CN118019780A

CN118019780A - Polyimide, polyimide precursor, composition, and method for producing polyimide

Info

Publication number: CN118019780A
Application number: CN202280065531.1A
Authority: CN
Inventors: 青岛俊荣
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2021-09-30
Filing date: 2022-09-26
Publication date: 2024-05-10
Also published as: WO2023054221A1; TW202332715A; KR20240046603A

Abstract

A polyimide containing a repeating unit represented by the following formula (1-1), a polyimide precursor for obtaining the polyimide, a composition containing the polyimide, and a method for producing the polyimide, wherein R ^A1 represents a tetravalent organic group, L ^A2 represents an n+m+1-valent linking group, R ^A2 independently represents a group containing a urethane bond and a poly (alkyleneoxy) group, n represents an integer of 1 or more, m represents an integer of 1 or more, and x represents a bonding site to other structures.

Description

Polyimide, polyimide precursor, composition, and method for producing polyimide

Technical Field

The present invention relates to a polyimide, a polyimide precursor, a composition, and a method for producing polyimide.

Background

Polyimide is excellent in mechanical properties, heat resistance, chemical resistance, electrical insulation, and the like, and therefore is suitable for various applications. The application is not particularly limited, and examples of the application include use as an insulating film, a sealing material, or a protective film when a semiconductor device for actual mounting is used. 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, polyimide is used in the form of a resin composition containing polyimide.

In the resin composition, polyimide is used in a particulate state, a state dissolved in a solvent, or the like.

Since the resin composition can be applied to a substrate or the like by a known coating method or the like, it can be said that the resin composition is excellent in manufacturing suitability, for example, the shape, size, application position and the like of the resin composition to be applied are highly flexible in design. In addition to the high performance of polyimide, the above resin composition is expected to be applicable in industrial fields from the viewpoint of excellent suitability for production.

Various studies have been made on such polyimide and polyimide-containing compositions.

For example, patent document 1 describes a method for producing polyimide particles from tetracarboxylic anhydride and a diisocyanate compound, the method comprising: (a) A first step of synthesizing a polyimide precursor by reacting a tetracarboxylic anhydride with a diisocyanate compound; and (b) a second step of imidizing the obtained polyimide precursor.

Patent document 2 describes a method for producing polyamide acid fine particles, which is characterized in that the method for synthesizing polyamide acid from tetracarboxylic anhydride and diamine compound comprises: (a) A first step of preparing a first solution containing a tetracarboxylic anhydride and a second solution containing a diamine compound, respectively; and (b) a second step of mixing the first solution with the second solution and precipitating polyamide acid fine particles from the mixed solution.

Technical literature of the prior art

Patent literature

Patent document 1: japanese patent laid-open No. 2004-292682

Patent document 2: japanese patent laid-open No. 11-140181

Disclosure of Invention

Technical problem to be solved by the invention

The present invention provides a novel polyimide, a polyimide precursor for obtaining the polyimide, a composition containing the polyimide, and a method for producing the polyimide.

Means for solving the technical problems

Examples of representative embodiments of the present invention are shown below.

<1> A polyimide comprising a repeating unit represented by the formula (1-1),

[ Chemical formula 1]

In the formula (1-1), R ^A1 represents a tetravalent organic group, L ^A2 represents an n+m+1-valent linking group, R ^A2 each independently represents a group containing a urethane bond and a poly (alkyleneoxy) group, n represents an integer of 1 or more, m represents an integer of 1 or more, and a bonding site to another structure is represented.

<2> The polyimide according to <1>, wherein,

R ^A2 in the formula (1-1) is a group represented by the following formula (R-1).

[ Chemical formula 2]

In the formula (R-1), R ^A4 independently represents an alkylene group, x represents an integer of 2 or more, R ^A5 represents a monovalent organic group, and the bonding site with L ^A2 in the formula (1-1) is represented.

<3> A polyimide obtained by imidizing a reactant of a tetracarboxylic dianhydride and a polyfunctional isocyanate compound,

The above-mentioned polyfunctional isocyanate compound contains a poly (alkyleneoxy) group,

<4> The polyimide according to <3>, wherein,

The polyfunctional isocyanate compound is a compound represented by the following formula (IC-1).

[ Chemical formula 3]

In the formula (IC-1), L ^A2 represents an n+m+1-valent linking group, R ^A2 each independently represents a group containing a urethane bond and a poly (alkyleneoxy) group, n represents an integer of 1 or more, and m represents an integer of 1 or more.

<5> The polyimide according to <3> or <4>, wherein,

The polyfunctional isocyanate compound is an adduct of a compound represented by the following formula (C-1) and a second polyfunctional isocyanate compound.

[ Chemical formula 4]

In the formula (C-1), X represents a linking group, m represents 0 or 1, A represents an arylene group or an alkylene group, Z represents an amino group or a hydroxyl group, L represents an alkylene group, n represents an average addition mole number of a poly (alkyleneoxy) group and represents a number of 10 to 120, and R represents an organic group having no active hydrogen.

<6> The polyimide according to <5>, wherein,

The second polyfunctional isocyanate compound is a reactant of a polyfunctional alcohol and a 2-functional isocyanate compound.

<7> A polyimide precursor comprising a repeating unit represented by the following formula (2-1),

[ Chemical formula 5]

In the formula (2-1), R ^A1 represents a tetravalent organic group, L ^A3 represents an m+1 valent linking group containing a poly (alkyleneoxy) group, m represents an integer of 1 or more, and x represents a bonding site to other structures.

<8> The polyimide precursor according to <7>, which is in the form of particles.

<9> The polyimide precursor according to <8>, which has a volume average particle diameter of 30nm to 500nm.

<10> A polyimide obtained by imidizing the polyimide precursor according to any one of <7> to <9 >.

<11> The polyimide according to any one of <1> to <6> and <10>, which is in the form of particles.

<12> The polyimide according to <11>, which has a volume average particle diameter of 30nm to 500nm.

<13> A composition comprising the polyimide of any one of <1> to <6> and <10> to <12> and a compound having a fluorine atom.

<14> A method for producing a polyimide according to any one of <1> to <6> and <10> to <12>, comprising:

a first step of reacting a tetracarboxylic dianhydride with a polyfunctional isocyanate compound to obtain a polyimide precursor; and

And a second step of imidizing the polyimide precursor.

<15> The method for producing polyimide according to <14>, wherein,

In the first step, a tetracarboxylic dianhydride is reacted with a polyfunctional isocyanate compound in the presence of an amine catalyst.

<16> The method for producing polyimide according to <14> or <15>, wherein,

In the second step, the polyimide precursor is heated in an organic solvent to imidize the polyimide precursor.

<17> The method for producing polyimide according to <16>, wherein,

In the second step, imidization is performed while removing carbon dioxide generated during the heating to the outside of the reaction system.

<18> The method for producing polyimide according to <16> or <17>, wherein,

In the second step, the heating temperature during the heating is 130 to 250 ℃.

Effects of the invention

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" means 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 (atomic groups) in the present specification, the label which is not labeled with a substituted or unsubstituted group includes a group (atomic group) having no substituent, and includes a group (atomic group) 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 not only exposure by light but also exposure by a particle beam such as an electron beam or an ion beam. 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 the components other than the solvent among all the components of the composition. 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, for example, HLC-8230 GPC (manufactured by TOSOH CORPORATION) in series with a protection column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION above) as columns. These molecular weights were measured using THF (tetrahydrofuran) as an eluent, unless otherwise specified. Among them, NMP (N-methyl-2-pyrrolidone) can be used when THF is not suitable as an eluent, for example, when solubility is low. Further, unless otherwise specified, a UV ray (ultraviolet ray) detector having a wavelength of 254nm is 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. Further, these vertical settings are for convenience in the present specification, and in a practical embodiment, the "upward" direction in the present specification may be different 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 ℃, 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.

(Polyimide)

The polyimide according to the first embodiment of the present invention contains a repeating unit represented by the formula (1-1).

[ Chemical formula 6]

The polyimide according to the second aspect of the present invention is a polyimide obtained by imidizing a reactant of a tetracarboxylic dianhydride and a polyfunctional isocyanate compound containing a poly (alkyleneoxy) group.

In the present invention, the polyimide according to the first aspect and the polyimide according to the second aspect are also collectively referred to as "specific polyimide".

In particular, when only the polyimide according to the first aspect is referred to, it is also referred to as "first specific polyimide", and when only the polyimide according to the second aspect is referred to, it is also referred to as "second specific polyimide".

The specific polyimide is a polyimide having a novel structure.

In addition, resin compositions containing polyimide particles have been used in various fields.

However, there is room for improvement in dispersibility of polyimide particles in the resin composition.

The polyimide according to the first embodiment of the present invention has a structure represented by formula (1-1). It is considered that when the polyimide according to the first aspect is in the form of particles, the poly (alkyleneoxy) group structure in the structure is present on the particle surface in the composition, so that the dispersion stability of the polyimide particles is improved.

The polyimide particles according to the second aspect of the present invention are obtained by imidizing a reactant of a tetracarboxylic dianhydride and a polyfunctional isocyanate having a poly (alkyleneoxy) group. It is considered that, when the polyimide according to the second aspect is in the form of particles, the structure of the poly (alkyleneoxy) group is present on the particle surface in the composition, so that the dispersion stability of the polyimide particles is improved.

As described above, it is considered that when the specific polyimide of the present invention is in the form of particles, polyimide particles excellent in dispersibility in the composition can be obtained.

The shape, particle diameter, etc. of the specific polyimide of the present invention in the form of particles will be described later.

The polyimide according to the first embodiment of the present invention contains a urethane bond.

Further, the polyimide according to the second aspect of the present invention preferably contains a urethane bond.

It is considered that a material containing a polyimide having a urethane bond (for example, a cured product of a composition containing a polyimide of the present invention) is excellent in chemical resistance. Specifically, it is considered that the resistance to an organic solvent or alkali is excellent.

In the polyimide according to the first aspect of the present invention, it is preferable that m in the formula (1-1) is2 or more.

Further, the polyimide according to the second aspect of the present invention is preferably a polyimide obtained by imidizing a reactant of a tetracarboxylic dianhydride and a polyfunctional isocyanate compound having 3 or more functions.

According to these embodiments, it is considered that the chemical resistance can be further improved because a branched structure (preferably a crosslinked structure such as a mesh structure) is formed in the polyimide.

It is also considered that a material containing the specific polyimide of the present invention (for example, a cured product of a composition containing the polyimide of the present invention) is also excellent in heat resistance by forming the branched structure (preferably, a crosslinked structure such as a mesh structure).

Here, patent documents 1 and 2 neither describe nor suggest the case where the polyfunctional isocyanate compound contains a poly (alkyleneoxy) group in polyimide particles obtained by imidizing a reactant of a tetracarboxylic dianhydride and the polyfunctional isocyanate compound with respect to a polyimide containing a repeating unit represented by the formula (1-1).

< Specific polyimide >

[ First specific polyimide ]

The first specific polyimide contains a repeating unit represented by the formula (1-1).

[ Chemical formula 7]

-R^A1-

In the formula (1-1), as the tetravalent organic group in R ^A1, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.

In the formula (5) or (6), each independently represents a bonding site to another structure.

[ Chemical formula 8]

In the formula (5), R ¹¹² is a single bond or a divalent linking group, preferably a single bond or a group selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms which may be substituted with fluorine atoms, -O-, -CO-, -S-, -SO ₂ -, and-NHCO-, and combinations of these, more preferably a single bond or a group selected from the group consisting of an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-and-SO ₂ -, and still more preferably a divalent group selected from the group consisting of-CH ₂-、-C(CF₃)₂-、-C(CH₃)₂ -, -O-, -CO-, -S-and-SO ₂ -.

Furthermore, R ^A1 is preferably free of imide groups. In the present invention, the imide group is a divalent group represented by-C (=O) NRC (=O) -and R represents a hydrogen atom or a monovalent organic group.

Specifically, R ^A1 is a tetracarboxylic acid residue remaining after the acid anhydride group is removed from the tetracarboxylic dianhydride.

That is, R ^A1 is preferably a structure derived from tetracarboxylic dianhydride.

The tetracarboxylic dianhydride is preferably represented by the following formula (0).

[ Chemical formula 9]

In formula (O), R ^A1 represents a tetravalent organic group. R ^A1 has the same meaning as R ^A1 in the formula (1-1), and the preferable range is 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, 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.

-L^A2-

In the formula (1-1), as the n+m+1-valent linking group in L ^A2, a hydrocarbon group or a group represented by a combination of a hydrocarbon group and at least 1 group selected from the group consisting of-O-, -C (=o) -, -S (=o) ₂ -and-NR ^N -, more preferably a group represented by a combination of a hydrocarbon group and-OC (=o) NR ^N -. R ^N represents a hydrogen atom or a hydrocarbon group, a hydrogen atom, more preferably an alkyl group or an aryl group, further preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom.

The bonding site between L ^A2 and the nitrogen atom and the bonding site in the formula (1-1) are preferably hydrocarbon groups.

The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, or may be a group represented by a combination of these, and is preferably an aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group.

The number of carbon atoms of the hydrocarbon group is preferably 1 to 30, more preferably 2 to 20, and still more preferably 4 to 15.

Moreover, L ^A2 is preferably free of imide groups.

L ^A2 is also preferably a group represented by a combination of structures represented by the following formula (LA-1) and structures represented by the following formula (LA-2).

[ Chemical formula 10]

In formula (LA-1), R ^L1 represents a valence linking group, a represents an integer of 2 or more, and 1 represents a bonding site to 2 in formula (LA-2).

In formula (LA-2), R ^L2 represents a b+c+d valence linking group, b represents an integer of 1 or more, c represents an integer of 0 or more, x2 represents a bonding site with R ^A2 in formula (1-1), d represents an integer of 0 or more, and x 4 represents a bonding site with a nitrogen atom bonded to L ^A2 in formula (1-1) or a bonding site with another structure having the same meaning as in formula (1-1).

The sum of c in all the structures represented by the formula (LA-2) contained in the group represented by the combination of the structure represented by the formula (LA-1) and the structure represented by the formula (LA-2) is n in the formula (1-1), and the sum of d in all the structures represented by the formula (LA-2) is m+1 in the formula (1-1).

