JP2022169155A - Film coated substrate and method for manufacturing film coated substrate - Google Patents

Abstract

To provide electronic component devices that have a high degree of cold thermal shock resistance and can suppress reliability failures.SOLUTION: A film coated substrate includes a mounting substrate (1) and a film coating material (2) that covers the mounting substrate (1), and the mounting substrate (1) includes a substrate (11), electronic components (12), and an underfill material (13) that connects the substrate (11) and electronic components (12).SELECTED DRAWING: Figure 2

Description

The present disclosure particularly relates to a film-coated substrate obtained by coating a mounting substrate with a film.

A technique is known in which a mounting substrate on which electronic components such as a coil are mounted is covered with a film in order to impart insulation, waterproofness, and the like (Patent Document 1). Patent Literature 1 discloses a method of fixing a thermoplastic covering film from an electronic component to its surrounding substrate surface by overlay molding by partially reducing the pressure in a sealed space.

JP 2015-228421 A

However, even if the various performances of electronic component devices are improved by using film coating, poor continuity and/or insulation may occur in harsh environments such as in-vehicle environments that require high thermal shock resistance. The inventors of the present application have found that the occurrence of defects may lead to poor reliability. It is presumed that this is because unintended internal stress is generated in the electronic component device under severe environments even if the coating film is used. The present disclosure has been made in view of such circumstances. That is, a main object of the present disclosure is to provide a product (eg, electronic component device) that has high thermal shock resistance (eg, conductivity after thermal shock) and can suppress reliability defects.

The present disclosure has been made in view of such circumstances. The present inventors have attempted to achieve the above object by addressing the problem in a new direction, rather than by extending the conventional technology, and have found that the above main object can be achieved, leading to the present disclosure. A preferred embodiment of the present disclosure is as follows:
[Section 1]
A film-coated substrate comprising a mounting substrate (1) and a film covering material (2) covering the mounting substrate (1),
A film-coated substrate, wherein said mounting substrate (1) comprises a substrate (11), an electronic component (12), and an underfill material (13) connecting said substrate (11) and said electronic component (12).
[Section 2]
Item 2. The film-coated substrate according to Item 1, wherein the underfill material (13) is a curable composition or a cured product thereof containing an epoxy resin (A), a curing agent (B) and an inorganic filler (C).
[Section 3]
Item 3. The film-coated substrate according to item 2, wherein the epoxy resin (A) comprises a silicone-modified epoxy resin.
[Section 4]
Item 4. The film-coated substrate according to Item 2 or 3, wherein the curing agent (B) is at least one selected from the group consisting of imidazole-based curing agents and imidazoline-based curing agents.
[Section 5]
Item 5. The film-coated substrate according to any one of Items 2 to 4, wherein the inorganic filler (C) comprises spherical inorganic particles.
[Section 6]
The epoxy resin (A) is 10% by weight or more and 60% by weight or less with respect to the curable composition,
The amine-based curing agent (B) is 0.01% by weight or more and 20% by weight or less with respect to the curable composition,
The inorganic filler (C) is 20% by weight or more and 80% by weight or less with respect to the curable composition.
Item 6. The film-coated substrate according to any one of items 2 to 5.
[Section 7]
A film-coated substrate according to any one of clauses 1-6, wherein said electronic component (12) comprises a ball grid array.
[Item 8]
Item 8. The film-coated substrate according to any one of Items 1 to 7, wherein the film coating material (2) comprises a polyamide resin.
[Item 9]
A film coated substrate according to any one of items 1 to 8, wherein said film coating (2) is in contact with a portion of said underfill material (13).
[Item 10]
A step (I) of obtaining a mounting substrate (1) comprising connecting a substrate (11) and an electronic component (12) with an underfill material (13); ), the coating step (II)
A method of making a film-coated substrate, comprising:
[Item 11]
Item 11. Item 10, wherein the step (I) of obtaining the mounting substrate (1) includes filling the gap between the substrate (11) and the electronic component (12) with the underfill material (13). A method for making a film-coated substrate according to claim 1.
[Item 12]
Item 12. The method for producing a film-coated substrate according to Item 10 or 11, wherein in the coating step (II), the mounting substrate (1) is coated with the film coating material (2) by vacuum forming.
[Item 13]
A device comprising a film-coated substrate according to any one of Items 1-9.
[Item 14]
14. The device according to Item 13, which is a vehicle-mounted device.

According to the present disclosure, it is possible to provide a device that achieves thermal shock resistance (eg, conductivity after thermal shock).

1 shows a schematic cross-sectional view of a film-coated substrate without underfill material (13) in the prior art; FIG. Figure 2 shows a schematic cross-sectional view of a film-coated substrate with an underfill material (13) according to the present disclosure;

<Film-coated substrate>
A film-coated substrate in the present disclosure includes a mounting substrate (1) and a film coating (2) covering said mounting substrate (1).

[Mounting board (1)]
A mounting substrate (1) includes a substrate (11), an electronic component (12), and an underfill material (13) connecting (or bonding) the substrate (11) and the electronic component (12).

(Substrate (11))
The board (11) is a board (a so-called printed board (bare board)) including paths having electrical conductivity, and is a board on which an electric circuit can be constructed by placing electronic components thereon. Substrate materials include, but are not limited to, bake, glass-based materials, ceramics, and silicon.

(Electronic parts (12))
The electronic component (12) is an electronic component connected to the substrate (11) by an underfill material (13). Examples of electronic components (12) include IC packages (insertion type packages, surface mount type packages), connectors, switches, transistors, LEDs, sockets, relays, resistors, capacitors, capacitors, coil bobbins, batteries, and the like. , preferably a surface mount type package, and in particular, it may be a BGA (Ball Grid Array). According to the present disclosure, excellent reliability can be obtained even when using an electronic component such as a BGA in which the reliability of bonding strength becomes a problem against external stress. In addition to the electronic component (12), other electronic components not provided with the underfill material (13) may be included on the substrate.

(Underfill material (13))
The underfill material (13) connects the substrate (11) and the electronic component (12). Here, "connection" means that the substrate (11) and the electronic component (12) are directly and physically connected via the underfill material (13). Since the underfill material (13) in the present disclosure has excellent permeability before curing, it has excellent workability. In addition, since the underfill material (13) after curing in the present disclosure has good insulating properties, it is possible to suppress the occurrence of problems of poor conductivity and poor insulation. Furthermore, since the thermal expansion of the underfill material (13) in the present disclosure is suppressed after curing, it is possible to suppress the occurrence of poor reliability of the device. The underfill material (13) may be a capillary underfill material or a pre-applied underfill material, but is preferably a capillary underfill material. In addition to the connection by the underfill material (13), the substrate (11) and the electronic component (12) are usually connected via solder for electrical connection.

The underfill material (13) may be a curable composition or its cured product containing an epoxy resin (A), a curing agent (B), and an inorganic filler (C). By curing the underfill material (13), a reinforced mounting board (1) can be obtained, and the reliability of the product can be improved.

○ Epoxy resin (A)
A curable composition in the present disclosure comprises an epoxy resin. As used herein, the term "epoxy resin" refers to an epoxy resin before curing (for example, before reacting with a curing agent). The epoxy resin may be liquid or solid at room temperature, preferably liquid at room temperature. The epoxy resin may be a monomeric epoxy resin, a prepolymeric epoxy resin, or a mixture of a monomeric epoxy resin and a prepolymeric resin (eg, with a degree of polymerization of 2-5 or 2-3).

Examples of the epoxy resin (A) include naphthalene-type epoxy resin (A1), glycidylamine-type epoxy resin (A2), silicone-modified epoxy resin (A3), and other epoxy resins.

・Naphthalene type epoxy resin (A1)
The curable composition in the present disclosure contains a naphthalene-type epoxy resin (A1). A “naphthalene-type epoxy resin” is an epoxy resin having a naphthalene skeleton in its molecule. The naphthalene-type epoxy resin (A1) may contain other groups such as aliphatic groups and aromatic groups. A glycidyl group (eg, a glycidyl ether group or a glycidyl amino group) may be used as the epoxy group-containing group. The naphthalene-type epoxy resin (A1) does not have to have a glycidylamino group.

The coefficient of linear expansion of the cured product obtained by using the epoxy resin (A1) tends to be low. Further, by using the epoxy resin (A1), even if the amount of filler (for example, silica) in the curable composition increases, the cured product can easily maintain a low linear expansion coefficient and insulating properties. It is presumed that this is because the volume occupied by the epoxy resin (A1) is small, so that the filler particles can be prevented from colliding with each other in the epoxy resin. By using the epoxy resin (A1), the adhesiveness with the film coating material (2) (in particular, the film coating material (2) using the polyamide resin) is improved.

The number of nitrogen atoms in the monomer structure of the epoxy resin (A1) is 0 to 2, preferably 0 to 1, more preferably 0. By reducing the number of nitrogen atoms in the epoxy resin (A1), the insulating properties of the cured product can be improved while maintaining the heat resistance.

The epoxy resin (A1) may be of the monomer type (degree of polymerization 1) or of the prepolymer type (eg degree of polymerization 2-5 or 2-3). Epoxy resin (A1) preferably comprises a monomeric type. The average degree of polymerization of the epoxy resin (A1) may be from 1 to 2.5, preferably from 1 to 1.5. Due to the low degree of polymerization of the epoxy resin, the viscosity tends to be low and the handleability can be excellent.

The number of naphthalene groups in the monomeric form of the epoxy resin (A1) may be 1, 2 or 3, preferably 1 or 2.

