TW202323367A - Composition, cured product, method for producing cured product, structure, and device - Google Patents

Abstract

Provided are: a composition containing polyimide particles and a fluorine atom-containing compound , wherein the fluorine atom-containing compound has at least one group selected from the group consisting of a nucleophilic functional group, an electrophilic functional group, and a group having an ethylenically unsaturated bond, and when the fluorine atom-containing compound does not include the group having an ethylenically unsaturated bond, a cross-linking agent having a group that reacts with the nucleophilic functional group or the electrophilic functional group contained in the fluorine atom-containing compound is further included; a cured product composed of the composition; a method for producing the cured product; a structure comprising the cured product and a metal layer; and a device comprising the cured product or the structure.

Description

Composition, cured product, manufacturing method of cured product, structure and element

The present invention relates to a composition, a cured product, a method for manufacturing the cured product, a structure and an element.

For example, for the practical application of the fifth-generation mobile communication system "5G (5th Generation)" and the realization of the subsequent sixth-generation mobile communication system "6G (6th Generation)", high integration of components and high-density wiring are being considered and multilayering. Along with this, substrates such as flexible printed wiring boards (FPC) are also required to have higher functionality from various viewpoints such as processability and low retardation. Flexible printed wiring board (FPC) is a substrate that forms a circuit (conductor pattern) using a metal-clad laminate made of an insulating thin and flexible base film (substrate) and a conductive metal. Features are thin and bendable. So far, various studies have been made on materials used for such substrates.

For example, Patent Document 1 discloses a data communication member comprising at least 80, 85 or 90% by mass of polymerized units composed of perfluoromonomers and a crosslinked fluoropolymer layer having hardened sites. Patent Document 2 describes an electrodeposition solution characterized in that it is composed of a dispersion medium and a solid component, the solid component includes polyimide resin particles and fluororesin particles, and the fluororesin particles in the solid component are The content ratio of the above-mentioned polyimide-based resin particles is 20 to 70% by mass, and the median diameter of the polyimide-based resin particles is 50 to 400 nm.

[Patent Document 1] International Publication No. 2021/088198 [Patent Document 2] International Publication No. 2018/151091

In materials such as the base film used for FPC, it is sometimes required to have a high tensile modulus and a low relative permittivity.

The object of the present invention is to provide a composition capable of obtaining a cured product having a high tensile modulus and a low relative permittivity, a cured product composed of the above composition, a method for producing the above cured product, a hardened product having the above-mentioned cured product and a metal layer. The structure and the element comprising the above-mentioned cured product or the above-mentioned structure.

Examples of representative embodiments of the present invention are shown below. <1> A composition comprising: Compounds having fluorine atoms; and polyimide particles, The above-mentioned compound having a fluorine atom has at least one group selected from the group consisting of a nucleophilic functional group, an electrophilic functional group, and a group having an ethylenically unsaturated bond, In the case where the above-mentioned compound having a fluorine atom does not contain a group having an ethylenically unsaturated bond, the above-mentioned composition further contains a crosslinking agent having the above-mentioned nucleophilic A functional group or a group reacting with the above-mentioned electrophilic functional group. <2> The composition as described in <1>, wherein The above-mentioned compound having a fluorine atom contains at least one kind of group selected from the group consisting of a hydroxyl group, a mercapto group, an amine group, and a carboxyl group as the above-mentioned nucleophilic functional group. <3> The composition as described in <1> or <2>, wherein The above-mentioned compound having a fluorine atom contains at least one group selected from the group consisting of epoxy group, oxetanyl group, maleimide group and oxazoline group as the above-mentioned electrophilic functional group . <4> The composition according to any one of <1> to <3>, wherein The content of the compound having a fluorine atom is 10% by mass or more relative to the total solid content of the composition. <5> The composition according to any one of <1> to <4>, wherein The above compound having a fluorine atom is a resin having a weight average molecular weight of 20,000 or more. <6> The composition according to any one of <1> to <5>, wherein The polyimide particles have a volume average particle diameter of 10 nm to 300 nm. <7> The composition according to any one of <1> to <6>, wherein The above-mentioned compound having a fluorine atom contains a group having an ethylenically unsaturated bond, and the above-mentioned composition contains a crosslinking agent and a radical polymerization initiator which react with the above-mentioned group having an ethylenically unsaturated bond. <8> The composition according to any one of <1> to <7>, which is used for forming an insulating film. <9> A hardened product obtained by hardening the composition described in any one of <1> to <8>. <10> A method of manufacturing a cured product, comprising: A film forming step in which a film is formed by applying the composition described in any one of <1> to <8> on a substrate; and A hardening step of hardening the above film. <11> The method for producing a hardened product according to <10>, wherein The aforementioned base material is a base material having a metal layer on the surface or a base material formed of metal. <12> The method for producing a hardened product according to <10> or <11>, wherein The curing step is a step of curing the film by heating. <13> A structure including the cured product described in <9> and a metal layer. <14> An element comprising the cured product described in <9>. [Invention effect]

According to the present invention, there are provided a composition capable of obtaining a cured product having a high tensile modulus and a low relative permittivity, a cured product composed of the above composition, a method for producing the above cured product, and a device comprising the above cured product and a metal layer. A structure and an element comprising the above-mentioned cured product or the above-mentioned structure.

Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the illustrated embodiments. In this specification, the numerical range represented by the symbol "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit, respectively. In this specification, the term "step" means not only an independent step, but also a step that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved. In the notation of a group (atomic group) in this specification, the notation of being substituted and unsubstituted includes both a group (atomic group) having no substituent and 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 this specification, unless otherwise specified, "exposure" includes not only exposure by light but also exposure by particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include bright line spectrum of a mercury lamp, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams and other active rays or radiation. In this specification, "(meth)acrylate" means both "acrylate" and "methacrylate" or either, and "(meth)acrylic" means "acrylic" and "methacrylic". "Both or either of them, and "(meth)acryl" means both or either of "acryl" and "methacryl". In this specification, Me in the structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of components other than the solvent among all the components of the composition. In addition, in this specification, the solid content concentration is the mass percentage of other components except a solvent with respect to the total mass of a composition. In this specification, unless otherwise specified, weight average molecular weight (Mw) and number average molecular weight (Mn) are the values measured by the gel permeation chromatography (GPC) method, and are defined as polystyrene conversion values. In this specification, for example, HLC-8220GPC (manufactured by TOSOH CORPORATION) is used to connect guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) in series By using it as a column, weight average molecular weight (Mw) and number average molecular weight (Mn) can be obtained. Unless otherwise specified, these molecular weights were measured using THF (tetrahydrofuran) as an eluent. Among them, NMP (N-methyl-2-pyrrolidone) can also be used when THF is not suitable as an eluent, such as when the solubility is low. In addition, unless otherwise specified, a UV ray (ultraviolet) detector with a wavelength of 254 nm was used for detection in the GPC measurement. In this specification, when referring to the positional relationship of the layers constituting the structure as "upper" or "lower", it is sufficient as long as there are other layers above or below the reference layer among the plurality of layers concerned. . That is, a third layer or a third element may be further interposed between the reference layer and the above-mentioned other layers, and the reference layer and the above-mentioned other layers do not need to be in contact. In addition, unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "upper", or when there is a composition layer, the direction from the substrate toward the composition layer is referred to as "upper", and vice versa. The direction is called "down". In addition, the setting of such up and down directions is for the convenience of explaining this specification, and in an actual situation, the "up" direction in this specification may also be different from the vertically upward direction. In this specification, unless otherwise specified, as each component contained in the composition, the composition may contain two or more compounds corresponding to the component. In addition, unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component. In this specification, unless otherwise specified, the temperature is 23° C., the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, the combination of preferable aspects is a more preferable aspect.

(composition) The composition of the present invention contains a compound having a fluorine atom and polyimide particles. The compound having a fluorine atom has a compound selected from a group consisting of a nucleophilic functional group, an electrophilic functional group, and a group having an ethylenically unsaturated bond. At least one group in the group, when the above-mentioned compound having a fluorine atom does not contain a group having an ethylenically unsaturated bond, the composition further contains a cross-linking agent having the same A group that reacts with the aforementioned nucleophilic functional group or the aforementioned electrophilic functional group contained in the compound.

In the millimeter wave band (26GHz band, 28GHz band) that is planned to be used in 5G communication or 6G communication, materials with low transmission loss and high flexibility are required. As such materials, compounds having fluorine atoms such as PTFE (polytetrafluoroethylene) have attracted attention. However, since PTFE does not have a cross-linked structure, etc., the mechanical strength is insufficient, and there are also problems in processing suitability. Also, a method of improving mechanical strength by introducing a cross-linked structure into a resin having fluorine atoms such as PTFE is also being studied, but the introduction of a cross-linked structure may impair flexibility. As described above, it is difficult to achieve low transmission loss, flexibility, and processability at the same time using PTFE. The composition of the present invention contains a compound having a fluorine atom and polyimide particles. The above-mentioned compound having a fluorine atom has a compound selected from a nucleophilic functional group, an electrophilic functional group, and a group having an ethylenically unsaturated bond. At least one group in the group, when the above-mentioned compound having a fluorine atom does not contain a group having an ethylenically unsaturated bond, the composition further contains a cross-linking agent having the same A group that reacts with the aforementioned nucleophilic functional group or the aforementioned electrophilic functional group contained in the compound. The cured product obtained from this composition contains a cross-linked product of a compound having a fluorine atom and polyimide particles. It is believed that such a cured product has a large tensile modulus and excellent processability due to the polyimide particles contained therein, and is considered to have a low relative permittivity and suppressed transmission loss due to the compound containing fluorine atoms.

Among them, in Patent Documents 1 and 2, there is neither description nor suggestion for the following aspects: a compound having a fluorine atom and polyimide particles, the compound having a fluorine atom having a compound selected from nucleophilic functional groups, At least one group of the group consisting of an electronic functional group and a group having an ethylenically unsaturated bond further contains A crosslinking agent having a group that reacts with the above-mentioned nucleophilic functional group or the above-mentioned electrophilic functional group contained in the above-mentioned compound having a fluorine atom.

Hereinafter, the components contained in the composition of the present invention will be described in detail.

<Compounds with fluorine atoms> The composition of the present invention contains a compound having a fluorine atom. The fluorine atom is not particularly limited, but it is preferably contained as a substituent of 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 80 atm%, more preferably 10 to 75 atm%, and still more preferably 15 to 70 atm%. 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 Plasma Mass Spectrometry: Inductively Coupled Plasma Mass Spectrometry).

The compound having a fluorine atom has at least one 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, from the viewpoint of lowering the dielectric constant of the cured product, the compound having a fluorine atom has at least one group selected from the group consisting of a nucleophilic functional group and a group having an ethylenically unsaturated bond. More preferably, it contains a group having an ethylenically unsaturated bond. Also, from the viewpoint of increasing the tensile modulus of the obtained cured product, it is preferable to have at least one group selected from the group consisting of nucleophilic functional groups and electrophilic functional groups.

A nucleophilic functional group refers to a group that reacts with an atom with a low electron density to form a bond, and a group that undergoes a nucleophilic substitution reaction is preferred. As a nucleophilic functional group, it is preferable that the compound having a fluorine atom contains at least one group selected from the group consisting of hydroxyl, mercapto, amine and carboxyl. At least one type of group is more preferable. The content of the nucleophilic functional group in the compound having a fluorine atom is not particularly limited, but is preferably 0.001-3000 mmol/g, more preferably 0.01-2000 mmol/g, and still more preferably 0.1-1000 mmol/g.

