TW201723062A - Nonaqueous dispersion containing fluorine-based resin, thermosetting resin composition containing fluorine-based resin and its cured product, and adhesive composition for circuit boards characterized by having properties of excellent adhesion, heat-resistance, and low viscosity - Google Patents

Abstract

An object of the present invention is to provide a nonaqueous dispersion containing fluorine-based resin that has excellent properties of fine particle diameter, low viscosity and stability for storage, a thermosetting resin composition containing said fluorine-based resin of the nonaqueous dispersion containing fluorine-based resin and its cured product, and an adhesive composition for circuit boards. A nonaqueous dispersion containing fluorine-based resin is characterized by having a fine powder at least containing a fluorine-based resin, a compound represented by the following formula (I) and a nonaqueous solvent, wherein l, m and n in formula (I) are positive integers.

Description

Non-aqueous dispersion of fluorine-based resin, thermosetting resin composition of fluorine-containing resin, cured product thereof, and adhesive composition for circuit board

The present invention relates to a non-aqueous dispersion of a fluorine-based resin having a fine particle diameter, a low viscosity, and excellent storage stability, and a thermosetting resin composition of a fluorine-containing resin containing a non-aqueous dispersion of the fluorine-based resin and a hardened resin composition thereof. The composition of the material and the adhesive for the circuit board.

A fluorine-based resin such as polytetrafluoroethylene (PTFE) or a fluorinated ethylene-propylene copolymer is a material excellent in heat resistance, electrical insulation, non-adhesiveness, weather resistance, and the like, particularly polytetrafluoroethylene (PTFE). It is a material excellent in heat resistance, electrical insulation properties, low dielectric properties, low friction properties, non-adhesive properties, weather resistance, etc., and is used in electronic equipment, sliding materials, automobiles, kitchens, and the like. A fluorine-based resin such as polytetrafluoroethylene having such characteristics is added to various resin materials (resist materials) or rubbers, adhesives, lubricants or greases, printing inks, paints, and the like in a fine powder to enhance the products. Features are used for the purpose.

For example, a fine powder of polytetrafluoroethylene is usually a stabilizer such as water, a polymerization initiator, a fluorinated emulsifier, or a paraffin by emulsion polymerization. In the presence of the tetrafluoroethylene (TFE) monomer, the aqueous dispersion containing the polytetrafluoroethylene fine particles is obtained by polymerization, and then concentrated, aggregated, dried, or the like (see, for example, Patent Document 1).

As a method of adding a fine powder of a fluorine-based resin such as polytetrafluoroethylene to a resin material or the like, for example, in addition to a method of directly mixing, it is known that it is dispersed in water or an oily solvent, and is dispersed in a dispersion such as PTFE. The method of mixing, etc. It can be uniformly mixed by temporarily dispersing it in water or an oily solvent and then adding it.

However, the fine powder of the fluorine-based resin such as polytetrafluoroethylene has a strong cohesive force between the particles, and is particularly difficult to be in the form of a fine particle diameter, a low viscosity, and excellent storage stability in a nonaqueous solvent such as an oil solvent. Decentralized topics.

Further, when it is added to a water-insoluble resin or a resist material or the like, an oil-based solvent-based polytetrafluoroethylene dispersion is required, and many inventions relating to an aqueous dispersion of polytetrafluoroethylene are known (for example, According to the patent documents 2 and 3), compared with the aqueous dispersion, there is a case where there is no report relating to the oil-based solvent-based polytetrafluoroethylene dispersion or the like (for example, refer to Patent Document 4).

The technique described in Patent Document 4 is a long-term stable oil-PTFE dispersion composed of PTFE particles and at least one mono- or polyene-based unsaturated oil or oil mixture, and the olefin-based unsaturated oil. The molecular system forms a covalent bond/chemical bond on the surface of the PTFE (primary) particle by a radical reaction, and at this time there is a permanent charge separation between the oil molecules bonded to the surface of the PTFE particle, and the PTFE particle is Oil or oil mixture Fine dispersion in the preparation method by mixing a modified PTFE (emulsion) polymer having a continuous perfluoro(peroxy) radical with at least one olefin-based unsaturated oil, Then, it is obtained by a method of applying mechanical stress to the modified PTFE (emulsion) polymer, etc., and the preparation method thereof is extremely complicated, and the widely used PTFE particles are not used, and the non-aqueous dispersion of the fluorine-based resin of the present invention is The technical ideas (constitution and effect) are completely different.

In the past, when a fine powder of a fluorine-based resin such as polytetrafluoroethylene is dispersed, a surfactant or a dispersant containing fluorine such as a fluoroalkyl group is usually used. The reason for this is that the surface of the PTFE or the like has a property of being extremely hard to be infiltrated with water or an oily solvent, and the cohesive force between the particles is extremely strong, and it is extremely difficult to disperse in a widely used fluorine-free surfactant or dispersant. The reason.

On the other hand, such a fluorine-containing surfactant or dispersant may thermally decompose at a high temperature, and there is a possibility of generating hydrogen fluoride, and there is a concern that the environmental surface or the safety surface may be adversely affected. There is an urgent need for a non-aqueous dispersion of a fluorine-based resin that can solve such problems.

In recent years, in recent years, the importance of high-speed communication or large-capacity information transmission has increased, and in order to reduce the speed of signal transmission to increase the processing speed, or to increase the frequency of use. The resulting transmission loss requires a material with a low specific dielectric ratio and a low dielectric tangent.

Thermosetting resin composition, in terms of its excellent adhesion or heat resistance It is widely used in the electrical and electronic fields. However, for example, epoxy resins have a problem of higher dielectric constant or dielectric tangent.

On the other hand, as a resin material having a low specific dielectric constant and a low dielectric tangent, a fluorine-based resin including polytetrafluoroethylene (PTFE) is widely known, but its adhesion or compatibility with other resins is poor. It is still rarely used as an electronic material.

As a method of utilizing characteristics such as low dielectric constant and low dielectric tangent of the fluorine-based resin, for example, it has been proposed to melt-mix PTFE or the like in various resin materials (for example, refer to Patent Document 5); however, since the melt-mixing system is Heating is carried out in a state where the resin is softened, and it is less suitable when it is mixed with a heat-resistant resin material, a reactive resin material, a PTFE resin material or the like, and is not suitable as a dielectric material for reducing the epoxy resin material. The method of adding rate or dielectric tangent.

As another method, a resin composition is known, which is characterized in that even if a PTFE filler is blended, the properties of the resin are not impaired, and as a resin composition having excellent low dielectric properties, for example, a specific formula is included. An epoxy resin, a phenol resin represented by a specific formula as a curing agent, and a polytetrafluoroethylene filler (see, for example, Patent Document 6).

In this embodiment, a polytetrafluoroethylene filler having an average particle diameter of 3 μm is dispersed in a bead mill together with an epoxy resin, a phenol resin, etc., but the dispersibility is poor, and the current situation is that it is not available. A sufficiently low dielectric ratio, low dielectric tangent epoxy resin composition.

In such a case, it is required to uniformly disperse a fluorine-based resin such as PTFE in an epoxy resin material which is widely used in electronic materials and the like. Further, it is a thermosetting resin composition such as an epoxy resin having a low specific dielectric constant and a low dielectric tangent.

Further, as an epoxy resin composition for forming an insulating layer, for example, Patent Document 7 discloses an epoxy resin composition containing an epoxy resin, a specific phenolic curing agent, a phenoxy resin, and rubber particles; Document 8 discloses an epoxy resin composition comprising an epoxy resin, a specific phenolic curing agent, and a polyvinyl acetal resin.

The insulating layer formed by the epoxy resin composition is disclosed as being low in thickness and excellent in peeling strength of the conductor layer formed by plating, but completely lower for low dielectric constant or low dielectric tangent Did not say.

In addition, as described above, an elastomer component such as rubber particles is added to the epoxy resin to adjust the flow characteristics of the thermosetting resin composition, or to strengthen the toughening of the thermosetting resin cured product, internal stress relaxation, and adhesion. When the filler component is used in combination with a filler component such as a fluorine resin powder, the elastomer component may affect the dispersibility of the filler component such as the fluorine resin powder, and the filler component may easily form agglomerates. .

Therefore, the current situation is that there is an urgent need for an insulating layer of a multilayer printed wiring board suitable for an electronic device having a dielectric property lower than a dielectric tangent and excellent in adhesion, heat resistance, dimensional stability, flame retardancy, and the like. A thermosetting resin composition which forms a thermosetting resin composition of a fluorine-containing resin or the like and a fluorine-based resin which is cured.

In addition, in recent years, with the progress of high-speed and high-performance electronic devices, the speed of communication has been demanded. In this case Under the circumstances, low dielectric constant and low dielectric tangentiality of various electronic device materials are required, and low dielectric constant and low dielectric tangentiality of insulating materials or substrate materials are also required.

One of such electronic device materials is a circuit board. As the circuit board, a copper clad laminate is used, and an electrically insulating film and a copper foil are joined via an adhesive layer.

Further, the copper clad laminate is processed by processing a copper foil portion to form a wiring pattern or the like. In order to protect the wiring pattern, an insulating coating film is coated, and the coating film is also bonded thereto via an adhesive layer.

Further, in the production of a prepreg for imparting insulation between layers and subsequent rigidity to a circuit board, it is also used by impregnating various fibers with an adhesive.

In such a circuit board, the adhesive layer between the electrically insulating film and the copper foil requires adhesion, heat resistance, dimensional stability, flame retardancy, etc., and electrical properties of low dielectric constant and low dielectric tangent are also required. .

As an adhesive composition for a circuit board, for example, an adhesive resin composition for producing a circuit board, which is characterized by comprising a cyanate resin and fluorine dispersed in the cyanate resin, is known. a resin powder and a rubber component (for example, refer to Patent Document 9); an adhesive epoxy resin composition comprising an epoxy resin, a reactive diluent containing an epoxy compound represented by a specific formula, and A hardener (for example, refer to Patent Document 10).

However, in the adhesive resin composition for manufacturing a circuit board described in the above Patent Document 9, it is difficult to control the fluorine-based resin powder in the resin group in a balanced manner. The state of dispersion in the product leaves a problem in sufficiently improving the electrical properties. In addition, the cyanate resin or the epoxy resin itself described in the above-mentioned Patent Documents 9 and 10 and the like as a composition for an adhesive for a circuit board are widely used, and the specific dielectric ratio or dielectric tangent of the resin of each of them is widely used. Higher, there are technical problems or limitations in terms of improving electrical characteristics, and the current situation is that a subsequent composition for a circuit board having improved electrical characteristics is required.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2012-92323 (Application No. Patent Application, Examples, etc.)

[Patent Document 2] Japanese Laid-Open Patent Publication No. 2006-169448 (Application No. Patent Application, Examples, etc.)

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2009-179802 (Application No. Patent Application, Examples, etc.)

[Patent Document 4] Japanese Laid-Open Patent Publication No. 2011-509321 (Application No. Patent Application, Examples, etc.)