The group represented by the combination of the structure represented by the formula (LA-1) and the structure represented by the formula (LA-2) preferably includes a plurality of the structures represented by the formula (LA-1) and the structure represented by the formula (LA-2).

Further, the group represented by the combination of the structure represented by the formula (LA-1) and the structure represented by the formula (LA-2) preferably contains the same number of structures represented by the formula (LA-1) and the structure represented by the formula (LA-2).

The number of the structures represented by the formula (LA-1) in the group represented by the combination of the structures represented by the formula (LA-1) and the structures represented by the formula (LA-2) is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10.

The number of the structures represented by the formula (LA-2) in the group represented by the combination of the structures represented by the formula (LA-1) and the structures represented by the formula (LA-2) is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10.

In the formula (LA-1), R ^L1 represents an a-valent linking group, preferably a hydrocarbon group or a group represented by a combination of a hydrocarbon group and at least 1 group selected from the group consisting of-O-, -C (=o) -, -S (=o) ₂ -, and-NR ^N -, more preferably a hydrocarbon group. The preferred manner of R ^N is as described above.

The number of carbon atoms of the aliphatic hydrocarbon group is preferably 2 to 30, more preferably 3 to 20, and still more preferably 4 to 15.

In the formula (LA-1), a is preferably an integer of 2 to 10, more preferably an integer of 3 to 8, and still more preferably an integer of 3 to 6.

Specific examples of the structure represented by the formula (LA-1) include, but are not limited to, the following structures. In the following structure, the meaning of 1 is the same as that of 1 in formula (LA-1).

[ Chemical formula 11]

Further, specific examples of the structure represented by the formula (LA-1) include: hydroquinone, resorcinol, catechol, naphthalene diol, bisphenol A, bisphenol F, tetramethyl bisphenol, 4- [4- [1, 1-bis (4-hydroxyphenyl) ethyl ] ] -alpha, a structure in which a hydrogen atom is removed from 2 or more phenolic hydroxyl groups in α -dimethylbenzyl phenol, 4' - (2-hydroxybenzylidene) bis (2, 3, 6-trimethylphenol), tris (4-hydroxyphenyl) methane, 1, 3-tris (5-cyclohexyl-4-hydroxy-2-methylphenyl) butane, 1, 2-tetrakis (4-hydroxyphenyl) ethane, 4',4",4 '" - (1, 4-phenylene-secondary) tetraphenol, phenol novolac resin, or the like.

In the formula (LA-2), R ^L2 is preferably a hydrocarbon group or a group represented by a combination of a hydrocarbon group and at least 1 group selected from the group consisting of-O-, -C (=o) -, -S (=o) ₂ -and-NR ^N -, more preferably a hydrocarbon group or a group represented by a combination of a hydrocarbon group and at least 1 group selected from the group consisting of-O-and-C (=o) -. The preferred manner of R ^N is as described above.

The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, or may be a group represented by a combination of these, and preferably contains an aromatic hydrocarbon group.

The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and still more preferably an aromatic hydrocarbon group having 6 carbon atoms.

As the aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable.

The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 8.

In the formula (LA-2), b represents an integer of 1 or more, preferably an integer of 1 to 4, and more preferably 1 or 2.

In the formula (LA-2), c represents an integer of 0 or more, preferably an integer of 0 to 4, and more preferably 0 or 1.

In the formula (LA-2), d represents an integer of 0 or more, preferably an integer of 0 to 4, and more preferably 0 or 1.

In the formula (LA-2), b+c+d is preferably an integer of 2 to 6, more preferably an integer of 2 to 4, further preferably 2 or 3, and particularly preferably 2.

In the formula (LA-2), the mode in which b is 1 or 2 and c+d is 0 or 1 is also one of the preferable modes of the present invention.

Specific examples of the structure represented by the formula (LA-2) include, but are not limited to, the following structures. In the following structure, x corresponds to any one of x 2, x 3 and x 4 in formula (LA-2).

[ Chemical formula 12]

-R^A2-

In the formula (1-1), R ^A2 each independently represents a group containing a urethane bond and a poly (alkyleneoxy) group.

In the present specification, the urethane bond means a bond represented by-OC (=O) NR ^N -. The preferred manner of R ^N is as described above.

In the present specification, the orientation is not particularly limited, when only a urethane bond is described.

The orientation of the urethane bond in R ^A2 is not particularly limited, and it is preferable that the nitrogen atom side in the urethane bond is bonded to L ^A2 in the formula (1-1).

In the present invention, the poly (alkyleneoxy) group means a divalent group in 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 oxide group contains a plurality of alkylene oxide groups having different alkylene groups, the alkylene oxide groups in the polyalkylene oxide group may be arranged randomly, 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 weight average molecular weight of the polyalkylene oxide is preferably 1000 to 8000, more preferably 2000 to 7000, and still more preferably 3000 to 6000.

From the viewpoint of dispersion stability of the specific polyimide, the polyalkylene oxide group is preferably a polyethylene oxide group, a polypropylene oxide group, a polytrimethylene oxide group, a polytetramethylene oxide 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. The ethyleneoxy groups and propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in an alternating pattern.

The number of urethane bonds in R ^A2 is not particularly limited, but is preferably 1 to 4, more preferably 1 or 2, and further preferably 1.

The number of poly (alkyleneoxy) groups in R ^A2 is not particularly limited, but is preferably 1 to 4, more preferably 1 or 2, and further preferably 1.

It is also preferable that the bonding site to L ^A2 in R ^A2 is a nitrogen atom in a urethane bond.

Further, R ^A2 is also preferably a structure in which L ^A2 is bonded to a poly (alkyleneoxy) group via a urethane bond.

Among them, R ^A2 is preferably a group represented by the following formula (R-1).

[ Chemical formula 13]

In the formula (R-1), R ^A4 is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, still more preferably an alkylene group having 2 to 5 carbon atoms, still more preferably an alkylene group having 2 to 4 carbon atoms, still more preferably an alkylene group having 2 or 3 carbon atoms, particularly preferably an ethylene or propylene group, and most preferably an ethylene group.

In the formula (R-1), x represents an integer of 2 or more, preferably an integer of 10 to 200, and more preferably an integer of 20 to 120.

In the formula (R-1), R ^A5 is preferably an alkyl group, more preferably an alkyl group having 1 to 20 carbon atoms, and still more preferably an alkyl group having 1 to 12 carbon atoms.

The alkyl group may be any of a linear alkyl group, a branched alkyl group, a cyclic alkyl group, or an alkyl group represented by a combination of these, and a linear alkyl group or a branched alkyl group is preferable.

-n-

In the formula (1-1), n represents an integer of 1 or more, preferably 1 to 5, more preferably 1 to 3.

-m-

In the formula (1-1), m represents an integer of 1 or more, preferably 2 to 10, more preferably 2 to 5.

Content-

In the first polyimide, the content of the repeating unit represented by the formula (1-1) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, based on the mass of the resin.

The first polyimide may contain only 1 kind of repeating unit represented by the formula (1-1), or may contain 2 or more kinds. When the first polyimide contains 2 or more repeating units represented by the formula (1-1), the total content of these is within the above-mentioned range.

Other repeat units

The first polyimide may also have other repeating units.

Examples of the other repeating unit include repeating units represented by the formula (1-2).

[ Chemical formula 14]

In the formula (1-2), R ^A1 represents a tetravalent organic group, R ^A3 is an m+1-valent linking group and represents a linking group having no at least one of a urethane bond and a poly (alkyleneoxy) group, m represents an integer of 1 or more, and represents a bonding site to other structures.

In the formula (1-2), the preferable mode of R ^A1 is the same as that of R ^A1 in the formula (1-1).

In the formula (1-2), R ^A3 is preferably a hydrocarbon group or a group represented by a combination of a hydrocarbon group and at least 1 group selected from the group consisting of-O-, -C (=o) -, -S (=o) ₂ -and-NR ^N -, more preferably a hydrocarbon group or a group represented by a combination of a hydrocarbon group and at least 1 group selected from the group consisting of-O-, -C (=o) -and-NR ^N -. The preferred manner of R ^N is as described above.

Furthermore, R ^A3 is preferably free of imide groups.

R ^A3 is also preferably a group represented by a combination of a structure represented by the following formula (LA-3) and a structure represented by the following formula (LA-4).

[ Chemical formula 15]

In formula (LA-3), R ^L1 represents a valence linking group, a represents an integer of 2 or more, and 1 represents a bonding site to 2 in formula (LA-4).

In formula (LA-4), R ^L2 represents a b+d valence linking group, b represents an integer of 1 or more, x 2 represents a bonding site to x 1 in formula (LA-3), d represents an integer of 0 or more, and x 4 represents a bonding site to a nitrogen atom bonded to R ^A3 in formula (1-2) or a bonding site of another structure having the same meaning as in formula (1-2).

The sum of d in all the structures represented by the formula (LA-4) contained in the group represented by the combination of the structure represented by the formula (LA-3) and the structure represented by the formula (LA-4) is m+1 in the above formula (1-2).

The group represented by the combination of the structure represented by the formula (LA-3) and the structure represented by the formula (LA-4) preferably includes a plurality of the structures represented by the formula (LA-3) and the structure represented by the formula (LA-4).

Further, the group represented by the combination of the structure represented by the formula (LA-3) and the structure represented by the formula (LA-4) preferably contains the same number of structures represented by the formula (LA-3) and the structure represented by the formula (LA-4).

The number of the structures represented by the formula (LA-3) in the group represented by the combination of the structures represented by the formula (LA-3) and the structures represented by the formula (LA-4) is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10.

The preferable modes of R ^L1, a and 1 in the formula (LA-3) are the same as the preferable modes of R ^L1, a and 1 in the formula (LA-1).

The preferred modes of R ^L2, b, d, 2 and 4 in formula (LA-4) are the same as the preferred modes of R ^L2, b, d, 2 and 4 when c in formula (LA-2) is 0.

In the formula (1-2), preferred modes of m are the same as those of m in the above formula (1-1).

The mode where m is 1 is also one of preferred modes of the present invention.

In the first polyimide, the content of the repeating unit represented by the formula (1-2) is preferably 0 to 95% by mass, more preferably 10 to 90% by mass, based on the mass of the resin.

Further, in the first polyimide, the total content of the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (1-2) is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, based on the mass of the resin.

[ Second specific polyimide ]

The second specific polyimide is a polyimide obtained by imidizing a reactant of a tetracarboxylic dianhydride and a polyfunctional isocyanate compound containing a poly (alkyleneoxy) group.

The details of the method for producing the above-mentioned reactant and the method for imidizing will be described later.

Tetracarboxylic dianhydride (S)

The tetracarboxylic dianhydride is preferably a compound represented by the formula (O). The tetracarboxylic dianhydride may be used in an amount of 1 or 2 or more.

Polyfunctional isocyanate compounds

The polyfunctional isocyanate compound is preferably a compound represented by the following formula (IC-1).

[ Chemical formula 16]

In the formula (IC-1), preferable modes of L ^A2、R^A2, n and m are the same as those of L ^A2、R^A2, n and m in the formula (1-1).

The polyfunctional isocyanate compound may be a compound represented by the following formula (IC-2).

[ Chemical formula 17]

In the formula (IC-2), L ^B1 represents an m-valent linking group, L ^B2 represents a single bond or a divalent linking group, L ^B3 represents a divalent linking group, R ^B1 represents an alkylene group, n represents an integer of 0 or more, m represents an integer of 2 or more, and at least 1 of m n is an integer of 2 or more.

In the formula (IC-2), L ^B1 is preferably a hydrocarbon group or a group represented by a combination of a hydrocarbon group and at least 1 group selected from the group consisting of-O-, -C (=o) -, -S (=o) ₂ -, and-NR ^N -, more preferably a hydrocarbon group. The preferred manner of R ^N is as described above.

In the formula (IC-2), L ^B2 is preferably a single bond, a hydrocarbon group, or a group represented by a combination of a hydrocarbon group and at least 1 group selected from the group consisting of-O-, -C (=o) -, -S (=o) ₂ -, and-NR ^N -, more preferably a single bond or a group represented by a combination of a hydrocarbon group and at least 1 group selected from the group consisting of-O-, -C (=o), and-NR ^N -. The preferred manner of R ^N is as described above.

The manner in which L ^B2 is a single bond is also one of the preferred embodiments of the present invention.

The number of carbon atoms of the hydrocarbon group is preferably 1 to 30, more preferably 2 to 20, and still more preferably 2 to 15.

Further, as L ^B2, a group represented by the following formula (LB-2) is also preferable.

[ Chemical formula 18]

In formula (LB-2), L ^B4 represents a divalent linking group, represents a bonding site to L ^B1 in formula (IC-2), and# represents a bonding site to R ^B1 in formula (IC-2).

In the formula (LB-1), the amino acid sequence, L ^B4 is preferably a hydrocarbon group or a mixture of a hydrocarbon group and a member selected from the group consisting of-O-, -C (=O) -, -S-, -S (=o) ₂ -and-NR ^N -a group represented by a combination of at least 1 groups, more preferably a hydrocarbon group. The preferred manner of R ^N is as described above.

In the formula (IC-2), L ^B3 is preferably a hydrocarbon group or a group represented by a combination of a hydrocarbon group and at least 1 group selected from the group consisting of-O-, -C (=o) -, -S (=o) ₂ -and-NR ^N -, more preferably a hydrocarbon group or a group represented by a combination of a hydrocarbon group and at least 1 group selected from the group consisting of-O-, -C (=o) and-NR ^N -. The preferred manner of R ^N is as described above.

In the formula (IC-2), when n is not 0, n is preferably 1 to 120, more preferably 4 to 100.

In the formula (IC-2), m is preferably 2 to 10, more preferably 2 to 5.

The polyfunctional isocyanate compound may be used in an amount of 1 or 2 or more.

The polyfunctional isocyanate compound is also preferably an adduct of a compound represented by the following formula (C-1) and a second polyfunctional isocyanate compound.

[ Chemical formula 19]

The second specific polyimide may be a reaction product obtained by reacting at least one compound selected from the group consisting of at least one of second polyfunctional isocyanates described later, at least one of 2 functional isocyanates described later, and other polyfunctional isocyanate compounds, in addition to the tetracarboxylic dianhydride and the polyfunctional isocyanate compound.

The second polyfunctional isocyanate compound is preferably a reactant of a polyfunctional alcohol and a 2-functional isocyanate compound.

