetting. The organic layer was dried over sodium sulfate, and the filtrate was concentrated under reduced pressure, whereby 26.7g of the objective product A-37-I1 was obtained (yield 89%). The following shows 1 H-NMR data.
1 H-NMR，400MHz，δ((DMSO-d6)ppm：0.99-1.15(2H，m)，1.21-1.38(7H，m)，1.46-1.59(2H，m)，1.67-1.76(7H，m)，2.24-2.33(2H，m)，2.89-3.04(1H，m)，3.45-3.50(1H，m)，4.05(2H，s)。
In a flask, 7.8g of A-37-I1, 39.0g of acetone, 2.7g of catechol, 6.9g of calcium carbonate were stirred with heating at 40 ℃. After stirring for 4 hours, cool to room temperature and remove solids by filtration. Acetone was distilled off by concentrating the filtrate under reduced pressure and heating. After 200mL of ethyl acetate was added and the crude product was dissolved, 80mL of 1N hydrochloric acid was added thereto, and the mixture was vigorously stirred for 15 minutes. Extracting the organic layer with 100mL of water The organic layer was dried over sodium sulfate and the filtrate was concentrated under reduced pressure and heated, whereby a crude product was obtained. Chromatography on silica gel (developing solvent: hexane/ethyl acetate=4/1 (volume ratio)). Purification of the desired product with hexane/ethyl acetate=4/1 (volume ratio), rf=0.45 gave 3.74g of the desired product a-37 (white solid) (yield 46%). The following shows 1 H-NMR data.
1 H-NMR，400MHz，δ((DMSO-d6)ppm：1.01-1.13(2H，m)，1.20-1.57(10H，m)，1.63-1.74(6H，m)，2.27-2.37(2H，m)，2.95-3.05(1H，m)，3.38-3.48(1H，m)，4.74(2H，s)，6.72(1H，ddd，J＝16，2)，6.76-6.86(2H，m)，6.92(1H，dd，J＝8，2)，9.57(1H，s)。
Synthesis example 16: synthesis of Compound A-38
[ chemical formula 91]
In the flask, 10.0g of 2, 6-tetramethylpiperidine, 8.6g of triethylamine and 93.8g of 1, 2-dichloroethane were stirred, and the solution was cooled to 0℃to 5℃under an ice bath. 15.7g of 2-bromoacetyl bromide was added dropwise thereto, and the mixture was then warmed to room temperature and stirred for 2 hours. The reaction solution was poured into 500mL of water and stirred for a further 15 minutes. The organic layer was extracted, the aqueous layer was extracted 1 time with 50.0g of 1, 2-dichloroethane, and the organic layers were combined. The organic layer was washed 3 times with 100mL of water, dried over sodium sulfate, and the filtrate was concentrated under heating and reduced pressure, whereby 5.7g of the objective product A-38-I1 was obtained (yield 30%). The following shows 1 H-NMR data.
1 H-NMR，400MHz，δ((DMSO-d6)ppm：1.38(12H，s)，1.67-1.74(16H，m)，4.08(2H，s)。
In the flask, 2.3g of catechol, 17.0g of acetone, 3.2g of calcium carbonate were stirred, and 6.4g of A-38-I1 was added thereto. Thereafter, the reaction solution was warmed to 40℃and stirred for 3 hours. After cooling to room temperature, the filtrate after removal of solids by filtration was concentrated under reduced pressure and heated, prepared by This distillation removes the acetone. After 150mL of ethyl acetate was added and dissolved, 60mL of 1N hydrochloric acid was added and stirred vigorously for 15 minutes. The organic layer was extracted, washed 3 times with 100mL of water, dried over sodium sulfate, and the filtrate was concentrated under reduced pressure and heated, whereby a crude product was obtained. Purification of the target product by silica gel chromatography (developing solvent: hexane/ethyl acetate=8/1 (volume ratio) →4/1 (volume ratio)) afforded 2.0g of the target product a-38 (colorless transparent oil) (yield 33%). The following shows 1 H-NMR data.