The number of epoxy groups possessed by the monomer type of the epoxy resin (A1) may be 1 to 6, 2 to 5, 2 to 4, 2 to 3 or 2 (diepoxy), preferably 2 to 3 or 2.

The weight average molecular weight of the epoxy resin (A1) may be 100-1200, 150-900 or 200-600, preferably 180-750. The weight average molecular weight may be a polystyrene equivalent value measured by gel permeation chromatography (GPC).

The epoxy equivalent weight of the epoxy resin (A1) may be 50-500, 60-400 or 100-300, preferably 80-350. JISK7236:2001, for example, can be referred to as a method for determining the epoxy equivalent of an epoxy resin.

Examples of the epoxy resin (A1) include monoepoxynaphthalenes such as 1-glycidyloxynaphthalene and 2-glycidyloxynaphthalene; Diepoxynaphthalene such as glycidyloxynaphthalene (e.g. EPICLON HP-4032D manufactured by DIC), 1,7-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene; triglycidyloxynaphthalene, 1,2,5,6- tetraglycidyloxynaphthalene; a bisnaphthalene-type epoxy resin having a structure in which two naphthalene groups are bonded via an organic group (eg, a hydrocarbon group) (eg, EPICLON HP-4700 manufactured by DIC); and prepolymers thereof, and Modified products of these are included. These may be used alone or in combination of two or more.

・Glycidylamine type epoxy resin (A2)
The curable composition in the present disclosure contains a glycidylamine type epoxy resin (A2). A "glycidylamine type epoxy resin" is an epoxy resin having a glycidylamino group in its molecule. By using the epoxy resin (A1) and the epoxy resin (A2) in combination, the permeability and heat resistance become suitable.

The epoxy resin (A2) preferably has an aromatic group. For example, the epoxy resin (A2) has an aromatic hydrocarbon skeleton such as a benzene skeleton, biphenyl skeleton, naphthalene skeleton, anthracene skeleton and phenanthrene skeleton; and/or a nitrogen group-containing aromatic hydrocarbon skeleton such as pyridine and triazine. you can Heat resistance can be improved because the epoxy resin (A2) has an aromatic group. In addition, since the epoxy resin (A2) has an aromatic group, the hygroscopicity can be reduced and the insulation can be improved. Furthermore, the adhesiveness with the film covering material (2) (especially the film covering material (2) containing polyamide resin) is improved.

The monomer structure of the epoxy resin (A2) has at least one nitrogen atom derived from a glycidylamino group, and the number of other nitrogen atoms is 0 to 2, preferably 0 to 1, more preferably 0. be. That is, the monomer structure of the epoxy resin (A2) preferably has only one nitrogen atom. Since the epoxy resin (A2) has a small number of nitrogen atoms, it is possible to reduce hygroscopicity and improve insulation of the cured product while maintaining heat resistance.

The nitrogen content of the epoxy resin (A2) (14×the number of nitrogen atoms in the monomer structure molecule of the epoxy resin (A2)/the molecular weight of the monomer structure of the epoxy resin (A2)×100) is 30% or less, 20% or less, It may be 10% or less, or 7.5% or less, preferably 15% or less, more preferably 6% or less.

The epoxy resin (A2) may be of the monomer type (degree of polymerization 1) or of the prepolymer type (eg degree of polymerization 2-5 or 2-3). Epoxy resin (A2) preferably comprises a monomeric type. The epoxy resin (A2) may have an average degree of polymerization of 1 to 2.5, preferably 1 to 1.5. Due to the low degree of polymerization of the epoxy resin, the viscosity tends to be low and the handleability can be excellent.

The number of glycidylamino groups possessed by the monomer type of the epoxy resin (A2) may be 1, 2 or 3, preferably 1 or 2.

From the viewpoint of heat resistance, the number of epoxy groups possessed by the monomer structure of the epoxy resin (A2) may be 1 to 7, 2 to 5, 2 to 4 or 2 to 3, preferably 3 to 4, particularly 3 (tri epoxy). The epoxy group other than the epoxy group contained in the glycidylamino group may be the epoxy group contained in the glycidyl ether group.

The weight average molecular weight of the monomer structure of the epoxy resin (A2) may be 100-1200, 150-900 or 200-600, preferably 180-750. The weight average molecular weight may be a polystyrene equivalent value measured by gel permeation chromatography (GPC).

The epoxy equivalent weight of the epoxy resin (A2) may be 50-450, 60-350 or 100-250, preferably 80-300. JISK7236:2001, for example, can be referred to as a method for determining the epoxy equivalent of an epoxy resin.

Examples of epoxy resins (A2) include N,N-diglycidyl-4-(glycidyloxy)aniline, 4,4′-methylenebis[N,N-bis(oxiranylmethyl)aniline], triglycidyl-o- Aromatic types such as aminophenol, triglycidyl-p-aminophenol; Aliphatic types such as 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane; Monoglycidyl isocyanurate, diglycidyl isocyanurate and triglycidyl isocyanurate type such as isocyanurate; hydantoin type such as diglycidylhydantoin; prepolymers thereof and modified products thereof. These may be used alone or in combination of two or more. The epoxy resin (A2) preferably has a diglycidylamino group.

・Silicone modified epoxy resin (A3)
The silicone-modified epoxy resin (A3) can be obtained as a reaction product of an epoxy resin and an organosiloxane having a functional group that reacts with an epoxy group. Examples of organosiloxanes having functional groups that react with epoxy groups include dimethylsiloxanes, diphenylsiloxanes, methylphenyl siloxane and the like. The weight average molecular weight of the organosiloxane may range from 300 to 5,000. The epoxy resin for obtaining the silicone-modified epoxy resin (A3) is not particularly limited, and various epoxy resins can be selected.

- Other epoxy resins The curable composition preferably contains an epoxy resin other than the naphthalene-type epoxy resin (A1), the glycidylamine-type epoxy resin (A2), and the silicone-modified epoxy resin (A3). Examples of organosiloxanes having functional groups that react with epoxy groups include dimethylsiloxanes, diphenylsiloxanes, methylphenylsiloxanes, etc. having one or more amino groups, carboxyl groups, hydroxyl groups, phenolic hydroxyl groups, mercapto groups, etc. per molecule. is mentioned.

Examples of other epoxy resins include bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol E (AD) type and bisphenol S type; type epoxy resin; aromatic type epoxy resins such as biphenyl type, triphenylmethane type, dicyclopentadiene type, fluorene type and anthracene type; cycloaliphatic epoxy resins such as norbornene type epoxy resin and adamantane type epoxy resin; epoxy resins; phosphorus-containing epoxy resins; and alkylphenol-type epoxy resins, and modified products thereof. From the viewpoint of heat resistance, an aromatic epoxy resin may be included as another epoxy resin. Moreover, from the viewpoint of heat resistance, the other epoxy resins may not contain an aliphatic epoxy resin. Other suitable examples of epoxy resins include bisphenol epoxy resins. The epoxy resin may not have active hydrogen-containing groups and active hydrogen-reactive groups other than epoxy groups. These may be used alone or in combination of two or more. Other epoxy resins may be free of aliphatic epoxy resins.

The number of nitrogen atoms in the monomer structure of other epoxy resins is 0 to 2, preferably 0 to 1, more preferably 0.

○ Curing agent (B)
The curable composition preferably contains a curing agent (B). Curing agent (B) is preferably an amine curing agent. In the present disclosure, an amine-based curing agent has an effect of promoting or accelerating a curing reaction when added to a thermosetting resin, and has an amino group in the molecule. Here, the "amino group" is recognized as an amino group by those skilled in the art and includes an amino group contained in an imidazole skeleton or an imidazoline skeleton. In addition, the term “curing agent” used herein may be a broad concept that also includes curing accelerators.

When a curable composition is used as an underfill material, from the viewpoint of workability, curing does not proceed sufficiently below a certain temperature, and curing proceeds rapidly above a certain temperature. It is important to select a curing agent that can be applied to the composition. As such a curing agent (B), one having a high melting point and having a plurality of nitrogen atoms in the molecule is suitable. The presence of nitrogen atoms is presumed to improve the reaction activity between the curing agent (B) and the epoxy resins (A1) and (A2), contributing to favorable curability.

From the viewpoint of curability when used as an underfill material, the melting point of the curing agent (B) is 50° C. or higher, 75° C. or higher, 100° C. or higher, 120° C. or higher, 150° C. or higher, 175° C. or higher, or 200° C. or higher. The temperature is preferably 70° C. or higher, 100° C. or higher, more preferably 150° C. or higher, more preferably 180° C. or higher, still more preferably 210° C. or higher, and even more preferably 240° C. or higher. Moreover, the melting point of the curing agent (B) may be 400° C. or lower, 350° C. or lower, 300° C. or lower, or 280° C. or lower.

From the viewpoint of curability when used as an underfill material, the number of nitrogen atoms in the molecule of the curing agent (B) is 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, or The number may be 8 or more, preferably 2 or more. The number of nitrogen atoms in the molecule of the curing agent (B) may be 8 or less, 6 or less, or 4 or less.

From the viewpoint of curability when used as an underfill material, the nitrogen content of curing agent (B) (14 x number of nitrogen atoms in curing agent (B) molecule/molecular weight of curing agent (B) x 100) is 10 weight. % or more, 15 wt% or more, 20 wt% or more, 25 wt% or more, 30 wt% or more, 35 wt% or more, 40 wt% or more or 42 wt% or more, for example 18 wt% or more, preferably 28% by weight or more, especially 38% by weight or more. Also, the nitrogen content of the curing agent (B) may be 80% by weight or less, 70% by weight or less, 60% by weight or less, or 50% by weight or less.