The details of the method for producing the above-mentioned reactant will be described later.

The polyfunctional alcohol may be an aromatic polyfunctional alcohol, and preferably an aliphatic polyfunctional alcohol.

The number of carbon atoms of the polyfunctional alcohol is preferably 2 to 20, more preferably 3 to 15, and still more preferably 4 to 12.

The number of hydroxyl groups in the polyfunctional alcohol is preferably 2 to 10, more preferably 3 to 10, and still more preferably 3 to 6.

As the polyfunctional alcohol, a compound represented by the formula (P0-1) is preferable.

[ Chemical formula 20]

In the formula (P0-1), R ^L1 represents a valence linking group, and a represents an integer of 2 or more.

In the formula (P0-1), R ^L1 and a are preferably the same as those of R ^L1 and a in the formula (LA-1).

Specific examples of the polyfunctional alcohol include propylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, 1, 5-pentylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, 1, 3-propylene glycol, 1, 3-butylene glycol, 2-methyl-2, 4-pentylene glycol, 1, 2-hexylene glycol, 1, 6-hexylene glycol, 1,2, 6-hexanetriol, 1,2, 4-butanetriol, 1,2, 3-butanetriol, 3-methyl-1, 3, 5-pentanetriol (Petriol), trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, neopentyltetraol, dipentyltetraol, tricyclopentylter, glycerol, diglycerol, trimethylmelamine, hydroquinone, resorcinol, catechol, naphthalene glycol, bisphenol A, bisphenol F, tetramethylbisphenol, 4- [4- [1, 1-bis (4-hydroxyphenyl) ethyl ] ] - α, alpha-dimethylbenzyl phenol, 4' - (2-hydroxybenzylidene) bis (2, 3, 6-trimethylphenol), tris (4-hydroxyphenyl) methane, 1, 3-tris (5-cyclohexyl-4-hydroxy-2-methylphenyl) butane, 1, 2-tetrakis (4-hydroxyphenyl) ethane, 4',4",4 '" - (1, 4-phenylene-secondary) tetraphenol, phenol novolac resins, etc., but are not limited thereto.

Further, the polyfunctional alcohol may be used in an amount of 1 or 2 or more.

As the above 2-functional isocyanate compound, a compound in which 2 hydrogen atoms of hydrocarbon are substituted with isocyanate groups is preferable.

The hydrocarbon may be any one of an aromatic hydrocarbon, an aliphatic hydrocarbon, and a combination of these, and preferably contains an aromatic hydrocarbon.

The aromatic hydrocarbon is preferably an aromatic hydrocarbon having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon having 6 to 10 carbon atoms, and still more preferably an aromatic hydrocarbon having 6 carbon atoms.

As the aliphatic hydrocarbon, a saturated aliphatic hydrocarbon is preferable.

The number of carbon atoms of the aliphatic hydrocarbon is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 8.

As the 2-functional isocyanate compound, a compound represented by the formula (DI-1) is preferable.

[ Chemical formula 21]

OCN-R^L2-NC○ (DI-1)

In the formula (D1-1), R ^L2 represents a divalent linking group.

In the formula (DI-1), the preferable mode of R ^L2 is the same as the preferable mode when R ^L2 in the above formula (LA-2) is a divalent linking group (i.e., when b is 2 and c and d are 0, or b is 1 and one of c and d is 1 and the other is 0).

Specific examples of the 2-functional isocyanate compound include aliphatic diisocyanates such as methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, 2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, octamethylene diisocyanate, 2, 4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1, 4-butanediol dipropyl ether diisocyanate, thiodihexyl diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, 1, 3-diisocyanate cyclohexane, 2, 4-diisocyanate-1-methylcyclohexane, 1, 3-diisocyanate-2-methylcyclohexane, methylene dicyclohexyl diisocyanate, dicyclohexylmethane 4,4' -diisocyanate;

Aromatic diisocyanates such as m-phenylene diisocyanate, p-phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, dimethylbiphenyl diisocyanate, methylene diphenyl diisocyanate, 1, 4-naphthalene diisocyanate, 1, 5-naphthalene diisocyanate, 2, 6-naphthalene diisocyanate, 2, 7-naphthalene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, tetramethyl xylylene diisocyanate, and the like, but are not limited thereto.

Furthermore, the 2-functional isocyanate may be used in an amount of 1 or 2 or more.

In the formula (C-1), X represents a linking group, preferably a hydrocarbon group or a group represented by a combination of a hydrocarbon group and at least 1 group selected from the group consisting of-O-, -C (=O) -, -S (=O) ₂ -and-NR ^N -, further preferred are groups represented by a combination of hydrocarbon groups and-OC (=o) NR ^N -. R ^N is as described above.

In the formula (C-1), the mode in which m is 0 is also one of the preferable modes of the present invention.

In the formula (C-1), A represents an arylene group or an alkylene group, preferably a divalent aromatic hydrocarbon group or an alkylene group, more preferably an alkylene group.

As the aromatic hydrocarbon group, phenylene is preferable.

The alkylene group is preferably an alkylene group having 2 to 5 carbon atoms, and more preferably an alkylene group having 2 to 3 carbon atoms.

In the formula (C-1), Z represents an amino group or a hydroxyl group, preferably a hydroxyl group.

In the formula (C-1), L is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, still more preferably an alkylene group having 2 to 5 carbon atoms, still more preferably an alkylene group having 2 to 4 carbon atoms, still more preferably an alkylene group having 2 or 3 carbon atoms, particularly preferably an ethylene or propylene group, and most preferably an ethylene group.

In the formula (C-1), n is an average addition mole number of the poly (alkyleneoxy) group, preferably a number of 10 to 200, more preferably a number of 20 to 180.

In the formula (C-1), R represents an organic group having no active hydrogen.

The active hydrogen in the present specification means a hydrogen atom directly bonded to an atom having reactivity with an isocyanate group, and examples thereof include hydrogen atoms in-OH, -SH, -NH-, -NH ₂, -COOH, and the like.

The above R is preferably a hydrocarbon group, more preferably an alkyl group, further preferably an alkyl group having 1 to 30 carbon atoms, and particularly preferably an alkyl group having 1 to 20 carbon atoms.

[ Specific polyimide ]

The specific polyimide is also preferably a polyimide obtained by imidizing the polyimide precursor of the present invention.

Details of the polyimide precursor and the imidization method will be described later.

The specific polyimide is also preferably in the form of particles.

When the specific polyimide is in the form of particles, the particle shape is not particularly limited, and examples thereof include isotropic shapes (e.g., spherical, polyhedral, etc.), anisotropic shapes (e.g., needle-like, rod-like, plate-like, etc.), irregular shapes, etc.

In addition, when the specific polyimide is in the form of particles, the particles may be hollow particles or solid particles, or may be porous.

When the specific polyimide is in the form of particles, the volume average particle diameter of the specific polyimide is preferably 10 to 500nm, more preferably 10 to 450hm, and even more preferably 10 to 400nm.

The volume average particle diameter was measured by the method described in examples.

When the specific polyimide is in the form of particles, the coefficient of variation of the particle diameter of the specific polyimide (standard deviation of particle diameter/volume average particle diameter) is preferably 30% or less, more preferably 20% or less. The lower limit is not particularly limited, and may be 0% or more.

The content of the poly (alkyleneoxy) group is preferably 10 to 80 mass%, more preferably 15 to 70 mass%, and still more preferably 20 to 60 mass% with respect to the total mass of the specific polyimide.

The imidization ratio of the specific polyimide is preferably 60 to 100%, more preferably 80 to 100%, and even more preferably 90 to 100%. The imidization ratio can be measured by infrared absorption spectroscopy.

[ Method for producing specific polyimide ]

The method for producing the specific polyimide is not particularly limited, and preferably includes a first step of reacting a tetracarboxylic dianhydride with a polyfunctional isocyanate compound to obtain a polyimide precursor, and a second step of imidizing the polyimide precursor.

[ First step ]

The method for producing a specific polyimide comprises a first step of reacting a tetracarboxylic dianhydride with a polyfunctional isocyanate compound to obtain a polyimide precursor.

The preferred modes of the tetracarboxylic dianhydride and the polyfunctional isocyanate compound are the same as those of the tetracarboxylic dianhydride and the polyfunctional isocyanate compound in the second specific polyimide.

In the first step, at least one compound selected from the group consisting of at least one of the second polyfunctional isocyanate, at least one of the 2 functional isocyanate, and other polyfunctional isocyanate compounds may be further reacted in addition to the tetracarboxylic dianhydride and the polyfunctional isocyanate compound.

The reaction can be carried out, for example, in an organic solvent.

The organic solvent is not particularly limited as long as it is a solvent that dissolves the tetracarboxylic dianhydride and the polyfunctional isocyanate compound (preferably, a solvent that further has low solubility of the obtained polyimide precursor and can precipitate the polyimide precursor), and examples thereof include 2-propanone, 3-pentanone, cyclic propanone, tetrahydropyrene, epichlorohydrin, acetone, methyl Ethyl Ketone (MEK), acetophenone, tetrahydrofuran (THF), ethyl acetate, butyl acetate, acetonitrile, acetanilide, toluene, xylene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and the like, and preferably, 1 of these is contained. These organic solvents may be used alone or in combination of at least 2 kinds.

In the case of carrying out the reaction in an organic solvent, for example, a solution obtained by dissolving tetracarboxylic dianhydride in an organic solvent and a solution obtained by dissolving a polyfunctional isocyanate compound in an organic solvent may be mixed, or tetracarboxylic dianhydride and a polyfunctional isocyanate compound may be added to an organic solvent.

In the case of carrying out the reaction in an organic solvent, it is also preferable to carry out the reaction under stirring. The stirring method is not particularly limited, and examples thereof include known ultrasonic stirring, stirring with a stirrer, and the like. Among them, in the case of obtaining polyimide particles, ultrasonic agitation is preferable from the viewpoint of monodispersity of particle diameters.

The reaction temperature is not particularly limited, but is preferably 0 to 130 ℃, more preferably 15 to 80 ℃, and still more preferably 20 to 40 ℃.

The reaction time is not particularly limited, but is preferably 30 seconds to 4 hours, more preferably 1 minute to 3 hours, and still more preferably 5 minutes to 2 hours.

However, the reaction temperature and the reaction time are not particularly limited, and may be appropriately adjusted within a range in which a polyimide precursor can be obtained.

The amounts of the tetracarboxylic dianhydride and the polyfunctional isocyanate compound used are not particularly limited, and can be determined in consideration of, for example, the molar ratio of the acid anhydride group to the isocyanate group. For example, the acid anhydride group and the isocyanate group can be used in a molar ratio of 0.5:1 to 1:0.5 (preferably 0.8:1 to 1:0.8, more preferably 0.9:1 to 1:0.9).

The concentration of the tetracarboxylic dianhydride in the reaction solution is not particularly limited, but is preferably, for example, 0.001 to 0.5mol/L, and more preferably 0.002 to 0.2mol/L.

The concentration of the polyfunctional isocyanate compound in the reaction liquid is not particularly limited, but is, for example, preferably 0.001 to 0.5mol/L, and more preferably 0.002 to 0.2mol/L.

In the first step, the tetracarboxylic dianhydride is preferably reacted with the polyfunctional isocyanate compound in the presence of the amine catalyst.

As the amine catalyst, 1, 4-diazabicyclo [2.2.2] octane, triethylamine, benzyl dimethylamine, 2-dimethylaminomethylphenol, 2,4, 6-tris-dimethylaminomethyl-3-isocyanate phenol and the like can be used. Among them, 1, 4-diazabicyclo [2.2.2] octane, triethylamine, and the like can be mentioned.

The polyimide precursor obtained in the first step may be recovered by solid-liquid separation according to a known method such as filtration or centrifugal separation. For example, if the conditions for obtaining the polyimide precursor in the form of a precipitate or particles are set by the selection of the type of tetracarboxylic dianhydride and the type of polyfunctional isocyanate compound, the selection of the type of organic solvent, and the like, the polyimide precursor can be recovered by the above-mentioned solid-liquid separation.

[ Procedure for Synthesis of multifunctional isocyanate ]

The method for producing a specific polyimide of the present invention may further include a polyfunctional isocyanate synthesis step of synthesizing a polyfunctional isocyanate before the first step.

The step of synthesizing a polyfunctional isocyanate is preferably, for example, a step of reacting the compound represented by the formula (C-1) with the second polyfunctional isocyanate compound.

The reaction can be carried out, for example, in an organic solvent.

The organic solvent is not particularly limited as long as it is a solvent that dissolves the compound represented by the formula (C-1) and the second polyfunctional isocyanate compound, and examples thereof include 2-propanone, 3-pentanone, cyclohexanone, acetophenone, tetrahydropyrene, epichlorohydrin, acetone, methyl Ethyl Ketone (MEK), tetrahydrofuran (THF), ethyl acetate, butyl acetate, acetonitrile, acetanilide, toluene, xylene, and the like.

The reaction temperature is not particularly limited, but is preferably 0 to 100 ℃, more preferably 5 to 90 ℃, and still more preferably 10 to 80 ℃.

The reaction time is not particularly limited, but is preferably 1 to 10 hours, more preferably 1 to 8 hours, and still more preferably 1 to 5 hours.

The first step may be performed by adding tetracarboxylic dianhydride to the reaction solution after the reaction in the polyfunctional isocyanate synthesis step.

[ Second polyfunctional isocyanate Synthesis procedure ]

Furthermore, the method for producing a specific polyimide of the present invention may further include a second polyfunctional isocyanate synthesis step of synthesizing a second polyfunctional isocyanate before the polyfunctional isocyanate synthesis step.

The second polyfunctional isocyanate synthesis step is preferably, for example, a step of reacting the polyfunctional alcohol with the 2-functional isocyanate compound.

The reaction can be carried out, for example, in an organic solvent.

The organic solvent is not particularly limited as long as it is a solvent for dissolving the polyfunctional alcohol and the 2-functional isocyanate compound, and examples thereof include 2-propanone, 3-pentanone, cyclohexanone, acetophenone, tetrahydropyrene, epichlorohydrin, acetone, methyl Ethyl Ketone (MEK), tetrahydrofuran (THF), ethyl acetate, butyl acetate, acetonitrile, acetanilide, toluene, xylene, and the like.