When the compound having a fluorine atom has a nucleophilic functional group, it is preferable that the composition further contains a crosslinking agent that reacts 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 refers to a group that reacts with an atom with high electron density to form a bond, and is preferably a group that undergoes an electrophilic substitution reaction. As an electrophilic functional group, the compound having a fluorine atom contains at least one group selected from the group consisting of epoxy group, oxetanyl group, maleimide group and oxazoline group More preferably, it contains at least 1 sort(s) of group selected from the group which consists of an epoxy group and a maleimide group. Also, the maleimide group is a group corresponding to a group having an ethylenically unsaturated bond described later. Depending on the other components contained in the composition, the hardening conditions of the film formed by the composition, etc., the maleimide group may function, for example, as an electrophilic functional group, or may act, for example, as a free radical polymerization group. Gender comes into play. The content of the electrophilic functional group in the compound having a fluorine atom is not particularly limited, but is preferably 0.001-3000 mmol/g, more preferably 0.01-2000 mmol/g, and still more preferably 0.1-1000 mmol/g.

When the compound having a fluorine atom has 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.

As a group having an ethylenically unsaturated bond, a radically polymerizable group is preferable, and examples include vinyl, allyl, isoallyl, 2-methallyl, and maleimide group, a group having an aromatic ring directly bonded to vinyl (for example, vinylphenyl, etc.), (meth)acrylamide, (meth)acryloxy, etc., having a direct bond to vinyl A group of an aromatic ring, a (meth)acrylamide group or a (meth)acryloxy group is preferable, and a (meth)acryloxy group is more preferable. 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 3000 mmol/g, more preferably 0.01 to 2000 mmol/g, and still more preferably 0.1 to 1000 mmol/g .

When the compound having a fluorine atom contains a group having an ethylenically unsaturated bond, it is preferable that the composition further contains a crosslinking agent having a group reactive with a group having an ethylenically unsaturated bond. A crosslinking agent and a radical polymerization initiator having a group reactive with an ethylenically unsaturated bond group are more preferable. The crosslinking agent and radical polymerization initiator having a group reactive with a group having an ethylenically unsaturated bond will be described later.

The compound having a fluorine atom is not particularly limited, but a resin having a fluorine atom is preferable, and a resin having a weight average molecular weight of 20,000 or more is more preferable, and a resin having a weight average molecular weight of 25,000 or more is still more preferable, and the weight average molecular weight is 30,000. The above resins are particularly preferred. The upper limit of the above-mentioned weight average molecular weight is not particularly limited, but is preferably 1,000,000 or less, more preferably 500,000 or less, and still more preferably 250,000 or less.

When the compound having a fluorine atom is a resin, examples of the resin include polyesters having a fluorine atom, polytetrafluoroethylene, tetrafluoroethylene-perfluorovinyl ether copolymer, tetrafluoroethylene-ethylene Copolymer, polyvinylidene fluoride, polyvinyl fluoride, chlorotrifluoroethylene-ethylene copolymer, polychlorotrifluoroethylene and other resins, introducing nucleophilic functional groups, electrophilic functional groups and ethylenically unsaturated Resin, etc. made of at least one group (hereinafter, also referred to as "crosslinking site") in the group consisting of bonded groups. The above-mentioned cross-linking sites can be introduced, for example, by introducing monomers having such cross-linking sites as copolymerization components, or these cross-linking sites can be introduced at the terminal. From the viewpoint of easy introduction of crosslinking sites, the compound having fluorine atoms is preferably polyester having fluorine atoms.

式（PE-1）中，L ^P1及L ^P2分別獨立地表示二價連結基，L ^P1及L ^P2中的至少一者具有氟原子。 The polyester preferably contains a repeating unit represented by the following formula (PE-1). [chemical 1]

In 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), L ^P1 is a hydrocarbon group or a hydrocarbon group 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 one group in the group is preferable, and a hydrocarbon group is more preferable. The above R ^N represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, further preferably a hydrogen atom or an alkyl group, and especially preferably a hydrogen atom. The above-mentioned hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, or a group represented by a combination thereof, but an aliphatic hydrocarbon group is preferred, and a saturated aliphatic hydrocarbon group is more preferred. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 2-30, more preferably 3-20, and still more preferably 4-15. The above-mentioned hydrocarbon group may have a substituent. For example, when L ^P1 has a fluorine atom, it is preferable that a part of the hydrogen atoms of the hydrocarbon group be substituted with a fluorine atom.

Specific examples of L ^P1 include the following structures, but the present invention is not limited thereto. [Chem 2]

In the formula (PE-1), L ^P2 is a hydrocarbon group or a hydrocarbon group 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 one group in the group is preferable, and a hydrocarbon group is more preferable. The above R ^N is as described above. The above-mentioned hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, or a group represented by a combination thereof, but an aliphatic hydrocarbon group is preferred, and a saturated aliphatic hydrocarbon group is more preferred. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 2-30, more preferably 3-20, and still more preferably 4-15. The above-mentioned hydrocarbon group may have a substituent. For example, when L ^P2 has a fluorine atom, it is preferable that a part of the hydrogen atoms of the hydrocarbon group be substituted by a fluorine atom.

Specific examples of L ^P2 include the following structures, but the present invention is not limited thereto. [Chem 3]

式（PE-2）中，L ^P3及L ^P4分別獨立地表示二價連結基，L ^P3及L ^P4均不具有氟原子。 式（PE-2）中，L ^P3的較佳態樣為上述的式（PE-1）中的L ^P1的較佳態樣，與不具有氟原子之情況下的態樣相同。 式（PE-2）中，L ^P4的較佳態樣為上述的式（PE-1）中的L ^P2的較佳態樣，與不具有氟原子情況下的態樣相同。 The polyester having a fluorine atom may have one type of repeating unit represented by formula (PE-1) alone, or may have two or more types of repeating units represented by formula (PE-1). Also, the polyester having a fluorine atom may further have repeating units other than the repeating unit represented by formula (PE-1). As such a repeating unit, for example, a repeating unit represented by formula (PE-2) can be mentioned. [chemical 4]

In formula (PE-2), L ^P3 and L ^P4 each independently represent a divalent linking group, and neither L ^P3 nor L ^P4 has a fluorine atom. In formula (PE-2), a preferable aspect of L ^P3 is a preferable aspect of L ^P1 in the above-mentioned formula (PE-1), and it is the same as the aspect in the case of not having a fluorine atom. In the formula (PE-2), a preferable aspect of L ^P4 is a preferable aspect of L ^P2 in the above-mentioned formula (PE-1), and it is the same as the aspect in the case of not having a fluorine atom.

The terminal of the polyester having a fluorine atom is not particularly limited, but preferably has 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 above-mentioned nucleophilic functional groups. [chemical 5]

In the formula (PE-3), L ^P1 represents a divalent linking group, and * represents a bonding site with other structures. In the formula (PE-4), L ^P2 represents a divalent linking group, and * represents a bonding site with other structures. In the formula (PE-3), a preferred aspect of L ^P1 is the same as that of the L ^P1 in the formula (PE-1). In formula (PE-3), * is preferably directly bonded to the oxygen atom in formula (PE-1) or the oxygen atom in formula (PE-2). In the formula (PE-4), a preferred aspect of L ^P2 is the same as that of the L ^P2 in the formula (PE-1). In formula (PE-4), * is preferably directly bonded to the carbonyl group in formula (PE-1) or the carbonyl group in formula (PE-2).

Also, for example, by introducing a compound having an electrophilic functional group and an ethylenically unsaturated bond into a compound having a fluorine atom having these terminals, a group having an ethylenically unsaturated bond can be introduced into a compound having a fluorine atom. Atomic compounds. Examples of such compounds include methacrylic acid, acrylic acid, 2-(meth)acryloxyethyl isocyanate, glycidyl (meth)acrylate, and the like, but are not limited thereto.

It is preferable that content of the compound which has a fluorine atom is 10 mass % or more with respect to the total solid content of the composition of this invention. The said content is more preferably 20 mass % or more, and it is still more preferable that it is 50 mass % or more. Moreover, the said content is preferably 95 mass % or less, More preferably, it is 90 mass % or less. The composition of the present invention may contain one compound having a fluorine atom alone, or may contain two or more compounds having a fluorine atom. When the composition of the present invention contains two or more compounds having fluorine atoms, the total amount thereof is preferably within the above-mentioned range.

＜Polyimide Particles＞ The composition of the present invention contains polyimide particles.

式（PI-1）中，R ^A1表示四價有機基團，R ^A2表示m+1價連結基，m表示1以上的整數，*表示與其他結構的鍵結部位。 [Repeating Unit Represented by Formula (PI-1)] The polyimide particles preferably contain a repeating unit represented by the following formula (PI-1). [chemical 6]

In the formula (PI-1), R ^A1 represents a tetravalent organic group, R ^A2 represents an m+1 valent linking group, m represents an integer of 1 or more, and * represents a bonding site with other structures.

式（5）中，R ¹¹²為單鍵或二價連結基，單鍵或選自可以被氟原子取代之碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO ₂-及-NHCO-、以及該等的組合中之基團為較佳，單鍵或選自可以被氟原子取代之碳數1～3的伸烷基、-O-、-CO-、-S-及-SO ₂-中之基團為更佳，選自由-CH ₂-、-C（CF ₃） ₂-、-C（CH ₃） ₂-、-O-、-CO-、-S-及-SO ₂-組成之群組中之二價基團為進一步較佳。 -R ^A1 - In the formula (PI-1), as the tetravalent organic group in R ^A1 , a tetravalent organic group containing an aromatic ring is preferable, represented by the following formula (5) or formula (6) Group is better. In formula (5) or formula (6), * each independently represents a bonding site with another structure. [chemical 7]

In formula (5), R ¹¹² is a single bond or a divalent linking group, a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons that may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - and -NHCO-, and the groups in their combinations are preferred, single bond or selected from C1-3 alkylene groups, -O-, -CO- that may be substituted by fluorine atoms , -S- and -SO ₂ - are more preferably selected from -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, The divalent group in the group consisting of -S- and -SO ₂ - is further preferred.

Also, R ^A1 preferably does not contain an imide group. 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.

在式（O）中，R ^A1表示四價有機基團。R ^A1的含義與式（PI-1）中的R ^A1的含義相同，較佳範圍亦相同。 Specific examples of R ^A1 include a tetracarboxylic acid residue remaining after removing an acid anhydride group from tetracarboxylic dianhydride. That is, it is preferable that R ^A1 is a structure derived from tetracarboxylic dianhydride. Tetracarboxylic dianhydride is preferably represented by the following formula (O). [chemical 8]

In formula (O), R ^A1 represents a tetravalent organic group. The meaning of R ^A1 is the same as that of R ^A1 in the formula (PI-1), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydride include pyromelite dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' -Diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride , 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4' -Biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7 -naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, 3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4 -tetracarboxylic dianhydride, 1,4,5,6-naphthalene tetracarboxylic dianhydride, 2,2',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 , 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1,2,3,4-benzene Tetracarboxylic dianhydride and these alkyl groups having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Moreover, tetracarboxylic dianhydride (DAA-1) - (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 can also be mentioned as a preferable example.

-R ^A2 - In the formula (PI-1), R ^A2 is a hydrocarbon group or a hydrocarbon group selected from -O-, -C(=O)-, -S-, -S(=O) ₂ -and -NR ^N -The group represented by a combination of at least one group in the group consisting of hydrocarbon groups or hydrocarbon groups and selected from the group consisting of -O-, -C(=O)- and -NR ^N- A group represented by a combination of at least one of them is more preferable. Preferred aspects of ^RN are as described above. Also, the aspect in which R ^A2 is a hydrocarbon group is also preferable, and m in the formula (PI-1) is 1, and the aspect in which R ^A2 is a hydrocarbon group is also one of the preferable aspects of the present invention. The above-mentioned hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, or may be a group represented by a combination thereof, but it is preferable to contain an aromatic hydrocarbon group. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, an aromatic hydrocarbon group having 6 to 10 carbon atoms is more preferable, and an aromatic hydrocarbon group having 6 carbon atoms is still more preferable. As the aforementioned aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group is preferred. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-20, more preferably 1-10, and still more preferably 1-8.