[Patent Document 5] Japanese Laid-Open Patent Publication No. 2001-49068 (Application No. Patent Application, Examples, etc.)

[Patent Document 6] Japanese Laid-Open Patent Publication No. 2013-79326 (Application No. Patent Application, Examples, etc.)

[Patent Document 7] Japanese Laid-Open Patent Publication No. 2007-254709 (Application No. Patent Application, Examples, etc.)

[Patent Document 8] JP-A-2007-254710 (Application Patent Range, Examples, etc.)

[Patent Document 9] Japanese Laid-Open Patent Publication No. 2015-509113 (Application No. Patent Application, Examples, etc.)

[Patent Document 10] JP-A-2015-13950 (Application Patent Range, Examples, etc.)

The present invention has been made in view of the above-mentioned conventional problems, current conditions, and the like, and the first object of the present invention is to provide a microparticle size and a low viscosity even if a surfactant or a dispersant containing no fluorine-containing group is added. Further, the non-aqueous dispersion of a fluorine-based resin which is excellent in storage stability and excellent in dispersibility after long-term storage, and the second object is to provide a non-aqueous dispersion using the fluorine-based resin, and has a specific dielectric ratio and a dielectric constant. A thermosetting resin composition of a fluorine-containing resin which is suitable for forming an insulating layer of a multilayer printed wiring board of an electronic device, and has excellent electrical tangential properties and excellent properties such as adhesion, heat resistance, dimensional stability, and flame retardancy. A cured product of a thermosetting resin of a fluorine-containing resin obtained by curing the same; a third object of the invention is to provide a non-aqueous dispersion using the above fluorine-based resin, which has a lower specific dielectric constant and dielectric tangent, and an adhesive property, An adhesive composition for a circuit board, a laminate for a circuit board, a coating film, a prepreg, or the like, which is excellent in heat resistance, dimensional stability, flame retardancy, and the like.

As a result of intensive studies on the above-mentioned conventional problems, the inventors of the present invention have found that a non-aqueous dispersion of the above-mentioned fluorine-based resin can be obtained by first transmitting a fine powder containing a fluorine-based resin and a compound represented by a specific formula. Finally, the first invention described below is completed. In addition, the non-aqueous dispersion of the above-mentioned fluorine-based resin is used, and the thermosetting resin composition of the fluorine-containing resin which can obtain the above object, the cured product thereof, and the circuit board are found according to the second invention to the tenth invention. The composition of the agent or the like is completed to complete the present invention.

That is, the present invention resides in the following first to tenth inventions.

The first invention is a non-aqueous dispersion of a fluorine-based resin, characterized in that it contains at least a fine powder of a fluorine-based resin, a compound represented by the following formula (I), and a non-aqueous solvent.

[In the above formula (I), l, m, n are positive integers].

The compound represented by the above formula (I) is preferably contained in an amount of 0.1 to 15% by mass based on the mass of the fine powder of the fluorine-based resin.

In the non-aqueous dispersion of the fluorine-based resin, the average particle diameter of the fine powder of the fluorine-based resin in the dispersed state (the average particle diameter of the cumulative amount in the scattering intensity distribution) is preferably 1 μm or less.

The second invention is a thermosetting resin composition containing a fluorine-containing resin, and is characterized in that it contains at least a fine powder containing a fluorine-based resin and a fluorine-based resin of a compound represented by the above formula (I) and a nonaqueous solvent. A non-aqueous dispersion and a resin composition containing a cyanate resin and/or an epoxy resin.

The third invention is a thermosetting resin composition of a fluorine-containing resin, characterized in that it is at least blended with a fine powder containing at least a fluorine resin, a compound represented by the above formula (I), an elastomer component, and a nonaqueous solvent. A non-aqueous dispersion of a fluorine-based resin and a resin composition containing a cyanate resin and/or an epoxy resin.

The fourth invention is a thermosetting resin composition of a fluorine-containing resin, characterized in that it is at least blended with a fine powder containing at least a fluorine-based resin, a compound represented by the above formula (I), and a cyanate-containing resin and/or Or a resin composition of an epoxy resin, a non-aqueous dispersion of a fluorine-based resin of a non-aqueous solvent, and an elastomer component.

The fifth invention is a thermosetting resin composition of a fluorine-containing resin, characterized in that it is at least blended with a fine powder containing at least a fluorine-based resin, a compound represented by the above formula (I), and a cyanate-containing resin and/or A resin composition of an epoxy resin, a non-aqueous dispersion of a fluorine-based resin of a non-aqueous solvent, and a resin composition containing a cyanate resin and/or an epoxy resin.

In the thermosetting resin composition of the fluorine-containing resin of the second invention to the fifth aspect of the invention, the fine powder of the fluorine-based resin is preferably selected from the group consisting of polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, and perfluoroalkane. Oxygen polymerization A fine powder of one or more fluorine-based resins in a group of chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, and polychlorotrifluoroethylene.

Moreover, in the thermosetting resin composition of the fluorine-containing resin, the compound represented by the above formula (I) is preferably contained in an amount of 0.1 to 15% by mass based on the mass of the fine powder of the fluorine-based resin; In the non-aqueous dispersion of the resin, the average particle diameter (average particle diameter of the cumulative amount analysis under the scattering intensity distribution) of the fine powder of the fluorine-based resin in a dispersed state is preferably 1 μm or less.

According to a sixth aspect of the invention, there is provided a thermosetting resin composition of a fluorine-containing resin, which is characterized in that the thermosetting resin composition of the fluorine-containing resin of the second invention to the fifth invention is cured.

According to a seventh aspect of the invention, there is provided a composition for an adhesive for a circuit board, characterized in that it comprises at least a non-aqueous dispersion of a fine powder containing at least a fluorine-based resin, a compound represented by the above formula (I) and a fluorine-based resin of a non-aqueous solvent. And a resin composition comprising a cyanate resin and/or an epoxy resin.

In the adhesive composition for a circuit board, the compound represented by the above formula (I) is preferably contained in an amount of 0.1 to 15% by mass based on the mass of the fine powder of the fluorine-based resin, and the non-aqueous dispersion of the fluorine-based resin. The water content measured by the Karl Fischer method is preferably 8000 ppm or less.

In the above-mentioned adhesive composition for a circuit board, the fine powder of the fluorine-based resin is preferably selected from the group consisting of polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene, and tetra Fluoroethylene-chlorotrifluoro A fine powder of one or more fluorine-based resins in a group of ethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, and polychlorotrifluoroethylene.

In the non-aqueous dispersion of the fine powder of the fluorine-based resin, the average particle diameter of the fine powder of the fluorine-based resin in the dispersed state (the average particle diameter of the cumulative amount analysis under the scattering intensity distribution) is preferably 1 μm or less.

The eighth aspect of the invention is a laminate for a circuit board, comprising a laminate for a circuit board comprising at least an insulating film, a metal foil, and an adhesive layer interposed between the insulating film and the metal foil. The adhesive layer is the adhesive composition for a circuit board according to the seventh aspect of the invention.

The insulating film is preferably selected from the group consisting of polyimine (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide. Ether (PPS), polyetherimide (PEI), polyphenylene ether (modified PPE), polyester, para-aramid, polylactic acid, nylon, polyoxazide, polyetheretherketone (PEEK) One or more kinds of films in the group formed.

According to a ninth aspect of the invention, there is provided a coated film which is an insulating film and a coating film having an adhesive layer formed on at least one surface of the insulating film, wherein the adhesive layer is the circuit substrate of the seventh invention The composition of the adhesive is used.

The insulating film in the coating film is preferably selected from the group consisting of polyimine (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), and polyethylene naphthalate (PEN). ), polyphenylene sulfide (PPS), polyether phthalimide (PEI), polyphenylene ether (modified PPE), polyester, para-aromatic polyamine, polylactic acid, nylon, polyoxazolium, poly 1 in the group formed by ether ether ketone (PEEK) More than one type of film.

The tenth invention is a prepreg characterized in that one or more types of fibers selected from the group consisting of carbon fibers, cellulose fibers, glass fibers, or aromatic polyamide fibers are used. The formed structure is at least impregnated with the adhesive composition for a circuit board of the seventh invention.

According to the first aspect of the invention, even if a surfactant or a dispersant containing a fluorine-containing group is not added, it is possible to provide a fluorine-based resin which is excellent in fine particle diameter, low in viscosity, and excellent in storage stability, and which is excellent in re-dispersibility after long-term storage. Non-aqueous dispersion.

According to the second invention to the sixth aspect of the invention, it is possible to provide a circuit board having a characteristic that the dielectric constant and the dielectric tangent are lower than that of the dielectric property, the heat resistance, the dimensional stability, the flame retardancy, and the like. Thermal hardening of a fluorine-containing resin such as an adhesive composition for a circuit board to be used, and an insulating layer such as a laminate for a circuit board, a coating film, a prepreg, or a multilayer printed wiring board for an electronic device. A cured resin composition of a resin composition and a fluorine-containing resin which is cured.

According to the seventh invention to the tenth aspect of the present invention, it is possible to provide an adhesive for a circuit board having characteristics lower than a dielectric constant and a dielectric tangent, and excellent in adhesion, heat resistance, dimensional stability, flame retardancy, and the like. A composition, a laminate for a circuit board, a coating film, and a prepreg.

10‧‧‧Insulating film

20‧‧‧A layer of adhesive for circuit board

30‧‧‧metal foil

Fig. 1 is a schematic view showing an example of an embodiment of a laminate for a circuit board of the present invention (the eighth invention) in a cross-sectional view.

Fig. 2 is a schematic view showing another example of the embodiment of the laminate for a circuit board of the present invention (the eighth invention).

Fig. 3 is a schematic view showing an example of an embodiment of a coating film of the present invention (the ninth invention) in a cross-sectional view.

[Formation of the Invention]

Hereinafter, each embodiment of the first invention to the tenth invention will be described in detail for each invention. In addition, the components common to the inventions are described in detail in the first invention, etc., and the second invention and the like are described in the following, and the detailed description thereof is omitted.

[First invention: non-aqueous dispersion of a fluorine-based resin]

The non-aqueous dispersion of the fluorine-based resin of the first aspect of the invention is characterized in that it contains at least a fine powder of a fluorine-based resin, a compound represented by the following formula (I), and a non-aqueous solvent.

[In the above formula (I), l, m, n are positive integers].

<Micro powder of fluorine resin>

The fine powder of the fluorine-based resin which can be used in the first invention is, for example, selected from the group consisting of polytetrafluoroethylene (PTFE), fluorinated ethylene-propylene copolymer (FEP), and perfluoroalkoxy polymer (PFA). ), chlorotrifluoroethylene polymer (CTFE), tetrafluoroethylene-chlorotrifluoroethylene copolymer (TFE/CTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polychlorotrifluoroethylene (PCTFE) A fine powder of at least one fluorine-based resin in the group.

Among the fine powders of the above fluorine-based resin, particularly as a material having a low specific dielectric constant and a low dielectric tangent, it is preferable to use polytetrafluoroethylene (PTFE, which has the most excellent characteristics among the resin materials, and has a specific dielectric constant of 2.1. ).