The step of synthesizing the polyfunctional isocyanate may be performed by adding the compound represented by the formula (C-1) to the reaction solution after the reaction in the step of synthesizing the second polyfunctional isocyanate.

[ Second step ]

The method for producing a specific polyimide of the present invention includes a second step of imidizing the polyimide precursor obtained in the first step.

In the second step, the polyimide precursor obtained in the first step is preferably heated in an organic solvent.

The organic solvent is preferably a solvent having low solubility of the polyimide precursor, and examples thereof include toluene, xylene, ethylbenzene, octane, cyclohexane, diphenyl ether, nonane, pyridine, dodecane, butyl acetate, acetophenone, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone. These organic solvents may be used alone or in combination of at least 2 kinds.

In the first step, when the polyimide precursor is obtained as a solution or dispersion in an organic solvent, the organic solvent may be used as it is.

In the second step, the polyimide precursor may be imidized by known chemical imidization or the like.

The change in the imidization ratio (i.e., the difference between the imidization ratio in the polyimide and the imidization ratio in the polyimide precursor) before and after the second step is preferably 60 to 100%, more preferably 80 to 100%, and even more preferably 90 to 100%.

The imidization ratio can be measured by infrared absorption spectroscopy.

In the second step, the imidization is preferably performed while removing carbon dioxide generated during the heating to the outside of the reaction system.

The method for removing carbon dioxide is not particularly limited, and a known removal method can be used, and examples thereof include removal by reduced pressure.

The heating temperature in the heating is preferably 130 to 250 ℃.

The heating temperature is preferably 150℃or higher, more preferably 180℃or higher.

The heating temperature is preferably 240℃or lower, more preferably 230℃or lower.

[ Other procedures ]

The method for producing a specific polyimide according to the present invention may further include other steps.

Examples of the other steps include a step of removing impurities by filtration through a filter or the like, and a step of capping the ends of a polyimide precursor or polyimide.

A step of capping the ends of the polyimide precursor or polyimide

When the terminal of the polyimide precursor or polyimide is blocked, a known blocking agent is allowed to react with the polyimide precursor or polyimide. The details of the reaction method such as the reaction conditions can be determined by referring to known methods.

When the carboxylic anhydride, acid anhydride derivative or isocyanate group remaining at the terminal of the polyimide precursor or polyimide is blocked, examples of the blocking agent include a monoalcohol, phenol, thiol, thiophenol, monoamine, and the like, and from the viewpoints of reactivity and stability of the film, the use of a monoalcohol, phenol, or monoamine is more preferable. Preferred examples of the monoalcohol include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol and the like; secondary alcohols such as isopropyl alcohol, 2-butanol, cyclohexanol, cyclopentanol, and 1-methoxy-2-propanol; tertiary alcohols such as t-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, or may be introduced into a plurality of different terminal groups by reacting a plurality of capping agents.

In addition, when the isocyanate group at the end of the resin is blocked, a compound having a functional group reactive with the isocyanate group can be used for blocking. Examples of such a compound include a compound having an acid anhydride group and a halogenated acyl group, and carboxylic acid anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic acid anhydride, and the like are preferable, and carboxylic acid anhydride and carboxylic acid chloride are more preferable. 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, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearoyl chloride, benzoyl chloride, and the like.

[ Specific example ]

Specific examples of the specific polyimide of the present invention include P-1 to P-9 in examples, but the present invention is not limited thereto.

< Polyimide precursor >

The polyimide precursor of the present invention is not particularly limited, and preferably contains a repeating unit represented by the following formula (2-1).

[ Chemical formula 22]

/>

In the formula (2-1), preferable modes of R ^A1 and m are the same as those of R ^A1 and m in the formula (1-1).

In the formula (2-1), L ^A3 is preferably a group represented by the following formula (L-1).

[ Chemical formula 23]

In the formula (L-1), L ^A2 represents an n+m+1-valent linking group, R ^A2 each independently represents a group containing a urethane bond and a poly (alkyleneoxy) group, n represents an integer of 1 or more, m represents an integer of 1 or more, and# represents a bonding site to a nitrogen atom in the formula (2-1), and x represents a bonding site to another structure.

In the formula (L-1), preferable modes of L ^A2、R^A2, n, and m are the same as preferable modes of L ^A2、R^A2, n, and m in the formula (1-1).

Further, L ^A3 may be a group represented by the following formula (L-2).

[ Chemical formula 24]

In the formula (L-2), L ^B1 represents an m-valent linking group, L ^B2 represents a single bond or a divalent linking group, L ^B3 represents a divalent linking group, R ^B1 represents an alkylene group, n represents an integer of 0 or more, m represents an integer of 2 or more, and at least 1 of m n represents an integer of 2 or more, and x represents a bonding site with other structure.

In the formula (L-2), preferable modes of L ^B1、L^B2、L^B3、R^B1, n, and m are the same as preferable modes of L ^B1、L^B2、L^B3、R^B1, n, and m in the formula (IC-2), respectively.

In the formula (L-2), one of m+1 is a bonding site with a nitrogen atom in the formula (2-1), and m in the formula (L-2) is the same as m in the formula (2-1).

In the polyimide precursor of the present invention, the content of the repeating unit represented by the formula (2-1) is preferably 30 to 100 mass%, more preferably 50 to 100 mass%, based on the mass of the resin.

The polyimide precursor of the present invention may contain only 1 repeating unit represented by the formula (2-1), or may contain 2 or more repeating units represented by the formula (2-1). When the polyimide precursor of the present invention contains 2 or more kinds of repeating units represented by the formula (2-1), the total content of these is preferably within the above-mentioned range.

Furthermore, the polyimide precursor of the present invention may further contain other repeating units.

The other repeating unit may be represented by the formula (2-2).

[ Chemical formula 25]

In the formula (2-2), R ^A1 represents a tetravalent organic group, L ^A4 represents an m+1 valent linking group containing no poly (alkyleneoxy) group, m represents an integer of 1 or more, and represents a bonding site to other structures.

In the formula (2-2), the preferable mode of R ^A1 is the same as that of R ^A1 in the formula (2-1).

In the formula (2-2), the preferable mode of L ^A4 is the same as that of R ^A3 in the formula (1-2).

In the formula (2-2), preferred modes of m are the same as those of m in the above formula (2-1).

The mode where m is 1 is also one of preferred modes of the present invention.

In the polyimide precursor of the present invention, the content of the repeating unit represented by the formula (2-2) is preferably 0 to 95 mass%, more preferably 10 to 90 mass%, relative to the mass of the resin.

Further, in the polyimide precursor of the present invention, the total content of the repeating unit represented by the formula (2-1) and the repeating unit represented by the formula (2-2) is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, based on the mass of the resin.

The polyimide precursor of the present invention is also preferably in the form of particles.

When the polyimide precursor of the present invention is in the form of particles, the particle shape thereof is not particularly limited, and examples thereof include isotropic shapes (e.g., spherical, polyhedral, etc.), anisotropic shapes (e.g., needle-like, rod-like, plate-like, etc.), irregular shapes, etc.

In the case where the polyimide precursor of the present invention is in the form of particles, the particles may be hollow particles or solid particles, or may be porous.

The volume average particle diameter of the polyimide precursor of the present invention is preferably 30 to 500nm, more preferably 50 to 450nm, and even more preferably 100 to 400nm.

When the polyimide precursor of the present invention is in the form of particles, the coefficient of variation of the particle diameter (standard deviation of particle diameter/volume average particle diameter) of the specific polyimide is preferably 1 to 30%, more preferably 1 to 20%.

The content of the poly (alkyleneoxy) group is preferably 10 to 80 mass%, more preferably 15 to 70 mass%, and even more preferably 20 to 60 mass% with respect to the total mass of the polyimide precursor of the present invention.

[ Method for producing polyimide precursor ]

The method for producing a polyimide precursor according to the present invention is not particularly limited, and is preferably produced by the first step in the above-mentioned method for producing a specific polyimide.

[ Specific example ]

Specific examples of the polyimide precursor of the present invention include polyimide precursors synthesized in examples P-1 to P-9, but the present invention is not limited thereto.

(Composition)

The composition of the present invention contains the polyimide of the present invention.

Examples of the composition of the present invention include: a composition obtained by replacing all or part of the polyimide in the composition described in International publication No. 2021/107024 with the polyimide of the present invention, and the like. Further, the composition described in International publication No. 2021/107024 may be a composition which further contains the polyimide of the present invention and in which the polyimide or polyimide precursor is changed to a conventionally known polyimide or polyimide precursor.

The composition of the present invention preferably contains the polyimide of the present invention and a compound having a fluorine atom.

Hereinafter, the polyimide and fluorine atom-containing compound composition of the present invention will be described in detail.

< Polyimide >

The polyimide of the present invention is described in detail and preferred embodiments thereof.

The content of the polyimide of the present invention in the composition of the present invention is preferably 1 mass% or more relative to the total solid content of the composition of the present invention. The content is preferably 5% by mass or more, more preferably 10% by mass or more. The content is preferably 60% by mass or less, more preferably 40% by mass or less.

The composition of the present invention may contain 1 kind of polyimide of the present invention alone or 2 or more kinds. When the composition of the present invention contains 2 or more kinds of the polyimide of the present invention, the total amount of these is preferably within the above range.

< Other polyimide >

The composition of the present invention may further contain a polyimide (hereinafter, also referred to as "other polyimide") different from the polyimide of the present invention described above.

Examples of the other polyimide include a polyimide having no poly (alkyleneoxy) group, and examples of the polyimide include a polyimide having no repeating unit represented by the formula (1-1) and having a repeating unit represented by the formula (1-2).

When the composition of the present invention contains another polyimide, the content of the other polyimide is preferably 0.1 mass% or more relative to the total solid content of the composition of the present invention. The content is preferably 0.5 mass% or more, more preferably 1 mass% or more. The content is preferably 40% by mass or less, and more preferably 20% by mass or less.

The composition of the present invention may contain 1 kind of other polyimide alone or 2 or more kinds. When the composition of the present invention contains 2 or more other polyimides, the total amount of these is preferably within the above range.

< Compound having fluorine atom >

The composition of the present invention preferably contains a compound having a fluorine atom.

The fluorine atom is not particularly limited, and is preferably contained as a substituent for a hydrogen atom in the hydrocarbon group.

The content of fluorine atoms in the compound having fluorine atoms is not particularly limited, but is preferably 5 to 80atm%, more preferably 10 to 75atm%, and still more preferably 15 to 70atm%. atm% refers to the ratio of the atomic number of a particular element to the atomic number of all elements contained. atm% was measured by ICP mass spectrometry (Inductively Coupled P1: 1asma Mass Spectrometry: inductively coupled plasma mass spectrometry).

The compound having a fluorine atom preferably contains at least 1 group selected from the group consisting of a nucleophilic functional group, an electrophilic functional group, and a group having an ethylenically unsaturated bond.

Among them, the compound having a fluorine atom preferably contains at least 1 group selected from the group consisting of a nucleophilic functional group and a group having an ethylenically unsaturated bond, more preferably contains a group having an ethylenically unsaturated bond, from the viewpoint of lowering the dielectric constant of the cured product.

Further, from the viewpoint of an increase in tensile elastic modulus of the obtained cured product, it is preferable that at least 1 group selected from the group consisting of nucleophilic functional groups and electrophilic functional groups is contained.

The nucleophilic functional group is a group that reacts with an atom having a low electron density to form a bond, and is preferably a group that undergoes nucleophilic substitution reaction.

The compound having a fluorine atom as the nucleophilic functional group preferably contains at least 1 group selected from the group consisting of a hydroxyl group, a mercapto group, an amino group, and a carboxyl group, and more preferably contains at least 1 group selected from the group consisting of a hydroxyl group and a carboxyl group.

The content of the nucleophilic functional group in the compound having a fluorine atom is not particularly limited, but is preferably 0.001 to 3000mmol/g, more preferably 0.01 to 2000mmol/g, and still more preferably 0.1 to 1000mmol/g.

In the case where the compound having a fluorine atom contains a nucleophilic functional group, the composition preferably further contains a crosslinking agent having a group reactive with the nucleophilic functional group.

The crosslinking agent having a group reactive with a nucleophilic functional group will be described later.

The electrophilic functional group is a group that reacts with an atom having a high electron density to form a bond, and is preferably a group that undergoes an electrophilic substitution reaction.

The compound having a fluorine atom as the electrophilic functional group preferably contains at least 1 group selected from the group consisting of an epoxy group, an oxetanyl group, a maleimide group and an oxazoline group, and more preferably contains at least 1 group selected from the group consisting of an epoxy group and a maleimide group.

The maleimide group corresponds to a group having an ethylenically unsaturated bond, which will be described later. Depending on other components contained in the composition, curing conditions of a film formed from the composition, and the like, the maleimide group may function, for example, as an electrophilic functional group or as a radical polymerizable group.

The content of the electrophilic functional group in the compound having a fluorine atom is not particularly limited, but is preferably 0.001 to 3000mmol/g, more preferably 0.01 to 2000mmol/g, and still more preferably 0.1 to 1000mmol/g.

In the case where the compound having a fluorine atom contains an electrophilic functional group, it is preferable that the composition further contains a crosslinking agent having a group reactive with the electrophilic functional group.

The crosslinking agent having a group reactive with an electrophilic functional group will be described later.

The radical polymerizable group is preferably a group having an ethylenically unsaturated bond, and examples thereof include a vinyl group, an allyl group, an isoallyl group, a 2-methallyl group, a maleimide group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group or the like), (meth) acrylamide group, a (meth) acryloyloxy group, and the like, preferably a group having an aromatic ring directly bonded to a vinyl group, (meth) acrylamide group, or (meth) acryloyloxy group, and more preferably (meth) acryloyloxy group.

The content of the group having an ethylenically unsaturated bond in the compound having a fluorine atom is not particularly limited, but is preferably 0.001 to 3000mmol/g, more preferably 0.01 to 2000mmol/g, and still more preferably 0.1 to 1000mmol/g.

In the case where the compound having a fluorine atom contains a group having an ethylenically unsaturated bond, the composition preferably further contains a crosslinking agent having a group reactive with the group having an ethylenically unsaturated bond, and more preferably contains a crosslinking agent having a group reactive with the group having an ethylenically unsaturated bond and a radical polymerization initiator.

The crosslinking agent having a group reactive with a group having an ethylenically unsaturated bond and the radical polymerization initiator will be described later.