1 H-NMR，400MHz，δ((DMSO-d6)ppm：1.40(12H，s)，1.64-1.75(6H，m)，4.63(2H，s)，6.68-6.73(1H，m)，6.78-6.84(2H，m)，6.92(1H，dd，J＝8，1)，9.32(1H，s)。
[ Synthesis example 17: synthesis of Compound A-46
[ chemical formula 92]
In a flask, 50.1g of cis-2, 6-dimethylpiperidine and 248.6g of acetonitrile (MeCN) were stirred, and the solution was cooled to 0℃to 5℃in an ice bath. After 25.0g of chloroacetyl chloride was added dropwise thereto, the reaction solution was warmed to room temperature and stirred for 3 hours. After that, 36.6g of catechol was added, and the reaction solution was heated to 75 ℃.1, 8-diazabicyclo [5.4.0 ] is added dropwise thereto]37.1g of 7-undecene (DBU) and stirred for 6 hours. After cooling the reaction solution to room temperature, 181.4g of 2-propanol was added, and the solution was cooled to-10 to-5 ℃. By dropping 546.8g of water, powder was precipitated, followed by further adding 546.8g of water, and stirring was performed for 30 minutes. The powder was filtered by adsorption filtration, and rinsed with 546.8g of water. The obtained wet powder was dried with a blow dryer at 45℃for 18 hours, whereby 45.0g of a desired product A-46 powder (containing 6.3% of water) (yield: 71%) was obtained. The following shows 1 H-NMR data.
1 H-NMR，400MHz，δ((DMSO-d6)ppm：1.20(6H，bd，J＝34.6Hz)，1.40-1.45(1H，m)，1.48-1.70(4H，m)，1.70-1.88(1H，m)，4.03(1H，bs)，4.56(1H，bs)，4.73(1H，bs)，4.91(1H，bs)，6.72(1H，td，J＝1.9Hz，7.3Hz)，6.78-6.87(2H，m)，6.91(1H，dd，J＝1.5Hz，8.0Hz)，9.52(1H，s)
[ polymerization inhibitor ]
B-1 to B-2: compounds of the structure
[ chemical formula 93]
[ silane coupling agent (Metal adhesion improver) ]
C-1 to C-2: in the following formula, et represents ethyl.
[ chemical formula 94]
[ migration inhibitor ]
D-1: compounds of the structure
[ chemical formula 95]
[ additives ]
E-1 to E-3: compounds of the structure
[ chemical formula 96]
[ solvent ]
NMP: n-methyl-2-pyrrolidone
EL: lactic acid ethyl ester
DMSO: dimethyl sulfoxide
GBL: gamma-butyrolactone
< evaluation >
[ evaluation of elongation at Break ]
The resin compositions and comparative compositions prepared in examples and comparative examples were applied to silicon wafers by spin coating, respectively, to form resin layers.
The obtained silicon wafer on which the resin layer was formed was dried on a hot plate at 100 ℃ for 5 minutes, and a resin composition layer having a thickness as described in the column "film thickness (μm)" and a uniform thickness was obtained on the silicon wafer.
In the example described as "negative" in the column of the development conditions in the following table, the development conditions were measured at 500mJ/cm 2 The entire surface of the resin composition layer on the silicon wafer is exposed to light. The exposure wavelength is shown in the table as "exposure wavelength (nm)". In the example in which the development condition is indicated as "positive" in the table, exposure is not performed.
In the example described as "M" in the column of exposure conditions, exposure was performed using a stepper as a light source.
In the example described as "D" in the column of exposure conditions, exposure was performed using a direct exposure apparatus (ADTEC DE-6UH III) as a light source.
In the example in which the values are shown in the column of "curing temperature (. Degree. C.)" the exposed resin composition layer was heated at a heating rate of 10℃per minute under a nitrogen atmosphere using a heating plate, and after the temperature shown in the column of "curing temperature (. Degree. C.)" was reached, the temperature was maintained for the "curing time (min)" in the table.
In the example described as "IR" in the column of "curing temperature (. Degree. C.) the resin films obtained in each example were heated at a heating rate of 10℃per minute under a nitrogen atmosphere using an infrared lamp heating device (RTP-6 manufactured by ADVANCE RIKO, inc.), and after reaching 230℃the above temperature was maintained for the" curing time (min) "in the table.
The cured resin composition layer (cured product) was immersed in a 4.9 mass% aqueous hydrofluoric acid solution, and the cured product was peeled from the silicon wafer. A test piece having a sample width of 3mm and a sample length of 30mm was produced by punching the peeled cured product with a punching machine. The elongation in the longitudinal direction of the obtained test piece was measured by a tensile Tester (TENSILON) in an environment of a crosshead speed of 300 mm/min, 25℃and 65% RH (relative humidity) in accordance with JIS-K6251. Each of the measurements was performed 5 times, and the arithmetic average of the elongation at break (elongation at break) of the test piece in the 5 measurements was used as an index value.