As the curing agent (B), for example, aliphatic monoamines, aliphatic polyamines, aromatic monoamines or aromatic polyamines can be used. The curing agent (B) may not be an amine adduct or the like with an epoxy resin. From the viewpoint of curability, the curing agent (B) does not have to have a hydroxyl group.

The curing agent (B) may be at least one selected from the group consisting of imidazole-based curing agents and imidazoline-based curing agents. The curing agent (B) may be used alone or in combination of two or more.

The “imidazole-based curing agent” is a curing agent having an imidazole skeleton in its molecule. Examples of imidazole curing agents include imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-aminoethyl-2-methylimidazole, 1-(2 -hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2 -methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole and 1-cyanoethyl-2-undecylimidazolium trimellitate, and modifications thereof. These may be used alone or in combination of two or more. From the viewpoint of curability, the imidazole-based curing agent does not have to have a hydroxyl group.

The “imidazoline-based curing agent” is a curing agent having an imidazoline skeleton in its molecule. Examples of imidazoline curing agents include 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-methylimidazoline, 2,4-dimethylimidazoline, 2-ethylimidazoline, 2-ethyl-4-methylimidazoline, 2-benzylimidazoline, 2-phenylimidazoline, 2-(o-tolyl)-imidazoline, tetramethylene-bis-imidazoline, 1, 1,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene -bis-4-methylimidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, 1,2-phenylene-bis-imidazoline, 1,3-phenylene-bis-imidazoline, 1,4-phenylene-bis-imidazoline and 1,4-phenylene-bis-4-methylimidazoline, and modifications thereof. These may be used alone or in combination of two or more. From the viewpoint of curability, the imidazoline curing agent does not have to have a hydroxyl group.

The curing agent (B) is a triazine skeleton-containing amine-based curing agent containing a triazine skeleton (especially a 1,3,5-triazine skeleton) in the molecule, that is, a triazine skeleton-containing imidazole curing agent and a triazine skeleton-containing imidazoline curing agent. It may be at least one selected from the group consisting of:

When the curing agent (B) contains a triazine skeleton, good permeability can be obtained, and good reaction acceleration can also be achieved. The reason for this is not entirely clear, but the presence of the triazine skeleton moderately increases the melting point of the curing agent, and the presence of three ring nitrogen atoms achieves moderate interaction with other components. This is considered to be due to Also, for the same reason, the adhesiveness to the film covering material (2) (especially the film covering material (2) containing polyamide resin) is improved.

The triazine skeleton-containing amine curing agent may have at least one (for example, one, two and three), preferably two, amino groups directly bonded to the triazine skeleton. From the viewpoint of curability, the triazine skeleton-containing amine-based curing agent may not have a hydroxyl group directly bonded to the triazine skeleton. The triazine skeleton-containing amine curing agent may be a compound represented by the following general formula (1).

（式（１）中、Ｒ^１、Ｒ^２及びＲ^３はそれぞれ独立して水素原子又は炭素数１～２５の一価の有機基であり、Ｒ^１、Ｒ^２及びＲ^３の少なくとも１個がイミダゾール骨格又はイミダゾリン骨格を含有する基である。）

(In Formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom or a monovalent organic group having 1 to 25 carbon atoms, and at least one of R ¹ , R ² and R ³ is A group containing an imidazole skeleton or an imidazoline skeleton.)

The monovalent organic groups in R ¹ _, R ² and R ³ can be aliphatic and aromatic groups. At least one (preferably one) of R ¹ , R ² and R ³ is a group containing an imidazole skeleton or imidazoline skeleton. It is preferred that at least one, preferably two, of R ¹ , R ² and R ³ are amino groups (alkylamino groups, —NH ₂ groups, preferably —NH ₂ groups). R ¹ , R ² and R ³ may have a molecular weight of 10-750, for example 200-400 (especially in the case of groups containing an imidazole or imidazoline skeleton). R ¹ , R ² and R ³ may have 0 to 20 carbon atoms, for example 1 to 15 carbon atoms.

When R ² and R ³ are amino groups, R ¹ may be a group containing an imidazole skeleton or an imidazoline skeleton, preferably a group containing an imidazole group. Here, R ¹ may or may not have a hydroxyl group.

The triazine skeleton-containing amine-based curing agent may be a compound represented by the following general formula (2).

（式（２）中、Ｒ^４はイミダゾール骨格又はイミダゾリン骨格を含有する炭素数３～２５の有機基であり、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８はそれぞれ独立して、水素原子又は炭素数１～２５の一価の有機基である。）

(In formula (2), R ⁴ is an organic group having 3 to 25 carbon atoms containing an imidazole skeleton or imidazoline skeleton, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or a carbon It is a monovalent organic group of numbers 1 to 25.)

The imidazole skeleton or imidazoline skeleton in R ⁴ and the triazine skeleton may be bonded via a spacer group (e.g., an aliphatic hydrocarbon group and a nitrogen-containing aliphatic hydrocarbon group), or may be directly bonded. . R ⁴ may have 3 to 20 carbon atoms, for example 3 to 15 carbon atoms.

The organic groups in R ⁵ , R ⁶ , R ⁷ and R ⁸ may each independently be an aliphatic group or an aromatic group, preferably an aliphatic group (e.g. an aliphatic hydrocarbon group), such as an alkyl group, alkenyl group, aryl group or hydroxyalkyl group, more preferably alkyl group or alkenyl group. The number of carbon atoms in the organic groups in R ⁵ , R ⁶ , R ⁷ and R ⁸ may be 1-20, for example 1-15. At least one (eg, one, two, or three) of R ⁵ , R ⁶ , R ⁷ and R ⁸ may be a hydrogen atom, and all of them may be hydrogen atoms.

The triazine skeleton-containing imidazole curing agent may be a compound represented by the following general formula (3).

（式（３）中、Ｒ^９、Ｒ^１０及びＲ^１１はそれぞれ独立して、水素原子又は炭素数１～２５の有機基であり、Ｌ^１は直接結合又は炭素数１～２５の有機基である。）

(In formula (3), R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom or an organic group having 1 to 25 carbon atoms, and L ¹ is a direct bond or an organic group having 1 to 25 carbon atoms. be.)

Each of the organic groups in R ⁹ , R ¹⁰ and R ¹¹ may independently be an aliphatic group or an aromatic group, preferably an aliphatic group (e.g. an aliphatic hydrocarbon group) such as an alkyl group, an alkenyl group, aryl group or hydroxyalkyl group, more preferably alkyl group or alkenyl group. The number of carbon atoms of the organic group in R ⁹ , R ¹⁰ and R ¹¹ may be 1-20, for example 1-15. At least one of R ⁹ , R ¹⁰ and R ¹¹ (eg, one or two, particularly one or both of R ⁹ and R ¹⁰ ) may be a hydrogen atom, and all may be hydrogen atoms.

The organic group in L ¹ may be a divalent aliphatic group or a divalent aromatic group, preferably an aliphatic group (e.g., an aliphatic hydrocarbon group, an oxygen-containing aliphatic hydrocarbon group or a nitrogen-containing aliphatic hydrocarbon group). The organic group in L ¹ may or may not have one or more nitrogen or oxygen atoms. The organic group in L ¹ may have 1 to 20 carbon atoms, for example 1 to 15 carbon atoms.

（式（４）中、Ｒ^１２、Ｒ^１３及びＲ^１４はそれぞれ独立して、水素原子又は炭素数１～２５の有機基であり、Ｌ^２は直接結合又は炭素数１～２５の有機基である。） The triazine skeleton-containing imidazoline curing agent may be a compound represented by the following general formula (4).

(In formula (4), R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom or an organic group having 1 to 25 carbon atoms, and L ² is a direct bond or an organic group having 1 to 25 carbon atoms. be.)

Each of the organic groups in R ¹² , R ¹³ and R ¹⁴ may independently be an aliphatic group or an aromatic group, preferably an aliphatic group (e.g. an aliphatic hydrocarbon group) such as an alkyl group, an alkenyl group, aryl group or hydroxyalkyl group, more preferably alkyl group or alkenyl group. The number of carbon atoms of the organic group in R ¹² , R ¹³ and R ¹⁴ may be 1-20, for example 1-15. At least one of R ¹² , R ¹³ and R ¹⁴ (eg, one or two, particularly one or both of R ¹² and R ¹³ ) may be a hydrogen atom, and all may be hydrogen atoms.

The organic group in L2 may be a ^divalent aliphatic group or a divalent aromatic group, preferably an aliphatic group (e.g., an aliphatic hydrocarbon group, an oxygen-containing aliphatic hydrocarbon group or a nitrogen-containing aliphatic hydrocarbon group). ^The organic group in L2 may or may not have one or more nitrogen or oxygen atoms. The organic group in L ² may have 1 to 20 carbon atoms, for example 1 to 15 carbon atoms.

A commercially available product may be used as the triazine skeleton-containing curing agent, or it may be produced by a method known to those skilled in the art. For example, International Publication No. 2014/142035, JP-A-2015-140394 and JP-A-2019-6972 can be referred to.