The compound having a fluorine atom is not particularly limited, but is preferably a resin having a fluorine atom, more preferably a resin having a weight average molecular weight of 20,000 or more, still more preferably a resin having a weight average molecular weight of 25,000 or more, and particularly preferably a resin having a weight average molecular weight of 30,000 or more.

The upper limit of the weight average molecular weight is not particularly limited, but is preferably 1,000,000 or less, more preferably 500,000 or less, and further preferably 250,000 or less.

In the case where the compound having a fluorine atom is a resin, examples of the resin include: resins obtained by introducing at least 1 group (hereinafter, also referred to as "crosslinking site") selected from the group consisting of nucleophilic functional groups, electrophilic functional groups and groups having ethylenic unsaturated bonds into resins such as polyesters having fluorine atoms, polytetrafluoroethylene, tetrafluoroethylene-perfluorovinyl ether copolymers, tetrafluoroethylene-ethylene copolymers, polyvinylidene fluoride, polyvinyl fluoride, chlorotrifluoroethylene copolymers and chlorotrifluoroethylene. The crosslinking sites may be introduced, for example, by using a monomer having these crosslinking sites as a copolymerization component, or these crosslinking sites may be introduced into the terminal.

The compound having a fluorine atom is preferably a polyester having a fluorine atom from the viewpoint of easy introduction of a crosslinking site.

The polyester preferably contains a repeating unit represented by the following formula (PE-1).

[ Chemical formula 26]

/>

In the formula (PE-1), L ^P1 and L ^P2 each independently represent a divalent linking group, and at least one of L ^P1 and L ^P2 has a fluorine atom.

In the formula (PE-1), the amino acid sequence of the formula (PE-1), L ^P1 is preferably a hydrocarbon group or a mixture of a hydrocarbon group and a member selected from the group consisting of-O-, -C (=O) -, -S-, -S (=o) ₂ -and-NR ^N -a group represented by a combination of at least 1 groups, more preferably a hydrocarbon group. R ^N represents a hydrogen atom or a hydrocarbon group, a hydrogen atom, more preferably an alkyl group or an aryl group, further preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom.

The above-mentioned hydrocarbon group may have a substituent. For example, in the case where L ^P1 has a fluorine atom, it is preferable that a part of hydrogen atoms of the hydrocarbon group is substituted with a fluorine atom.

The following structure is given as a specific example of L ^P1, but the present invention is not limited thereto.

[ Chemical formula 27]

In the formula (PE-1), the amino acid sequence of the formula (PE-1), L ^P2 is preferably a hydrocarbon group or a mixture of a hydrocarbon group and a member selected from the group consisting of-O-, -C (=O) -, -S-, -S (=o) ₂ -and-NR ^N -a group represented by a combination of at least 1 groups, more preferably a hydrocarbon group. R ^N is as described above.

The above-mentioned hydrocarbon group may have a substituent. For example, in the case where L ^P2 has a fluorine atom, it is preferable that a part of hydrogen atoms of the hydrocarbon group is substituted with a fluorine atom.

The following structure is given as a specific example of L ^P2, but the present invention is not limited thereto.

[ Chemical formula 28]

The polyester having a fluorine atom may have 1 kind of repeating unit represented by the formula (PE-1) alone or 2 or more kinds.

Furthermore, the polyester having fluorine atoms may further have a repeating unit other than the repeating unit represented by the formula (PE-1). Examples of such a repeating unit include a repeating unit represented by the formula (PE-2).

[ Chemical formula 29]

In the formula (PE-2), L ^P3 and L ^P4 each independently represent a divalent linking group, and neither of L ^P3 nor L ^P4 has a fluorine atom.

In the formula (PE-2), the preferable mode of L ^P3 is the same as that in the case where the preferable mode of L ^P1 in the above formula (PE-1) does not have a fluorine atom.

In the formula (PE-2), the preferable mode of L ^P4 is the same as that in the case where the preferable mode of L ^P2 in the formula (PE-1) has no fluorine atom.

The terminal of the polyester having a fluorine atom is not particularly limited, and is preferably a structure represented by the following formula (PE-3) or the following formula (PE-4). The carboxyl or hydroxyl groups contained in these structures correspond to the nucleophilic functional groups described above.

[ Chemical formula 30]

In formula (PE-3), L ^P1 represents a divalent linking group, and represents a bonding site with other structures.

In formula (PE-4), L ^P2 represents a divalent linking group and represents a bonding site to other structures.

In formula (PE-3), the preferred mode of L ^P1 is the same as that of L ^P1 in formula (PE-1).

In formula (PE-3), it is preferable that the oxygen atom in formula (PE-1) or the oxygen atom in formula (PE-2) is directly bonded.

In formula (PE-4), the preferred mode of L ^P2 is the same as that of L ^P2 in formula (PE-1).

In formula (PE-4), it is preferable to bond directly to the carbonyl group in formula (PE-1) or the carbonyl group in formula (PE-2).

The content of the compound having a fluorine atom is preferably 10 mass% or more with respect to the total solid content of the composition of the present invention. The content is more preferably 20% by mass or more, and still more preferably 50% by mass or more. The content is preferably 95% by mass or less, and more preferably 90% by mass or less.

The composition of the present invention may contain 1 kind of compound having a fluorine atom alone or 2 or more kinds of compounds. When the composition of the present invention contains 2 or more compounds having fluorine atoms, the total amount of these compounds is preferably within the above range.

< Crosslinking agent >

The composition of the invention preferably further comprises a cross-linking agent.

In the case where the compound having a fluorine atom contained in the composition does not contain a group having an ethylenically unsaturated bond, the composition preferably further contains a crosslinking agent having a group reactive with the nucleophilic functional group or the electrophilic functional group contained in the compound having a fluorine atom.

[ Cross-linking agent having a group reactive with a nucleophilic functional group ]

When the compound having a fluorine atom contained in the composition contains a nucleophilic functional group, the composition preferably contains at least 1 compound selected from the group consisting of a crosslinking agent having an epoxy group, a crosslinking agent having an oxetanyl group, a crosslinking agent having a benzoxazole group, a crosslinking agent having a maleimide group, a crosslinking agent having an alkoxysilyl group and a compound having a (blocked) isocyanate group, more preferably contains at least 1 compound selected from the group consisting of a crosslinking agent having an epoxy group, a crosslinking agent having an alkoxysilyl group and a compound having a (blocked) isocyanate group, as the crosslinking agent.

Crosslinking agents having epoxy groups

As the crosslinking agent having an epoxy group (hereinafter also referred to as "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, low-temperature curing and warpage of the 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 a group having 2 or more repeating units of ethylene oxide, and the number of repeating units is preferably 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, examples thereof include 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 (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (the above trade names, DIC Corporation), RIKARESTN (registered trademark) BEO-20E, RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, E, RIKARESIN (registered trademark) DME-100, E, RIKARESIN (registered trademark) L-200 (trade name, E, RIKARESIN co., ltd.) EP-4003E, RIKARESIN-4000E, RIKARESIN-4088E, RIKARESIN-3950S (trade name, E, RIKARESIN system), E, RIKARESIN (registered trademark) 2021E, RIKARESIN (registered trademark) 2081, E, RIKARESIN (registered trademark) 2000, EHPE3150, E, RIKARESIN (registered trademark) GT401, E, RIKARESIN (registered trademark) PB4700, E, RIKARESIN (registered trademark) PB3600 (trade name, E, RIKARESIN system and Nippon Kayaku co., ltd.) and the like. Moreover, the following compounds may also be preferably used.

[ Chemical formula 31]

Wherein n is an integer of 1 to 5, and m is an integer of 1 to 20.

In the above-described structure, n is preferably 1 to 2 and m is preferably 3 to 7 in terms of both heat resistance and improvement of elongation.

Crosslinking agents having oxetanyl groups

Examples of the crosslinking agent having an oxetanyl group (hereinafter also referred to as "oxetane compound") 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, 1, 4-benzenedicarboxylic acid-bis [ (3-ethyl-3-oxetanyl) methyl ] ester, and the like. 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.

Crosslinking agents having benzoxazolyl groups

A crosslinking agent having a benzoxazole group (hereinafter also referred to as "benzoxazine compound") is preferable because it does not undergo degassing during curing due to a crosslinking reaction caused by a ring-opening addition reaction, and further reduces heat shrinkage to suppress warpage.

Preferable examples of the benzoxazine compound include P-d type benzoxazine, F-a type benzoxazine (trade name, shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac type dihydrobenzoxazine compounds. These may be used alone, or 2 or more kinds may be mixed.

Crosslinking agents having maleimide groups

As the crosslinking agent having a maleimide group (hereinafter also referred to as "maleimide compound"), a compound having 2 or more maleimide groups is preferable.

Examples of the maleimide compound include 4,4 '-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide (m-PHENYLENE BISMALEIMIDE), bisphenol A diphenyl ether bismaleimide, 3' -dimethyl-5, 5 '-diethyl-4, 4' -diphenylmethane bismaleimide, 4-methyl-1, 3-phenylene bismaleimide and the like. These may be used alone, or 2 or more kinds may be mixed.

Crosslinking agents having alkoxysilyl groups

As the crosslinking agent having an alkoxysilyl group (hereinafter also referred to as "alkoxysilane compound"), a tetraalkoxysilane compound, a compound having a trialkoxysilyl group or a dialkoxysilyl group is preferable, and a tetraalkoxysilane compound is more preferable. In the present invention, a crosslinking agent having an alkoxysilyl group is regarded as an alkoxysilane compound even if it has a crosslinkable group other than an alkoxysilyl group.

Examples of the tetraalkoxysilane compound include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-t-butoxysilane.

Specific examples of the trialkoxysilane compound or the compound having a dialkoxysilyl group include γ -aminopropyl trimethoxysilane, γ -aminopropyl triethoxysilane, γ -glycidoxypropyl trialkoxysilane, γ -glycidoxypropyl alkyl dialkoxysilane, γ -methacryloxypropyl trialkoxysilane, γ -methacryloxypropyl alkyl dialkoxysilane, γ -chloropropyl trialkoxysilane, γ -mercaptopropyl trialkoxysilane, β - (3, 4-epoxycyclohexyl) ethyl trialkoxysilane, and vinyl trialkoxysilane. Among them, gamma-glycidoxypropyl trialkoxysilane, gamma-methacryloxypropyl trialkoxysilane, and the like can be mentioned.

Furthermore, as the alkoxysilane compound, a compound represented by the following formula can also be preferably used.

(R¹)_4-n-Si-(OR²)_n

Wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms and not having a reactive group, R ² is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and n is an integer of 1 to 3.

The alkoxysilane compound may be used alone or in combination of 2 or more.

Crosslinking agents having blocked isocyanate groups

As the crosslinking agent having a (blocked) isocyanate group, a compound having 2 or more (blocked) isocyanate groups is preferable.

The (blocked) isocyanate group means either an isocyanate group or a blocked isocyanate group. The blocking agent for blocking the isocyanate group is not particularly limited, and examples thereof include lactams, oximes, amines, aliphatic alcohols, phenols and alkylphenols, imidazoles, pyrazoles, imines, active methylene groups, blocking agents described in JP-A2002-309217 and JP-A2008-239890, and the like.

Examples of the crosslinking agent having an isocyanate group include 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hydrogenated toluene diisocyanate, 1, 3-xylylene diisocyanate, 1, 4-xylylene diisocyanate, hexamethylene diisocyanate, diphenylmethane-4, 4-diisocyanate, isophorone diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, 1, 5-naphthalene diisocyanate, triphenylmethane triisocyanate, adducts of these polyisocyanate compounds with a polyol compound such as trimethylolpropane, biuret or isocyanurate of these polyisocyanate compounds, and the like.

Examples of the crosslinking agent having a blocked isocyanate group include compounds in which an isocyanate group in the crosslinking agent having an isocyanate group is blocked with the blocking agent.

The crosslinking agent having a blocked isocyanate group may be used alone or in combination of 2 or more.

[ Cross-linking agent having a group reactive with electrophilic functional group ]

In the case where the compound having a fluorine atom contained in the composition contains an electrophilic functional group, the composition preferably contains at least 1 group selected from the group consisting of a hydroxyl group, a mercapto group, an amino group, and a carboxyl group as a crosslinking agent.

Crosslinking agents having hydroxyl groups

As the crosslinking agent having a hydroxyl group, a compound having 2 or more hydroxyl groups is preferable.

As the compound having 2 or more hydroxyl groups, other compounds are not particularly limited as long as they have 2 or more hydroxyl groups, and aliphatic polyol compounds, alicyclic polyol compounds, aromatic polyol compounds, and the like can be exemplified.

The hydroxyl group in the crosslinking agent having a hydroxyl group may be an alcoholic hydroxyl group or a phenolic hydroxyl group.

As the crosslinking agent having 2 or more hydroxyl groups, examples of the catalyst include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, neopentyl glycol, 1, 3-butanediol, 2, 4-trimethyl-1, 3-pentanediol, 1, 4-bis-beta-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, ethylene oxide adducts of bisphenol F, propylene oxide adducts of bisphenol F, ethylene oxide adducts of hydrogenated bisphenol A, propylene oxide adducts of hydrogenated bisphenol A, hydroquinone dihydroxyethyl ether, p-xylylene glycol dihydroxyethyl sulfone, bis (2-hydroxyethyl) -2, 4-toluenedicarbamate, 2, 4-toluenebis (2-hydroxyethyl urea), bis (2-hydroxyethyl) -isophthalic acid dicarbamate, bis (2-hydroxyethyl) isophthalate, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, cis-2-butene-1, 4-diol, trans-2-butene-1, 4-diol, catechol, resorcinol, hydroquinone, 4-methyl catechol, 4-t-butyl catechol, 4-acetyl catechol, 3-methoxy catechol, 4-phenyl catechol, 4-methyl resorcinol, 4-ethyl resorcinol, 4-tert-butylresorcinol, 4-hexylresorcinol, 4-chlororesorcinol, 4-benzylresorcinol, 4-acetylresorcinol, 4-methoxyresorcinol, 2-methylresorcinol, 5-methylresorcinol, tert-butylhydroquinone, 2, 5-di-tert-amylhydroquinone, tetramethylhydroquinone, tetrachlorohydroquinone, methylformamidohydroquinone (methylcarboaminohydroquinone), methylureidohydroquinone (methylureidohydroquinone), methylthiohydroquinone (methylthiohydroquinone), benzonorbornene-3, 6-diol, bisphenol A, bisphenol S, 3 '-dichloro bisphenol S4, 4' -dihydroxybenzophenone, 4 '-dihydroxybiphenyl, 4' -thiodiphenol (4, 4 '-thiodiphenol), 2' -dihydroxydiphenylmethane, 3, 4-bis (p-hydroxyphenyl) hexane, 1, 4-bis (2- (p-hydroxyphenyl) propyl) benzene, bis (4-hydroxyphenyl) methylamine, 1, 3-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, 1,5-dihydroxyanthraquinone (1, 5-dihydroxyanthraquinone), 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-hydroxy-3, 5-di-tert-butylbenzyl alcohol, 4-hydroxy-3, 5-di-tert-butylbenzyl alcohol, 4-hydroxyphenylethanol (4-hydroxyphenethyl alcohol), 2-hydroxyethyl-4-hydroxybenzoate, 2-hydroxyethyl-4-hydroxyphenylacetate, resorcinol mono-2-hydroxyethyl ether, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, di-1, 2-propanediol, tri-1, 2-propanediol, tetra-1, 2-propanediol, hexa-1, 2-propanediol, di-1, 3-propanediol, tri-1, 3-propanediol, tetra-1, 3-propanediol, di-1, 3-butanediol, tri-1, 3-butanediol, hexa-1, 3-butanediol, and the like.