The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the column of "elongation at break" in the table. It can be said that the greater the index value, the more excellent the film strength of the cured product.
In the examples described as "-" in the column of "elongation at break", the elongation at break was not evaluated.
Evaluation criterion-
A: the index value is 65% or more.
B: the index value is 60% or more and less than 65%.
C: the index value is 55% or more and less than 60%.
D: the index value is lower than 55%.
[ evaluation of drug resistance ]
The resin composition or the composition for comparison prepared in each example or comparative example was coated on a silicon wafer by spin coating. The silicon wafer was dried on a hot plate at 100℃for 5 minutes, and a resin composition layer having a uniform thickness as described in the column "film thickness (μm)" was formed on the silicon wafer.
In the example in which the developing condition is described as "negative" and the exposing condition is described as "M", the resin composition layer on the silicon wafer is exposed by a stepper. The entire surface of the photosensitive film was exposed without using a photomask by using light having a wavelength described in "exposure wavelength nm" in the table. The exposure amount is set to an exposure amount at which the minimum line width in the analysis to be described later becomes the minimum.
In the example where the developing condition is described as "negative" and the exposing condition is described as "D", the exposure was performed using a direct exposure apparatus (ADTEC DE-6UH III). The entire surface of the photosensitive film was exposed using light having a wavelength described in "exposure wavelength nm" in the table. The exposure amount is set to an exposure amount at which the minimum line width in the analysis to be described later becomes the minimum.
In the example described as "positive" in the development condition, exposure was not performed
In the example in which the values are shown in the column of "curing temperature (. Degree. C.)" the resin films obtained in each example or comparative example were heated at a heating rate of 10℃per minute under a nitrogen atmosphere using a heating plate, and after the temperature shown in the table "curing temperature (. Degree. C.)" was reached, the temperature was maintained for a period of time shown in the table "curing time (min)", whereby a cured film was formed.
In the example described as "IR" in the column of "curing temperature (. Degree. C.) an infrared lamp heating device (RTP-6 manufactured by ADVANCE RIKO, inc.) was used, and the resin films obtained in each example were heated at a heating rate of 10℃per minute under a nitrogen atmosphere to 230℃and then maintained for a period of time described as" curing time (min) ", whereby a cured film was formed.
The obtained cured film was immersed in the following drug under the following conditions, and the dissolution rate was calculated.
Medicine: dimethyl sulfoxide (DMSO) with 25 mass% aqueous tetramethylammonium hydroxide (TMAH) 90:10 (mass ratio) of the mixture
Evaluation conditions: the cured film was immersed in the drug at 75℃for 15 minutes, and the film thicknesses of the cured film before and after immersion were compared to calculate the dissolution rate (nm/min).
The obtained dissolution rate was evaluated according to the following evaluation criteria, and is described in the column "chemical resistance". It can be said that the slower the dissolution rate, the more excellent the chemical resistance.
Evaluation criterion-
A: the dissolution rate was below 250 nm/min.
B: the dissolution rate is 250 nm/min or more and less than 500 nm/min.
C: the dissolution rate is 500 nm/min or more and less than 750 nm/min.
D: the dissolution rate is 750 nm/min or more.
[ evaluation of Pattern rectangularity ]
In each of the examples and comparative examples, each of the resin compositions or the comparative compositions was applied (coated) in layers on a silicon wafer by spin coating, thereby forming resin composition films.
In each of examples and comparative examples, a silicon wafer to which the obtained resin composition film was applied was dried on a hot plate at 100℃for 3 minutes, and a resin film was formed on the silicon wafer.
In the example described as "M" in the exposure conditions, the exposure wavelength described in the table was used at 500mJ/cm 2 The resin film on the silicon wafer is exposed to light by the exposure energy of (a). The exposure was performed through a mask (line and space) having a pattern of 1:1, and a line width of a binary mask having a line width described in the column "pattern size (μm)" in the table.
In the example described as "D" in the column of exposure conditions, exposure was performed using a direct exposure apparatus (ADTEC DE-6UH III). For exposure, laser direct imaging exposure was performed at a wavelength of 405nm so that the exposed portion became a 1:1 line of 10 μm in width and a line portion in the gap pattern. Setting the exposure to 500mJ/cm 2 。
After the exposure, in the example of positive development (the example described as "positive" in the column of "development conditions"), the development was performed for 60 seconds using the developer described in the column of "developer" in the table, and the line and space pattern of the resin film after exposure was obtained by rinsing with pure water for 20 seconds. The expression "TMAH aqueous solution" in the table means a 2.5 mass% tetramethylammonium hydroxide aqueous solution. In the case of negative development (the example described as "negative" in the column of "development conditions"), the development was performed for 60 seconds using the developer described in the column of "developer" in the table, and the resin film was rinsed with Propylene Glycol Monomethyl Ether Acetate (PGMEA) for 20 seconds, thereby obtaining a line-and-space pattern of the resin film.