Examples of triazine skeleton-containing curing agents include 1-(4,6-diamino-s-triazin-2-yl)butyl-2-undecylimidazole; 1-(4,6-diamino-s-triazine-2- yl) propylimidazole; 1-(4,6-diamino-s-triazin-2-yl)propyl-2-methylimidazole; 1-(4,6-diamino-s-triazin-2-yl)propyl-2- Undecylimidazole; 1-(4,6-diamino-s-triazin-2-yl)propyl-2-heptadecylimidazole; 1-(4,6-diamino-s-triazin-2-yl)propyl-2- Ethyl-4-methylimidazole; 1-(4,6-diamino-s-triazin-2-yl)propyl-2-phenylimidazole; 1-(4,6-diamino-s-triazin-2-yl)propyl- 2-phenyl-4-methylimidazole; 1-(4,6-diamino-s-triazin-2-yl)propyl-2-phenyl-4,5-dihydroxymethylimidazole; 1-(4,6-diamino-s -triazin-2-yl)propyl-2-phenyl-4-hydroxymethyl-5-methylimidazole; 1-(4,6-diamino-s-triazin-2-yl)butylimidazole; 1-(4,6- Diamino-s-triazin-2-yl)butyl-2-methylimidazole; 1-(4,6-diamino-s-triazin-2-yl)butyl-2-undecylimidazole; 1-(4,6-diamino -s-triazin-2-yl)butyl-2-heptadecylimidazole; 1-(4,6-diamino-s-triazin-2-yl)butyl-2-ethyl-4-methylimidazole; 1-(4, 6-diamino-s-triazin-2-yl)butyl-2-phenylimidazole; 1-(4,6-diamino-s-triazin-2-yl)butyl-2-phenyl-4-methylimidazole; 1-( 4,6-diamino-s-triazin-2-yl)butyl-2-phenyl-4,5-dihydroxymethylimidazole; 1-(4,6-diamino-s-triazin-2-yl)butyl-2-phenyl -4-hydroxymethyl-5-methylimidazole; 1-(4,6-diamino-s-triazin-2-yl)pentylimidazole; 1-(4,6-diamino-s-triazin-2-yl)pentyl- 2-methylimidazole; 1-(4,6-diamino-s-triazine-2 -yl)pentyl-2-undecylimidazole; 1-(4,6-diamino-s-triazin-2-yl)pentyl-2-heptadecylimidazole; 1-(4,6-diamino-s-triazine-2 -yl)pentyl-2-ethyl-4-methylimidazole; 1-(4,6-diamino-s-triazin-2-yl)pentyl-2-phenylimidazole; 1-(4,6-diamino-s-triazine -2-yl)pentyl-2-phenyl-4-methylimidazole; 1-(4,6-diamino-s-triazin-2-yl)pentyl-2-phenyl-4,5-dihydroxymethylimidazole; 1-( 4,6-diamino-s-triazin-2-yl)pentyl-2-phenyl-4-hydroxymethyl-5-methylimidazole; 1-(4,6-diamino-s-triazin-2-yl)hexylimidazole; 1-(4,6-diamino-s-triazin-2-yl)hexyl-2-methylimidazole; 1-(4,6-diamino-s-triazin-2-yl)hexyl-2-undecylimidazole; 1 -(4,6-diamino-s-triazin-2-yl)hexyl-2-heptadecylimidazole; 1-(4,6-diamino-s-triazin-2-yl)hexyl-2-ethyl-4-methyl imidazole; 1-(4,6-diamino-s-triazin-2-yl)hexyl-2-phenylimidazole; 1-(4,6-diamino-s-triazin-2-yl)hexyl-2-phenyl-4 -methylimidazole; 1-(4,6-diamino-s-triazin-2-yl)hexyl-2-phenyl-4,5-dihydroxymethylimidazole; 1-(4,6-diamino-s-triazine-2- yl)hexyl-2-phenyl-4-hydroxymethyl-5-methylimidazole; 1-(4,6-diamino-s-triazin-2-yl)heptylimidazole; 1-(4,6-diamino-s-triazine -2-yl)heptyl-2-methylimidazole; 1-(4,6-diamino-s-triazin-2-yl)heptyl-2-undecylimidazole; 1-(4,6-diamino-s-triazine- 2-yl)heptyl-2-heptadecylimidazole; 1-(4,6-diamino-s-triazin-2-yl)heptyl-2-ethyl-4-methylimidazole; 1-(4,6-diamino-s -triazin-2-yl)heptyl-2-phenyl Imidazole; 1-(4,6-diamino-s-triazin-2-yl)heptyl-2-phenyl-4-methylimidazole; 1-(4,6-diamino-s-triazin-2-yl)heptyl-2 -phenyl-4,5-dihydroxymethylimidazole; 1-(4,6-diamino-s-triazin-2-yl)heptyl-2-phenyl-4-hy; droxymethyl-5-methylimidazole; and imidazole skeletons thereof to the imidazoline skeleton, and modified products thereof. Specific examples of products include 2MZ-A, 2MZA-PW, C11Z-A and 2E4MZ-A manufactured by Shikoku Kasei Co., Ltd. These may be used alone or in combination of two or more. From the viewpoint of curability, the imidazoline curing agent does not have to have a hydroxyl group.

When the curing agent (B) is solid, the curing agent (B) may be pulverized to a predetermined median particle size. Examples of median particle size of curing agent (B) are 10 μm or less, 5 μm or less, 2.5 μm or less and 1.5 μm or less. For the pulverization, airflow pulverizers such as jet mills; ball mills such as vibrating ball mills, continuous rotary ball mills and batch ball mills; pot mills such as wet pot mills and planetary pot mills; pulverizers such as roller mills can be used.

• Other Curing Agents The curable composition of the present disclosure may contain curing agents other than the amine-based curing agent. Examples of other curing agents include amine compounds (e.g., aliphatic amines, alicyclic and heterocyclic amines, aromatic amines and modified amines), imidazole compounds, imidazoline compounds, amide compounds. , ester compounds, phenol compounds, alcohol compounds, thiol compounds, ether compounds, thioether compounds, urea compounds, thiourea compounds, Lewis acid compounds, phosphorus compounds, acid anhydride compounds, onium Examples include salt compounds (or cationic polymerization initiators) and active silicon compound-aluminum complexes. From the viewpoint of insulation, the curable composition of the present disclosure may not use an acid anhydride-type curing agent. The curable composition may not contain a curing agent that is liquid at room temperature.

○ Inorganic filler (C)
The curable composition is
The curable composition in the present disclosure contains an inorganic filler (C). The inorganic filler (C) may be an inorganic filler commonly used in curable compositions, preferably at least one selected from the group consisting of silica particles and alumina particles.

- Spherical inorganic particles The curable composition in the present disclosure preferably contains spherical inorganic particles as a filler. The spherical inorganic particles are preferably at least one selected from the group consisting of silica particles and alumina particles. The spherical inorganic particles may be treated with various surface treatment agents (for example, silane coupling agents). In the present specification, the spherical shape is not limited to a true spherical shape, an ellipsoidal shape, or the like, and may be spherical to the extent that a person skilled in the art recognizes it to be spherical. For example, particles having some unevenness on the surface may be spherical particles.

The spherical inorganic particles may contain a plurality of (for example, 2, 3 or 4) particles with different particle size distributions. The spherical inorganic particles may comprise a plurality (eg, 2, 3 or 4) of different particle distributions with median particle sizes ranging from 0.5 to 20 μm. The spherical inorganic particles may contain spherical inorganic particles (Cs) with a small center particle size and spherical inorganic particles (Cl) with a large center particle size. The median particle size of the spherical inorganic particles (Cs) may be 0.5-5 μm, 0.5-4.5 μm or 0.5-3 μm, preferably 0.5-4 μm. The central particle size of the spherical inorganic particles (Cl) having a large central particle size may be 5 to 20 μm, 7 to 20 μm or 9 to 20 μm, preferably 7.5 to 20 μm. The difference in median particle size between the spherical inorganic particles (Cs) and the spherical inorganic particles (Cl) may be at least 1 μm, at least 2.5 μm, at least 5 μm, or at least 10 μm. The median particle size and particle size distribution can be measured using, for example, a laser diffraction/scattering particle distribution analyzer. Specifically, it can be carried out by a wet method using a laser diffraction/scattering particle distribution analyzer (Partica LA-950V2 manufactured by Horiba Ltd.) using methanol as a dispersion medium. The "median particle size" means the value of d50 in volume-based particle size distribution measurement.

In the measurement of the volume-based particle size distribution of spherical inorganic particles, in a chart of the abundance ratio of particles obtained by plotting the particle diameter on the horizontal axis and the abundance ratio of particles on the vertical axis, multiple ( For example, 2, 3 or 4) peaks or shoulder peaks (here, shoulder peaks are two or more peaks, and if one peak is significantly smaller than the other peak, they are It is preferable to have a peak that appears as a shoulder on a large peak when overlapped. The particle size difference between any two peaks of the plurality of peaks may be at least 1 μm, at least 2.5 μm, at least 5 μm, or at least 10 μm.

・Other inorganic fillers Examples of other inorganic fillers other than the above spherical inorganic particles include glass, calcium carbonate, fatty acid-treated calcium carbonate, fumed silica, precipitated silica, carbon black, talc, mica, clay, and glass. Beads, shirasu balloons, glass balloons, silica balloons, plastic balloons, glass fibers, inorganic fibers such as metal fibers, aluminum borate, silicon carbide, silicon nitride, potassium titanate, graphite, needle-shaped crystalline calcium carbonate, magnesium borate , titanium diboride, chrysotile, and wollastonite.

The inorganic filler may be surface-treated in advance with a coupling agent such as a silane coupling agent or a titanate coupling agent in order to strengthen the bonding strength between the resin and the inorganic filler. Examples of such coupling agents include epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, reaction product of imidazole and γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltrimethoxy aminosilanes such as silane; silane coupling agents such as mercaptosilanes such as γ-mercaptosilane and γ-episulfidoxypropyltrimethoxysilane.