Such a fine powder of a fluororesin such as a polytetrafluoroethylene can be obtained by an emulsion polymerization method, and can be generally used, for example, by a method described in the fluororesin manual (edited by Nishikawa Hideyuki, Nikkan Kogyo Shimbun Co., Ltd.). The method comes. Then, the fine powder of the fluorine-based resin obtained by the emulsion polymerization is agglomerated and dried, and the secondary particles which are agglomerated as the primary particle diameter are recovered as a fine powder, but the production of various fine powders which are generally used can be employed. method.

The polytetrafluoroethylene fine powder or the like used in the first invention The primary particle diameter of the fine powder of the fluorine-based resin is not particularly limited, and is irradiated by a laser. The average particle diameter (50% by volume, median diameter) of the volume basis measured by a scattering method, a dynamic light scattering method, an image forming method, or the like is preferably 1 μm or less; in order to make it more stable in a nonaqueous solvent In terms of dispersion, it is preferably 0.5 μm or less, more preferably 0.3 μm or less, whereby a more uniform dispersion is formed.

When the primary particle diameter of the fine powder of the fluorine-based resin exceeds 1 μm, it is likely to settle in an oily solvent, and it is more difficult to stably disperse.

In addition, the lower limit of the average particle diameter is preferably as low as possible, and is preferably 0.05 μm or more in terms of manufacturability, cost, and the like.

In addition, the primary particle diameter of the fine powder of the fluorine-based resin of the present invention is a value measured by an emulsion polymerization stage of a fine powder of a fluorine-based resin such as a polytetrafluoroethylene fine powder (by laser diffraction) ‧The value obtained by the scattering method or the dynamic light scattering method); if it is a polytetrafluoroethylene fine powder which is in a powder state after being dried, it is difficult to easily use the thunder due to the strong cohesive force between the primary particles The primary particle diameter is measured by a diffraction, a scattering method, a dynamic light scattering method, or the like, and therefore, may also mean a value obtained by an image forming method. The measuring device is, for example, a dynamic light scattering method using FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), a laser diffraction scatter method using Microtrac (manufactured by Nikkiso Co., Ltd.), or a Mac- Image imaging method of VIEW (made by Mountech Co., Ltd.).

The fine powder of the fluorine-based resin such as the polytetrafluoroethylene fine powder used in the first invention preferably has a specific surface area of preferably 15 m ² /g or less, more preferably 2 to 15 m ² /g, particularly preferably 2~13m ² /g, more preferably 2~11m ² /g. In the present invention (including the examples described later), the "specific surface area" is a value obtained by a gas adsorption method using a BET formula.

When the specific surface area of the fine powder of the fluororesin such as PTFE exceeds 15 m ² /g, it is likely to aggregate and precipitate in a nonaqueous solvent, and it is more difficult to stably disperse.

In addition, the finer surface area of the fine powder of the fluorine-based resin is preferably as low as possible, and is preferably 2 m ² /g or more in terms of manufacturability, cost, and the like.

The fine powder of the fluorine-based resin such as polytetrafluoroethylene fine powder which can be specifically used is selected from those having a suitable specific surface area or primary particle diameter. For example, the PTFE having a specific surface area of the above may be Dyneon TF Micropowder TF-9201Z, Dyneon TF Micropowder TF-9207Z (all manufactured by 3M Company), Nano FLON119N, FLUORO E (all manufactured by Shamrock Co., Ltd.), and TLP10F-1 ( Du Pont-Mitsui Fluorochemicals Co., Ltd., KTL-500F (made by Kitamura Co., Ltd.), Algoflon L203F (made by SOLVAY Co., Ltd.), and the like.

The preferred embodiment of the fine powder of the fluorine-based resin such as the polytetrafluoroethylene fine powder used in the first aspect of the invention is as described above, and the primary particle diameter is 1 μm or less, or the specific surface area is 15 m ² / g or less; each use of various non-aqueous dispersions of fluorine-based resins (various resin materials, resist materials, rubbers, adhesives, lubricants or greases, printing inks or coatings, and use in the manufacture of circuit boards) For the use of an adhesive composition for a circuit board, a laminate for a circuit board using the same, a coating film, a prepreg, or an insulating layer of a multilayer printed wiring board for an electronic device, etc.), a primary particle diameter of 1 μm or less, or When the specific surface area is 15 m ² /g or less, the primary particle diameter may be 1 μm or less, and the specific surface area may be 15 m ² /g or less.

In the first aspect of the invention, the fine powder of the fluorine-based resin such as the polytetrafluoroethylene fine powder is contained in an amount of 5 to 60% by mass, preferably 10 to 50% by mass, based on the total amount of the dispersion.

When the content is less than 5% by mass, the amount of the non-aqueous solvent is large, and the viscosity of the fine powder of the fluorine-based resin such as polytetrafluoroethylene is more likely to be precipitated or mixed with a material such as a resin. The inconvenience caused by the large amount of the non-aqueous solvent, for example, the removal of the solvent takes a time-consuming condition. On the other hand, when the amount is more than 60% by mass, the fine powder of the fluorine-based resin such as polytetrafluoroethylene becomes more likely to aggregate, and it is extremely difficult to stably maintain the state of the fine particles in a fluid state. Not good.

<Compound represented by the above formula (I)>

The compound represented by the above (I) used in the first aspect of the invention is a fine powder of a fluorine-based resin such as a polytetrafluoroethylene fine powder, which is uniformly and stably dispersed in a nonaqueous solvent. The molecular structure is a terpolymer composed of vinyl butyral/vinyl acetate/vinyl alcohol, which is obtained by reacting polyvinyl alcohol (PVA) with butyraldehyde (BA), and has a butyral group, B. The structure of the sulfhydryl group and the hydroxy group; by changing the ratio of the three structures (the ratio of l, m, n), the solubility in an oily solvent can be controlled, and even a polytetrafluoroethylene fine powder is added to various resin materials. Chemical reactivity in the case of a non-aqueous dispersion of fine powder of a fluorine-based resin.

As the compound represented by the above (I), a S-LEC B series, a K (KS) series, an SV series, a MOWITAL series manufactured by KURARAY Co., Ltd., and the like can be used as a commercial product.

Specifically, the product name of Sekisui Chemical Industry Co., Ltd.; S-LEC BM-1 (amount of hydroxyl group: 34 mol%, degree of butyralization 65±3 mol%, molecular weight: 40,000) With BH-3 (hydroxyl amount: 34mol%, butyralization degree 65±3 mol%, molecular weight: 110,000), same as BH-6 (hydroxyl number: 30 mol%, butyralization degree 69±3 Mo Ear %, molecular weight: 92,000), same as BX-1 (hydroxyl number: 33 ± 3 mol%, acetalization degree 66 mol%, molecular weight: 100,000), same as BX-5 (hydroxyl number: 33 ± 3 mol%, Degree of acetalization of 66 mol%, molecular weight: 130,000), same as BM-2 (amount of hydroxyl group: 31 mol%, degree of butyralization 68 ± 3 mol%, molecular weight: 52,000), same as BM-5 (hydroxyl group Amount: 34 mol%, butyralization degree 65 ± 3 mol%, molecular weight: 53,000), same as BL-1 (hydroxyl group: 36 mol%, butyralization degree 63 ± 3 mol%, molecular weight: 19,000 ), with BL-1H (hydroxyl amount: 30 mol%, butyralization degree 69 ± 3 mol%, molecular weight: 20,000), same as BL-2 (hydroxyl number: 36 mol%, butyralization degree 63 ± 3) Molar%, molecular weight: 2.7), same as BL-2H (hydroxyl amount: 29 mol%, butyralization degree 70±3 mol%, molecular weight: 28,000), same as BL-10 (hydroxyl group: 28 mol%, shrinkage Butyraldehyde degree 71±3 Ear %, molecular weight: 15,000), same as KS-10 (hydroxy amount: 25 mol%, acetalization degree 65 ± 3 mol%, molecular weight: 17,000), etc.; KURARAY (share) product name; MOWITAL B145 ( Hydroxyl group: 21~26.5 mol%, acetalization degree 67.5~75.2 mol%), same as B16H (hydroxyl number: 26.2~30.2 mol%, acetalization degree 66.9~73.1 mol%, molecular weight: 1~) 20000) Wait.

These may be used alone or in combination of two or more.

The content of the compound represented by the above (I) is preferably from 0.1 to 15% by mass based on the fine powder of the fluorine-based resin such as polytetrafluoroethylene fine powder. When the content of the compound is less than 0.1% by mass, the dispersion stability is deteriorated, and the fine powder of the fluorine-based resin such as the polytetrafluoroethylene fine powder is more likely to settle. When the content exceeds 15% by mass, the viscosity is high and it is not preferable.

Furthermore, if various thermosetting resin materials such as epoxy resin, polyimide resin precursor material, rubber, adhesive, lubricant or grease, printing ink or paint are added, polytetrafluoroethylene fine powder is added. The characteristics of the non-aqueous dispersion of the fine powder of the fluorine-based resin are preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 3% by mass.

The non-aqueous dispersion of the fine powder of the fluorine-based resin such as the polytetrafluoroethylene fine powder of the first invention may be combined with the compound represented by the above (I) in a range not impairing the effects of the first invention. Use other surfactants or dispersants in combination.

For example, a fluorine-free or non-fluorine-based surfactant may be used as a surfactant or a dispersant such as a nonionic, anionic or cationic surfactant, or a polymer surfactant such as a nonionic, anionic or cationic surfactant. The molecular dispersant or the like can be used without being limited thereto.

<non-aqueous solvent>

The nonaqueous solvent used in the first invention may, for example, be selected. Free γ-butyrolactone, acetone, methyl ethyl ketone, hexane, heptane, octane, 2-heptanone, cycloheptanone, cyclohexanone, cyclohexane, methylcyclohexane, ethyl ring Hexane, methyl n-amyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monoacetate, ethylene glycol Methyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diethyl ether, propylene glycol monoacetate, dipropylene glycol monoacetate, propylene glycol Diacetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexyl acetate, ethyl 3-ethoxypropionate, dioxane, lactate Ester, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, anisole, ethyl Benzyl ether, tolyl methyl ether, diphenyl ether, benzhydryl ether, phenylethyl ether, butylphenyl ether, benzene, ethylbenzene, diethylbenzene, pentylbenzene, cumene , toluene, xylene, and Propyltoluene, mesitylene, methanol, ethanol, isopropanol, butanol, methyl monoglycidyl ether, ethyl monoglycidyl ether, butyl monoglycidyl ether, phenyl monoglycidyl ether, methyl di Glycidyl ether, ethyl diglycidyl ether, butyl diglycidyl ether, phenyl diglycidyl ether, cresol monoglycidyl ether, phenol monoglycidyl ether, butyl phenol monoglycidyl ether, mineral spirits, 2-hydroxyethyl acrylate, tetrahydrofurfuryl acrylate, 4-vinyl pyridine, N-methyl-2-pyrrolidone, 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate, hydroxy group Propyl ester, glycidyl methacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate, methacrylate, methyl methacrylate, styrene, perfluoro Carbon, hydrofluoroether, hydrochlorofluorination Carbon, hydrofluorocarbon, perfluoropolyether, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dioxolane, various eucalyptus oils One type of non-aqueous solvent in the group, or one or more of these non-aqueous solvents.