The silicon wafer thus obtained, on which the wire and gap patterns are formed, is cut so as to be perpendicular to the wire and gap patterns, and the pattern profile is exposed. The cross-sectional shape of the pattern was evaluated by observing the pattern cross-section of the line and space pattern at a magnification of 200 times using an optical microscope.
Specifically, in each of examples and comparative examples, the taper angles formed by the surface of the silicon wafer (substrate surface) and the side surface of the cured film were measured, and evaluated according to the following evaluation criteria. The evaluation results are shown in the column "rectangularity" of the table. It can be said that the taper angle does not exceed 90 ° and the cross-sectional shape of the pattern is not a constricted shape, and the pattern shape is more excellent as the taper angle approaches 90 °.
Evaluation criterion-
A: the taper angle is 85 DEG to 90 deg.
B: the taper angle is 80 DEG or more and less than 85 deg.
C: the cross-sectional shape of the pattern is an inverted cone shape having a cone angle of less than 80 ° or the cross-sectional shape of the pattern is a necked shape having a cone angle of more than 90 °.
From the above results, it was found that the drug resistance of the cured product obtained by using the resin composition of the present invention was improved.
The comparative compositions in comparative examples 1 and 2 did not contain a specific alkali generator. In such a method, the obtained cured product was found to have poor drug resistance.
< example 101>
The resin composition used in example 1 was applied to the copper thin layer surface of the resin substrate having a copper thin layer formed thereon in a layer form by spin coating, dried at 100℃for 5 minutes to form a photosensitive film having a film thickness of 20. Mu.m, and then exposed to light by a stepper (manufactured by Nikon Corporation, NSR1505 i 6). Exposure was performed at 365nm wavelength through a mask (binary mask with pattern 1:1 lines and spaces, line width 10 μm). After the above heating, the layer was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds, thereby obtaining a pattern of the layer.
Then, the temperature was raised at a temperature rise rate of 10 ℃/min in a nitrogen atmosphere, and after reaching 230 ℃, the temperature was maintained at 230 ℃ for 180 minutes, thereby forming an interlayer insulating film for a rewiring layer. The interlayer insulating film for a rewiring layer is excellent in insulation properties.
Further, as a result of manufacturing a semiconductor device using these interlayer insulating films for a rewiring layer, normal operation was confirmed.

Claims (19)

1. A resin composition comprising a resin and a base generator represented by the following formula (1-1),
in the formula (1-1), R is independently a hydrogen atom or a 1-valent organic group, and when 2R are each a hydrogen atom, 2R are optionally linked to form a ring structure, 0H in the formula (1-1) represents a hydroxyl group, and L is a 2-valent organic group having at least 1 heteroatom in the linking chain connecting the shortest paths of adjacent oxygen atoms and carbon atoms.
2. The resin composition according to claim 1, wherein,
the heteroatom present in the shortest path linking chain contained in L of formula (1-1) is any one of a nitrogen atom, an oxygen atom, or a sulfur atom.
3. The resin composition according to claim 1 or 2, which comprises a compound represented by the following formula (1-2) as the base generator,
in the formula (1-2), R is independently a hydrogen atom or an optional 1-valent organic group, and when 2R are hydrogen atoms, 2R are optionally linked to form a ring structure, L 1 Represents optionally substituted alkylene, Z represents-O-, -S-or-NR N -，R N Represents a hydrogen atom or a 1-valent organic group, R 1 R is R 2 Each independently represents a hydrogen atom or an organic group, optionally 2R 1 R is R 2 Wherein n represents 0 or 1, n represents 1 when the bond having the dotted line is a double bond, and n represents 0 when the bond having the dotted line is a single bond.
4. The resin composition according to any one of claim 1 to 3, comprising a compound represented by the following formula (1-3) as the base generator,
in the formula (1-3), R is independently a hydrogen atom or an optional 1-valent organic group, and when 2R are hydrogen atoms, 2R are optionally linked to form a ring structure, L 1 Represents optionally substituted alkylene, Z represents-O-, -S-or-NR N -，R N Represents a hydrogen atom or a 1-valent organic group, R 3 Each independently is a hydrogen atom or a 1-valent organic group, optionally R 3 Is joined to form a ring structure.