The crosslinking agent having a hydroxyl group may be used alone or in combination of 2 or more.

Crosslinking agents having mercapto groups

As the crosslinking agent having a mercapto group, a compound having 2 or more mercapto groups is preferable.

The compound having 2 or more mercapto groups is not particularly limited as long as it has 2 or more mercapto groups, and examples thereof include aliphatic polythiol compounds, alicyclic polythiol compounds, aromatic polythiol compounds, and the like.

Specific examples of the crosslinking agent having a mercapto group which can be used in the present invention include compounds having 2 or more crosslinkable groups, such as thioglycolic acid, ammonium thioglycolate, monoethanolamine thioglycolic acid, 3-mercaptopropionic acid, methoxybutyl mercaptopropionate, thiomalic acid, 2-mercaptoethanol, 2-mercaptopropionic acid, thiodiglycol, thioglycerol, 2-amino-3-mercapto-1_propanol, 4, 6-diaminopyrimidine-2-thiol, 2-amino-3-mercaptopropionic acid, 4-aminophenylthiophenol, 3-amino-N- (2-2-mercaptoethyl) propionamide, 6-amino-2-thiouracil, 2-amino-4-chlorobenzenethiol, 1-amino-2-methyl-2-mercaptopropane-1-carboxylic acid, and the like, wherein the 1 crosslinkable groups are thiol groups; 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 4-butanedithiol, 2, 3-butanedithiol, 1, 5-pentanedithiol, 1, 6-hexanedithiol, 1, 8-octanedithiol, 1, 9-nonanedithiol, 2, 3-dimercapto-1-propanol, dithioerythritol, 2, 3-dimercaptosuccinic acid, 1, 2-benzenedithiol, 1, 3-benzenedimethylthiol, 1, 4-benzenedimethylthiol, 3, 4-dimercaptotol, o-, m-or p-xylene dithiol, 4-chloro-1, 3-benzenedithiol, 2,4, 6-trimethyl-1, 3-benzenedimethylthiol, 4' -thiodiphenol, 2-hexylamino-4, 6-dimercapto-1, 3, 5-triazine, 2-diethylamino-4, 6-dimercapto-1, 3, 5-triazine, 2-dithiamino-4, 6-triazino-1, 3-benzenedithiol, 3-triazino-4, 3-diaminothiodiglycol, 4-mercaptoethylene glycol, 4-mercaptoethyl-4-thioglycollate, 4-bis (4-thioglycollate), bis (2, 6-mercaptoethylene glycol) and bis (4, 6-thioglycollate, 4-thioglycollate, bis-4-thioglycollate, bis (4-thioglycollate) bis-4, 4-thioglycollate, bis-4-butyldiglycol), compounds having 2 or more crosslinkable groups, such as 2,2' - (ethyldithio) diethyl mercaptan, 2-bis (2-hydroxy-3-mercaptopropoxyphenyl propane), 1, 4-bis (3-mercaptobutyryloxy) butane, 2- (dimethylamino) -1, 3-propanedithiol, 1, 3-dimercapto-2-propanol, 2, 3-dimercapto-1-propanol, and 2, 5-dimethylamino-1, 4-benzenedithiol, wherein the 2 crosslinkable groups are thiol groups; compounds having 3 or more crosslinkable groups, such as 1,2, 6-hexanetriol trithioglycolate, 1,3, 5-cyanuric acid (1, 3,5-trithiocyanuric acid), 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, tris-hydroxyethyl triisocyanurate trithiopropionate, tris [ (ethyl-3-mercaptopropionyloxy) ethyl ] isocyanurate, and the 3 crosslinkable groups are thiol groups; and compounds having 4 or more crosslinkable groups and the 4 or more crosslinkable groups being thiol groups, such as neopentyl tetraol tetrakis (3-mercaptopropionate), neopentyl tetraol tetrakis (3-mercaptobutyrate), neopentyl tetraol tetrathioglycolate, and dipentaerythritol hexa-3-mercaptopropionate.

Examples of the crosslinking agent having a mercapto group include ethylene glycol dithiopropionate (EGTG) (registered trademark), trimethylolpropane trithiopropionate (TMTG) (registered trademark), neopentyl tetraol tetrathiopropionate (PETG) (registered trademark) (YODO KAGAKU co., ltd. System) and 1, 4-bis (3-mercaptobutyryloxy) butane (Karenz MT BD 1) (registered trademark), neopentyl tetraol tetra (3-mercaptobutyrate) (Karenz MT PE 1) (registered trademark), 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6 (1 h,3h,5 h) -trione (Karenz MT NR 1) (registered trademark) (both SHOWA DENKO k.k. System) and trimethylolpropane tri-3-mercaptopropionate (TMMP) (registered trademark), neopentyl tetraol tetra-3-mercaptopropionate (PEMP) (registered trademark), dipentyl hexa-3-mercaptopropionate (registered trademark) and dpd (34) which are not commercially available, and the crosslinking agent is not limited to the present invention.

The crosslinking agent having a mercapto group may be used alone or in combination of 2 or more.

Crosslinking agents having amino groups

As the crosslinking agent having an amino group, a compound having 2 or more amino groups is preferable.

As the compound having 2 or more amino groups, there are no particular restrictions on the other compounds as long as they have 2 or more amino groups, and aliphatic polyamine compounds, alicyclic polyamine compounds, aromatic polyamine compounds, heterocyclic amine compounds, and the like can be exemplified.

Examples of the crosslinking agent having an amino group include: aliphatic diamine compounds such as ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, dodecamethylenediamine, propane-1, 2-diamine, bis (3-aminopropyl) methylamine, 1, 3-bis (3-aminopropyl) tetramethylsiloxane, piperazine, 2, 5-dimethylpiperazine, N- (2-aminoethyl) piperazine, 4-amino-2, 2-6, 6-tetramethylpiperidine, N-dimethylethylenediamine, lysine, L-cystine, isophoronediamine, and the like; aromatic diamine compounds such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2, 4-toluenediamine, benzidine, o-xylylenediamine, o-dianiline, 4-nitrom-phenylenediamine, 2, 5-dimethoxy-p-phenylenediamine, bis- (4-aminophenyl) sulfone, 4-carboxy-o-phenylenediamine, 3-carboxy-m-phenylenediamine, 4' -diaminophenyl ether, 1, 8-naphthalenediamine and the like; heterocyclic amine compounds such as 2-aminoimidazole, 3-aminotriazole, 5-amino-1H-tetrazole, 4-aminopyrazole, 2-aminobenzimidazole, 2-amino-5-carboxy-triazole, 2, 4-diamino-6-methyl-s-triazine, 2, 6-diaminopyridine, L-histidine, DL-tryptophan, adenine and the like; such as ethanolamine, N-methylethanolamine, N-ethylethanolamine, 1-amino-2-propanol, 1-amino-3-propanol, 2-aminoethoxyethanol, 2-aminothioethoxyethanol, 2-amino-2-methyl-1-propanol, p-aminophenol, m-aminophenol, o-aminophenol, 4-methyl-2-aminophenol, 2-chloro-4-aminophenol, 4-methoxy-3-aminophenol, 4-hydroxybenzylamine, 4-amino-1-naphthol, 4-aminosalicylic acid, 4-hydroxy-N-phenylglycine, 2-aminobenzyl alcohol, 4-aminophenol, 2-carboxy-5-amino-1-naphthol, L-tyrosine, etc., and the like.

The crosslinking agent having an amino group may be used alone or in combination of 2 or more.

Crosslinking agents having carboxyl groups

As the crosslinking agent having a carboxyl group, a compound having 2 or more carboxyl groups is preferable.

Preferable examples of the compound having 2 or more carboxyl groups include polyfunctional carboxylic acids (oxalic acid, adipic acid, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 2 to 10 polymers of (meth) acrylic acid, and the like).

The crosslinking agent having a carboxyl group may be used alone or in combination of 2 or more.

[ Crosslinking agent reactive with groups having ethylenic unsaturation ]

Examples of the crosslinking agent that reacts with the group having an ethylenically unsaturated bond include a crosslinking agent having an ethylenically unsaturated bond, the crosslinking agent having a mercapto group, and the like, and a crosslinking agent containing a group having an ethylenically unsaturated bond is preferable.

Crosslinking agents containing groups having ethylenic unsaturation

The crosslinking agent containing a group having an ethylenically unsaturated bond is preferably a compound having 1 or more groups having an ethylenically unsaturated bond, more preferably a compound having 2 or more groups having an ethylenically unsaturated bond. The crosslinking agent containing a group having an ethylenically unsaturated bond may have 3 or more groups having an ethylenically unsaturated bond.

The compound having 2 or more groups having an ethylenically unsaturated bond 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.

Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methallyl group, and a group having an aromatic ring directly bonded to a vinyl group (for example, a vinyl phenyl group or the like), (meth) acrylamide group, and (meth) acryloyloxy group, and the group having an aromatic ring directly bonded to a vinyl group is preferable, and (meth) acrylamide group or (meth) acryloyloxy group is more preferable.

The group having an ethylenically unsaturated bond is preferably a radical polymerizable group.

The molecular weight of the crosslinking agent containing a group having an ethylenically unsaturated bond 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 is preferably 100 or more.

Specific examples of the crosslinking agent containing a group having an ethylenically unsaturated bond 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. It is also preferable to use 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 mercapto 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. Further, addition reactants of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, thiols are preferable, and substitution reactants of unsaturated carboxylic acid esters or amides having releasable substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, thiols are more preferable. Further, as another example, a compound group substituted with an unsaturated phosphonic acid, a vinyl benzene derivative such as styrene, a vinyl ether, an allyl ether, or the like may be used instead of the unsaturated carboxylic acid. For a specific example, reference may be made to the descriptions in paragraphs 0113 to 0122 of Japanese patent application laid-open No. 2016-027357, incorporated herein by reference.

Further, as the crosslinking agent containing a group having an ethylenically unsaturated bond, a compound having a boiling point of 100 ℃ or higher at normal pressure is also preferable. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol tri (meth) acrylate, neopentyl glycol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloxypropyl) ether, tris (acryloxyethyl) isocyanurate, a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then subjecting the resultant to (meth) acrylation, a functional acrylate such as those described in Japanese patent publication No. 48-041708, japanese patent publication No. 50-006034, japanese patent publication No. 51-037193, a polyester acrylate described in Japanese patent publication No. 48-064183, japanese patent publication No. 49-043191, japanese patent publication No. 52-030490, and the like, as a reaction product of an epoxy resin with an acrylic acid (meth) acrylate; 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 polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth) acrylate, and the like can also be mentioned.

Further, as a preferable crosslinking agent containing a group having an ethylenically unsaturated bond other than the above, a compound having a fluorene ring and having 2 or more groups having an ethylenically unsaturated bond, a carbo (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 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, 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, it is also possible to use the compounds described as photopolymerizable monomers and oligomers in Journal of the Adhesion Society of Japan vol.20, no.7, pages 300 to 308 (1984).

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 preferably used.

Further, the compounds described in JP-A-10-062986 as the specific examples of the compounds represented by the formulas (1) and (2) can be used as a crosslinking agent containing a group having an ethylenically unsaturated bond, and the compounds are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylating the resulting mixture.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A2015-187211 can also be used as a crosslinking agent containing a group having an ethylenically unsaturated bond, and these are incorporated herein.

As the crosslinking agent containing a group having an ethylenically unsaturated bond, a structure in which a dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku co., ltd.)), a dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku co., ltd.)), a-TMMT (Shin-Nakamura Chemical co., manufactured by ltd.)), a dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku co., ltd.)), a dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku co., ltd.)), a-DPH (manufactured by Shin-Nakamura Chemical co., ltd.)), and these (meth) acryl groups are bonded via an ethylene glycol residue or a propylene glycol residue is preferable. These oligomer types can also be used.

Examples of the commercially available crosslinking agent containing a group having an ethylenically unsaturated bond include 4-functional acrylate SR-494 having 4 ethyleneoxy chains, manufactured by Sartomer Company, inc., 2-functional methacrylate Sartomer Company having 4 ethyleneoxy chains, manufactured by Inc., SR-209, 231, 239, nippon Kayaku Co., ltd., 6-functional acrylate DPCA-60 having 6 ethyleneoxy chains, 3-functional acrylate TPA-330 having 3 isobutyleneoxy chains, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD), NK ESTER M-40G, NK ESTER 4G, 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 TPA-330 having 3 isobutyleneoxy chains, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD. LTD), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, UA A-7200 (manufactured by Shin-Nakamura Chemical Co., ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., ltd.) and so on, and the like, manufactured by MMF 600, and so on (manufactured by Table 600).