○ Other Additives The curable composition of the present disclosure may contain other additives. Examples of other additives include colorants such as organic dyes and organic pigments; organic fillers such as organic particles and organic fibers; vinyltrimethoxysilane, vinyltriethoxysilane, aminosilane, mercaptosilane, epoxysilane and silicone oil ( silicone additives such as amino-modified silicone oil and epoxy-modified silicone oil); epoxy compounds such as glycidyl ether having a polyoxyalkylene skeleton; hindered phenols, mercaptans, sulfides, dithiocarboxylates, thioureas, Antiaging agents/antioxidants such as thiophosphates and thioaldehydes; UV absorbers/light stabilizers such as benzotriazoles and hindered amines; Thixotropy such as colloidal silica, organic bentonite, fatty acid amides and hydrogenated castor oil Agent; modifiers such as thermoplastic elastomer, NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic rubber, urethane rubber, silicone rubber, and the like. For example, a silane coupling agent such as epoxysilane may be added in combination with silicone oil.

○ Composition of underfill material (13) The composition of the underfill material may be as follows. In addition, the following composition means a composition before hardening.

- Total amount of epoxy resin The total amount of epoxy resin may be 10% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, 30% by weight or more, or 35% by weight or more of the composition, It is preferably 18% by weight or more, more preferably 28% by weight or more. Also, the total amount of the epoxy resin may be 60% by weight or less, 55% by weight or less, 50% by weight or less, 45% by weight or less, 40% by weight or less or 35% by weight or less, preferably 58% by weight or less, based on the composition. % by weight or less, more preferably 48% by weight or less.

- Amount of naphthalene-type epoxy resin (A1) The amount of the epoxy resin (A1) is 10% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, 30% by weight or more, based on the amount of organic matter in the composition. It may be at least 35% by weight, or at least 40% by weight, preferably at least 22% by weight, more preferably at least 28% by weight, even more preferably at least 33% by weight. Further, the amount of the epoxy resin (A1) may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, or 40% by weight or less relative to the amount of organic matter in the composition. It is preferably 67% by weight or less, more preferably 57% by weight or less or 52% by weight or less. In this specification, the term "amount of organic matter in the composition" may be the amount other than the inorganic particles in the composition, and may be read as the total amount of epoxy resin in the composition.

- Weight occupied by the naphthalene skeleton of the epoxy resin (A1) The weight of the naphthalene skeleton of the epoxy resin (A1) is 1% by weight or more, 2.5% by weight or more, or 4.5% by weight or more of the composition. , 6% by weight or more, or 7.5% by weight or more, preferably 3% by weight or more, more preferably 5.5% by weight or more, and even more preferably 6.5% by weight or more. Further, the weight occupied by the naphthalene skeleton of the epoxy resin (A1) is 30% by weight or less, 25% by weight or less, 20% by weight or less, 15% by weight or less, or 10% by weight or less relative to the composition. It is preferably 26% by weight or less, more preferably 16% by weight or less, and still more preferably 11% by weight or less.

- Amount of glycidylamine type epoxy resin (A2) It may be 30% by weight or more or 35% by weight or more, preferably 21% by weight or more, more preferably 28% by weight or more, and even more preferably 35% by weight or more. Further, the amount of the epoxy resin (A2) may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, or 40% by weight or less relative to the amount of organic matter in the composition. It is preferably 65% by weight or less, more preferably 45% by weight or less.

Amount of silicone-modified epoxy resin (A3) The amount of silicone-modified epoxy resin (A3) is 1% by weight or more, 2% by weight or more, 3% by weight or more, 4% by weight or more relative to the amount of organic matter in the composition. , 5% by weight or more or 7.5% by weight or more, preferably 2.5% by weight or more or 5% by weight or more. In addition, the amount of the silicone-modified epoxy resin (A3) is 30% by weight or less, 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, or 7% by weight or less based on the amount of organic matter in the composition. .5% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less.

・Amount of other epoxy resins The amount of other epoxy resins is 0.5% by weight or more, 1% by weight or more, 2% by weight or more, 3% by weight or more, or 5% by weight or more relative to the amount of organic matter in the composition. It may be present, preferably 0.7% by weight or more, or 2% by weight or more. In addition, the amount of other epoxy resins is 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 40% by weight or less, 30% by weight or less, 25% by weight or less, based on the amount of organic matter in the composition. It may be less than or equal to 15 wt%, preferably less than or equal to 50 wt%, more preferably less than or equal to 30 wt% or less than or equal to 20 wt%.

- Weight occupied by nitrogen atoms The weight occupied by nitrogen atoms in the composition may be 0.5% by weight or more, 0.8% by weight or more, or 1.0% by weight or more relative to the composition. In addition, the weight of nitrogen atoms in the composition is 15% by weight or less, 12% by weight or less, 9% by weight or less, 6% by weight or less, 3% by weight or less, or 1.5% by weight or less relative to the composition. It may be present, preferably 7.5% by weight or less, more preferably 2.5% by weight or less.

Amount of curing agent (B) The amount of curing agent (B) is 0.01% by weight or more, 0.2% by weight or more, 0.4% by weight or more, and 0.6% by weight or more relative to the composition. , 0.8% by weight or more, or 1.0% by weight or more, preferably 0.3% by weight or more, more preferably 0.7% by weight or more. In addition, the total amount of the curing agent (B) is 30% by weight or less, 20% by weight or less, 15% by weight or less, 5% by weight or less, 4.5% by weight or less, or 3.5% by weight or less with respect to the composition. , 3 wt% or less, 2.5 wt% or less, or 2 wt% or less, preferably 3.6 wt% or less, more preferably 2.2 wt% or less.

From the viewpoint of curing speed, the blending ratio of the epoxy resin and the curing agent is such that the ratio of the epoxy resin to the curing agent (weight of epoxy resin/weight of curing agent) is less than 100, less than 50, or less than 25. may be set.

- Total amount of inorganic filler (C) It may be 55 wt% or more, 60 wt% or more, or 65 wt% or more, preferably 43 wt% or more, more preferably 53 wt% or more. In addition, the total amount of the inorganic filler (C) may be 80% by weight or less, 75% by weight or less, 70% by weight or less, 65% by weight or less or 60% by weight or less, preferably 70% by weight or less, based on the composition. % by weight or more, preferably 66% by weight or less, more preferably 63% by weight or less. When the amount of the inorganic filler is within the above range, the permeability and/or linear expansion coefficient of the curable composition can be improved.

The total amount of the inorganic filler (C) is 30% by volume or more, 33% by volume or more, 36% by volume or more, 39% by volume or more, 41% by volume or more, or 43% by volume or more with respect to the composition, It is preferably 35% by volume or more, more preferably 40% by volume or more. In addition, the total amount of the inorganic filler (C) is 80% by volume or less, 65% by volume or less, 50% by volume or less, 45% by volume or less, 40% by volume or less, or 35% by volume or less with respect to the composition. Well, preferably 76% by volume or less, more preferably 66% by volume or less.

- Amount of spherical inorganic particles The amount of spherical inorganic particles is 70% by weight or more, 75% by weight or more, 80% by weight or more, 90% by weight or more, or 95% by weight or more with respect to the total amount of the inorganic filler (C). It may be, preferably 85% by weight or more, more preferably 95% by weight or more. In addition, the amount of the spherical inorganic particles may be 100% by weight or less, 97% by weight or less, 93% by weight or less, 90% by weight or less, 85% by weight or less, or 80% by weight or less with respect to the total amount of the filler. .

- Amount of spherical inorganic particles (Cl) The amount of spherical inorganic particles (Cl) may be 30% by weight or more, 30% by weight or more, 40% by weight or more, or 50% by weight or more of the composition, preferably is 42% by weight or more, more preferably 45% by weight or more. In addition, the total amount of the inorganic filler (Cl) is 70% by weight or less, 65% by weight or less, 60% by weight or less, 55% by weight or less, 50% by weight or less, 48% by weight or less, or 45% by weight with respect to the composition. % or less, preferably 65 wt % or less, more preferably 55 wt % or less. When the amount of the inorganic filler is within the above range, the permeability and/or linear expansion coefficient of the curable composition can be improved.

- Amount of spherical inorganic particles (Cs) The amount of spherical inorganic particles (Cs) is 3% by weight or more, 5% by weight or more, 7.5% by weight or more, 15% by weight or more, or 17.5% by weight, based on the composition. % by weight or more, preferably 4.5% by weight or more, more preferably 8% by weight or more. In addition, the total amount of the inorganic filler (C) may be 40% by weight or less, 25% by weight or less, or 15% by weight or less, preferably 18% by weight or less, more preferably 13% by weight, based on the composition. % or less. When the amount of the inorganic filler is within the above range, the permeability of the curable composition can be improved.

- Total amount of other additives The total amount of other additives may be appropriately selected according to each component. For example, the amount of other additives is 0.01% by weight or more, 0.05% by weight or more, 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, or It may be 0.8% by weight or more. In addition, the total amount of other additives is 5% by weight or less, 4.5% by weight or less, 3.5% by weight or less, 3% by weight or less, 2.5% by weight or less, or 2% by weight or less based on the composition. can be

○Method for Preparing Curable Composition Any method for preparing the curable composition may be used as long as the various components can be uniformly dispersed and mixed. It can be obtained by kneading the components using a mixer such as a planetary mixer. Degassing may be performed as necessary during the preparation.

The curable composition may be of a one-pack type or a multi-pack type (for example, a two-pack type), but the one-pack type is preferred from the viewpoint of workability. From the viewpoint of storage stability, a multi-liquid type is preferred.