Among these non-aqueous solvents, it is preferably changed depending on the respective applications (resin species such as a resin species and the use of a circuit board), and examples thereof include methyl ethyl ketone, cyclohexanone, toluene, and xylene. , N-methylpyrrolidone, methanol, ethanol, isopropanol, N,N-dimethylformamide, N,N-dimethylacetamide, dioxolane.

The water content of the nonaqueous solvent used in the first invention by the Karl Fischer method is preferably 8000 ppm or less [0 ≦ water content ≦ 8000 ppm].

In the first invention (including the examples and the like described later), the measurement of the water content by the Karl Fischer method is carried out by MCU-610 (manufactured by Kyoto Electronics Manufacturing Co., Ltd.) in accordance with JIS K 0068:2001.

It is considered that the higher the polarity of the non-aqueous solvent to be used, the higher the compatibility with water. However, if the water content is 8000 ppm or more, the fine powder of the fluorine-based resin such as the polytetrafluoroethylene fine powder is significantly inhibited. The dispersibility in the nonaqueous solvent or the solubility of the compound represented by the above (I) in the nonaqueous solvent is the main cause of the increase in viscosity or the aggregation of the particles.

In the first aspect of the invention, the water content of the non-aqueous solvent is 8000 ppm or less, whereby a fine powder of a fluorine-based resin such as a fine particle diameter, a low viscosity, and a storage stability which is excellent in storage stability can be formed. Water dispersion body. More preferably, the water content of the nonaqueous solvent is preferably 5,000 ppm or less, more preferably 3,000 ppm or less, and particularly preferably 2,500 ppm or less.

In addition, the water content of the non-aqueous dispersion of the fluorine-based resin of the first invention is preferably 8000 ppm or less by the Karl Fischer method [0 ≦ water content ≦ 8000 ppm].

In addition to the water content of the water-based solvent, it is considered that the water contained in the fine powder of the fluorine-based resin or the compound represented by the above (I) or the fine powder of the fluorine-based resin is dispersed in the non-aqueous system. In the production step in the solvent, the water content from the outside (the moisture in the air, the condensed water on the wall of the device, etc.) is obtained, and the water content of the non-aqueous dispersion of the fine powder of the fluorine resin is finally 8000 ppm or less. A non-aqueous dispersion of a fine powder of a fluorine-based resin which is more excellent in storage stability is obtained. More preferably, the water content of the nonaqueous dispersion is more preferably 5,000 ppm or less, more preferably 3,000 ppm or less, and particularly preferably 2,500 ppm or less.

In order to make the water content of the non-aqueous solvent and the water content of the non-aqueous dispersion of the fluorine-based resin 8000 ppm or less, a dehydration method of a non-aqueous solvent which is generally used may be employed. For example, a molecular sieve or the like may be used. Further, the fine powder of the fluorine-based resin or the compound represented by the above (I) can be used in a state where the water content is sufficiently lowered by dehydration by heating or decompression.

Further, after the non-aqueous dispersion of the fine powder of the fluorine-based resin is produced, the water may be removed by a molecular sieve or a membrane separation method, and the method may be such that the water content of the non-aqueous dispersion can be reduced. Can be It is used without particular limitation.

In the first invention, the non-aqueous solvent is used, but it may be used in combination with another non-aqueous solvent or other non-aqueous solvent, and may be used depending on the use (various thermosetting resin materials, rubber, and adhesive). , lubricants or greases, printing inks or coatings, etc., are selected as appropriate.

The content of the nonaqueous solvent to be used is the remainder of the fine powder of the above fluorine-based resin, the compound represented by the above (I), and the like.

In the first invention, the average particle diameter (average particle diameter of the cumulative amount analysis under the scattering intensity distribution) obtained by the dynamic light scattering method of the fine powder of the fluorine-based resin in the non-aqueous dispersion is preferably 1 μm. the following.

When a fine powder of a fluorine-based resin such as a polytetrafluoroethylene fine powder having a primary particle diameter of 1 μm or less is used, usually, the primary particles are aggregated, and fine particles having a particle diameter of 1 μm or more are formed as secondary particles. By dispersing the secondary particles of the fine polytetrafluoroethylene powder to a particle diameter of 1 μm or less, the dispersion is dispersed by using a disperser such as an ultrasonic disperser, a three-roll mill, a ball mill, a bead mill, or a jet mill. A dispersion which is low in viscosity and stable during long-term storage can be obtained.

In terms of making it more stably dispersed, it is preferably 0.5 μm or less, more preferably 0.3 μm or less, whereby a more uniform dispersion is formed.

The non-aqueous dispersion of the fluorine-based resin of the first aspect of the present invention has a fine particle diameter and a low viscosity even if a surfactant or a dispersant containing a fluorine-containing group is not added, and has excellent storage stability and is preserved after long-term storage. Excellent redispersibility. Further, a resin material added to various thermosetting resins and the like It can also be uniformly mixed during the application of rubber, adhesives, lubricants or greases, printing inks or paints.

[The second invention: a thermosetting resin composition of a fluorine-containing resin]

The thermosetting resin composition of the fluorine-containing resin according to the second aspect of the present invention is characterized in that it contains at least a non-fluorinated resin containing at least a fluorine-based resin and a compound represented by the above formula (I) and a non-aqueous solvent. An aqueous dispersion and a resin composition containing a cyanate resin and/or an epoxy resin.

<Non-aqueous dispersion of fluorine-based resin>

The non-aqueous dispersion of the fluorine-based resin to be used in the second invention is not particularly limited as long as it is a non-aqueous dispersion containing at least a fine powder of a fluorine-based resin, a compound represented by the above formula (I), and a non-aqueous solvent. For example, it can be prepared by using a fine powder of a fluorine-based resin having a particle diameter of at least 1 μm, a compound represented by the above formula (I), a non-aqueous solvent, or the like.

The fine powder of the fluorine-based resin used in the second aspect of the invention, the compound represented by the above (I), the nonaqueous solvent, the preferred content of each component, the nonaqueous solvent, and the nonaqueous system of the fluorine resin can be used. The water content (8000 ppm or less [0 ≦ water content ≦ 8000 ppm] obtained by the Karl Fischer method is preferably a non-aqueous dispersion of the fluorine-based resin of the first invention described above, and the fluorine-based resin is omitted. The water content of each of the fine powder, the compound represented by the above (I), each component of the nonaqueous solvent, the nonaqueous solvent, and the nonaqueous dispersion of the fluorine resin will be described in detail.

The non-aqueous dispersion of the fluorine-based resin according to the second aspect of the invention At least a fine powder of a fluorine-based resin, a compound represented by the above formula (I), and the like are sufficiently mixed in a nonaqueous solvent, and, for example, a disperser, an ultrasonic disperser, a planetary mixer, a three-roll mill, or the like, Various mixers and dispersers such as a ball mill, a bead mill, a jet mill, and a homogenizer are mixed and dispersed to obtain a dispersion which is stable even when stored for a long period of time.

These various mixers and dispersing machines are selected depending on the type of each material, the blending ratio, the viscosity of the non-aqueous dispersion which is stirred and mixed, and the like.

In the non-aqueous dispersion of the second aspect of the invention, the average particle diameter of the fine powder of the fluorine-based resin in the dispersed state (the average particle diameter of the cumulative amount in the scattering intensity distribution) is preferably 1 μm or less.

When a fine powder of a fluorine-based resin having a primary particle diameter of 1 μm or less is used, usually, the primary particles are aggregated, and fine particles having a particle diameter of 1 μm or more are formed as secondary particles. By dispersing the secondary particles of the fine powder of the fluorine-based resin to a particle diameter of 1 μm or less, for example, a disperser, an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, and a wet jet mill are used. A dispersing machine such as a machine or a high-pressure homogenizer is dispersed to obtain a dispersion which is low in viscosity and stable even during long-term storage, and can be further uniformly mixed with the resin composition.

The content of the fine powder of the fluorine-based resin used in the second invention is based on the amount of the fine powder of the fluorine-based resin and the nonaqueous solvent contained in the dispersion, and depending on the cyanate resin or epoxy resin species used. In the case of the non-aqueous solvent in the thermosetting resin composition of the fluorine-containing resin, the composition is finally removed after the composition is prepared, and therefore, it is reasonable. It is adjusted that the content of the fine powder of the fluorine-based resin is preferably from 1 to 100 parts by mass, more preferably from 5 to 70, per 100 parts by mass of the total resin amount of the cyanate resin or the epoxy resin. The dispersion is used in parts by mass.

When the content of the fine powder of the fluorine-based resin is 1 part by mass or more, the specific dielectric constant or dielectric tangent of the thermosetting resin composition of the fluorine-containing resin after curing can be reduced; When the amount is 100 parts by mass or less, the effects of the present invention can be exerted without impairing the various properties or stability of the thermosetting resin composition of the fluorine-containing resin or the cured product thereof.

In addition, since the non-aqueous dispersion of the fluorine-based resin contains a fine powder of a fluorine-based resin having an average particle diameter of 1 μm or less in a dispersed state, it is excellent in fine particle diameter, low viscosity, and storage stability, and after long-term storage. Excellent redispersibility.

[Resin composition]

The resin composition used in the second invention is at least a cyanate resin and/or an epoxy resin. These resins are used as the base resin of the thermosetting resin composition, and can be used without particular limitation as long as it is suitable for the insulation or adhesion of an electronic device.

The cyanate ester resin which can be used in the second invention includes, for example, at least a bifunctional aliphatic cyanate, at least a bifunctional aromatic cyanate, or a mixture thereof. Examples thereof include 1,3,5-tricyanooxybenzene, 1,3-dicyanooxynaphthalene, 1,4-dicyanooxynaphthalene, 1,6-dicyanooxynaphthalene, and 1, Polymer of polyfunctional cyanate of at least one of 8-dicyanoyloxynaphthalene, 2,6-dicyanooxynaphthalene, and 2,7-dicyanooxynaphthalene, double Phenolic A type cyanate resin or such hydrogenated, bisphenol F type cyanate resin or such hydrogenated, 6F bisphenol A dicyanate resin, bisphenol E type dicyanate resin, four At least one of methyl bisphenol F dicyanate resin, bisphenol M dicyanate resin, dicyclopentadienyl bisphenol dicyanate resin, or cyanate phenol resin. Further, a commercially available product of such cyanate resins can also be used.

Examples of the epoxy resin that can be used include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, tertiary butyl catechol type epoxy resin, and naphthalene type ring. Oxygen resin, naphthalene ether type epoxy resin, glycidylamine type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic type Epoxy resin, epoxy resin containing spiro ring, cyclohexane dimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, and the like.

These epoxy resins may be used alone or in combination of two or more.