As the crosslinking agent containing a group having an ethylenically unsaturated bond, urethane acrylate compounds having an ethylene oxide skeleton as described in Japanese patent publication No. Sho 48-041708, japanese patent publication No. Sho 51-037193, japanese patent publication No. Hei 02-032293 and Japanese patent publication No. Hei 02-016765, japanese patent publication No. Sho 58-049860, japanese patent publication No. Sho 56-017654, japanese patent publication No. Sho 62-039417 and Japanese patent publication No. Sho 62-039418 are also preferred. Further, as the crosslinking agent containing a group having an ethylenically unsaturated bond, 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 crosslinking agent having a group having an ethylenically unsaturated bond may be a crosslinking agent having an acid group such as a carboxyl group or a phosphate group. The crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a crosslinking agent having an ethylenically unsaturated bond, which reacts an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to have an acid group. Particularly preferred are the following compounds: in a crosslinking agent containing a group having an ethylenically unsaturated bond, which is obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to have an acid group, the aliphatic polyhydroxy compound is a compound of neopentyl glycol or dipentaerythritol. Examples of commercial products include TOAGOSEI CO., LTD. Polyacid modified acrylic oligomers M-510 and M-520.

The acid value of the crosslinking agent further having an acid group is preferably 0.1 to 300mgKOH/g, particularly preferably 1 to 100mgKOH/g. When the acid value of the crosslinking agent containing a group having an ethylenically unsaturated bond is within the above range, the production workability is excellent, and further the developability is 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, the composition preferably uses 2-functional methacrylate or acrylate.

Specific examples of the compound include 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, bisphenol a E0 (ethylene oxide) adduct diacrylate, bisphenol a E0 adduct dimethacrylate, bisphenol a P0 (propylene oxide) adduct diacrylate, bisphenol a P0 adduct dimethacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid E0 modified diacrylate, isocyanuric acid modified dimethacrylate, and other 2-functional acrylates having a urethane bond and 2-functional methacrylate having a urethane bond. 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.

From the viewpoint of suppressing warpage accompanying control of the elastic modulus of a pattern (cured product), the composition of the present invention can preferably use a crosslinking agent having only 1 ethylenically unsaturated bond as the crosslinking agent containing a group having an ethylenically unsaturated bond. As the crosslinking agent having only 1 ethylenically unsaturated bond, 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, (meth) epoxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and other (meth) acrylic acid derivatives, N-vinyl pyrrolidone, N-vinyl caprolactam and other N-vinyl compounds, allyl glycidyl ether and the like can be preferably used. As the crosslinking agent having only 1 ethylenically unsaturated bond, 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 crosslinking agent containing a group having an ethylenically unsaturated bond include allyl compounds such as diallyl phthalate and triallyl trimellitate.

The crosslinking agent containing a group having an ethylenically unsaturated bond may be used alone in an amount of 1 kind or in an amount of 2 or more kinds.

[ Content ]

The content of the crosslinking agent is preferably 3% by mass or more relative to the total solid content of the composition of the present invention. The content is preferably 5% by mass or more, more preferably 10% by mass or more. The content is preferably 95% by mass or less, and more preferably 90% by mass or less.

The composition of the present invention may contain 1 kind of crosslinking agent alone or 2 or more kinds of crosslinking agents. When the composition of the present invention contains 2 or more crosslinking agents, the total amount of these is preferably within the above range.

< Polymerization initiator >

The composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat.

In particular, in the case where the composition contains a crosslinking agent containing the above-mentioned group having an ethylenically unsaturated bond, it preferably contains a polymerization initiator, more preferably contains a radical polymerization initiator.

The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator.

[ Thermal polymerization initiator ]

The 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 that generates radicals by thermal energy and initiates or accelerates the polymerization reaction of a compound having polymerizability. Further, a photopolymerization initiator described later may 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, 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 composition of the present invention. The composition may contain only 1 kind of thermal polymerization initiator, or may contain 2 or more kinds. When the thermal polymerization initiator is contained in an amount of 2 or more, the total amount is preferably within the above range.

[ Photopolymerization initiator ]

As the photopolymerization initiator, a photo radical polymerization initiator is preferable.

The photo radical polymerization initiator preferably contains at least 1 compound having an absorbance of at least about 50 L.mol ^-1·cm^-1 mol in a wavelength range of about 240 to 800nm (preferably 330 to 500 nm). The molar absorptivity of the compound can be measured by a known method. For example, it is preferable to measure the concentration of the solvent by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Co.) using ethyl acetate 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, 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 Japanese unexamined patent publication (Kokai) No. 2016-027357 and paragraphs 0138 to 0151 of International publication (Kokai) No. 2015/199219, which are incorporated herein by reference. Examples of the compounds include those described in paragraphs 0065 to 0111 of Japanese patent application laid-open No. 2014-130173, those described in Japanese patent application laid-open No. 6301489, those described in MATERIAL STAGE to 60p, vol.19, no.3,2019, those described in International publication No. 2018/221177, those described in International publication No. 2018/110179, those described in Japanese patent application laid-open No. 2019-043864, those described in Japanese patent application laid-open No. 2019-044030, and those described in Japanese patent application laid-open No. 2019-167313, and those described in the specification.

As these photopolymerization initiators, those described in paragraphs 0141 to 0147 of International publication No. 2021/157571 can be preferably used.

As the photo radical polymerization initiator, an oxime compound can be 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.

As a specific example of the oxime compound, the compounds described in paragraphs 0149 to 0154 of International publication No. 2021/157571 can be preferably used.

Further, as the photo radical polymerization initiator, the compounds described in paragraphs 0155 to 0162 of International publication No. 2021/157571 can be preferably used.

[ Content ]

When the polymerization 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 composition of the present invention. The polymerization initiator may be contained in an amount of 1 or 2 or more. When the polymerization initiator is contained in an amount of 2 or more, the total amount is preferably within the above range.

< Solvent >

The composition of the present invention may contain a solvent.

The composition of the present invention may be substantially free of solvent. Substantially free of solvent means that the content of solvent is 5 mass% or less, preferably 1 mass% or less, more preferably 0.1 mass% or less, relative to the total mass of the composition.

As the solvent, for example, examples of the solvent include acetone, methyl ethyl ketone, hexane, heptane, octane, 2-heptanone, cycloheptanone, cyclohexanone, cyclohexane, methylcyclohexane, ethylcyclohexane, methyl-n-amyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diethyl ether, propylene glycol monoacetate, dipropylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexyl acetate, ethyl 3-ethoxypropionate, dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate methyl methoxypropionate, ethyl ethoxypropionate, anisole, ethylbenzyl ether, methylphenylmethyl ether (CRESYL METHYL ETHER), diphenyl ether, dibenzyl ether, phenetole, butylphenyl ether, benzene, ethylbenzene, diethylbenzene, pentylbenzene, cumene, toluene, xylene, isopropyltoluene, mesitylene, methanol, ethanol, isopropanol, butanol, methyl monoepoxypropyl ether, ethyl monoepoxypropyl ether, butyl monoepoxypropyl ether, phenyl monoepoxypropyl ether, methyl diglycidyl ether, ethyl diglycidyl ether, butyl diglycidyl ether, phenyl diglycidyl ether, methylphenol monoepoxypropyl ether, ethylphenol monoepoxypropyl ether, butylphenol monoepoxypropyl ether, mineral spirits, perfluorocarbon, hydrofluoroether, hydrochlorofluorocarbon, perfluoropolyether, dimethylimidazoline, tetrahydrofuran, pyridine, formamide, acetanilide, dioxolane (dioxalane), o-cresol, m-cresol, p-cresol, phenol, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-dimethylformamide, N-diethylformamide, N-dimethylacetamide, N-diethylacetamide, 1, 3-dimethyl-2-imidazolidinone, dimethylsulfoxide, diethylsulfoxide, dimethylsulfone, diethylsulfone, gamma-butyrolactone, sulfolane, halogenated phenols, various polysilicone oils, and the like.

These solvents may be used alone or in combination of 2 or more.

When the composition contains a solvent, the content of the solvent is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and even more preferably 15 to 85% by mass, based on the total mass of the composition.

< Adhesion promoter >

The composition of the present invention may contain an adhesion promoter.

Examples of the adhesion auxiliary agent include a silane coupling agent and a chelating agent.

The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group capable of chemically bonding to an inorganic material as a substrate, and is preferably a silane coupling agent having a group such as a (meth) acryloyl group, a phenyl group, a secondary or tertiary mercapto group, an epoxy group, or an aminosilane, which interacts with or forms a bond with an organic resin and exhibits affinity, and among these, more preferably (meth) acryloyltrimethoxysilane or epoxypropyltrimethoxysilane. Examples of such materials include KBM-303, KBM-403, KBM-503 (from Shin-Etsu Chemical Co., ltd.).

In the present invention, these compounds may be contained as the above-mentioned crosslinking agent having an alkoxysilyl group. In the case where the compound having a fluorine atom contains an electrophilic functional group, the crosslinking agent having a group reactive with the electrophilic functional group and the adhesion promoter may be contained. In addition, when the compound having a fluorine atom contains a group having an ethylenically unsaturated bond, a crosslinking agent which reacts with the group having an ethylenically unsaturated bond and the adhesion promoter may be contained.

Examples of the chelating agent include an aluminum chelate, a titanium chelate, and a zirconium chelate.

The aluminum chelate compound is not particularly limited, and for example, ethylacetoacetate-diisopropanol aluminum (aluminum ethylacetoacetate diisopropylate), triethylacetoacetate aluminum, alkylacetoacetate-diisopropanol aluminum (aluminum alkyl acetoacetate diisopropylate), diethylacetoacetate-monoacetoacetate aluminum (aluminum bisethylacetoacetate monoacetylacetonate), and triacetylacetonate aluminum (aluminum trisacetylacetonate) can be used.

The titanium chelate compound is not particularly limited, and for example, titanium acetylacetonate, titanium tetra-acetylacetonate, titanium ethylacetoacetate (titanium ethyl acetoacetate), and the like can be used.

The zirconium chelate complex is not particularly limited, and zirconium tetra-acetylacetonate, zirconium monoacetylacetonate, and the like can be used, for example.

When the composition of the present invention contains an adhesion promoter, the content of the adhesion promoter is preferably 0.1 to 10% by mass, more preferably 0.3 to 5% by mass, based on the total solid content of the composition.

The composition of the present invention may contain 1 kind of adhesive auxiliary alone or 2 or more kinds. When the composition of the present invention contains 2 or more kinds of adhesion promoters, the total amount of these is preferably within the above range.

< Other additives >

The composition of the present invention may further contain other additives as needed within a range where the effects of the present invention can be obtained.

Examples of the other additives include known additives such as surfactants, acid generators, alkali generators, inorganic particles, ultraviolet absorbers, antioxidants, anticoagulants, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers, flame retardants, etc.).

By properly containing these components, properties such as film physical properties can be adjusted. When these additives are blended, the blending amount of each is preferably 3% by mass or less of the solid content of the composition of the present invention. Further, the total content of other additives is preferably 5% by mass or less of the solid content of the composition of the present invention.

[ Use ]

The composition of the present invention is preferably used for forming an insulating film.

Specifically, a cured product obtained by curing the composition of the present invention is preferable as an insulating film.

Examples of the insulating film include an insulating film in a resin circuit board, an insulating film in a metal-clad laminate, and an insulating film in a metal-clad laminate having an inner circuit.

In particular, the composition of the present invention is preferably used for forming an insulating film which is a protective film (cover film) for a substrate (base film) for a flexible printed wiring board, or the like. The composition of the present invention can be used as a buffer coating, a surface coating agent for a lens, an adhesive (for example, an adhesive for bonding a metal film and an insulating film in a metal-clad laminate), or the like.

[ Preparation of the composition ]

The composition of the present invention can be prepared by mixing the above-described components. The mixing method is not particularly limited, and can 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 40 ℃, more preferably 15 to 30 ℃.

< Cured product >

The cured product of the present invention is a cured product obtained by curing the composition of the present invention.

For example, a cured product of the composition of the present invention can be obtained by heating the composition of the present invention.

The heating temperature is preferably 120 to 400 ℃, more preferably 140 to 380 ℃, and even more preferably 170 to 350 ℃.

The form of the cured product 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. The shape of the cured product can be selected by patterning the composition according to the use of forming a protective film on the wall surface, forming a through hole for conduction, adjusting impedance, electrostatic capacitance or internal stress, imparting a heat dissipation function, and the like.

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 volume resistivity of the cured product is preferably 10 ¹⁴～10¹⁹ Ω·cm, more preferably 10 ¹⁵～10¹⁸ Ω·cm, and even more preferably 10 ¹⁶～10¹⁷ Ω·cm.

The dielectric loss tangent of the cured product at 10GHz is preferably 0.002 or less, more preferably 0.0018 or less, and still more preferably 0.0016 or less. The lower limit of the dielectric loss tangent is not particularly limited, and is preferably, for example, 0.0001 or more.

The relative dielectric constant of the cured product is preferably less than 3.3, more preferably less than 3.0, and even more preferably less than 2.8. The lower limit of the relative dielectric constant is not particularly limited, and is preferably 0.1 or more, for example.

(Method for producing cured product)

The method for producing a cured product of the present invention preferably includes a film forming step of forming a film by applying the composition of the present invention to a substrate and a curing step of curing the film.

< Film Forming Process >

[ Substrate ]

The substrate is not particularly limited, and a substrate having a metal layer on the surface or a substrate formed of a metal (for example, a metal foil) is preferable.

Examples of the metal in the substrate having a metal layer on the surface thereof or the metal in the substrate made of a metal include gold, silver, copper, nickel, stainless steel, titanium, aluminum, indium, tin, manganese, nickel, cobalt, molybdenum, tungsten, chromium, neodymium, an alloy containing these, and the like, and copper or an alloy containing copper is preferable.

Further, examples of the other base material include polyimide, liquid crystal polymer, polyethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, polyetherimide, polyphenylene ether, polyester, para-aromatic polyamide (para-aramid), polylactic acid, nylon, polyhydantoin (polyparabanic acid), and polyether ether ketone.

Furthermore, an adhesive layer may be further provided on the surface of these substrates. The pressure-sensitive adhesive layer may be any pressure-sensitive adhesive layer known in the field of flexible printed wiring boards.

In the production of the cured product of the present invention, a method (no adhesive layer) in which such an adhesive layer is omitted is also one of preferred embodiments.

The shape of the substrate is not particularly limited, and a film shape is preferable.

The substrate has a film-like shape, for example, a width of 30 to 600cm and a length of 100 to 1000m.