○ Hardened material

The curable composition is cured by heating to form a cured product. The heating temperature may be 50-250°C, for example 100-175°C. The heating time is usually 120 minutes or less, for example 60 minutes or less, preferably 30 minutes or less, more preferably 15 minutes or less, still more preferably 10 minutes or less. When the curable composition is used as the underfill material, the curing temperature is set in consideration of the heat resistance of electronic parts, and is usually 50 to 200°C, for example 80 to 150°C.

The glass transition temperature of the cured product may be 125° C. or higher, 130° C. or higher, 135° C. or higher, or 140° C. or higher. Moreover, the glass transition temperature of the cured product may be 250° C. or lower, 200° C. or lower, 175° C. or lower, or 150° C. or lower. Heat resistance can be improved by increasing the glass transition temperature of the cured product.

Examples of bonds produced by curing are ether bonds, ester bonds or tertiary amino bonds. The ratio of generated ether bonds may be 50 mol % or more, 60 mol % or more, 70 mol % or more, or 80 mol % or more with respect to 100 mol % of generated bonds. The ratio of ester bonds generated may be 20 mol% or less, 15 mol% or less, 10 mol% or less, or 7 mol% or more, preferably 12 mol% or less, more preferably 8 mol%, relative to 100 mol% of the generated bonds. % or less. The ratio of tertiary amino bonds generated may be 12 mol% or less, 9 mol% or less, 6 mol% or less, or 3.5 mol% or more, preferably 7.5 mol%, relative to 100 mol% of the generated bonds. 2.5 mol % or less, more preferably 2.5 mol % or less. Identification of the bond produced can be performed by using various spectroscopic methods such as NMR and IR.

The coefficient of linear expansion of the cured product may be 31 ppm or less, 29 ppm or less, 25 ppm or less, or 23 ppm or less, preferably 30 ppm or less, more preferably 29 ppm or less. The low coefficient of linear expansion of the cured product can reduce the occurrence of device defects.

[Film covering material (2)]
The film covering material (2) is a film covering material suitable for covering a device (or electronic device) such as a printed circuit board on which electronic components are mounted. The film-like sealant may be in the form of a single sheet, a folded sheet capable of sandwiching the device, or a bag-like shape capable of containing the device.

The film coating (2) may be in contact with a portion of the underfill material (13). Part of the underfill material (13) may protrude from the gap formed by the substrate (11) and the electronic component (12) (see FIG. 2). The contact between the film coating material (2) and the protruding underfill material improves the adhesiveness between the substrate (11), the electronic component (12), and the underfill material (13), thereby increasing the reliability of the electronic component. can improve sexuality.

The film covering material (2) may be an unstretched film or a stretched film (uniaxially or biaxially stretched film), and may be heat-shrinkable by stretching or orientation. The draw ratio of the film may be, for example, 1.2 times or more, 1.5 times or more, or 2 times or more, and may be 10 times or less, 7 times or less, or 5 times or less in one direction. .

The thickness of the film covering material (2) may be, for example, 1 μm or more, 5 μm or more, 10 μm or more, 25 μm or more, 50 μm or more, or 75 μm or more, 1000 μm or less, 500 μm or less, 300 μm or less, 250 μm or less, 200 μm or less Alternatively, it may be 150 μm or less. The small thickness makes it easy to conform to the unevenness of the surface of the device. A large thickness makes it easy to sufficiently cover corners and the like.

The water vapor transmission rate (40° C., 90% RH) of the film covering material (2) is, for example, 100 g/m ² /day or less, 50 g/m ² /day or less, or 30 g/m ² /day or less in terms of thickness of 1 mm. , 10 g/m ² /day or less, 5 g/m ² /day or less, 2.5 g/m ² /day or less, 1 g/m ² /day or less, 0.5 g/m ² /day or less. It is preferably 50 g/m ² /day or less. In particular, when the film covering material (2) contains polyamide, it can have excellent water vapor barrier properties. The water vapor transmission rate can be measured by a conventional method, for example, the cup method of JIS Z0208.

(Thermoplastic resin)
The film coating (2) preferably comprises a resin, more preferably a thermoplastic resin.

The thermoplastic resin may be amorphous or crystalline. The crystallinity of the thermoplastic resin may be 20% or less, or 10% or less, preferably 10% or less. The degree of crystallinity can be measured by a conventional method, for example, a method based on density or heat of fusion, an X-ray diffraction method, an infrared absorption method, or the like. The thermal meltability of the amorphous copolyamide resin can be measured as a softening temperature with a differential scanning calorimeter, and the melting point of the crystalline copolyamide resin can be measured with a differential scanning calorimeter (DSC).

The melting point or softening point of the thermoplastic resin may be 80° C. or higher, 90° C. or higher, 105° C. or higher, 115° C. or higher, or 125° C. or higher, and 160° C. or lower, 150° C. or lower, 140° C. or lower, 135° C. or lower. , or 130° C. or less. Having the melting point or softening point in this range can improve the durability of the vehicle-mounted device. Since the thermoplastic resin has a relatively low melting point or softening point, it is useful for melting to conform to surface shapes such as irregularities on the device surface (corners of steps, etc.). In addition, the melting point of the thermoplastic resin means the temperature corresponding to a single peak when each component is compatible and a single peak occurs in DSC, each component is incompatible, and multiple peaks are generated in DSC. When a peak occurs, it means the temperature corresponding to the peak on the high temperature side among the plurality of peaks.

The thermoplastic resin preferably has a high melt flowability so that it can follow the surface shape of the mounting substrate surface such as irregularities and can flow or penetrate into gaps and the like. The melt flow rate (MFR) of the thermoplastic resin may be 1 g/10 min or more, 3 g/10 min or more, or 5 g/10 min or more at a temperature of 160° C. and a load of 2.16 kg, and is 350 g/10 min. It may be 300 g/10 minutes or less, or 250 g/10 minutes or less.

Examples of thermoplastic resins include polyesters, polyolefins, polyamides, polyurethanes, and the like, with polyamides being preferred.

(polyamide)
Polyamide, which is a preferred example of the thermoplastic resin, will be described in detail below.

Polyamides may be aliphatic or aromatic, preferably aliphatic. Polyamides may be linear, branched or cyclic. The polyamide may be a polyamide into which a branched chain structure is introduced using a small amount of polycarboxylic acid component and/or polyamine component.

Polyamides are multi-copolymers of amide-forming components, e.g. can be

The number average molecular weight of the polyamide may be 3000 or higher, 5000 or higher, 7500 or higher, 10000 or higher, 30000 or higher, 50000 or higher, 100000 or higher, or 250000 or higher, preferably 5000 or higher. The number average molecular weight of the polyamide may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, or 30,000 or less, preferably 100,000 or less. The molecular weight of the copolymerized polyamide resin may be measured in terms of polymethyl methacrylate by gel permeation chromatography using HFIP (hexafluoroisopropanol) as a solvent.

The polyamide preferably contains repeating units having long-chain aliphatic groups (long-chain alkylene or alkenylene groups). A repeating unit having a long-chain aliphatic group may be a repeating unit derived from a long- _chain component. Included are moieties with alkylene groups, more preferably C _10-14 alkylene groups). Examples of long chain components include C _8-18 alkanedicarboxylic acids (preferably C _10-16 alkanedicarboxylic acids, more preferably C _10-14 alkanedicarboxylic acids, etc.), C _9-17 lactams (preferably laurolactam, etc.) and amino C _9-17 alkanecarboxylic acids (preferably amino C _{11-15 alkanecarboxylic} acids such as aminoundecanoic acid and aminododecanoic acid). These components may be used alone or in combination of two or more. Polyamides containing units derived from such components can be excellent in water resistance, adhesion to electronic devices, abrasion resistance, and impact resistance.

The polyamide may be formed by copolymerizing at least one selected from the group consisting of a diamine component, a dicarboxylic acid component, a lactam component, and an aminocarboxylic acid component. That is, the polyamide is at least selected from repeating units derived from a diamine component, repeating units derived from a dicarboxylic acid component, repeating units derived from a lactam component, and/or repeating units derived from an aminocarboxylic acid component. may have one. For example, a diamine component and a dicarboxylic acid component may form a polyamide amide bond, or a lactam component and an aminocarboxylic acid component may each independently form a polyamide amide bond.

Diamine component Examples of diamine components include aliphatic diamines or alkylenediamine components (e.g., _C4-16 alkylenediamines such as tetramethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, octamethylenediamine, dodecanediamine, etc.), etc. is mentioned. These diamine components can be used individually or in combination of 2 or more types. A preferred diamine component comprises at least an alkylenediamine (preferably a C _6-14 alkylenediamine, more preferably a C _6-12 alkylenediamine).

If necessary, diamine components include alicyclic diamine components (diaminocycloalkanes such as diaminocyclohexane (diamino C _5-10 cycloalkanes, etc.); bis(4-aminocyclohexyl)methane, bis(4-amino- bis(aminocycloalkyl)alkanes [such as bis(amino C _5-8 cycloalkyl)C _1-3 alkanes] such as 3-methylcyclohexyl)methane, 2,2-bis(4′-aminocyclohexyl)propane; xylylenediamine, etc.) and an aromatic diamine component (meta-xylylenediamine, etc.) may be used in combination. A diamine component (eg, an alicyclic diamine component) may have a substituent such as an alkyl group (C _1-4 alkyl group such as a methyl group or an ethyl group).