Also, it is preferable that R ^A2 does not contain an imide group.

In addition, R ^A2 is also preferably a structure derived from a bifunctional isocyanate compound described later or a trifunctional or higher isocyanate compound described later.

Specific examples of the structure represented by R ^A2 include, for example, the following structures, but are not limited thereto. In the following structures, * represents the bonding site with other structures, one of the * represents the bonding site with the nitrogen atom in the formula (PI-1), and the other one of the * is the bond site with the nitrogen atom in the formula (PI-1). *same. [chemical 9]

-m- In formula (PI-1), m represents an integer of 1 or more, preferably 2-10, and more preferably 2-5. Moreover, the aspect in which m is 1 is also one of the preferable aspects of this invention.

-content- In the polyimide particles, the content of the repeating unit represented by the formula (PI-1) is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, based on the mass of the resin. The polyimide particle may contain only one kind of repeating unit represented by formula (PI-1), or may contain two or more kinds of repeating units represented by formula (PI-1). In the case where the polyimide particles contain two or more types of repeating units represented by the formula (PI-1), the total content thereof is preferably within the above-mentioned range.

[Polyimide obtained by imidizing the reactant of tetracarboxylic dianhydride and polyfunctional isocyanate compound] Moreover, it is also preferable that the polyimide particle is the polyimide obtained by imidizing the reactant of tetracarboxylic dianhydride and a polyfunctional isocyanate compound.

-Tetracarboxylic dianhydride- It is preferable that the above-mentioned tetracarboxylic dianhydride is a compound represented by the above-mentioned formula (O). Only 1 type may be used for tetracarboxylic dianhydride, and 2 or more types may be used.

-Polyfunctional isocyanate compound- The polyfunctional isocyanate compound may be a bifunctional isocyanate compound, or may be a trifunctional or more isocyanate compound.

Examples of bifunctional isocyanate compounds include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, and hexamethylene diisocyanate. , dipropyl ether diisocyanate, 2,2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, Nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butanediol dipropyl ether diisocyanate, thiodihexyl diisocyanate, hydrogenated xylene diisocyanate, Isophorone diisocyanate, 1,3-diisocyanatocyclohexane, 2,4-diisocyanate-1-methylcyclohexane, 1,3-diisocyanate-2-methylcyclohexane, Aliphatic diisocyanates such as methylene dicyclohexyl diisocyanate and dicyclohexylmethane 4,4'-diisocyanate; m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, Toluidine diisocyanate, methylene diphenyl diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate, isophthalic diisocyanate Aromatic diisocyanates such as methyl diisocyanate, p-xylylene diisocyanate, and tetramethylxylyl diisocyanate, etc., are not limited thereto.

As a trifunctional or more isocyanate compound, the reactant of a polyfunctional alcohol and a bifunctional isocyanate compound is preferable. The details of the production method of the above-mentioned reactant will be described later.

The above polyfunctional alcohol may be an aromatic polyfunctional alcohol, but an aliphatic polyfunctional alcohol is preferred. The carbon number of the polyfunctional alcohol is preferably 2-20, more preferably 3-15, and still more preferably 4-12. The number of hydroxyl groups in the polyfunctional alcohol is preferably 2-10, more preferably 3-10, and still more preferably 3-6.

式（PO-1）中，R ^L1表示a價連結基，a表示2以上的整數。 As the polyfunctional alcohol, a compound represented by the formula (PO-1) is preferable. [chemical 10]

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

In the formula (PO-1), R ^L1 is a hydrocarbon group or is composed of a hydrocarbon group and a group selected from -O-, -C(=O)-, -S-, -S(=O) ₂ - and -NR ^N - A group represented by a combination of at least one group in the group is preferable, and a hydrocarbon group is more preferable. Preferred aspects of ^RN are as described above. The above-mentioned hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, or a group represented by a combination thereof, but an aliphatic hydrocarbon group is preferred, and a saturated aliphatic hydrocarbon group is more preferred. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 2-30, more preferably 3-20, and still more preferably 4-15. In formula (PO-1), a is preferably an integer of 2 to 10, more preferably an integer of 3 to 8, and further preferably an integer of 3 to 6.

Specific examples of the compound represented by the formula (PO-1) include propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol , ethylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 2-methyl-2,4-pentanediol, 1,2-hexanediol, 1, 6-hexanediol, 1,2,6-hexanetriol, 1,2,4-butanetriol, 1,2,3-butanetriol, 3-methyl-1,3,5-pentanetriol (3-Methyl-1,3,5-pentanetriol), Trimethylolethane, Ditrimethylolethane, Trimethylolpropane, Ditrimethylolpropane, Neoerythritol, Dineopentyl Tetrol, Trineopentaerythritol, Glycerin, Diglycerin, Trimethylol Melamine, Hydroquinone, Resorcinol, Catechol, Naphthalene Diol, Bisphenol, Bisphenol A, Bisphenol F, Tetramethyl Bisphenol, phenol novolac resin, etc. are mentioned, but it is not limited to these.

Examples of the bifunctional isocyanate compound include the above-mentioned compounds.

〔Manufacturing method of polyimide particle〕 The method for producing polyimide particles is not particularly limited, and includes the first step of reacting tetracarboxylic dianhydride with a polyfunctional isocyanate compound to obtain a polyimide precursor, and converting the above polyimide precursor into imide The second step of amination is preferred. Also, the method for producing polyimide particles is not particularly limited, and may include a step of reacting tetracarboxylic dianhydride with a polyfunctional amine compound to obtain a polyimide precursor, and converting the above polyimide precursor to a The step of imidization.

-first step- The method for producing polyimide particles preferably includes the first step of reacting tetracarboxylic dianhydride with a polyfunctional isocyanate compound to obtain a polyimide precursor. The preferable aspect of a tetracarboxylic dianhydride and a polyfunctional isocyanate compound is the same as the preferable aspect of the said tetracarboxylic dianhydride and a polyfunctional isocyanate compound.

The above reaction can be performed, for example, in an organic solvent. As the organic solvent, as long as it is a solvent that can dissolve tetracarboxylic dianhydride and polyfunctional isocyanate compound (preferably a solvent that has low solubility of the polyimide precursor obtained separately and can precipitate the polyimide precursor), then It is not particularly limited, and examples thereof include 2-acetone, 3-pentanone, cyclopropanone, tetrahydropyrene, epichlorohydrin, acetone, methyl ethyl ketone (MEK), acetophenone, and tetrahydrofuran (THF). , ethyl acetate, butyl acetate, acetonitrile, acetaniline, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. , it is preferable to contain one of these. These organic solvents may be used individually by 1 type, and may mix and use 2 or more types. In the case of carrying out the above-mentioned 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 four Carboxylic dianhydride and polyfunctional isocyanate compound are added to the organic solvent. Moreover, when carrying out the said reaction in an organic solvent, it is also preferable to carry out under stirring. The stirring method is not particularly limited, and known ultrasonic stirring, stirring with a stirrer, and the like can be mentioned. Among them, when obtaining polyimide particles, ultrasonic stirring is preferable from the viewpoint of monodispersity of particle diameters.

Although it does not specifically limit as reaction temperature, 0-130 degreeC is preferable, 15-80 degreeC is more preferable, 20-40 degreeC is still more preferable. The reaction time is not particularly limited, but is preferably from 30 seconds to 4 hours, more preferably from 1 minute to 3 hours, and still more preferably from 5 minutes to 2 hours. However, the reaction temperature and reaction time are not particularly limited, and may be appropriately adjusted within the range in which the polyimide precursor can be obtained.

The quantity of the tetracarboxylic dianhydride and polyfunctional isocyanate compound used is not specifically limited, For example, it can consider and determine the molar ratio of an acid anhydride group and an isocyanate group, etc. For example, it can be used so that the molar ratio of an acid anhydride group and an isocyanate group may be 0.5:1-1:0.5 (preferably 0.8:1-1:0.8, more preferably 0.9:1-1:0.9). Moreover, the concentration in the reaction liquid of tetracarboxylic dianhydride is not specifically limited, For example, 0.001-0.5 mol/L is preferable, and 0.002-0.2 mol/L is more preferable. The concentration in the reaction solution of the polyfunctional isocyanate compound is not particularly limited, for example, 0.001-0.5 mol/L is preferable, and 0.002-0.2 mol/L is more preferable.

In the first step, it is also preferable to react the tetracarboxylic dianhydride and the polyfunctional isocyanate compound in the presence of an amine catalyst. As the amine catalyst, 1,4-diazabicyclo[2.2.2]octane, triethylamine, benzyldimethylamine, 2-dimethylaminomethylphenol, 2,4,6-tris -Dimethylaminomethyl-3-isocyanatephenol and the like. Among these, 1,4-diazabicyclo[2.2.2]octane, triethylamine, etc. are mentioned.

The polyimide precursor obtained in the first step can be recovered by solid-liquid separation according to known methods such as filtration and centrifugation. For example, if the conditions for obtaining the polyimide precursor as 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, etc., the above-mentioned Solid-liquid separation to recover polyimide precursors.

Also, it is preferable that the polyimide precursor obtained in the first step has a repeating unit represented by the following formula (PP-1). [chemical 11] In the formula (PP-1), R ^A1 represents a tetravalent organic group, R ^A2 represents an m+1 valent linking group, m represents an integer of 1 or more, and * represents a bonding site with other structures.

In formula (PP-1), preferable aspects of R ^A1 , R ^A2 and m are the same as those of R ^A1 , R ^A2 and m in formula (PI-1) above.

[Synthesis procedure of polyfunctional isocyanate] Also, the method for producing polyimide particles of the present invention may have a polyfunctional isocyanate synthesis step for synthesizing polyfunctional isocyanate prior to the first step. The polyfunctional isocyanate synthesis step is preferably, for example, a step of reacting the above-mentioned polyfunctional alcohol with the above-mentioned bifunctional isocyanate compound. The above reaction can be performed, for example, in an organic solvent. The organic solvent is not particularly limited as long as it dissolves the above-mentioned polyfunctional alcohol and the above-mentioned bifunctional isocyanate compound, for example, 2-acetone, 3-pentanone, cyclohexanone, acetophenone, Tetrahydropyrene, epichlorohydrin, acetone, methyl ethyl ketone (MEK), tetrahydrofuran (THF), ethyl acetate, butyl acetate, acetonitrile, acetaniline, toluene, xylene, etc. Although it does not specifically limit as reaction temperature, 0-100 degreeC is preferable, 5-90 degreeC is more preferable, 10-80 degreeC is still more preferable. Although it does not specifically limit as reaction time, 1-10 hours are preferable, 1-8 hours are more preferable, 1-5 hours are still more preferable. Moreover, the said 1st process can also be performed by adding anhydrous tetracarboxylic dianhydride to the reaction liquid after performing the reaction of this polyfunctional isocyanate synthesis process.

〔Second step〕 The method for producing polyimide particles of the present invention preferably includes a second step of imidizing the polyimide precursor obtained in the first step.