5. The resin composition according to any one of claims 1 to 4, comprising a compound represented by the following formula (1-4) as the base generator,
in the formula (1-4), R 2 R is R 4 Each independently represents a 1-valent organic group, 2R 2 Each other or R 2 And R is R 4 Optionally joined to form a ring structure, L 1 Represents optionally substituted alkylene, Z represents-O-, -S-or-NR N -，R N Represents a hydrogen atom or a 1-valent organic group, R 3 Each independently is a hydrogen atom or a 1-valent organic group, optionally R 3 Is joined to form a ring structure.
6. The resin composition according to any one of claims 1 to 5, wherein,
the resin is a precursor of the cyclized resin.
7. The resin composition according to any one of claims 1 to 6, further comprising a photopolymerization initiator.
8. The resin composition according to any one of claims 1 to 7, further comprising a polymerizable compound.
9. The resin composition according to any one of claims 1 to 8, which is used for forming an interlayer insulating film for a rewiring layer.
10. A cured product obtained by curing the resin composition according to any one of claims 1 to 9.
11. A laminate comprising 2 or more layers of the cured product of claim 10, wherein any of the layers of the cured product comprises a metal layer between the layers.
12. A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of claims 1 to 9 to a substrate to form a film.
13. The method for producing a cured product according to claim 12, comprising:
an exposure step of selectively exposing the film; a kind of electronic device with high-pressure air-conditioning system
And a developing step of developing the film with a developer to form a pattern.
14. The method for producing a cured product according to claim 12 or 13, comprising a heating step of heating the film at 50 to 450 ℃.
15. A semiconductor device comprising the cured product of claim 10 or the laminate of claim 11.
16. A base generator represented by the following formula (1-1),
in the formula (1-1), R is independently a hydrogen atom or a 1-valent organic group, and when 2R are each a hydrogen atom, 2R are optionally linked to form a ring structure, OH in the formula (1-1) represents a hydroxyl group, and L is a 2-valent organic group having at least 1 heteroatom in the linking chain connecting the shortest paths of adjacent oxygen atoms and carbon atoms.
17. The base generator according to claim 16, which is represented by the following formula (1-2),
in the formula (1-2), R is independently a hydrogen atom or an optional 1-valent organic group, and when 2R are hydrogen atoms, 2R are optionally linked to form a ring structure, L 1 Represents optionally substituted alkylene, Z represents-O-, -S-or-NR N -，R N Represents a hydrogen atom or a 1-valent organic group, R 1 R is R 2 Each independently represents a hydrogen atom or an organic group, optionally 2R 1 R is R 2 Wherein n represents 0 or 1, n represents 1 when the bond having the dotted line is a double bond, and n represents 0 when the bond having the dotted line is a single bond.
18. The base generator according to claim 16 or 17, which is represented by the following formula (1-3),
in the formula (1-3), R is independently a hydrogen atom or an optional 1-valent organic group, and when 2R are hydrogen atoms, 2R are optionally linked to form a ring structure, L 1 Represents optionally substituted alkylene, Z represents-O-, -S-or-NR N -，R N Represents a hydrogen atom or a 1-valent organic group, R 3 Each independently is a hydrogen atom or a 1-valent organic group, optionally R 3 Is joined to form a ring structure.
19. The base generator according to any one of claims 16 to 18, which is represented by the following formula (1-4),
in the formula (1-4), R 2 R is R 4 Each independently represents a 1-valent organic group, 2R 2 Each other or R 2 And R is R 4 Optionally joined to form a ring structure, L 1 Represents optionally substituted alkylene, Z represents-O-, -S-or-NR N -，R N Represents a hydrogen atom or a 1-valent organic group, R 3 Each independently is a hydrogen atom or a 1-valent organic group, optionally R 3 Is joined to form a ring structure.
CN202280014903.8A 2021-02-15 2022-02-10 Resin composition, cured product, laminate, method for producing cured product, semiconductor device, and alkali generator Pending CN116888217A (en)

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JP2021-021714 2021-02-15
JP2021-168773 2021-10-14
JP2021168773 2021-10-14
PCT/JP2022/005364 WO2022172996A1 (en) 2021-02-15 2022-02-10 Resin composition, cured product, laminated body, method for producing cured product, semiconductor device, and base generator

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