Dicarboxylic acid component Examples of dicarboxylic acid components include aliphatic dicarboxylic acid or alkanedicarboxylic acid components (e.g., carbon such as adipic acid, pimelic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, or hydrogenated products thereof. 4 to 36 dicarboxylic acids or C _4-36 alkanedicarboxylic acids). These dicarboxylic acid components can be used alone or in combination of two or more. Examples of preferred dicarboxylic acid components include C _6-36 alkanedicarboxylic acids (eg, C _6-16 alkanedicarboxylic acids, preferably C _8-14 alkanedicarboxylic acids, etc.). Furthermore, if necessary, alicyclic dicarboxylic acid components (such as C _5-10 cycloalkane-dicarboxylic acids such as cyclohexane-1,4-dicarboxylic acid and cyclohexane-1,3-dicarboxylic acid), aromatic dicarboxylic acids ( terephthalic acid, isophthalic acid, etc.) may be used in combination. As a diamine component and a dicarboxylic acid component, an alicyclic obtained by using the above-exemplified aliphatic diamine component and/or an aliphatic dicarboxylic acid component together with an alicyclic diamine component and/or an alicyclic dicarboxylic acid component. Group polyamide resins are known as so-called transparent polyamides and can be excellent in transparency.

Lactam component and aminocarboxylic acid component Examples of lactam components include δ-valerolactam, ε-caprolactam, ω-heptalactam, ω-octalactam, ω-decanelactam, ω-undecanelactam, ω-laurolactam (or and C4-20 lactams such as ω-laurinlactam). Examples of aminocarboxylic acid components include C6-20 aminocarboxylic acids such as ω-aminodecanoic acid, ω-aminoundecanoic acid and ω-aminododecanoic acid. These lactam components and aminocarboxylic acid components may be used alone or in combination of two or more.

Examples of preferred lactam components include C _6-19 lactams, C _8-17 lactams, or C _10-15 lactams (such as laurolactam), and preferred amino carboxylic acids include amino C _6-19 alkanes. carboxylic acids, amino C _8-17 alkanecarboxylic acids, amino C _10-15 alkanecarboxylic acids or (aminoundecanoic acid, aminododecanoic acid, etc.).

Polyamides may have repeat units derived from at least one monomer selected from, for example, polyamide 11 monomers, polyamide 12 monomers, polyamide 610 monomers, polyamide 612 monomers and polyamide 1010 monomers. The polyamide may be a copolymer of a plurality of these monomers, and may have repeating units derived from the above and at least one monomer selected from polyamide 6 monomers and polyamide 66 monomers.

• Block Copolymer Polyamide The polyamide may be a block copolymer polyamide comprising a polyamide as hard block and a soft block. Examples of block copolymer polyamides include, for example, polyamide-polyether block copolymers, polyamide-polyester block copolymers, polyamide-polycarbonate block copolymers, and the like.

The polyamide constituting the hard block may be a homopolymer or copolymer (homopolyamide, copolyamide) of one or more of the amide-forming components. The homopolyamide as the hard block may contain the long-chain components exemplified above as constitutional units, and the preferred long-chain components are the same as above. Typical homopolyamides include polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012 and the like. The copolyamide as the hard block is the same as the copolyamides exemplified above. Among these polyamides, homopolyamides such as polyamide 11, polyamide 12, polyamide 1010 and polyamide 1012 are preferred.

A typical block copolymer polyamide is a polyamide-polyether block copolymer. In the polyamide-polyether block copolymer, the polyether (polyether block) includes, for example, polyalkylene glycol (e.g., poly C _2-6 alkylene glycol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, preferably Poly C _2-4 alkylene glycol) and the like.

Polyamide-polyether block copolymers include, for example, block copolymers obtained by copolycondensation of polyamide blocks having reactive terminal groups and polyether blocks having reactive terminal groups, such as polyether amides [ For example, a block copolymer of a polyamide block having a diamine end and a polyalkylene glycol block (or polyoxyalkylene block) having a dicarboxyl end, a polyamide block having a dicarboxyl end and a polyalkylene glycol block having a diamine end (or polyoxyalkylene block)], polyether ester amide [block copolymer of a polyamide block having a dicarboxyl end and a polyalkylene glycol block (or polyoxyalkylene block) having a dihydroxy end] etc. The block copolymer polyamide may have an ester bond, but may not have an ester bond in order to improve acid resistance. The block copolymer polyamide may have few amino groups.

In the block copolymer polyamide, the number average molecular weight of the soft block (polyether block, polyester block, polycarbonate block, etc.) can be selected from, for example, a range of about 100 to 10,000, preferably 300 to 6,000 (e.g., 300 to 5,000 ), more preferably 500 to 4,000 (eg, 500 to 3,000), particularly about 1,000 to 2,000.

• Polyamide composition The amide bond content of the polyamide may be 30 units or more, 40 units or more, 50 units or more, or 60 units or more per polyamide. The amide bond content of the polyamide may be 200 units or less, 150 units or less, 100 units or less, 75 units or less, or 50 units or more per polyamide. The amide bond content can be calculated, for example, by dividing the number average molecular weight by the molecular weight of the repeating unit (one unit).

The amino group concentration of the polyamide may be 10 mmol/kg or more, 10 mmol/kg or more, 15 mmol/kg or more, 20 mmol/kg or more, or 25 mmol/kg or more. The amino group concentration of the polyamide may be 500 mmol/kg or less, 400 mmol/kg or less, 300 mmol/kg or less, or 250 mmol/kg or less. A high concentration of amino groups can improve the adhesion of the film coating (2).

The carboxy group concentration of the polyamide may be 10 mmol/kg or more, 10 mmol/kg or more, 15 mmol/kg or more, 20 mmol/kg or more, or 25 mmol/kg or more. The carboxy group concentration of the polyamide may be 500 mmol/kg or less, 400 mmol/kg or less, 300 mmol/kg or less, or 250 mmol/kg or less. When the carboxyl group concentration is high, it can be excellent in thermal stability and/or long-term stability (continuous workability).

The amount of repeating units derived from long-chain components may be 10 mol% or more, 30 mol% or more, 50 mol% or more, or 75 mol% or more, preferably 50 mol% or more, relative to the polyamide. be. The amount of repeat units derived from long chain components may be 100 mol % or less, 95 mol % or less, 90 mol % or less, or 85 mol % or less relative to the polyamide.

The amount of the repeating unit derived from the diamine component is 0.7 mol or more, 0.8 mol or more, 0.9 mol or more, 0.95 mol or more per 1 mol of the repeating unit derived from the dicarboxylic acid component. and may be 1.3 mol or less, 1.2 mol or less, 1.1 mol or less, or 1.05 mol or less.

The total amount of repeating units derived from a diamine component and a dicarboxylic acid component is 0 mol% or more with respect to the total amount of repeating units derived from a diamine component, a dicarboxylic acid component, a lactam component and an aminocarboxylic acid component, It may be mol % or more, 10 mol % or more, 15 mol % or more, 20 mol % or more, or 25 mol % or more. The total amount of repeating units derived from a diamine component and a dicarboxylic acid component is 100 mol% or less with respect to the total amount of repeating units derived from a diamine component, a dicarboxylic acid component, a lactam component and an aminocarboxylic acid component, It may be 95 mol % or less, 90 mol % or less, 85 mol % or less, 80 mol % or less, 75 mol % or less, 70 mol % or less, or 60 mol % or less, preferably 75 mol % or less.

When the polyamide is a block copolymer polyamide, the amount of polyamide blocks, based on the sum of the hard blocks and soft blocks, is 5% or more, 10% or more, 20% or more, 30% or more, 40% or more. % or more, and may be 50% or more by weight. The amount of polyamide blocks may be 90 wt% or less, 80 wt% or less, 70 wt% or less, 60 wt% or less, or 50 wt% or less based on the sum of hard blocks and soft blocks.

(Composition of film covering material (2))
The film covering material (2) may further contain a thermoplastic resin such as an ethylene-vinyl acetate copolymer in addition to the polyamide. The ratio of other resins is, for example, 100 parts by weight or less (for example, about 1 to 80 parts by weight), preferably 2 to 70 parts by weight, more preferably 2 to 50 parts by weight, with respect to 100 parts by weight of polyamide, especially It may be 30 parts by weight or less (for example, about 3 to 20 parts by weight).

The film coating material (2) may optionally contain various additives such as fillers, stabilizers (heat stabilizers, weather stabilizers, etc.), colorants, plasticizers, lubricants, flame retardants, antistatic agents, heat conductors, etc. It may contain a drug or the like. Additives may be used alone or in combination of two or more.

The film coating material (2) may have an adhesive layer on the substrate side surface in addition to the thermoplastic resin layer containing the thermoplastic resin as a main component. The adhesive layer may be provided on part or all of the substrate-side surface of the thermoplastic resin layer. Components in the adhesive layer may be components of conventional adhesives or pressure sensitive adhesives, such as vinyl chloride adhesives, vinyl acetate adhesives, olefin adhesives, acrylic adhesives, polyester adhesives, urethane adhesives, adhesives, epoxy adhesives, rubber adhesives, and the like.

The film coating material (2) comprises a thermoplastic resin layer containing the thermoplastic resin as a main component, a protective layer containing a heat-resistant resin as a main component, and an adhesive layer between the thermoplastic resin layer and the protective layer. may have. The adhesive layer may be provided on part or all of the interface with the protective layer. Examples of heat-resistant resins in the protective layer include fluorine resins, olefin resins (including cyclic olefin resins), styrene resins, polyester resins, polycarbonate resins, polyurethane resins, polyamide resins, polyimide resins ( polyamideimide, polyetherimide, etc.), polyacetal resin, polyphenylene ether resin, polyetherketone resin (e.g., polyetherketone (PEK), polyetheretherketone (PEEK), etc.), polyphenylene sulfide resin, polyether Examples include sulfone-based resins, cellulose derivatives, and aromatic epoxy resins. Components in the adhesive layer may be components of conventional adhesives or pressure sensitive adhesives, such as vinyl chloride adhesives, vinyl acetate adhesives, olefin adhesives, acrylic adhesives, polyester adhesives, urethane adhesives, adhesives, epoxy adhesives, rubber adhesives, and the like.