The shape of the substrate is not particularly limited, and may be, for example, a plate shape.

The substrate may be in the form of a roll, and the steps may be advanced in the order of unreeling the substrate, applying the composition to the film forming step, curing the composition in the curing step, and reeling the substrate on which the cured product is formed. In the case of performing the metal layer forming step described later, for example, the metal layer forming step may be performed after applying the composition to the film forming step and before curing the composition in the curing step.

As a method for applying the composition of the present invention to a substrate, coating is preferable, and casting coating is more preferable.

Examples of the casting method include roll coating, gravure coating, doctor blade coating, knife coating, bar coating, dip coating, spray coating, curtain coating, slit coating, and screen printing.

Furthermore, the composition may be applied to both sides of the substrate.

The temperature for casting is preferably 60 to 300℃and more preferably 100 to 250 ℃.

The thickness of the cast composition is not particularly limited, and is preferably 1 to 500. Mu.m.

In addition, in the case where the composition contains a solvent, drying may be performed after application. The drying temperature is preferably 50 to 150 ℃, more preferably 70 to 130 ℃, still more preferably 90 to 110 ℃. Further, drying may be performed by decompression. The drying time may be exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

< Curing Process >

In the curing step, the film formed on the substrate is cured.

In the curing step, a cross-linking is formed between cross-linking sites contained in the compound having a fluorine atom or between the cross-linking sites and a cross-linking agent, thereby obtaining a cured product.

Curing is preferably performed by at least one of heating and exposure to light.

In particular, in the present invention, the curing step is preferably a step of curing the film by heating.

[ Heating ]

In the case of performing the curing step by heating, the heating temperature (maximum heating temperature) 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 time is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and still more preferably 15 to 240 minutes.

The heating may be performed under a reduced pressure by passing an inert gas such as nitrogen, helium, or argon through the heating, or the like, and the heating may be performed under an atmosphere having a low oxygen concentration or a low humidity. 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 hot plate, an infrared oven, an electrothermal oven, a hot air oven, an infrared oven, and the like.

[ Exposure ]

In the curing step, the film may be exposed to light. In this case, the entire surface of the film is preferably exposed.

The exposure amount is not particularly limited as long as the composition of the present invention can be cured, and for example, it is preferably 50 to 10,000mJ/cm ², more preferably 200 to 8,000mJ/cm ² in terms of exposure energy at 365 nm.

The exposure wavelength may be, for example, a wavelength at which the polymerization initiator can be sensitized, and may be appropriately determined within a range of 190 to 1,000nm, preferably 240 to 550nm.

Regarding the exposure wavelength, in relation to the light source, there are exemplified (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h-ray (wavelength 405 nm), i-ray (wavelength 365 nm), broad wavelength (g, h, 3 wavelengths of i-ray), (4) excimer laser, krF excimer laser (wavelength 248 nm), arF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), and (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, (7) second harmonic 532nm, third harmonic 355nm of YAG laser, etc. With respect to the 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.

< Metal layer Forming Process >

The method for producing a cured product according to the present invention may further include a metal layer forming step.

For example, in the case of using a substrate having a metal layer on the surface or a substrate made of metal as the substrate in the film forming step, a metal layer may be further formed on the surface of the film on the side opposite to the metal.

In addition, when a substrate having no metal layer is used as the substrate in the film forming step, the metal layer can be formed on the side of the film opposite to the substrate. For example, the film may be formed on both sides of a substrate, and a metal layer may be formed on each side of the film opposite to the substrate.

Examples of the metal in the metal layer to be formed include gold, silver, copper, nickel, stainless steel, titanium, aluminum, indium, tin, manganese, nickel, cobalt, molybdenum, tungsten, chromium, neodymium, an alloy containing these, and the like, and copper or an alloy containing copper is preferable.

The thickness of the metal layer is preferably 0.1 to 500. Mu.m.

The method of forming the metal layer is not particularly limited, and a known method such as a method of pressing a metal foil against the film may be used.

After the metal layer is formed, the interface between the base material and the cured product may be peeled off to obtain a structure composed of the cured product and the metal layer.

< Other procedure >

The method for producing a cured product of the present invention may further include other steps.

Examples of the other steps include a step of activating the surface of the substrate, a step of cleaning the cured product, and a step of winding the cured product in a roll shape.

(Structure)

The structure of the present invention includes the cured product of the present invention and the metal layer.

In the structure of the present invention, the cured product of the present invention may be in direct contact with the metal layer, or a known adhesive layer or the like may be present between the cured product of the present invention and the metal layer, and it is also preferable that the cured product of the present invention be in direct contact with the metal layer.

The structure of the present invention may be, for example, a structure in which a metal layer is present only on one side of the cured product of the present invention as in the case of a metal layer-cured product, a structure in which a metal layer is present on both sides of the cured product of the present invention as in the case of a metal layer-cured product-metal layer, or a structure in which a cured product of the present invention in which a metal layer is present on both sides of another base layer as in the case of a metal layer-cured product-another base layer-cured product-metal layer.

Further, the metal layer-cured product-other base material layer-metal layer may be used.

In these embodiments, as described above, a known adhesive layer or the like may be present between the cured product and the metal layer in the present invention.

The metal layer may be a metal layer of the above-mentioned substrate having a metal layer on the surface or a substrate itself made of a metal. The metal layer may be formed by the metal layer forming step.

The thickness of the metal layer is preferably 0.1 to 1000. Mu.m, more preferably 1 to 500. Mu.m.

The structure of the present invention is produced, for example, by using a substrate having a metal layer on the surface or a substrate made of metal as the substrate in the method for producing a cured product of the present invention.

The structure of the present invention can be used, for example, as a metal-clad laminate (for example, a single-sided metal-clad laminate or a double-sided metal-clad laminate) for forming a printed wiring board.

For example, a substrate having a metal wiring formed on the surface can be manufactured by removing a part of the metal layer in the structure of the present invention by etching or the like.

(Device)

The invention also discloses a device with the cured product.

Specific examples of such devices include electronic devices such as printed wiring boards and lead frames, and devices used for 5G communication and 6G communication using millimeter wave bands (26 GHz band and 28GHz band).

It is considered that the cured product of the present invention is excellent in processability, and thus various devices can be easily manufactured.

Further, it is considered that the cured product of the present invention has a low relative dielectric constant, and thus can contribute to low elongation, low transmission loss, and the like in various devices.

Examples

The present invention will be described in further detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment order, 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.

(Synthesis example)

< Synthesis of P-1 >

300Mg of 3,3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) was dissolved in 48ml of acetophenone, and 2.44g of polyfunctional isocyanate A-1 (50 mass% mixed solution of ethyl acetate and acetonitrile) and 35mg of 1, 4-diazabicyclo [2.2.2] octane were added, and ultrasonic irradiation was performed at 25℃for 1 hour using yamato 5510 brabson (42 kHz). After the irradiation, stirring was carried out at 25℃for 3 hours, followed by standing for 24 hours, to obtain an intermediate solution. The intermediate solution was heated at 200℃for 2 hours using an aluminum block thermostat with Stirrer (Stirrer) (EYELA RCH-20L), cooled and then added dropwise to 48ml of methanol. The precipitate was collected by filtration, whereby 1.28g of the polyimide particles of the present invention was obtained. The volume average particle diameter of the polyimide particles was 80nm.

The volume average particle diameter of the polyimide precursor thus produced is shown in the column "volume average particle diameter (μm)" of the "polyimide precursor" in the table, and the volume average particle diameter of the polyimide is shown in the column "volume average particle diameter (μm)" of the "polyimide" in the table.

The volume average particle diameters were measured by a laser diffraction/scattering particle diameter distribution measuring apparatus LA-920 (HORIBA, manufactured by ltd.).

< Synthesis of P-2 to P-9 >

In the synthesis of P-1, P-2 to P-9 were synthesized by the same method as in the synthesis of P-1 except that the polyfunctional isocyanate compound was changed to the compound in the column of "type" of the polyfunctional isocyanate compound "described in the table, and the tetracarboxylic dianhydride was changed to the compound in the column of" type "of the tetracarboxylic dianhydride" described in the table.

The amounts used are described in the column of "parts by mass" of each compound.

The volume average particle diameters of the polyimide precursors produced in the synthesis of P-2 to P-9 are shown in the column of "volume average particle diameter (μm)" of the "polyimide precursor" in the table, and the volume average particle diameters of the polyimide are shown in the column of "volume average particle diameter (μm)" of the "polyimide" in the table.

< Synthesis of CP-1 to CP-3 >

In the synthesis of P-1, CP-1 to CP-3 were synthesized by the same method as in the synthesis of P-1 except that the polyfunctional isocyanate compound was changed to the compound in the column of "type" of the polyfunctional isocyanate compound "described in the table, and the tetracarboxylic dianhydride was changed to the compound in the column of" type "of the tetracarboxylic dianhydride" described in the table.

The volume average particle diameters of the polyimide precursors produced in the synthesis of CP-1 to CP-3 are shown in the column of "volume average particle diameter (μm)" of the "polyimide precursor" in the table, and the volume average particle diameters of the polyimide are shown in the column of "volume average particle diameter (μm)" of the "polyimide" in the table.

TABLE 1

The abbreviations in the tables are detailed below.

[ Polyfunctional isocyanate Compound ]

A-1: TAKENATE D-110N (the addition reactant of trimethylolpropane and m-xylylene diisocyanate) and polyoxyethylene monomethyl ether in a mass ratio of 1:1.

The mass content (% by mass) of the poly (alkyleneoxy) group relative to the mass of the above-mentioned A-1 is described in the column "poly (alkyleneoxy) group content (% by mass)". This value can be changed by adjusting the ratio of the amount of polyoxyethylene monomethyl ether to the total mass of TAKENATE D to 110N and polyoxyethylene monomethyl ether.

The weight average molecular weight of the poly (ethyleneoxy) group in the polyoxyethylene monomethyl ether used is described in the column "Mw of poly (alkyleneoxy) group".

A-12: isophorone diisocyanate

A-13: m-xylylene diisocyanate

A-2 to A-4: the molecular weight and the amount of the polyoxyethylene monomethyl ether to be used were changed so that the weight average molecular weight of the poly (alkyleneoxy) group and the mass ratio of the poly (alkyleneoxy) group to the mass of the polyfunctional isocyanate compound were as values shown in the above table, except that the compound had the same structure as the A-1

A-5: addition reaction product of trimethylolpropane and xylylene diisocyanate and addition reaction product of polyoxypropylene monomethyl ether

CA-1: addition reaction product of trimethylolpropane and xylylene diisocyanate

CA-2: isophorone diisocyanate

CA-3: m-xylylene diisocyanate

[ Tetracarboxylic dianhydride ]

B-1:4,4' -diphthalic anhydride

B-2:4,4' -Oxyphthalic anhydride

B-3:3,3', 4' -benzophenone tetracarboxylic dianhydride

B-4:4,4' - (hexafluoroisopropylidene) diphthalic anhydride

B-5:9, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride

< Evaluation >

[ Measurement of thermal decomposition temperature ]

The thermal decomposition temperature (Td) was determined by thermal mass-differential thermal simultaneous measurement (TG-DTA). The measurement conditions were set at a heating rate of 10℃per minute and 50 ml/min of nitrogen.

Based on the measured thermal decomposition temperature, evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the column of "thermal decomposition temperature" in the table.

Evaluation criterion-

A: the mass reduction temperature of 5% is 500 ℃ or higher.

B: the mass reduction temperature of 5% is 300 ℃ or more and less than 500 ℃.

C: the 5% mass reduction temperature is less than 300 ℃.

[ Measurement of Dispersion stability ]

In each of examples and comparative examples, 1g of polyimide particles described in the table was dispersed in 100g of water for 10 minutes using a stirring rotor MR-3 (AS ONE) to prepare a dispersion. The dispersion was allowed to stand for 24 hours, and from the time of the standing, the presence or absence of precipitation of particles was visually confirmed at each of the 8 th and 24 th hours. The case where no particle precipitation occurred was evaluated as "none", and the case where precipitation of polyimide particles occurred was evaluated as "present".

Evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the column of "dispersion stability" of the table.

A: standing for 24 hours without precipitation

B: no sediment is left for 8 hours, and sediment is left for 24 hours

C: standing for 8 hr to precipitate

From the above results, it was found that the particles composed of the polyimide of the present invention are excellent in dispersion stability.

The polyimides in comparative examples 1 to 3 were neither a first specific polyimide nor a second specific polyimide. In this method, dispersion stability was poor.

Claims

1. A polyimide comprising a repeating unit represented by the formula (1-1),

2. The polyimide according to claim 1, wherein,

R ^A2 in the formula (1-1) is a group represented by the following formula (R-1),

3. A polyimide obtained by imidizing a reactant comprising a tetracarboxylic dianhydride and a polyfunctional isocyanate compound,

The polyfunctional isocyanate compound contains a poly (alkyleneoxy) group.

4. The polyimide according to claim 3, wherein,

The polyfunctional isocyanate compound is a compound represented by the following formula (IC-1),

5. The polyimide according to claim 3 or 4, wherein,

The polyfunctional isocyanate compound is an adduct of a compound represented by the following formula (C-1) and a second polyfunctional isocyanate compound,

6. The polyimide according to claim 5, wherein,

7. A polyimide precursor comprising a repeating unit represented by the following formula (2-1),

8. The polyimide precursor according to claim 7, which is in the form of particles.

9. The polyimide precursor according to claim 8, which has a volume average particle diameter of 30nm to 500nm.

10. A polyimide obtained by imidizing the polyimide precursor according to any one of claims 7 to 9.

11. The polyimide according to any one of claims 1 to 6 and claim 10, which is in the form of particles.

12. The polyimide according to claim 11, which has a volume average particle diameter of 30nm to 500nm.

13. A composition comprising the polyimide according to any one of claims 1 to 6 and 10 to 12 and a compound having a fluorine atom.

14. A method for producing the polyimide according to any one of claims 1 to 6 and 10 to 12, comprising:

And a second step of imidizing the polyimide precursor.

15. The method for producing a polyimide according to claim 14, wherein,

16. The method for producing a polyimide according to claim 14 or 15, wherein,

In the second step, imidization is performed by heating the polyimide precursor in an organic solvent.

17. The method for producing a polyimide according to claim 16, wherein,

18. The method for producing a polyimide according to claim 16 or 17, wherein,