In the second step, it is preferable to heat the polyimide precursor obtained in the first step in an organic solvent. As the organic solvent, a solvent with low solubility of the polyimide precursor is preferable, for example, toluene, xylene, ethylbenzene, octane, cyclohexane, diphenyl ether, nonane, pyridine, dodecane Alkane, butyl acetate, acetophenone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. These organic solvents may be used individually by 1 type, and may mix and use 2 or more types. Also, in the first step, when the polyimide precursor is obtained as a solution dispersed in an organic solvent or a dispersion in an organic solvent, the organic solvent can be used as it is. In addition, in the second step, the polyimide precursor can also be imidized by known chemical imidization or the like. As a change in the imidization ratio before and after the second step (that is, the difference between the imidization ratio in the polyimide and the imidization ratio in the polyimide precursor), 60 to 100 % is more preferable, 80 to 100% is more preferable, and 90 to 100% is still more preferable. The said imidization rate can be measured by infrared absorption spectrometry.

In the second step, it is also preferable to carry out imidization while removing carbon dioxide generated during the above-mentioned heating to the outside of the reaction system. The removal method of the carbon dioxide is not particularly limited, and a known removal method can be used, for example, removal by reduced pressure, etc. can be mentioned.

The heating temperature in the above heating is preferably 130 to 250°C. The above heating temperature is preferably 150°C or higher, more preferably 180°C or higher. Moreover, it is preferable that the said heating temperature is 240 degreeC or less, and it is more preferable that it is 230 degreeC or less.

[other steps] The method for producing polyimide particles of the present invention may further include other steps. Examples of other steps include a step of removing impurities by filtering with a filter, a step of blocking a polyimide precursor or a terminal of polyimide, and the like.

-The step of capping the end of the polyimide precursor or polyimide- When blocking the terminal of the polyimide precursor or polyimide, what is necessary is just to make a well-known blocking agent react with a polyimide precursor or polyimide. Details of the reaction method such as reaction conditions can be determined by referring to known methods. When blocking the carboxylic acid anhydride, acid anhydride derivative, or isocyanate group remaining on the polyimide precursor or polyimide terminal, examples of the blocking agent include monoalcohol, phenol, mercaptan, thiophenol, and monoamine etc. From the viewpoint of reactivity and membrane stability, it is more preferable to use monoalcohols, phenols or monoamines. Preferable compounds of monoalcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecyl alcohol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloro Methanol, furfuryl alcohol and other primary alcohols; isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols; grade alcohol. Preferable compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. In addition, preferred compounds of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7- Aminenaphthalene, 1-hydroxy-6-aminenaphthalene, 1-hydroxy-5-aminenaphthalene, 1-hydroxy-4-aminenaphthalene, 2-hydroxy-7-aminenaphthalene, 2-hydroxy-6-aminenaphthalene, 2- Hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-amine Naphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-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-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. Two or more kinds of these can be used, and a plurality of different terminal groups can also be introduced by reacting a plurality of kinds of end-capping agents. In addition, when blocking the isocyanate group at the terminal of the resin, it can be blocked with a compound having a functional group capable of reacting with the isocyanate group. Examples of such compounds include compounds having an acid anhydride group and an acyl halide group, among which carboxylic acid anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic acid anhydride, etc. are preferred. Acid anhydrides and carboxylic acid chlorides are more preferred. Preferred compounds of carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-di Carboxylic anhydride, etc. In addition, preferred compounds of carboxylic acid chlorides include acetyl chloride, acryl chloride, propionyl chloride, methacryl chloride, pivalyl chloride, cyclohexaneformyl chloride, 2-ethylhexyl chloride, and Acyl chloride, cinnamyl chloride, 1-adamantaneformyl chloride, heptafluorobutyryl chloride, stearyl chloride, benzoyl chloride, etc.

〔Physical properties〕 The particle shape of the polyimide particles is not particularly limited, and examples include isotropic shapes (for example, spherical, polyhedral, etc.), anisotropic shapes (for example, needle-like, rod-like, plate-like, etc.), different Shapes such as regular shapes. In addition, the polyimide particles may be either hollow particles or solid particles, or may have a porous shape.

The volume average particle diameter of the polyimide particles is preferably from 10 to 300 nm, more preferably from 15 to 250 nm, and still more preferably from 20 to 200 nm. The said volume average particle diameter is measured by the method described in an Example. Also, the coefficient of variation of the particle diameter of the polyimide particles (standard deviation of particle diameter/volume average particle diameter) is preferably 1 to 30%, more preferably 1 to 20%.

The imidization rate of the polyimide particles is preferably from 60 to 100%, more preferably from 80 to 100%, and still more preferably from 90 to 100%. The said imidization rate can be measured by infrared absorption spectrometry.

〔content〕 The content of the polyimide particles in the composition of the present invention is preferably 1% by mass or more with respect to the total solid content of the composition of the present invention. The above content is preferably at least 5% by mass, and more preferably at least 10% by mass. Moreover, the above-mentioned content is preferably 40% by mass or less, and more preferably 20% by mass or less. The composition of the present invention may contain one type of polyimide particles alone, or may contain two or more types of polyimide particles. When the composition of the present invention contains two or more types of polyimide particles, the total amount thereof is preferably within the above-mentioned range.

〔Specific example〕 Specific examples of polyimide particles include P-1 in Examples and the like, but the present invention is not limited thereto.

＜Crosslinking agent＞ It is preferable that the composition of this invention further contains a crosslinking agent. In the case where the above-mentioned compound having a fluorine atom contained in the composition does not contain a group having an ethylenically unsaturated bond, the composition further contains a crosslinking agent having the same The above-mentioned nucleophilic functional group or the above-mentioned electrophilic functional group reacting group.

[Crosslinking agent having a group reactive with a nucleophilic functional group] In the case where the compound having a fluorine atom contained in the composition contains a nucleophilic functional group, as a cross-linking agent, the composition contains a cross-linking agent selected from a cross-linking agent having an epoxy group, a cross-linking agent having an oxetanyl group Linking agent, cross-linking agent with benzoxazole group, cross-linking agent with maleimide group, cross-linking agent with alkoxysilyl group and compound with (blocked) isocyanate group Preferably, at least one compound in the group is selected from the group consisting of crosslinking agents with epoxy groups, crosslinking agents with alkoxysilyl groups, and compounds with (blocked) isocyanate groups. At least one compound is more preferred.

-Crosslinking agent with epoxy group- As the crosslinking agent (hereinafter, also referred to as "epoxy compound") having an epoxy group, a compound having two or more epoxy groups in one molecule is preferable. The epoxy group undergoes cross-linking reaction below 200°C and does not cause dehydration reaction due to cross-linking, so it is not easy to cause film shrinkage. Therefore, by containing an epoxy compound, low-temperature hardening and warpage of the composition of this invention can be suppressed effectively.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the modulus of elasticity is further reduced, and warpage can be suppressed. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2-15.

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol bicyclo Oxypropyl ether, Butanediol Diglycidyl Ether, Hexylene Glycol Diglycidyl Ether, Trimethylolpropane Triglycidyl Ether, etc. Alkylene Glycol Type Epoxy Resin or Polyol Hydrocarbon Type Epoxy resins; polyalkylene glycol-type epoxy resins such as polypropylene glycol diglycidyl ether; polymethyl (glycidoxypropyl) siloxane and other polysiloxanes containing epoxy groups, etc. But not limited to these. Specifically, EPICLON (registered trademark) 850-S, 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) trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (the above are product names, manufactured by DIC Corporation), RIKARESIN (registered trademark) BEO-20E, RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) Trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700 , EPOLEAD (registered trademark) PB3600 (the above are trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000- L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER- 1020, EPPN-201, BREN-S, BREN-10S (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), etc. Moreover, the following compounds can also be preferably used.

[chemical 12]

In the formula, n is an integer of 1-5, and m is an integer of 1-20.

In the above structure, it is preferable that n is 1-2 and m is 3-7 from the viewpoint of achieving both heat resistance and elongation improvement.

-Crosslinking agent with oxetanyl group- Examples of crosslinking agents having an oxetane group (hereinafter also referred to as "oxetane compounds") include compounds having two or more oxetane rings in one molecule, 3 -Ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl -3-(2-Ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As a specific example, ARON OXETANE series (for example, OXT-121, OXT-221) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these may be used individually, or may mix 2 or more types.

-Crosslinking agent with benzoxazolyl group- Cross-linking agents with benzoxazolyl groups (hereinafter also referred to as "benzoxazolium compounds") do not degas during hardening due to crosslinking reactions caused by ring-opening addition reactions, thereby reducing heat loss. It is preferable to suppress the occurrence of warpage due to shrinkage.

Preferable examples of benzodiazepine compounds include P-d-type benzodiazepines, F-a-type benzodiazepines (the above are trade names, manufactured by Shikoku Chemicals Corporation), and benzos of polyhydroxystyrene resins.㗁Well adducts, phenol novolak type dihydrobenzo 㗁Well compounds. These can be used individually or in mixture of 2 or more types.

-Crosslinking agent having a maleimide group- As a crosslinking agent having a maleimide group (hereinafter also referred to as a "maleimide compound"), a compound having two or more maleimide groups is preferred. good. Examples of maleimide compounds include 4,4'-diphenylmethanebismaleimide, polyphenylmethanemaleimide, m-phenylenebismaleimide m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'- Diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, and the like. These can be used individually or in mixture of 2 or more types.

-Crosslinking agent with alkoxysilyl group- As a crosslinking agent with an alkoxysilyl group (hereinafter also referred to as "alkoxysilane compound"), a tetraalkoxysilane compound, a compound with a trialkoxysilyl group or a dialkoxysilyl group More preferably, tetraalkoxysilane compounds are more preferable. In the present invention, even if a crosslinking agent having an alkoxysilyl group has a crosslinkable group other than an alkoxysilyl group, it is treated as an alkoxysilane compound.

As the tetraalkoxysilane compound, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-two -butoxysilane, quaternary-tertiary-butoxysilane, etc. As a trialkoxysilane compound or a compound having a dialkoxysilyl group, specifically, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methyl Acryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β-(3,4-epoxycyclohexyl)ethyl Trialkoxysilane, Vinyltrialkoxysilane. Among them, γ-glycidoxypropyltrialkoxysilane, γ-methacryloxypropyltrialkoxysilane, and the like are mentioned.

Moreover, the compound represented by the following formula can also be used preferably as an alkoxysilane compound. (R ¹ ) _4-n -Si-(OR ² ) _n In the formula, R ¹ is a hydrocarbon group with 1 to 20 carbons without reactive groups, and R ² is an alkyl or phenyl group with 1 to 4 carbons, n is an integer of 1-3.

An alkoxysilane compound may be used individually or in mixture of 2 or more types.

-Crosslinking agents with (blocked) isocyanate groups- As a crosslinking agent which has a (block) isocyanate group, the compound which has 2 or more (block) isocyanate groups is preferable. The (blocked) isocyanate group refers to any one of an isocyanate group or a blocked isocyanate group. The blocking agent in the blocked isocyanate group is not particularly limited, and examples thereof include lactamides, oximes, amines, aliphatic alcohols, phenols and alkylphenols, imidazoles, pyrazoles, imines, activated methylenes, Blocking agents described in JP-A-2002-309217 and JP-A-2008-239890, etc. Examples of crosslinking agents having isocyanate groups include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hydrogenated toluene diisocyanate, 1,3-xylene diisocyanate, and 1,4-xylene diisocyanate , hexamethylene diisocyanate, diphenylmethane-4,4-diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, tetramethylxylyl diisocyanate Isocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, adducts of these polyisocyanate compounds and polyol compounds such as trimethylolpropane, biurets or isocyanates of these polyisocyanate compounds Urate ester body, etc. Examples of the crosslinking agent having a blocked isocyanate group include compounds in which the isocyanate group in the crosslinking agent having the above-mentioned isocyanate group is blocked by the above-mentioned blocking agent.