The epoxy resin to be used in the second aspect of the invention is not limited to the above-mentioned resin as long as it has one or more epoxy groups in one molecule, and is preferably bisphenol A, hydrogenated bisphenol A or cresol novolac.

In the second aspect of the invention, the cyanate ester resin and the epoxy resin may be used singly or in combination, and when used in combination, the mass ratio may be in the range of 1:10 to 10:1. And use it.

When the cyanate resin or the epoxy resin is used in the second invention, an active ester compound may be used as an additive in terms of reactivity, curability, and moldability.

As the active ester compound which can be used, it is generally preferred to be in one molecule. Examples of the compound having two or more active ester groups include a carboxylic acid compound, a phenol compound, and a naphthol compound. Examples of the carboxylic acid compound include acetic acid, benzoic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or the naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, and methyl group. Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 , 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadienyl diphenol, phenol novolac, and the like.

These active ester compounds may be used alone or in combination of two or more. Examples of the commercially available active ester compound include EXB-9451, EXB-9460 (manufactured by DIC Corporation), DC808, YLH1030 (manufactured by Japan Epoxy Resin Co., Ltd.), and the like.

The amount of such active ester compound is determined depending on the kind of the active ester compound used in the base resin of the thermosetting resin composition to be used.

Further, as the active ester compound, an active ester compound hardening accelerator may be used as needed.

As the active ester compound curing accelerator, an organic metal salt or an organic metal complex is used, and for example, an organic metal salt or an organic metal complex containing iron, copper, zinc, cobalt, nickel, manganese, tin or the like is used. Specifically, the cyanate hardening accelerator may, for example, be manganese naphthenate, iron naphthenate, copper naphthenate, zinc naphthenate, cobalt naphthenate, iron octoate, copper octoate or octanoic acid. An organic metal salt such as zinc or cobalt octoate; an organic metal complex such as lead acetonate pyruvate or cobalt acetylacetonate.

The active ester compound hardening accelerator may be used in an amount of 0.05 to 5 parts by mass, preferably 0.1 to 100 parts by mass, based on the concentration of the metal, based on the reactivity, curability, and moldability. 3 parts by mass.

Further, when the epoxy resin is used in the second invention, a curing agent may be used as an additive in terms of reactivity, curability, and moldability. Examples of the hardener which can be used include ethylenediamine, triethyleneamine, hexamethylenediamine, dimer acid modified ethylenediamine, N-ethylaminopiperazine, isophoronediamine, and the like. Aliphatic amines, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenylanthracene, 4,4'-diaminodiphenylanthracene, 4,4'-diaminodiyl Mercaptans such as phenylmethane or 4,4'-diaminodiphenyl ether, thiols such as mercaptopropionate, and epoxy thiol compounds, polysebacic anhydride, methyltetrahydrogen Phthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-northene-2,3-dicarboxylic anhydride, norbornane- An alicyclic acid anhydride such as 2,3-dicarboxylic anhydride, methyl-5-northene-2,3-dicarboxylic anhydride, methyl-norbornane-2,3-dicarboxylic anhydride, ortho-benzene An aromatic acid anhydride such as acetic anhydride, trimellitic anhydride or pyromellitic dianhydride; imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole or 2-phenylimidazole, and salts thereof, and the like Amine amines, aromatic amines, and/or amine additions obtained by reaction of imidazoles with epoxy resins Terpenoids such as anthracene, adipic acid, dimethyl benzylamine, 1,8-diazabicyclo [5.4.0] undecene-7, etc., triphenylphosphine Organophosphine At least one of a class such as dicyandiamide or the like.

The amount of these hardeners is determined depending on the kind of hardener used in the epoxy resin used.

The resin composition according to the second aspect of the invention may further contain an inorganic filler, a thermoplastic resin component, a rubber component, a flame retardant, a colorant, a thickener, an antifoaming agent, a leveling agent, a coupling agent, and an adhesion property. The material is used in a material generally used for a thermosetting resin composition for electronic equipment.

[Thermosetting resin composition of fluorine-containing resin]

The thermosetting resin composition of the fluorine-containing resin according to the second aspect of the present invention contains at least a fine powder containing at least a fluorine resin, a compound represented by the above formula (I), and a nonaqueous solvent (the first invention of the present invention) The non-aqueous dispersion of the fluorine-based resin and the resin composition containing the cyanate resin and/or the epoxy resin may be a non-aqueous dispersion containing the fluorine-based resin, and a cyanate resin and/or a ring. The resin composition of the oxygen resin is mixed by a disperser or a homogenizer, and various agitators such as an ultrasonic disperser, a planetary mixer, a three-roll mill, a ball mill, a bead mill, and a jet mill are used. Disperser to modulate.

In the second aspect of the invention, the fluorine resin powder can be uniformly aggregated without being aggregated by adjusting the total resin concentration of the cyanate resin or the epoxy resin which is finally required for the thermosetting resin composition of the fluorine-containing resin. It is excellent in dielectric properties and dielectric tangent, and is excellent in adhesion, heat resistance, dimensional stability, flame retardancy, and the like.

The thermosetting resin composition of the fluorine-containing resin of the second aspect of the present invention contains at least a non-aqueous dispersion of a fluorine-based resin containing at least a fine powder of a fluorine-based resin and a compound represented by the above formula (I) and a non-aqueous solvent. Further, a resin composition containing a cyanate resin and/or an epoxy resin can be molded and cured by a method similar to a thermosetting resin composition such as a known epoxy resin composition to form a cured product. The molding method and the curing method can be carried out in the same manner as the thermosetting resin composition of a known epoxy resin composition, and the method of the thermosetting resin composition of the fluorine-containing resin of the second invention is not required. limited.

The cured product obtained by curing the thermosetting resin composition of the fluorine-containing resin of the second aspect of the invention (the sixth invention) can be in the form of a laminate, a molded article, a laminate, a coating film, a film, or the like.

The thermosetting resin composition of the fluorine-containing resin of the second invention and the cured product thereof do not impair the adhesion or heat resistance of the thermosetting resin such as an epoxy resin, and have a low specific dielectric constant and a low dielectric constant. Since the dielectric tangential electrical characteristics are excellent, it is suitable for use as an electronic substrate material, an insulating material, a bonding material, etc., and is used as, for example, a sealing material for an electronic component, a copper-clad laminate, an insulating coating, a composite material, an insulating adhesive, or the like. The material is particularly suitable for the formation of an insulating layer of a multilayer printed wiring board of an electronic machine.

[Third invention: thermosetting resin composition of fluorine-containing resin]

The thermosetting resin composition of the fluorine-containing resin according to the third aspect of the present invention is characterized in that at least a fine powder containing a fluorine resin, a compound represented by the above formula (I), an elastomer component, and a nonaqueous solvent are blended. Non-fluorinated resin A water-based dispersion and a resin composition containing a cyanate resin and/or an epoxy resin.

<Non-aqueous dispersion of fluorine-based resin>

The non-aqueous dispersion system of the fluorine-based resin used in the third invention is a fine powder of a fluorine-based resin used in the first invention, a compound represented by the formula (I), a non-aqueous solvent, and further contains at least an elastomer. The component is not particularly limited as long as it contains these components.

The fine powder of the fluorine-based resin used in the third invention, the compound represented by the above (I), the non-aqueous solvent, the preferred content of each component, the non-aqueous dispersion of the non-aqueous solvent and the fluorine-based resin Since the water content and the like of the body are the same as those of the first invention described above, detailed description thereof will be omitted.

The elastomer component used in the third aspect of the invention includes, for example, a liquid rubber such as polybutadiene or butadiene-acrylonitrile copolymer (NBR), and a terminal carboxybutadiene-acrylonitrile copolymer (CTBN). a reactive liquid rubber such as a two-terminal aminobutadiene-acrylonitrile copolymer (ATBN), or a polyoxyxene rubber having a terminal or a side chain having an amine group or an epoxy group, such as polydimethyl siloxane. And a particulate rubber such as crosslinked NBR particles, crosslinked polyfluorene oxide particles, or acrylic core-shell particles.

These elastomer components can be used alone or in combination of two or more.

In the third aspect of the invention, the content of the elastomer component contained in the non-aqueous dispersion of the fluorine-based resin is preferably 100 parts by mass based on the total amount of the non-aqueous solvent in the non-aqueous dispersion. Preferably, it contains 1 to 150 parts by mass, more preferably 5 to 100 parts by mass, and even more preferably 10 to 80 parts by mass.

When the elastomer component is contained in an amount of 1 part by mass or more based on 100 parts by mass of the total amount of the nonaqueous solvent in the nonaqueous dispersion, the cyanate resin and/or epoxy resin used for the subsequent blending can be suppressed. When the resin composition is mixed and the thermosetting resin composition of the fluorine-containing resin is adjusted, the fluorine-based resins are agglomerated with each other. On the other hand, when the content is more than 150 parts by mass, the viscosity of the non-aqueous dispersion increases, and problems such as deterioration of dispersibility tend to occur.

In the non-aqueous dispersion of the fluorine-based resin of the third aspect of the invention, the fine powder of the fluorine-based resin, the compound represented by the above formula (I), and the elastomer component are sufficiently stirred and mixed in a non-aqueous solvent, and used. For example, various mixers and dispersers such as a disperser, an ultrasonic disperser, a planetary mixer, a three-roll mill, a ball mill, a bead mill, a jet mill, and a homogenizer are dispersed, and are stable even in long-term storage. Dispersion.

These various mixers and dispersing machines are selected according to the kind of each material, the blending ratio, the viscosity of the composition which is stirred and mixed, and the like.

In the third aspect of the invention, the elastomer component is present at the stage of producing the non-aqueous dispersion of the fluorine-based resin, and by dispersing the dispersion, the fine powder of the fluorine-based resin can be further micronized. Stabilized.

Furthermore, in the non-aqueous dispersion of the fluorine-based resin powder of the third aspect of the invention, the average particle diameter of the fluorine-based resin powder in a state of being dispersed (the average particle diameter of the cumulative amount analysis under the scattering intensity distribution) is preferably 1 μm or less.

When a fine powder of a fluorine-based resin having a primary particle diameter of 1 μm or less is used, usually, the primary particles are aggregated, and fine particles having a particle diameter of 1 μm or more are formed as secondary particles. By dispersing the secondary particles of the fine powder of the fluorine-based resin to a particle diameter of 1 μm or less, for example, a disperser, an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, and a wet jet mill are used. A dispersing machine such as a machine or a high-pressure homogenizer is dispersed to obtain a dispersion which is low in viscosity and stable even during long-term storage, and can be further uniformly mixed with the resin composition. It is preferably 0.5 μm or less, more preferably 0.3 μm or less, whereby a uniform dispersion is further formed.

Furthermore, the water content of the fluorine-based resin powder non-aqueous dispersion of the third invention by the Karl Fischer method is preferably 8000 ppm or less (0 ≦ water content ≦ 8000 ppm). In addition to the water content of the aqueous solvent, it is considered that the fine powder of the fluorine-based resin or the material of the compound represented by the above (I) or the fine powder of the fluorine-based resin is dispersed in the non-aqueous powder. In the production process in the aqueous solvent, the water content of the non-aqueous dispersion of the fluorine-based resin is 8000 ppm or less, and a non-aqueous dispersion of a fluorine-based resin which is more excellent in storage stability can be obtained. It is also possible to uniformly mix with the resin composition. The water content is more preferably 5,000 ppm or less, more preferably 3,000 ppm or less, and particularly preferably 2,500 ppm or less.