<Method for producing film-coated substrate>
A method for manufacturing a film-coated substrate in the present disclosure includes a step (I) of obtaining a mounting substrate (1), including connecting a substrate (11) and an electronic component (12) with an underfill material (13); It involves coating a mounting substrate (1) with a film coating (2).

[Step (I) for obtaining mounting board (1)]
The step (I) of obtaining a mounting board (1) includes connecting a board (11) and an electronic component (12) with an underfill material (13). The step (I) of obtaining the mounting substrate (1) may include filling the gap between the substrate (11) and the electronic component (12) with an underfill material (13). Here, the electronic component (12) may be mounted on the board. Mounting means placing an electronic component on a board, the component may be soldered (e.g. cream soldered) to the board, and/or the lead of the component may be inserted into a hole for the lead of the printed circuit board. may be inserted.

The filling of the underfill material (13) as the capillary underfill material may be performed by filling the gap between the substrate (11) and the electronic component (12) with the underfill material (13). The underfill material (13) before hardening is applied to the entrance of the gap formed by the substrate (11) and the electronic component (12) (for example, the edge portion of the electronic component), and the substrate (11) and the electronic component (12) are ) can be filled with the underfill material (13) by infiltrating the uncured underfill material (13) into the gap between the . The filling may be performed mechanically using a dispenser or the like. After that, the mounting board containing the filled unfill material (13) is heated at a predetermined temperature for a predetermined time, or the underfill material (13) is irradiated with light, thereby removing the underfill material (13). It can be cured to bond the electronic component and the substrate. Since the underfill material of the present disclosure can have excellent permeability, it can be used as a capillary underfill material to fill narrow gaps after electronic components are mounted.

[Coating step (II)]
The coating step (II) includes coating the mounting substrate (1) with the film coating material (2). Covering means that at least part of the mounting substrate (1) is covered with the film covering material (2), for example, both surfaces of the mounting substrate (1) may be covered (or wrapped), and mounting One surface of the substrate (1) may be entirely covered, or at least one surface of the mounting substrate (1) may be partially covered (for example, a predetermined portion (electronic component mounting area, wiring area, etc.)). . Preferably, the film coating (2) is coated in contact with a portion of the underfill material (13). One surface or both surfaces (including the mounting portion) of the mounting substrate (1) is covered with the film covering material (2), and the entire film covering material (2) can be tightly covered by heat softening or heat melting, The mounting board (1) can be effectively protected. When the film coating material (2) has an adhesive layer on the substrate side surface, a vacuum forming technique (hot melt method) may be used. A film-covered substrate can be obtained by bonding the film-covering material (2) and at least part of the mounting substrate (1) via a layer.

After coating the mounting substrate (1) with the film coating material (2) (for example, the film coating material (2) softened by heating) in order to increase the adhesion between the mounting substrate (1) and the film coating material (2) Alternatively, the mounting substrate (1) and the film covering material (2) may be brought into close contact with each other by discharging the gas between them under reduced pressure. In order to improve the adhesion between the mounting substrate (1) and the film covering material (2), the mounting substrate (1) is coated with the film covering material (2) (for example, a heat-softened film covering material) by vacuum forming using differential pressure. material (2)). Examples of vacuum forming include TOM (Three-dimension Over-lay Method) or neo-TOM from Fuse Shinku Co., Ltd., NATS (Navitas Air-heat Transfer System) from Navitas Co., TFH from Asano Laboratory Co., Ltd., and the like.

<Application of film-coated substrate>
The film-coated substrates described above can be provided in a variety of devices. Since the film-coated substrate has excellent thermal shock resistance (e.g., conductivity after thermal shock), it is suitable for devices that can be placed in harsh environments (e.g., high temperature and/or low temperature environments) such as in-vehicle devices. suitable for the application. Examples of such devices, particularly in-vehicle devices, include control ECUs, various sensors, in-vehicle secondary batteries, speakers, displays, cameras, and various other modules.

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. Parts and percentages are by weight unless otherwise specified.

[Underfill]
Raw materials shown in Table 1 below were mixed to obtain underfill materials (UF) 1 to 3 before curing.

[Film covering material]
The film coating materials used are shown in Table 2 below.

[Film-coated substrate]
(Example 1)
On a BGA (Ball Grid Array) mounting board, an underfill material (UF1) was applied and permeated into the gap between the semiconductor element (size: 20×20 mm) and the board. Then, it was cured by heating at 150° C. for 3 minutes to obtain a mounting substrate sealed with an underfill material (UF1). Then, using a vacuum forming apparatus (heating temperature 120 to 170° C., pressure 70 kPa or less), the obtained mounting substrate was coated with a film coating material (polyamide 1) to prepare a film-coated substrate. In the obtained film-coated substrate, the underfill material protruding from the gap between the semiconductor element and the substrate was in contact with the film coating material.

(Examples 2 to 6, Comparative Example 1)
A film-coated substrate was produced in the same manner as in Example 1, except that the underfill material and film coating material used were changed as shown in Table 3. In Comparative Example 1, a film-coated substrate was produced without using an underfill material.

(water resistant)
The prepared film-coated substrate was immersed in water at 23° C. for 100 hours, and the presence or absence of peeling of the film was visually evaluated. When there was no abnormality, it was rated as ◯, and when partial peeling of the film was confirmed, it was rated as Δ. Table 3 shows the results.

(conductivity)
The continuity of the circuit board was confirmed using a digital multimeter. A case in which continuity was confirmed was indicated by ◯, and a case in which disconnection was observed was indicated by ×. Table 3 shows the results.

(Durability evaluation conditions)
After subjecting the film-coated substrate to thermal shock (-40 to 125°C for 30 minutes each x 3500 cycles), the circuit substrate was evaluated for conductivity and water resistance. Table 3 shows the results.

From the results of Comparative Example 1, it was found that the film-coated substrate using no underfill material was broken after the thermal shock and did not have the thermal shock resistance. It was found that an underfill material is necessary to develop thermal shock resistance.
From the results of Examples 1, 2 and 3, it was found that the film-coated substrates using UF1 had excellent adhesion after thermal shock (Examples 2 and 3 had slightly lower levels than Example 1). ). It is considered that this is because the composition of UF1 contributes favorably.
From the results of Examples 1, 4, 5 and 6, it was found that film-coated substrates using polyamide 1 or polyamide 2 have excellent adhesion after thermal shock (Examples 5 and 6 are It was a little lower level than 4). It is considered that this is because the compositions and high melting points (higher than the temperature of the thermal shock test) of polyamide 1 and polyamide 2 contribute favorably.

The film-coated substrates of the present disclosure can be utilized as part of electronic component devices, and are particularly suitable for use in devices that can be placed in harsh environments (e.g., high temperature and/or low temperature environments) such as automotive devices. ing.

REFERENCE SIGNS LIST 11 substrate 12 electronic component 13 underfill material 14 solder 2 film covering material

Claims (14)

A film-coated substrate comprising a mounting substrate (1) and a film covering material (2) covering the mounting substrate (1),
A film-coated substrate, wherein said mounting substrate (1) comprises a substrate (11), an electronic component (12), and an underfill material (13) connecting said substrate (11) and said electronic component (12). The film-coated substrate according to claim 1, wherein the underfill material (13) is a curable composition or a cured product thereof comprising an epoxy resin (A), a curing agent (B) and an inorganic filler (C). 3. The film coated substrate of claim 2, wherein said epoxy resin (A) comprises a silicone modified epoxy resin. 4. The film-coated substrate according to claim 2, wherein said curing agent (B) is at least one selected from the group consisting of imidazole-based curing agents and imidazoline-based curing agents. A film-coated substrate according to any one of claims 2 to 4, wherein said inorganic filler (C) comprises spherical inorganic particles. The epoxy resin (A) is 10% by weight or more and 60% by weight or less with respect to the curable composition,
The amine-based curing agent (B) is 0.01% by weight or more and 20% by weight or less with respect to the curable composition,
The inorganic filler (C) is 20% by weight or more and 80% by weight or less with respect to the curable composition.
A film-coated substrate according to any one of claims 2-5. A film-coated substrate according to any preceding claim, wherein the electronic component (12) comprises a ball grid array. A film-coated substrate according to any one of the preceding claims, wherein said film coating (2) comprises a polyamide resin. A film coated substrate according to any one of the preceding claims, wherein said film coating (2) is in contact with a portion of said underfill material (13). A step (I) of obtaining a mounting substrate (1) comprising connecting a substrate (11) and an electronic component (12) with an underfill material (13); ), the coating step (II)
A method of making a film-coated substrate, comprising: 11. The method according to claim 10, wherein the step (I) of obtaining the mounting substrate (1) includes filling the gap between the substrate (11) and the electronic component (12) with the underfill material (13). A method of making the described film-coated substrate. 12. The method for producing a film-coated substrate according to claim 10, wherein in the coating step (II), the mounting substrate (1) is coated with the film coating material (2) by vacuum forming. A device comprising a film-coated substrate according to any one of claims 1-9. 14. The device of claim 13, which is a vehicle-mounted device.

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