The crosslinking agent which has a blocked isocyanate group may be used individually, or may mix and use 2 or more types.

[Crosslinking agent having a group reactive with an electrophilic functional group] When the compound having a fluorine atom contained in the composition contains an electrophilic functional group, the composition contains at least one group selected from the group consisting of hydroxyl, mercapto, amine and carboxyl as a crosslinking agent. Group is better.

-Crosslinking agent with hydroxyl group- As the crosslinking agent having a hydroxyl group, a compound having two or more hydroxyl groups is preferable. The compound having two or more hydroxyl groups is not particularly limited except that it has two or more hydroxyl groups, and examples thereof include aliphatic polyol compounds, alicyclic polyol compounds, and aromatic polyol compounds. The hydroxyl group in the crosslinking agent having a hydroxyl group may be an alcoholic hydroxyl group or a phenolic hydroxyl group.

Examples of crosslinking agents having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, neopentyl glycol, 1,3-butanediol, 2, 2,4-Trimethyl-1,3-pentanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A, Hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol F, propylene oxide adduct of bisphenol F , ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, hydroquinone dihydroxyethyl ether, p-xylylene glycol, dihydroxyethyl sulfide, bis(2- Hydroxyethyl)-2,4-toluene dicarbamate, 2,4-toluene bis(2-hydroxyethylurea), bis(2-hydroxyethyl)-isophthalic dicarbamate ester, 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-tertiary butyl catechol, 4-acetyl catechol, 3-methoxy catechol, 4-phenyl catechol, 4-methyl m-benzene Diphenol, 4-ethylresorcinol, 4-tertiary butylresorcinol, 4-hexylresorcinol, 4-chlororesorcinol, 4-benzylresorcinol, 4- Acetyl resorcinol, 4-methoxyresorcinol, 2-methylresorcinol, 5-methylresorcinol, tertiary butylhydroquinone, 2,5-di- Tertiary butyl hydroquinone, 2,5-di-tertiary pentyl hydroquinone, tetramethyl hydroquinone, tetrachlorohydroquinone, methylaminoformyl hydroquinone ( methylcarboaminohydroquinone), methylureidohydroquinone, methylthiohydroquinone, benzonorbornene-3,6-diol, bisphenol A, bisphenol S, 3,3' -Dichlorobisphenol S, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxybiphenyl, 4,4'-thiodiphenol (4,4'-thiodiphenol), 2,2 '-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-tertiary-butylbenzyl alcohol, 4-hydroxy-3,5-di-tertiary-butylbenzyl alcohol, 4-hydroxyphenethyl alcohol, 2-hydroxyethyl-4-hydroxybenzoate, 2-hydroxyethyl-4-hydroxyphenylacetate, resorcinol mono-2-hydroxyethyl Base ether, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, di-1,2-propanediol, tri-1,2-propanediol, tetra-1,2-propanediol, six-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, etc.

The crosslinking agent which has a hydroxyl group may be used individually, or may mix and use 2 or more types.

-Crosslinking agent with mercapto group- As a crosslinking agent having a mercapto group, a compound having two or more mercapto groups is preferable. The compound having two or more mercapto groups is not particularly limited except that it has two or more mercapto groups, and examples thereof include aliphatic polythiol compounds, alicyclic polythiol compounds, and aromatic polythiol compounds.

Specific examples of the cross-linking agent having a mercapto group that can be used in the present invention include thioglycolic acid, ammonium thioglycolate, monoethanolamine thioglycolic acid, 3-mercaptopropionic acid, methoxybutyl mercaptopropionate, thioapple acid, 2-mercaptoethanol, 2-mercaptopropionic acid, thiodiethylene glycol, thioglycerol, 2-amino-3-mercapto-1-propanol, 4,6-diaminopyrimidine-2-thiol, 2-amino-3-mercaptopropionic acid, 4-aminothiophenol, 3-amino-N-(2-2-mercaptoethyl)propionamide, 6-amino-2-thiouracil, 2 -Amino-4-chlorobenzenethiol, 1-amino-2-methyl-2-mercaptopropane-1-carboxylic acid, etc. have two or more crosslinkable groups and one of the crosslinkable groups is sulfur Alcohol compounds; 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 2,3-dimercapto-1-propanol, dithioerythritol, 2,3- Dimercaptosuccinic acid, 1,2-benzenedithiol, 1,2-benzenedimethylthiol, 1,3-benzenedithiol, 1,3-benzenedimethanol, 1,4-benzenedimethanol Methylmercaptan, 3,4-dimercaptotoluene, o-, m-, or p-xylenedithiol, 4-chloro-1,3-benzenedithiol, 2,4,6-trimethyl-1 ,3-Benzyldimethylthiol, 4,4'-thiobisphenol, 2-hexylamino-4,6-dimercapto-1,3,5-three wells, 2-diethylamino-4 ,6-dimercapto-1,3,5-three wells, 2-cyclohexylamino-4,6-dimercapto-1,3,5-three wells, 2-di-n-butylamino-4, 6-dimercapto-1,3,5-three wells, ethylene glycol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol Dithiol propionate, butanediol dithiopropionate, hexanediol dithioglycolate, 2,5-dimercapto-1,3,4-thiadiazole, 2,2'-( ethylenedithio)diethanethiol, 2,2-bis(2-hydroxy-3-mercaptopropoxyphenylpropane), 1,4-bis(3-mercaptobutyryloxy)butane, 2- (Dimethylamino)-1,3-propanedithiol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 2,5-dimethylamino-1 , 4-benzenedithiol and other compounds having two or more cross-linking groups and the two cross-linking groups are thiol groups; 1,2,6-hexanetriol trithioglycolate, 1, 3,5-trithiocyanuric acid (1,3,5-trithiocyanuric acid), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-three wells-2,4 ,6. Trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, trihydroxyethyl triisocyanurate Ester trithiopropionate, tris[(ethyl-3-mercaptopropionyloxy)ethyl]isocyanurate, etc. have 3 or more crosslinkable groups and the 3 crosslinkable groups are Thiol-based compounds; Neopentylthritol Tetrakis(3-Mercaptopropionate), Neopentylthritol Tetrakis(3-Mercaptobutyrate), Neopentylthritol Tetrathioglycolate, Dineopentylritritol Compounds such as hexa-3-mercaptopropionate having four or more crosslinkable groups and the four or more crosslinkable groups are thiol groups, etc., but are not limited thereto.

As a crosslinking agent having a mercapto group, commercially available ones include ethylene glycol dithiopropionate (EGTG) (registered trademark), trimethylolpropane trithiopropionate (TMTG) (registered trademark) ), neopentylitol tetrathiopropionate (PETG) (registered trademark) (both manufactured by YODO KAGAKU CO.,LTD.) or 1,4-bis(3-mercaptobutyryloxy)butane (Karenz MT BD1) (registered trademark), neopentylitol tetrakis(3-mercaptobutyrate) (Karenz MT PE1) (registered trademark), 1,3,5-tris(3-mercaptobutoxyethyl)-1 ,3,5-three wells-2,4,6(1H,3H,5H)-trione (Karenz MT NR1) (registered trademark) (both manufactured by SHOWA DENKO K.K.) or trimethylolpropane tri-3- Mercaptopropionate (TMMP) (registered trademark), neopentylitol tetrakis-3-mercaptopropionate (PEMP) (registered trademark), diperythritol hexa-3-mercaptopropionate (DPMP) (registered trademark), tris[(ethyl-3-mercaptopropionyloxy)ethyl]isocyanurate (TEMPIC) (registered trademark) (both manufactured by SAKAI CHEMICAL INDUSTRY CO.,LTD.), etc., can be used for The cross-linking agent with mercapto group of the present invention is not limited to these commercially available products.

The crosslinking agent which has a mercapto group may be used individually, or may mix and use 2 or more types.

-Crosslinking agent with amine group- As the crosslinking agent having an amino group, a compound having two or more amino groups is preferable. The compound having two or more amino groups is not particularly limited except that it has two or more amino groups, and examples include aliphatic polyamine compounds, alicyclic polyamine compounds, aromatic polyamine compounds, and heterocyclic cyclic amines. compounds etc.

Examples of crosslinking agents having amino groups include ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, Methylenediamine, dodecamethylenediamine, propane-1,2-diamine, bis(3-aminopropyl)methylamine, 1,3-bis(3-aminopropyl)tetramethylamine siloxane, piperone, 2,5-dimethylpiperone, N-(2-aminoethyl)piperone, 4-amino-2,2-6,6-tetramethylpiperidine, Aliphatic diamine compounds such as N,N-dimethylethylenediamine, lysine, L-cystine, and isophorone diamine; such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-toluenediamine, benzidine, o-xylidine, o-dianisidine, 4-nitro-m-phenylenediamine, 2,5-dimethoxy-p-phenylenediamine, bis-(4-amino Aromatic diamine compounds such as phenyl) phenylene, 4-carboxy-o-phenylenediamine, 3-carboxy-m-phenylenediamine, 4,4'-diaminophenylene ether, 1,8-naphthalene diamine; 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-three wells, 2,6-diaminopyridine, L-histidine, DL-tryptophan, adenine and other heterocyclic amine compounds; 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-amino Phenol, 4-methoxy-3-aminophenol, 4-hydroxybenzylamine, 4-amino-1-naphthol, 4-aminosalicylic acid, 4-hydroxy-N-phenylglycine, 2 - Amino alcohols or aminophenol compounds such as aminobenzyl alcohol, 4-aminophenethyl alcohol, 2-carboxy-5-amino-1-naphthol, and L-tyrosine.

The crosslinking agent which has an amino group may be used individually, or may mix and use 2 or more types.

-Crosslinking agent with carboxyl group- As the crosslinking agent having a carboxyl group, a compound having two or more carboxyl groups is preferable. As a compound having two or more carboxyl groups, polyfunctional carboxylic acids (oxalic acid, adipic acid, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 2 to 10-mer, etc.) are preferred.

The crosslinking agent which has a carboxyl group may be used individually, or may mix and use 2 or more types.

[Crosslinking agent that reacts with groups having ethylenically unsaturated bonds] As a crosslinking agent which reacts with a group having an ethylenically unsaturated bond, a crosslinking agent having an ethylenically unsaturated bond, the above-mentioned crosslinking agent having a mercapto group, etc. can be mentioned, but those containing a group having an ethylenically unsaturated bond A group crosslinking agent is preferred.

-Crosslinking agent containing a group having an ethylenically unsaturated bond- A crosslinking agent containing a group having an ethylenically unsaturated bond, preferably a compound having one or more groups having an ethylenically unsaturated bond, and a compound having two or more groups having an ethylenically unsaturated bond compound is more preferred. The crosslinking agent containing a group having an ethylenically unsaturated bond may have three or more groups having an ethylenically unsaturated bond. As a compound having two or more groups having the aforementioned ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferred, and a compound having 2 to 10 ethylenically unsaturated bonds is more preferred. , compounds having 2 to 6 ethylenically unsaturated bonds are further preferred. Examples of the group having the aforementioned ethylenically unsaturated bond include vinyl, allyl, isoallyl, 2-methallyl, and a group having an aromatic ring directly bonded to vinyl (e.g. , vinylphenyl, etc.), (meth)acrylamide, (meth)acryloxy, etc., a group having an aromatic ring directly bonded to vinyl, (meth)acrylamide or A (meth)acryloxy group is preferred, and a (meth)acryloxy group is further preferred. Moreover, it is preferable that the group which has an ethylenically unsaturated bond is a radically 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 still more preferably 900 or less. The lower limit of the above-mentioned 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, acid, etc.) or its esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyvalent amine compounds. In addition, addition reactants of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl groups, amine groups, and sulfhydryl groups and monofunctional or polyfunctional isocyanates or epoxides can also be preferably used. , Dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. Also, the addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and further have halogen groups Or the substitution reactants of unsaturated carboxylic acid esters or amides with detachable substituents such as toluenesulfonyloxy and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. In addition, as another example, instead of the above-mentioned unsaturated carboxylic acid, a compound group substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, and allyl ether can also be used. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in this specification.