Further, as for the adjustment of the above water content, a dehydration method of an oil solvent which is generally used may be employed, and for example, a molecular sieve or the like may be used.

Further, the non-aqueous dispersion of the fluorine-based resin may be used in a state where the water content is sufficiently lowered by dehydration such as heating or decompression. Enter In addition, after the fluorine-based resin powder non-aqueous dispersion is produced, the water content can be removed by a molecular sieve or a membrane separation method, and the water content of the fluorine-based resin powder non-aqueous dispersion can be reduced as long as the above method is used. Any one can be used without particular limitation.

In addition, in the adjustment of the non-aqueous dispersion of the fluorine-based resin in which the fine powder of the fluorine-based resin, the compound represented by the above formula (I), the elastomer component, and the non-aqueous solvent are blended, Further, a cyanate resin or an epoxy resin may be added as appropriate, and the viscosity of the thermosetting resin composition of the fluorine-containing resin or the physical properties after curing may be selected and adjusted.

[Thermosetting resin composition of fluorine-containing resin]

The thermosetting resin composition of the fluorine-containing resin according to the third aspect of the invention is characterized in that at least a nonaqueous dispersion of the fluorine resin and a resin composition containing a cyanate resin and/or an epoxy resin are blended.

In the production stage of the non-aqueous dispersion, the elastomer component is not blended and dispersed (a dispersion of a fine powder of a fluorine-based resin and a dispersant and a non-aqueous solvent), and then an elastomer component is blended, and fluorine is added. The fine powder or the elastomer component of the resin tends to aggregate, and the thermosetting resin composition of the fluorine-containing resin in a state in which the fluorine resin powder is uniformly dispersed is not easily obtained.

The resin composition used in the third invention is at least a cyanate resin and/or an epoxy resin. These resins are used as the base resin of the thermosetting resin composition, and can be used without particular limitation as long as it is suitable for the insulation or adhesion of an electronic device. A detailed description of the resin composition containing these cyanate resins and/or epoxy resins is due to the Since it is the same as the resin composition of the above second invention, detailed description thereof will be omitted.

The thermosetting resin composition of the fluorine-containing resin according to the third aspect of the invention is a method of mixing a non-aqueous dispersion of a fluorine-based resin and a resin composition containing a cyanate resin and/or an epoxy resin, in addition to dispersion. In addition to stirring such as a machine or a homogenizer, various mixers and dispersers such as an ultrasonic disperser, a planetary mixer, a three-roll mill, a ball mill, a bead mill, and a jet mill can be used.

After the non-aqueous dispersion of the fluorine-based resin containing the elastomer component is prepared, the concentration of the cyanate resin and/or the epoxy resin finally required for the thermosetting resin composition of the fluorine-containing resin is further adjusted. The fluorine-based resin powder is uniformly present without being aggregated, and is capable of exhibiting properties superior to dielectric constant and dielectric tangent, and also excellent in adhesion, heat resistance, dimensional stability, flame retardancy, and the like.

The content of the fluorine-based resin powder in the thermosetting resin composition of the fluorine-containing resin in the third aspect of the invention is based on the amount of the fluorine-based resin powder or the solvent contained in the non-aqueous dispersion of the fluorine-based resin powder, and is used according to the use. The cyanate resin, the epoxy resin species, the elastomer component, and the like are changed, and the solvent in the thermosetting resin composition of the fluorine-containing resin is finally removed after the composition is prepared after curing, so that It is preferable that the content of the fine powder of the fluorine-based resin is preferably from 1 to 100 parts by mass, based on 100 parts by mass of the total resin amount of the cyanate resin and/or the epoxy resin or the elastomer component. More preferably, it is 5 to 70 parts by mass to use a dispersion.

When the content of the fluorine-based resin powder is 1 part by mass or more, the specific dielectric constant of the thermosetting resin composition of the fluorine-containing resin after curing can be reduced. Or the dielectric tangent; on the other hand, when it is 100 parts by mass or less, the effects of the present invention can be exerted without impairing the various properties or stability of the thermosetting resin composition of the fluorine-containing resin or the cured product thereof. .

The thermosetting resin composition of the fluorine-containing resin according to the third aspect of the invention may further contain a nonaqueous solvent, an inorganic filler, a thermoplastic resin component, a flame retardant, a colorant, a tackifier, an antifoaming agent, and a leveling agent. The agent, the coupling agent, and the adhesion imparting material are used in a material generally used for a thermosetting resin composition for electronic equipment.

The thermosetting resin composition of the fluorine-containing resin according to the third aspect of the present invention is at least blended with at least a fluorine-based resin containing at least a fluorine-based resin powder, a compound represented by the above formula (I), an elastomer component, and a non-aqueous solvent. The aqueous dispersion and the resin composition containing a cyanate resin and/or an epoxy resin can be molded and cured by the same method as a thermosetting resin composition such as a known epoxy resin composition. A hardened substance is formed. The molding method and the curing method can be carried out in the same manner as the thermosetting resin composition such as the known epoxy resin composition, and the method of the thermosetting resin composition of the fluorine-containing resin of the third invention is not required. limited.

The cured product obtained by curing the thermosetting resin composition of the fluorine-containing resin of the third aspect of the invention (the sixth invention) can be in the form of a laminate, a molded article, a laminate, a coating film, a film, or the like.

The thermosetting resin composition of the fluorine-containing resin of the third invention and the cured product thereof do not impair the adhesion or heat resistance of the thermosetting resin such as an epoxy resin, and have a low specific dielectric constant and a low dielectric constant. Dielectric tangential electrical properties are excellent, so it is suitable for electronic substrate materials, insulating materials, and subsequent materials. There are materials such as a sealing material, a copper-clad laminate, an insulating coating, a composite material, and an insulating adhesive used for electronic components, and are particularly suitable for use as an adhesive composition for a circuit board used in the production of a circuit board, and use thereof. The insulating layer for a multilayer printed wiring board for a circuit board for a circuit board, a coating film, a prepreg, or an electronic device.

[The fourth invention: a thermosetting resin composition of a fluorine-containing resin]

The thermosetting resin composition of the fluorine-containing resin according to the fourth aspect of the invention is characterized in that at least a fine powder containing a fluorine-based resin, a compound represented by the above formula (I), and a cyanate-containing resin and/or A resin composition of an epoxy resin, a non-aqueous dispersion of a fluorine-based resin of a non-aqueous solvent, and an elastomer component.

<Non-aqueous dispersion of fluorine-based resin>

The non-aqueous dispersion of the fluorine-based resin used in the fourth invention is a fine powder containing at least a fluorine resin, a compound represented by the above formula (I), and a resin containing a cyanate resin and/or an epoxy resin. The composition and the non-aqueous solvent are not particularly limited as long as they contain such components.

The fine powder of the fluorine-based resin used in the fourth invention, the compound represented by the above (I), the resin composition containing the cyanate resin and/or the epoxy resin, and the nonaqueous solvent, and the components thereof The water content of each of the non-aqueous solvent and the non-aqueous dispersion of the fluorine-based resin in the respective ranges is the same as that of the third invention described above, and thus detailed description thereof will be omitted.

The non-aqueous dispersion of the fluorine-based resin of the fourth invention, At least a fine powder of a fluorine-based resin, a compound represented by the above formula (I), and a resin composition containing a cyanate resin and/or an epoxy resin are sufficiently stirred and mixed in a nonaqueous solvent to obtain a composition. The composition is dispersed in various mixers and dispersers using a disperser, an ultrasonic disperser, a planetary mixer, a three-roll mill, a ball mill, a bead mill, a jet mill, a homogenizer, etc., and can be stored for a long period of time. It is still a stable dispersion.

These various mixers and dispersing machines are selected according to the kind of each material, the blending ratio, the viscosity of the composition which is stirred and mixed, and the like.

In the fourth aspect of the invention, the resin composition containing the cyanate resin and/or the epoxy resin is present at the stage of producing the non-aqueous dispersion of the fluorine-based resin, and the dispersion can be produced by disposing the dispersion. The fluorine-based resin powder is further micronized to stabilize.

In addition, in the non-aqueous dispersion of the fluorine-based resin of the fourth aspect of the invention, the average particle diameter of the fluorine-based resin powder in the dispersed state (the average particle diameter of the cumulative amount analysis under the scattering intensity distribution) is preferably 1 μm or less.

When a fine powder of a fluorine-based resin having a primary particle diameter of 1 μm or less is used, usually, the primary particles are aggregated, and fine particles having a particle diameter of 1 μm or more are formed as secondary particles. By dispersing the secondary particles of the fine powder of the fluorine-based resin to a particle diameter of 1 μm or less, for example, a disperser, an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, and a wet jet mill are used. A disperser such as a machine or a high-pressure homogenizer is dispersed to obtain a dispersion having a low viscosity and being stable during long-term storage, and may further be combined with a resin composition. Mix evenly. It is preferably 0.5 μm or less, more preferably 0.3 μm or less, whereby a uniform dispersion is further formed.

Furthermore, in the non-aqueous dispersion of the fluorine-based resin of the fourth aspect of the invention, the water content by the Karl Fischer method is preferably 8000 ppm or less [0 ≦ water content ≦ 8000 ppm] as in the third invention.

[Thermosetting resin composition of fluorine-containing resin]

The thermosetting resin composition of the fluorine-containing resin according to the fourth aspect of the invention is characterized in that at least the non-aqueous dispersion of the fluorine-based resin and the elastomer component are blended.

In the production stage of the non-aqueous dispersion, a resin composition containing a cyanate resin and/or an epoxy resin is not added and dispersed (a dispersion composed of a fluorine-based resin powder and a dispersant and a non-aqueous solvent), and When blended with a cyanate resin and/or an epoxy resin or an elastomer component, the fluorine resin powder or the elastomer component is easily aggregated, and the heat of the fluorine-containing resin in a state in which the fluorine resin powder is uniformly dispersed is not easily obtained. Hardened resin composition.

Since the elastomer component used in the fourth invention is the same as the elastomer component of the third invention, the detailed description thereof will be omitted.

As a method of mixing a non-aqueous dispersion of a fluorine-based resin and an elastomer component, in addition to stirring by a disperser or a homogenizer, an ultrasonic disperser, a planetary mixer, a three-roll mill, a ball mill, or the like may be used. Various mixers and dispersers such as bead mills and jet mills.

After preparing a non-aqueous dispersion of a fluorine-based resin containing a cyanate resin and/or an epoxy resin, further blending at least the elastomer component In this way, the fine powder of the fluorine-based resin can be uniformly present without being aggregated, and can exhibit a dielectric constant and a dielectric tangent, and is excellent in adhesion, heat resistance, dimensional stability, flame retardancy, and the like. characteristic.