Moreover, as a crosslinking agent containing the group which has an ethylenically unsaturated bond, the compound which has a boiling point of 100 degreeC or more under 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, Neopentylthritol tetra(meth)acrylate, Dineopentylthritol penta(meth)acrylate, Dineopentylthritol hexa(meth)acrylate, Hexylene glycol di( Meth) acrylate, trimethylolpropane tris(acryloxypropyl) ether, tris(acryloxyethyl) isocyanurate, glycerin or trimethylolethane, etc. in polyfunctional alcohols Compounds that undergo (meth)acrylation after adding ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Application Publication No. 51-037193 Urethane (meth)acrylates described in the gazettes, polyesters described in the gazettes of JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490 Acrylates, polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acid; and mixtures thereof. Also, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also preferable. Moreover, the polyfunctional (meth)acrylate obtained by making polyfunctional carboxylic acid and the compound which has a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate, react, etc. are also mentioned.

In addition, as a preferred crosslinking agent containing a group having an ethylenically unsaturated bond other than the above, JP-A-2010-160418, JP-A-2010-129825, and JP-A-4364216 can also be used. Compounds having an oxene ring and two or more groups having ethylenically unsaturated bonds, and cardo resins described in et al.

In addition, as other examples, Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, specific unsaturated compounds described in Japanese Patent Publication No. 01-040336, Japanese Patent Laid-Open No. 02- Vinylphosphonic acid-based compounds described in Publication No. 025493, etc. In addition, perfluoroalkyl-containing compounds described in JP-A-61-022048 can also be used. Furthermore, those introduced as photopolymerizable monomers and oligomers in Journal of the Adhesion Society of Japan vol. 20, No. 7, pages 300 to 308 (1984) can also be used.

In addition to the above, compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used. are included in this manual.

Also, the compounds described in Japanese Patent Application Laid-Open No. 10-062986 as formula (1) and formula (2) together with their specific examples can also be used as a crosslinking agent containing a group having an ethylenically unsaturated bond. The compound is a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then carrying out (meth)acrylic esterification.

In addition, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as a crosslinking agent containing a group having an ethylenically unsaturated bond, and these contents are incorporated in this specification.

As a crosslinking agent containing a group having an ethylenically unsaturated bond, diperythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), diperythritol Tetraacrylate (commercially available: KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), diperythritol penta(methyl) Acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), diperythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) (manufactured by Shin-Nakamura Chemical Co., Ltd.), A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

As a commercially available crosslinking agent containing a group having an ethylenically unsaturated bond, for example, SR-494 manufactured by Sartomer Company, Inc., which is a tetrafunctional acrylate having four ethyleneoxy chains, and SR-494 having SR-209, 231, 239 manufactured by Sartomer Company, Inc. of 2-functional methacrylate with 4 ethyleneoxy chains, SR-209, 231, 239 manufactured by Nippon Kayaku Co., Ltd. as a hexa-functional acrylate with 6 pentyloxy chains DPCA-60, TPA-330 which is a trifunctional acrylate having three isobutoxy chains, urethane oligomers 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 (Nippon Kayaku Co., Ltd. Manufactured by Kyoeisha Chemical Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION.), etc.

As a crosslinking agent containing a group having an ethylenically unsaturated bond, Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765 Urethane acrylates described in the publication No. 58-049860, 56-017654, 62-039417, 62-039418 Urethane compounds having an oxirane-based skeleton as described in are also preferred. In addition, as a cross-linking agent containing a group having an ethylenically unsaturated bond, it is also possible to use those described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238. The described compound has an amine structure or a thioether structure in the molecule.

The crosslinking agent containing a group having an ethylenically unsaturated bond may further have an acid group such as a carboxyl group or a phosphoric acid group. The cross-linking agent with acid groups is preferably an ester of aliphatic polyhydroxy compound and unsaturated carboxylic acid. The unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with non-aromatic carboxylic acid anhydride to make it have acid groups. A cross-linking agent with an ethylenically unsaturated bond group is more preferable. It is especially preferred among the cross-linking agents containing groups having ethylenically unsaturated bonds for reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic acid anhydrides to make them have acid groups. The aliphatic polyhydroxy compounds are novel Compounds of pentylene glycol or dipenteoerythritol. As a commercial item, polybasic-acid-modified acrylic oligomer M-510, M-520 etc. by TOAGOSEI CO., LTD. are mentioned, for example.

The preferred acid value of the crosslinking agent further having an acid group is 0.1-300 mgKOH/g, more preferably 1-100 mgKOH/g. If the acid value of the crosslinking agent containing a group having an ethylenically unsaturated bond is within the above-mentioned range, it will be excellent in workability in production, and will also be excellent in developability. Also, the polymerizability is good. The said acid value is measured according to description of JISK0070:1992.

From the viewpoint of pattern resolution and film stretchability, it is preferable to use bifunctional methacrylate or acrylate for the composition. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene 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 diacrylate, 1,6-hexanediol dimethacrylate , dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct of bisphenol A diacrylate, bisphenol A EO adduct dimethacrylate, PO (propylene oxide) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryl Oxypropyl methacrylate, EO-modified isocyanuric acid diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates with urethane bonds, carbamate-containing Bifunctional methacrylate with ester linkage. These can mix and use 2 or more types as needed. Furthermore, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate having a formula weight of about 200 polyethylene glycol chains. From the viewpoint of suppressing the warpage accompanying the control of the modulus of elasticity of the pattern (hardened product), the composition of the present invention can preferably use a crosslinking agent having only one ethylenically unsaturated bond as the crosslinking agent containing A crosslinking agent with ethylenically unsaturated groups. As a crosslinking agent having only one ethylenically unsaturated bond, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate can be preferably used Butoxyethyl (meth)acrylate, Carbitol (meth)acrylate, Cyclohexyl (meth)acrylate, Benzyl (meth)acrylate, Phenoxyethyl (meth)acrylate , N-methylol(meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allylglycidyl ether. As the crosslinking agent having only one ethylenically unsaturated bond, since volatilization before exposure is suppressed, a compound having a boiling point of 100° C. or higher under normal pressure is also preferable. Moreover, allyl compounds, such as diallyl phthalate and triallyl trimellitate, are mentioned as a crosslinking agent containing the group which has an ethylenically unsaturated bond.

The crosslinking agent containing the group which has an ethylenically unsaturated bond may be used individually by 1 type, and may mix and use 2 or more types.

〔content〕 The content of the crosslinking agent is preferably 3% by mass or more with respect to the total solid content of the composition of the present invention. The above content is preferably at least 5% by mass, and more preferably at least 10% by mass. Moreover, the said content is preferably 95 mass % or less, More preferably, it is 90 mass % or less. The composition of the present invention may contain one type of cross-linking agent alone, or may contain two or more types of cross-linking agents. When the composition of the present invention contains two or more types of crosslinking agents, the total amount thereof is preferably within the above-mentioned 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, when the composition contains a crosslinking agent containing the above-mentioned group having an ethylenically unsaturated bond, it is preferable to contain a polymerization initiator, and it is more preferable to contain 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, particularly a thermal radical polymerization initiator. The thermal free radical polymerization initiator is a compound that generates free radicals by thermal energy and initiates or accelerates the polymerization reaction of polymerizable compounds. Moreover, the photopolymerization initiator mentioned later may also have the 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 JP-A-2008-063554, and the content thereof is incorporated in the present specification.

When a thermal polymerization initiator is contained, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 20% by mass, based on the total solid content of the composition of the present invention. 15% by mass. The composition may contain only one type of thermal polymerization initiator, or may contain two or more types of thermal polymerization initiators. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.

[Photopolymerization Initiator] As the photopolymerization initiator, a photoradical polymerization initiator is preferable. It is preferable that the photoradical polymerization initiator contains at least one compound having a molar absorption coefficient of at least about 50 L·mol ^-1 ·cm ^-1 in the wavelength range of about 240-800 nm (preferably 330-500 nm). The molar absorptivity of a compound can be measured by a known method. For example, it is preferable to measure at a concentration of 0.01 g/L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As a photoradical polymerization initiator, a well-known compound can be used arbitrarily. For example, halogenated hydrocarbon derivatives (such as compounds having a three-well skeleton, compounds having a oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbis Oxime compounds such as imidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxyl compounds such as hydroxyacetophenone Ketone compounds, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. For such details, reference can be made to the descriptions in paragraphs 0165 to 0182 of JP-A-2016-027357 and descriptions in paragraphs 0138 to 0151 of International Publication No. 2015/199219, which are incorporated in this specification. Also, the compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in JP-A-6301489, and those described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019 can be mentioned. Peroxide-based photopolymerization initiator, photopolymerization initiator described in International Publication No. 2018/221177, photopolymerization initiator described in International Publication No. 2018/110179, Japanese Patent Laid-Open No. 2019-043864 The photopolymerization initiator described in the Publication No. 2019-044030, the photopolymerization initiator described in the Japanese Patent Application Publication No. 2019-044030, and the peroxide-based initiator described in the Japanese Patent Application Publication No. 2019-167313, These contents are incorporated into this manual.

As such photopolymerization initiators, compounds described in paragraphs 0141 to 0147 of International Publication No. 2021/157571 can be preferably used.

More preferably, an oxime compound is mentioned as a photoradical polymerization initiator. By using an oxime compound, exposure latitude can be improved more effectively. Since the exposure latitude (exposure margin) of an oxime compound is wide and it functions also as a photocuring accelerator, it is especially preferable.

As specific examples of oxime compounds, compounds described in paragraphs 0149 to 0154 of International Publication No. 2021/157571 can be preferably used. In addition, as the photoradical polymerization initiator, compounds described in paragraphs 0155 to 0162 of International Publication No. 2021/157571 can be preferably used.

〔content〕 When a polymerization initiator is contained, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 15% by mass relative to the total solid content of the composition of the present invention. % by mass is further preferably 1.0 to 10% by mass. A polymerization initiator may contain only 1 type, and may contain 2 or more types. When containing 2 or more types of polymerization initiators, it is preferable that the total amount is in the said range.

<Solvent> The composition of the present invention may contain a solvent. Moreover, the composition of this invention can also be set as the form which does not contain a solvent substantially. Substantially no solvent means that the content of the solvent is 5% by mass or less, preferably 1% by mass or less, more preferably 0.1% by mass or less, based on the total mass of the composition.