When the total amount of solid components (total of components other than the nonaqueous solvent) in the thermosetting resin composition of the fluorine-containing resin is 100 parts by mass, it is preferable to use the elastomer solid content. The amount is preferably from 1 to 150 parts by mass, more preferably from 5 to 100 parts by mass, even more preferably from 10 to 80 parts by mass.

When the content of the elastomer component is 1 part by mass or more based on the elastomer solid content, elasticity and adhesion of the cured resin can be imparted. On the other hand, when it exceeds 150 parts by mass, the viscosity increases or the fluorine resin is more. Easy to agglutinate.

In addition, in the adjustment of the thermosetting resin composition of the fluorine-containing resin in which the non-aqueous dispersion of the fluorine-based resin and the elastomer component are blended, a cyanate resin may be appropriately added, The epoxy resin, the non-aqueous solvent, and the like are selected and adjusted in consideration of the viscosity of the thermosetting resin composition of the fluorine-containing resin or the physical properties after curing.

The thermosetting resin composition of the fluorine-containing resin according to the fourth aspect of the present invention is at least blended with a fine powder containing at least a fluorine resin, a compound represented by the above formula (I), and a cyanate resin and/or an epoxy resin. The resin composition and the non-aqueous dispersion of the fluorine-based resin of the non-aqueous solvent and the elastomer component can be molded by the same method as the thermosetting resin composition such as a known epoxy resin composition. Hardened to form a hardened substance. The molding method and the hardening method can be used with a well-known epoxy resin composition. The same method as the thermosetting resin composition of the present invention does not require a method inherent to the thermosetting resin composition of the fluorine-containing resin of the present invention, and is not particularly limited.

The cured product (the sixth invention) obtained by curing the thermosetting resin composition of the fluorine-containing resin of the fourth invention can be used in the form of a laminate, a molded article, a laminate, a coating film, a film, or the like.

The thermosetting resin composition of the fluorine-containing resin of the fourth invention and the cured product thereof do not impair the adhesion or heat resistance of the thermosetting resin such as an epoxy resin, and have a low specific dielectric constant and a low dielectric constant. Since the dielectric tangential electrical characteristics are excellent, it is suitable for use as an electronic substrate material, an insulating material, a bonding material, etc., and is used as, for example, a sealing material for an electronic component, a copper-clad laminate, an insulating coating, a composite material, an insulating adhesive, or the like. The material is particularly suitable for an adhesive composition for a circuit board used for the production of a circuit board, and an insulating layer for a multilayer printed wiring board using a laminate for a circuit board, a coating film, a prepreg, and an electronic device. .

[The fifth invention: a thermosetting resin composition of a fluorine-containing resin]

The thermosetting resin composition of the fluorine-containing resin according to the fifth aspect of the present invention is characterized in that at least a fine powder containing a fluorine-based resin, a compound represented by the above formula (I), and a cyanate-containing resin and/or A resin composition of an epoxy resin, a non-aqueous dispersion of a fluorine-based resin of a non-aqueous solvent, and a resin composition containing a cyanate resin and/or an epoxy resin.

<Non-aqueous dispersion of fluorine-based resin>

The fluorine-based resin powder non-aqueous dispersion used in the fifth invention In addition, it is not particularly limited as long as it contains at least a fluorine-based resin powder, a compound represented by the above formula (I), a resin composition containing a cyanate resin and/or an epoxy resin, and a non-aqueous solvent.

The fine powder of the fluorine-based resin used in the fifth invention, the compound represented by the above formula (I), the resin composition containing the cyanate resin and/or the epoxy resin, and the nonaqueous solvent, and the components thereof The water content of each of the preferred ranges, the nonaqueous solvent, and the nonaqueous dispersion of the fluorine resin are the same as those of the third invention and the fourth invention described above, and thus detailed description thereof will be omitted.

In addition, in the non-aqueous dispersion of the fluorine-based resin of the fifth aspect of the invention, the average particle diameter (average particle diameter of the cumulative amount analysis under the scattering intensity distribution) of the fluorine-based resin powder in a state of being dispersed is preferably 1 μm or less.

When a fine powder of a fluorine-based resin having a primary particle diameter of 1 μm or less is used, usually, the primary particles are aggregated, and fine particles having a particle diameter of 1 μm or more are formed as secondary particles. By dispersing the secondary particles of the fine powder of the fluorine-based resin to a particle diameter of 1 μm or less, for example, a disperser, an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, and a wet jet mill are used. A dispersing machine such as a machine or a high-pressure homogenizer is dispersed to obtain a dispersion which is low in viscosity and stable even during long-term storage, and can be further uniformly mixed with the resin composition. It is preferably 0.5 μm or less, more preferably 0.3 μm or less, whereby a uniform dispersion is further formed.

Furthermore, in the non-aqueous dispersion of the fluorine-based resin of the fifth aspect of the invention, the water content by the Karl Fischer method is preferably 8000 ppm or less [0 ≦ water content ≦ 8000 ppm] as in the third invention.

[Thermosetting resin composition of fluorine-containing resin]

The thermosetting resin composition of the fluorine-containing resin according to the fifth aspect of the present invention is obtained by blending at least a nonaqueous dispersion of the fluorine-based resin and a resin composition containing a cyanate resin and/or an epoxy resin.

The cyanate resin or epoxy resin to be added to the nonaqueous dispersion of the fluorine resin powder can be used as the cyanate resin or the epoxy resin composition, and the type thereof and the cyanide contained in the nonaqueous dispersion of the fluorine resin powder. The acid ester resin and the epoxy resin may be the same or different, and various combinations may be used in the range in which the properties of the present invention can be obtained, and one type or a combination of two or more types may be used.

As a method of blending a non-aqueous dispersion of a fluorine-based resin and a cyanate resin and/or an epoxy resin, in addition to stirring by a disperser or a homogenizer, an ultrasonic disperser or a planetary mixer can be used. Various mixers and dispersers such as a three-roll mill, a ball mill, a bead mill, and a jet mill.

In the fifth invention, a non-aqueous dispersion of a fluorine-based resin containing the above-described cyanate resin and/or epoxy resin is prepared, and then the cyanide finally required to be a thermosetting resin composition of a fluorine-containing resin is further adjusted. By adjusting the concentration of the acid ester resin and/or the epoxy resin, the fluorine resin powder can be uniformly present without being aggregated, and the specific dielectric constant and the dielectric tangent can be exhibited, and the adhesiveness, heat resistance, dimensional stability, and Excellent characteristics such as flame retardancy.

The thermosetting resin composition of the fluorine-containing resin according to the fifth aspect of the present invention is at least blended with a fine powder containing at least a fluorine resin, a compound represented by the above formula (I), and a cyanate resin and/or an epoxy resin. Non-aqueous dispersion of a resin composition and a fluorine-based resin of a non-aqueous solvent, and a package A resin composition containing a cyanate resin and/or an epoxy resin can be molded and cured by a method similar to a thermosetting resin composition such as a known epoxy resin composition to form a cured product. The molding method and the curing method can be carried out in the same manner as the thermosetting resin composition of a known epoxy resin composition, and the method of the thermosetting resin composition of the fluorine-containing resin of the present invention is not required, and is not particularly limited.

The cured product (the sixth invention) obtained by curing the thermosetting resin composition of the fluorine-containing resin of the fifth invention can be used in the form of a laminate, a molded article, a laminate, a coating film, a film, or the like.

The thermosetting resin composition of the fluorine-containing resin of the present invention and the cured product thereof do not impair the adhesion or heat resistance of the thermosetting resin such as an epoxy resin, and have a low specific dielectric constant and a low dielectric property. Since the tangential electrical characteristics are excellent, it is suitable for use as an electronic substrate material, an insulating material, a bonding material, etc., and is used as a sealing material for a metal component, a copper-clad laminate, an insulating coating, a composite material, an insulating adhesive, or the like. In particular, it is suitable for an adhesive composition for a circuit board used for the production of a circuit board, and an insulating layer for a multilayer printed wiring board using a laminate for a circuit board, a coating film, a prepreg, and an electronic device.

[This seventh invention: an adhesive composition for a circuit board]

The adhesive composition for a circuit board according to the seventh aspect of the present invention, characterized in that it comprises at least a non-aqueous dispersion containing at least a fine powder of a fluorine-based resin, a compound represented by the above formula (I) and a fluorine-based resin of a non-aqueous solvent. And a resin composition comprising a cyanate resin and/or an epoxy resin.

[Non-aqueous dispersion of fluorine-based resin]

The non-aqueous dispersion of the fluorine-based resin used in the seventh invention is not particularly limited as long as it contains at least a fine powder of a fluorine-based resin, a compound represented by the above formula (I), or a non-aqueous dispersion. For example, it can be prepared by using the fine powder of the fluorine-based resin used in the first invention, the compound represented by the formula (I), the nonaqueous solvent, the water content thereof, and the like.

In addition, in the non-aqueous dispersion of the seventh aspect of the invention, the average particle diameter of the fine powder of the fluorine-based resin in a state of being dispersed (the cumulative amount method under the scattering intensity distribution) The average particle diameter) is preferably 1 μm or less.

Furthermore, in the seventh invention, the water content of the non-aqueous dispersion of the fine powder of the fluorine-based resin by the Karl Fischer method is preferably 8000 ppm or less as in the above-described first invention. The amount of water is ≦ 8000ppm].

[Binder composition for circuit board]

The adhesive composition for a circuit board according to the seventh aspect of the present invention includes at least a non-aqueous dispersion of a fluorine-based resin containing at least a fine powder of a fluorine-based resin, a compound represented by the above formula (I), and a non-aqueous dispersion, and The resin composition containing a cyanate resin and/or an epoxy resin may further contain a rubber component dispersed in the cyanate resin or epoxy resin.

In the adhesive composition for a circuit board of the present invention, in order to be used for the production of a flexible printed circuit board or the like which can be bent on a wiring or a substrate, the composition itself must have sufficient flexibility (Flexible, the same applies hereinafter). To make up In order to achieve such flexibility, the adhesive composition for a circuit board preferably further contains a rubber component.

Examples of the rubber component which can be used include natural rubber (NR) or synthetic rubber, and preferably styrene butadiene rubber (SBR), isoprene rubber (IR), and acrylonitrile butadiene rubber (NBR). ), ethylene propylene diene monomer (EPDM) rubber, polybutadiene rubber, and denatured, modified polybutadiene rubber; preferably, EPDM rubber having an ethylene content of 10 to 40% by mass, Or SBR, NBR, etc., especially EPDM rubber which can reduce the specific dielectric constant and dielectric loss coefficient value of the resin composition.

The content of the rubber component is preferably from 1 to 80 parts by mass, based on 100 parts by mass of the resin (cyanate resin or epoxy resin), from the viewpoint of further exerting the effects of the present invention, adhesion and heat resistance. 10 to 70 parts by mass, more preferably 20 to 60 parts by mass.