Examples of solvents include acetone, methyl ethyl ketone, hexane, heptane, octane, 2-heptanone, cycloheptanone, cyclohexanone, cyclohexane, methylcyclohexane, ethyl Cyclohexane, methyl-n-amyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monoacetate, ethylene glycol Alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diethyl ether, propylene glycol monoacetate, dipropylene glycol monoacetate, propylene glycol diacetic acid Esters, Propylene Glycol Monomethyl Ether, Propylene Glycol Monomethyl Ether Acetate, Propylene Glycol Monoethyl Ether Acetate, Cyclohexyl Acetate, Ethyl 3-Ethoxypropionate, Er㗁口山, Methyl Lactate, Ethyl Lactate, Methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, anisole, ethyl benzyl ether, cresol Cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butyl phenyl ether, benzene, ethylbenzene, diethylbenzene, pentylbenzene, cumene, toluene, xylene, isopropylbenzene Propyl toluene, mesitylene, methanol, ethanol, isopropanol, butanol, methyl monoglycidyl ether, ethyl monoglycidyl ether, butyl monoglycidyl ether, phenyl monoglycidyl ether Oxypropyl Diglycidyl Ether, Methyl Diglycidyl Ether, Ethyl Diglycidyl Ether, Butyl Diglycidyl Ether, Phenyl Diglycidyl Ether, Cresol Monoglycidyl Ether , ethylphenol monoglycidyl ether, butylphenol monoglycidyl ether, mineral spirits, perfluorocarbons, hydrofluoroethers, hydrochlorofluorocarbons, hydrofluorocarbons, perfluoropolyethers, dimethyl imidazoline, tetrahydrofuran, pyridine, formamide, acetaniline, dioxolane, o-cresol, m-cresol, p-cresol, phenol, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-di Ethylacetamide, 1,3-dimethyl-2-imidazolidinone, dimethylsulfide, diethylsulfide, dimethylsulfide, diethylsulfide, γ-butyrolactone, cyclobutane Pine, halogenated phenols, various polysiloxane oils, etc. These solvents may be used individually by 1 type, and may use 2 or more types together.

When the composition contains a solvent, the content of the solvent is preferably 20 to 90% by mass, more preferably 30 to 80% by mass, and still more preferably 40 to 70% by mass, based on the total mass of the composition.

＜Adhesive agent＞ The composition of the present invention may contain an adhesion aid. As an adhesion aid, a silane coupling agent, a chelating agent, etc. are mentioned.

The silane coupling agent has an alkoxysilyl group as a hydrolyzable group (capable of chemically bonding with the inorganic material as the substrate), which shows affinity through the interaction or bond formation with the organic resin. (Meth)acryl, phenyl, secondary or tertiary mercapto, epoxy, aminosilane and other silane coupling agents are preferred, among which (meth)acrylpropyltrimethoxysilane , Glycidyltrimethoxysilane is more preferred. Examples of such materials include KBM-303, KBM-403, and KBM-503 (the above are manufactured by Shin-Etsu Chemical Co., Ltd.). In the present invention, these compounds may be included as the above-mentioned crosslinking agent having an alkoxysilyl group. Moreover, when the compound which has a fluorine atom contains an electrophilic functional group, you may contain the above-mentioned crosslinking agent which has a group reactive with an electrophilic functional group, and this adhesion assistant. Moreover, when the compound which has a fluorine atom contains the group which has an ethylenically unsaturated bond, it may contain the crosslinking agent which reacts with the group which has an ethylenically unsaturated bond, and this adhesion aid.

As a chelating agent, an aluminum chelate, a titanium chelate, a zirconium chelate, etc. are mentioned. The aluminum chelate compound is not particularly limited, and for example, aluminum ethylacetoacetate diisopropylate, aluminum ethylacetoacetate diisopropylate, and alkylacetoacetate-diisopropylate can be used. Aluminum (aluminum alkyl acetoacetate diisopropylate), aluminum bisethylacetoacetate monoacetylacetonate, aluminum trisacetylacetonate, etc. It does not specifically limit as a titanium chelate compound, For example, titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethyl acetoacetate (titanium ethyl acetoacetate) etc. can be used. It does not specifically limit as a zirconium chelate compound, For example, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, etc. can be used.

When the composition of the present invention contains an adhesion aid, the content of the adhesion aid 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 one type of adhesion aid alone, or may contain two or more types of adhesion aid. When the composition of this invention contains 2 or more types of adhesion aids, it is preferable that these total amounts are in the said range.

＜Other additives＞ The composition of the present invention may further contain other additives as necessary within the range in which the effects of the present invention can be obtained. Examples of other additives include surfactants, acid generators, base generators, inorganic particles, ultraviolet absorbers, antioxidants, anti-agglomerates, other polymer compounds, plasticizers, and other additives (such as , defoamer, flame retardant, etc.) and other known additives. Properties such as film physical properties can be adjusted by appropriately containing these components. When blending these additives, it is also preferable to set their respective blending amounts to 3% by mass or less of the solid content of the composition of the present invention. Moreover, it is also preferable to make the total content of other additives into 5 mass % or less of the solid content of the composition of this invention.

〔use〕 The composition of the present invention is preferably used for insulating film formation. 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, an insulating film in a metal-clad laminate having an inner layer circuit, and the like. In particular, the composition of the present invention is preferably used to form an insulating film as a base material (base film) for a flexible printed wiring board or a protective film (cover film) for a flexible printed wiring board. In addition, the composition of the present invention can also be used as a buffer coating, surface coating agent for lenses, adhesive agent (for example, an adhesive agent for bonding a metal film and an insulating film in a metal-clad laminate), and the like.

〔Preparation of composition〕 The composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and it can be performed by a conventionally known method. For mixing, mixing by a stirring blade, mixing by a ball mill, mixing by rotating the tank itself, etc. can be used. The temperature during mixing is preferably from 10 to 40°C, more preferably from 15 to 30°C.

＜hardened material＞ 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 above heating temperature is preferably from 120 to 400°C, more preferably from 140 to 380°C, and still more preferably from 170 to 350°C. The shape of the cured product is not particularly limited, and film, rod, spherical, granular, etc. can be selected according to the application. In the present invention, the cured product is preferably in the form of a film. Also, by patterning the composition, the shape of the cured product such as forming a protective film on the wall surface, forming via holes for conduction, adjusting impedance, electrostatic capacitance or internal stress, and imparting a heat dissipation function can be selected according to the application. The film thickness of the cured product (film composed of the cured product) is preferably not less than 0.5 μm and not more than 150 μm.

The volume resistivity of the cured product is preferably 10 ¹⁴ to 10 ¹⁹ Ω·cm, more preferably 10 ¹⁵ to 10 ¹⁸ Ω·cm, and still more preferably 10 ¹⁶ to 10 ¹⁷ Ω·cm. The dielectric loss tangent of the cured product at 10 GHz is preferably at most 0.002, more preferably at most 0.0018, and still more preferably at most 0.0016. The lower limit of the above-mentioned dielectric loss tangent is not particularly limited, for example, it is preferably 0.0001 or more. The relative permittivity of the cured product is preferably less than 3.3, more preferably less than 3.0, and still more preferably less than 2.8. The lower limit of the above-mentioned relative permittivity is not particularly limited, for example, it is preferably 0.1 or more.

(Manufacturing method of hardened product) The method for producing a cured product of the present invention preferably includes a film forming step of applying the composition of the present invention to form a film on a substrate, and a curing step of curing the film.

＜Film formation process＞ 〔Substrate〕 Although it does not specifically limit as a base material, The base material which has a metal layer on the surface, or the base material which consists of metal (for example, a metal foil) is preferable. As the metal in the substrate having a metal layer on the surface, or the metal in the substrate formed of metal, gold, silver, copper, nickel, stainless steel, titanium, aluminum, indium, tin, manganese, nickel, Cobalt, molybdenum, tungsten, chromium, neodymium or alloys containing these, copper or alloys containing copper are preferred. Moreover, examples of other substrates include polyimide, liquid crystal polymer, polyethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, polyetherimide, polyphenylene ether , polyester, para-aramid, polylactic acid, nylon, polyparabanic acid, polyether ether ketone, etc.

Moreover, an adhesive layer may be further provided on the surface of these base materials. As an adhesive bond layer, what is well-known in the field of a flexible printed wiring board is mentioned. In addition, in the production of the cured product of the present invention, the aspect in which such an adhesive layer is omitted (no adhesive layer) is also one of the preferable aspects.

Moreover, the shape of a base material is not specifically limited, A film shape is preferable. As a size of a base material, if it is a film form, width is 30-600 cm, and length is 100-1000 m, for example. Moreover, the shape of a base material is not specifically limited, For example, a plate shape etc. are sufficient. The base material may be in the form of a roll, for example, unwinding of the base material, application of the composition by the film forming step, hardening of the composition by the curing step, and winding of the base material on which the hardened product is formed can be performed in order. step. When performing the metal layer forming step described later, for example, the metal layer forming step can also be performed after applying the composition in the film forming step and before curing the composition in the curing step.

As a method of applying the composition of the present invention to a substrate, coating is preferred, and casting coating is more preferred. Examples of casting methods include roll coating, gravure coating, knife coating, blade coating, bar coating, dip coating, spray coating, curtain coating, and slit coating. , screen printing, etc. Also, the composition can be applied to both surfaces of the substrate. As temperature at the time of casting, 60-300 degreeC is preferable, and 100-250 degreeC is more preferable. The thickness of the cast composition is not particularly limited, but is preferably 1-500 μm. Also, when the composition contains a solvent, it may be dried after application. The drying temperature is preferably from 50°C to 150°C, more preferably from 70°C to 130°C, and still more preferably from 90°C to 110°C. Moreover, drying can be performed by reducing pressure. As a drying time, 30 seconds - 20 minutes can be illustrated, Preferably it is 1 minute - 10 minutes, More preferably, it is 2 minutes - 7 minutes.

＜Hardening step＞ In the hardening step, the film formed on the substrate is hardened. In the hardening step, crosslinking is formed between crosslinking sites contained in the compound having a fluorine atom or between the above crosslinking sites and a crosslinking agent to obtain a cured product. Hardening is preferably performed by at least one of heating and exposure. In particular, in the present invention, the curing step is preferably a step of curing the above-mentioned film by heating.

〔heating〕 When the hardening step is performed by heating, the heating temperature (maximum heating temperature) is preferably 50 to 450°C, more preferably 150 to 350°C, further preferably 150 to 250°C, and 160 to 250°C It is still more preferable, especially 160-230 degreeC. The heating time is preferably from 5 to 360 minutes, more preferably from 10 to 300 minutes, and still more preferably from 15 to 240 minutes.

Heating can be performed in an atmosphere of low oxygen concentration or low humidity by flowing an inert gas such as nitrogen, helium, or argon, or performing under reduced pressure. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less. It does not specifically limit as a heating method in a heating process, For example, a hot plate, an infrared oven, an electric oven, a hot-air oven, an infrared oven, etc. are mentioned.

[Exposure] In the hardening step, the above film may be subjected to exposure. In this case, it is preferable to expose the entire surface of the film. The amount of exposure is not particularly limited as long as it can harden the composition of the present invention. For example, in terms of exposure energy at a wavelength of 365 nm, it is preferably 50-10,000 mJ/cm ² , and more preferably 200-8,000 mJ/cm ² .

The exposure wavelength should just be the wavelength which can sensitize a polymerization initiator, for example, and can be suitably determined in the range of 190-1,000 nm, Preferably it is 240-550 nm.

Regarding the exposure wavelength, in terms of the relationship with the light source, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamp, (3) High-pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (three wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser Radiation (wavelength 248nm), ArF excimer laser (wavelength 193nm), F ₂ excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG Laser second harmonic 532nm, third harmonic 355nm, etc. Regarding the composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferable, and among them, exposure by i-rays is preferable.

＜Metal layer formation process＞ The method for producing a cured product of the present invention may further include a metal layer forming step. For example, when using a substrate having a metal layer on its 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 opposite to the metal. Also, in the case of using a base material that does not have a metal-free layer as the base material in the film forming step, the metal layer can be formed on the opposite side of the film from the base material. For example, the above-mentioned films may be formed on both surfaces of the substrate, and a metal layer may be formed on the side of each of the above-mentioned films opposite to the substrate. Examples of metals in the formed metal layer include gold, silver, copper, nickel, stainless steel, titanium, aluminum, indium, tin, manganese, nickel, cobalt, molybdenum, tungsten, chromium, neodymium, or alloys containing these etc. Copper or an alloy containing copper is preferred. The thickness of the metal layer is preferably 0.1-500 μm. The method of forming the metal layer is not particularly limited, and known methods such as a method of pressure-bonding a metal foil to the above-mentioned film can be used. In addition, after forming the metal layer, the interface between the substrate and the cured product can be peeled off to obtain a cured product and a structure composed of the metal layer.

＜Other steps＞ The method for producing a cured product of the present invention may further include other steps. Examples of other steps include a step of activating the surface of the substrate, a step of washing 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 and the metal layer of the present invention. In the structure of the present invention, the cured product of the present invention and the metal layer may be in direct contact, or there may be a known adhesive layer between the cured product of the present invention and the metal layer, but the cured product of the present invention and the metal layer Direct contact is also preferred. Also, the structure of the present invention may be, for example, a metal layer-hardened product in which the metal layer exists only on one side of the hardened product of the present invention, or may be a metal layer-hardened product-metal layer in this invention. The embodiment in which the metal layer is present on both sides of the hardened product of the invention may be, for example, metal layer-hardened product-other base material layer-hardened product-metal layer, in which the metal layer is formed on one side on both sides of the other base material layer. An aspect of the cured product of the present invention. In addition, aspects such as metal layer-cured product-other base material layer, metal layer-hardened material-other base material layer-metal layer are also possible. In these aspects, as described above, a known adhesive layer or the like may be present between the cured product of the present invention and the metal layer. Examples of the metal layer include the above-mentioned metal layer of the base material having a metal layer on its surface, or the base material itself formed of metal. Moreover, it may be the metal layer formed by the metal layer formation process mentioned above. The thickness of the metal layer is preferably from 0.1 to 1000 μm, more preferably from 1 to 500 μm. The structure of the present invention is produced, for example, by using, as the base material, a base material having a metal layer on its surface or a base material formed of metal in the above-mentioned 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 forming a printed wiring board (for example, a single-sided metal-clad laminate or a double-sided metal-clad laminate). For example, by removing a part of the metal layer in the structure of the present invention by etching or the like, the structure of the present invention can be used as a substrate on which metal wiring is formed on the surface.

(element) The present invention also discloses components having the cured article of the present invention. Specific examples of such components include, for example, electronic components such as printed wiring boards and lead frames, components used for 5G communication and 6G communication using the millimeter wave band (26GHz band, 28GHz band), and the like. It is considered that since the cured product of the present invention is excellent in workability, it is considered easy to manufacture various devices. In addition, it is considered that the cured product of the present invention can contribute to low retardation, low transmission loss, and the like in various devices because of its low relative permittivity. [Example]

Hereinafter, the present invention will be described in more detail with reference to examples. Materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed unless departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

(synthesis example) ＜Synthesis of P-1＞ The following solutions were prepared respectively: a solution obtained by dissolving 1.07g (3.33mmol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride in acetone (30ml) was used as the first solution ; 0.74 g (3.33 millimoles) of isophorone diisocyanate dissolved in acetone (30 ml) obtained as a second solution; and 0.13 g of 1,4-diazabicyclo [2.2.2 ] octane dissolved in acetone (7ml) in the resulting solution. After mixing these at 25° C., the mixed solution was reacted under ultrasonic stirring (frequency 28 KHz, 1 hour) using an ultrasonic cleaner. Thereafter, the polyimide precursor was precipitated by stirring for about 12 hours using a stirrer. After recovering the precipitated polyimide precursor with a centrifuge, the steps of washing with acetone and further centrifugation were repeated, and the polyimide precursor was purified. As a result of observing the obtained polyimide precursor with a scanning electron microscope (SEM), it was confirmed that it was composed of monodisperse uniform spherical particles. Next, about 1.0 g of the above-mentioned polyimide precursor was dispersed in n-dodecane (150 ml) and refluxed at 210° C. for 5 hours to perform imidization to produce polyimide particles. The produced polyimide particles were collected by a centrifuge, washed with acetone and centrifuged repeatedly, and purified. The volume average particle diameter of the produced polyimide precursor was 0.2 μm, and the volume average particle diameter of the polyimide was 0.2 μm. The volume average particle diameters were respectively measured with a concentration-type particle diameter analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).

＜Synthesis of A-1＞ Add 3.65g (30.9mmol) of 1,6-hexanediol and 11.7g (30.0mmol) of dodecafluorosuberic acid and 0.03g of tetraisopropoxytitanium into a 100ml flask. Stirring was carried out at 215°C for 6 hours. The obtained A-1 is a polyester diol. As A-1, the weight average molecular weight was 100,000. Also, by changing the usage ratio of 1,6-hexanediol and dodecafluorosuberic acid and the reaction time, one with a weight average molecular weight of 20,000 and one with a weight average molecular weight of 70,000 were respectively synthesized.

＜Synthesis of A-2＞ In addition to changing the amount of 1,6-hexanediol used in the synthesis of A-1 to 3.54 g (30.0 moles) and the amount of dodecafluorosuberate to 12.1 g (30.9 moles), Otherwise, A-2 was synthesized by the same method as A-1. A-2 is polyester dicarboxylic acid. The weight average molecular weight of A-2 was 70,000.

＜Synthesis of CA-1＞ CA-1 was synthesized by the same method as A-1, except that dodecafluorosuberic acid in the synthesis of A-1 was changed to the same molar amount of suberic acid. The weight average molecular weight of CA-1 was 70,000.

＜Example and Comparative Example＞ In each of the Examples and Comparative Examples, the components described in the following tables were mixed to prepare compositions.

[Table 1] Example Example Example Example Example Example Example comparative example comparative example comparative example 1 2 3 4 5 6 7 1 2 3 raw material resin type A-1 A-1 A-2 A-1 A-1 A-1 A-1 CA-1 A-1 CA-1 mw 70000 70000 70000 70000 70000 20000 100000 70000 70000 70000 parts by mass 85 85 85 70 50 85 85 85 85 85 crosslinking agent type B-1 B-2 B-3 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 5.0 5.0 5.0 20.0 40.0 5.0 5.0 5.0 5.0 5.0 Polyimide Particles type P-1 P-1 P-1 P-1 P-1 P-1 P-1 P-1 - - parts by mass 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 - - evaluate Tensile modulus A A A A A A A A C C relative permittivity A A A A B A A C A C

The details of the abbreviations in the table are as follows. [resin] ・A-1 to A-2: Synthetic products of the above. A-1 and A-2 correspond to compounds having a fluorine atom. ・CA-1: A synthetic product of the above. CA-1 does not correspond to compounds having fluorine atoms.

〔Crosslinking agent〕 ・B-1: Tetrabutoxysilane ・B-2: Hexamethylene diisocyanate ・B-3: Bisphenol A Diglycidyl Ether

〔Polyimide particles〕 ・P-1: Synthesis of the above

＜Evaluation＞ 〔Measurement of tensile modulus〕 The test pieces described in JIS K 7161 (2014) "Plastics - Determination of tensile properties" were produced from the compositions prepared in each example or comparative example, and this The tensile modulus recorded in the standard. Specifically, the polymer is dissolved in, for example, methylene chloride or N-methylpyrrolidone (NMP), coated on, for example, a polytetrafluoroethylene sheet, and dried at, for example, 160°C. A cast film with a thickness of about 200 μm was obtained. This cast film was cut into a size of 10 mm × 20 mm, and it was set in a tensile testing machine so that the distance between chucks (distance between grips) was 10 mm, and the slope of the stress/strain curve was evaluated, and The modulus of elasticity was found. Based on the measured elastic modulus, evaluation was performed according to the following evaluation criteria, and the evaluation results were described in the column of "tensile modulus" in the table. -Evaluation criteria- A: The above elastic modulus is 1.0 GPa or more. B: The above elastic modulus is 0.5 GPa or more and less than 1.0 GPa. C: The above elastic modulus is less than 0.5 GPa.

〔Measurement of Relative Permittivity〕 In each example or comparative example, PNA-L network analyzer N5230A (manufactured by KEYSIGHT TECHNOLOGIES Co., Ltd.) was used, and CP521 (manufactured by Kanto Electronics Application & Development Inc.) was used as a dielectric coefficient measuring device for cavity resonance disturbance method, The dielectric coefficient (ε) and dielectric loss tangent (tanδ) of the cast film produced in the evaluation of the tensile modulus were evaluated at 23°C and a frequency of 10 GHz by the cavity resonator perturbation method. determined. The relative permittivity was calculated by dividing the measured permittivity (ε) by the permittivity of vacuum, and evaluated according to the following evaluation criteria, and the evaluation results were described in the "relative permittivity" column of the table middle. -Evaluation criteria- A: The relative permittivity is less than 2.8. B: The relative permittivity is 2.8 or more and less than 3.3. C: The relative permittivity is 3.3 or more.

From the above results, it can be seen that the cured product composed of the composition of the present invention has a high tensile modulus and a low relative permittivity. The composition of Comparative Example 1 does not contain a compound having a fluorine atom. It can be seen that the relative permittivity of the cured product obtained from this composition is high. The compositions of Comparative Examples 2 and 3 did not contain polyimide particles. It can be seen that the tensile modulus of the cured product obtained from such a composition is low.

Claims (14)

A composition comprising: Compounds having fluorine atoms; and polyimide particles, The aforementioned compound having a fluorine atom has at least one group selected from the group consisting of a nucleophilic functional group, an electrophilic functional group, and a group having an ethylenically unsaturated bond, In the case where the aforementioned compound having a fluorine atom does not contain a group having an ethylenically unsaturated bond, the aforementioned composition further contains a crosslinking agent having the same nucleophilicity as that contained in the aforementioned compound having a fluorine atom. Sexual functional groups or groups that react with the aforementioned electrophilic functional groups. The composition as described in claim 1, wherein The compound having a fluorine atom contains at least one group selected from the group consisting of a hydroxyl group, a mercapto group, an amine group, and a carboxyl group as the nucleophilic functional group. The composition as described in claim 1 or 2, wherein The aforementioned compound having a fluorine atom contains at least one group selected from the group consisting of an epoxy group, an oxetanyl group, a maleimide group, and an azoline group as the aforementioned electrophilic functional group. base. The composition as described in claim 1 or 2, wherein The content of the compound having a fluorine atom is 10% by mass or more relative to the total solid content of the composition. The composition as described in claim 1 or 2, wherein The aforementioned compound having a fluorine atom is a resin having a weight average molecular weight of 20,000 or more. The composition as described in claim 1 or 2, wherein The volume average particle diameter of the aforementioned polyimide particles is 10 nm to 300 nm. The composition as described in claim 1 or 2, wherein The compound having a fluorine atom contains a group having an ethylenically unsaturated bond, and the composition contains a crosslinking agent and a radical polymerization initiator that react with the group having an ethylenically unsaturated bond. The composition according to claim 1 or 2, which is used for forming an insulating film. A hardened product obtained by hardening the composition described in any one of claims 1 to 8. A method of manufacturing a cured product, comprising: A film forming step in which a film is formed by applying the composition described in any one of claims 1 to 8 on a substrate; and A hardening step of hardening the aforementioned film. The manufacturing method of the hardened object as described in Claim 10, wherein The aforementioned base material is a base material having a metal layer on the surface or a base material formed of metal. The method for producing a hardened product according to claim 10 or 11, wherein The aforementioned hardening step is a step of hardening the aforementioned film by heating. A structure comprising the hardened product described in claim 9 and a metal layer. An element comprising the cured product described in Claim 9.