In the adhesive composition for a circuit board according to the seventh aspect of the invention, the non-aqueous dispersion of the fluorine-based resin containing the fine powder of the fluorine-based resin, the compound represented by the above formula (I) and a non-aqueous solvent, and cyanide It is preferably produced by a general method of mixing a resin composition composed of an acid ester resin or an epoxy resin; preferably, the mass of the fine powder containing the fluorine-based resin and the fine powder relative to the fluorine-based resin is 0.1 to 15% by mass of the compound represented by the above formula (I), and a nonaqueous dispersion of a fluorine-based resin having a water content of 8000 ppm or less obtained by a Karl Fischer method, and a cyanate resin or an epoxy resin. It is produced by a method of mixing a constituent resin composition or the like; more preferably, a resin composition containing a cyanate resin, an epoxy resin, and a rubber component may be added to a non-aqueous dispersion of a fluorine-based resin. And mix it to make it.

In the adhesive composition for a circuit board according to the seventh aspect of the invention, it is preferable to further contain inorganic particles such as a phosphorus-based flame retardant in order to further improve the flame retardancy. The inorganic particles such as the phosphorus-based flame retardant are preferably from 1 to 30 parts by mass, preferably from 5 to 20 parts by mass, per 100 parts by mass of the cyanate resin or the epoxy resin.

Further, in the adhesive composition for a circuit board of the present invention, in addition to the above components, a suitable amount of a hardening accelerator, an antifoaming agent, a coloring agent, a phosphor, a modifier, an anti-tarnishing agent other than the above may be blended as needed. A well-known additive such as an inorganic filler, a decane coupling agent, a light diffusing agent, or a thermally conductive filler.

As the curing (reaction) accelerator other than the above, for example, an imidazole such as 2-methylimidazole or 2-ethyl-4-methylimidazole or a 1,8-diazabicyclo(5,4,0) can be used. Tertiary amines such as undecene-7 and salts thereof, phosphines such as triphenylphosphine, sulfonium salts such as triphenylsulfonium bromide, amine triazoles, tin octoate, and dilauric acid A tin-based such as butyltin or a zinc-based zinc octylate or a metal catalyst such as acetoacetate such as aluminum, chromium, cobalt or zirconium. These hardening (reaction) accelerators may be used singly or in combination of two or more.

The adhesive composition for a circuit board according to the seventh aspect of the invention can be molded and cured by a method similar to the known cyanate resin composition or epoxy resin composition to form a cured product. The molding method and the curing method can be carried out in the same manner as the known cyanate resin or epoxy resin composition, and the method inherent to the adhesive composition for a circuit board of the sixth invention is not particularly limited.

The adhesive composition for a circuit board according to the seventh aspect of the invention can be further formed into various forms such as a laminate, a molded product, a laminate, a coating film, and a film.

In the adhesive composition for a circuit board according to the seventh aspect of the invention, a non-aqueous dispersion which is stably and uniformly dispersed by using a fine powder of a fluorine-based resin is used as a binder composition for a circuit board, and thus has a specific dielectric ratio. The dielectric tantalum is low, and the properties such as adhesion, heat resistance, dimensional stability, and flame retardancy are excellent, and it is suitable for use as an adhesive material for a circuit board. For example, it can be used for a laminate or a coated film for a circuit board using the same. , prepreg, adhesive sheet, etc. The coating film, the prepreg, the adhesive sheet, and the like can be applied to a circuit board, for example, a flexible printed circuit board (FPCB) such as a flexible metal foil laminate, and the circuit board of the present invention is used in the manufacture of the same. When the composition of the adhesive is used, it is possible to realize an adhesive composition for a circuit board having characteristics lower than a dielectric constant and a dielectric tangent, and excellent in adhesion, heat resistance, dimensional stability, flame retardancy, and the like.

[8th invention: Laminate for circuit board]

The laminate for a circuit board according to the eighth aspect of the present invention is characterized in that the laminate for a circuit board comprising at least an insulating film, a metal foil, and an adhesive layer interposed between the insulating film and the metal foil is characterized in that The adhesive layer is composed of the adhesive composition for a circuit board according to the sixth aspect of the invention.

Fig. 1 is a schematic view showing a metal foil laminate (FPCB) which is an example of an embodiment of a laminate for a circuit board according to the eighth aspect of the invention.

The laminate board A for a circuit board of the present embodiment is an insulating film. The upper laminated metal foil 30 includes at least the adhesive resin layer 20 interposed between the insulating film 10 and the metal foil 30, and the adhesive resin layer 20 is composed of the adhesive composition for a circuit board having the above configuration. (joined).

Fig. 2 is a schematic view showing a metal foil laminate (FPCB) of another example of the embodiment of the laminate for a circuit board according to the eighth aspect of the invention.

As shown in Fig. 2, the laminated board B for a circuit board of the present embodiment has a double-sided structure instead of the one-sided structure of Fig. 1, and the metal foils 30 and 30 are laminated on both surfaces of the insulating film 10, and at least The adhesive resin layers 20 and 20 are sandwiched between the insulating film 10 and the metal foils 30 and 30, respectively. The adhesive resin layers 20 and 20 are formed of the adhesive composition for a circuit board having the above-described configuration. ).

In the laminate sheet for a circuit board according to the eighth aspect of the invention, the insulating film 10 to be used is not particularly limited as long as it is electrically insulating, and heat resistance, flexibility, and mechanical properties can be used. Strength and approximate thermal expansion coefficient of metal.

The insulating film 10 which can be used is, for example, selected from the group consisting of polyimine (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), and polyethylene naphthalate ( PEN), polyphenylene sulfide (PPS), polyetherimide (PEI), polyphenylene ether (modified PPE), polyester, para-aromatic polyamine, polylactic acid, nylon, polyoxazide, One or more films selected from the group consisting of polyetheretherketone (PEEK) are preferably polyimine (PI) films.

Moreover, it is preferable to use a film formed by such a material based on the viewpoint of further improving the adhesion to the interface between the adhesive resin layer 20 and the like. A film which is further subjected to surface treatment by low temperature plasma or the like on the surface of the film.

The thickness of the insulating film 10 can be selected within a suitable range in consideration of sufficient electrical insulating properties, thickness of the metal foil laminate, flexibility, and the like, and is preferably 5 to 50 μm, more preferably It is 7~45μm.

The adhesive resin layer 20 is formed (joined) with the adhesive composition for a circuit board having the above-described configuration, and the thickness thereof is preferably based on the interface adhesiveness with the insulating film, the flexibility of the laminate, and the strength of the laminate. Preferably, it is preferably 1 to 50 μm, more preferably 3 to 30 μm.

Examples of the metal foil 30 include those having a conductive metal foil, and examples thereof include gold, silver, copper, stainless steel, nickel, aluminum, and the like. Copper foil or stainless steel foil is preferably used from the viewpoints of conductivity, ease of handling, price, and the like. Any copper foil can be used by calendering or electrolysis.

The thickness of the metal foil is based on the so-called electrical conductivity, the interface adhesiveness with the insulating film, the flexibility of the laminate, the improvement of the bending resistance, or the formation of a fine pattern in the circuit processing. A preferred range is set, for example, preferably in the range of 1 to 35 μm, more preferably in the range of 5 to 25 μm, and particularly preferably in the range of 8 to 20 μm.

Further, the surface roughness Rz (ten-point average roughness) of the rough surface of the metal foil to be used is preferably in the range of 0.1 to 4 μm, more preferably in the range of 0.1 to 2.5 μm, particularly in the range of 0.2 to 2.0 μm. It is better inside.

The laminate for a circuit board of the eighth invention of the present invention (Example, for example, Fig. 1 or Fig. 2), the adhesive resin layer 20 is formed by applying the adhesive composition for a circuit board according to the sixth aspect of the present invention to the insulating film 10, for example. Drying is performed in a semi-hardened state, and secondly, the method of laminating the metal foil 30 on the adhesive resin layer 20 and performing thermocompression bonding (thermal lamination) can be made to have a lower dielectric constant and dielectric tangent, and adhesion. A laminate for a circuit board having excellent properties such as heat resistance, dimensional stability, and flame retardancy. At this time, the flexible metal foil laminate is post-cured to completely cure the semi-cured adhesive resin layer 20, whereby a final flexible metal foil laminate can be obtained.

[This ninth invention: coating film]

The coating film-based insulating film according to the ninth aspect of the invention, and the coating layer film having the adhesive layer formed on at least one of the insulating film, wherein the adhesive layer is the circuit substrate of the seventh invention. The composition of the adhesive is used.

Fig. 3 is a schematic view showing an example of an embodiment of the coating film of the ninth invention in a sectional form.

The coating layer film C of the present embodiment is used as a surface protective film for a flexible printed wiring board (FPC) or the like, and the adhesive resin layer 50 is formed on the insulating film 40. A film (peeling film) 60 such as paper or a PET film as a protective layer is bonded to the layer 50. Further, the separator (release film) 60 can be set as needed depending on workability, storage stability, and the like.

As the insulating film 40 used, it is the circuit described above The insulating film 10 used in the laminate sheet for a substrate is the same, and is, for example, selected from the group consisting of polyimine (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), and polyphthalene. Ethylene formate (PEN), polyphenylene sulfide (PPS), polyether phthalimide (PEI), polyphenylene ether (modified PPE), polyester, para-aromatic polyamine, polylactic acid, nylon, One or more films selected from the group consisting of polyoxazide and polyetheretherketone (PEEK).

Further, from the viewpoint of further improving the adhesion to the interface between the adhesive resin layer 50 and the like, it is preferable to use a film which has been subjected to surface treatment by low-temperature plasma or the like on the surface of the film.

In particular, when considering the heat resistance, dimensional stability, mechanical properties, and the like of the coating layer, a polyimide film (PI) film is preferable, and a polyimide film treated with a low temperature plasma is particularly preferably used for the coating layer.

The thickness of the insulating film 40 can be selected within a suitable range in consideration of sufficient electrical insulating properties, protective properties, flexibility, etc., and preferably 5 to 200 μm, more preferably 7 to 100 μm. .

The adhesive resin layer 50 is formed (joined) with the adhesive composition for a circuit board having the above-described configuration, and it is preferable that the thickness is based on the interface adhesiveness with the insulating film, the adhesion strength, and the like. 1 to 50 μm, more preferably 3 to 30 μm.

In the coating film of the ninth aspect of the present invention, the adhesive composition for a circuit board according to the sixth aspect of the present invention is applied by a chamfer roll coater, a reverse roll coater or the like. The adhesive film 40 is formed on the insulating film 40, and dried to be semi-hardened. (The state in which the composition is dried or in a state in which a part of the composition is subjected to a hardening reaction), and secondly, a separator (release film) 60 which is a layer of the above-mentioned protective layer can be manufactured to have a specific dielectric constant and dielectric tangent, and adhesion A coating film having excellent properties such as heat resistance, dimensional stability, and flame retardancy.

[This 10th invention: prepreg]

The prepreg of the tenth invention is characterized in that it is formed of one or more kinds of fibers selected from the group consisting of carbon fibers, cellulose fibers, glass fibers, or aromatic polyamide fibers. In the structure of the present invention, at least the composition for an adhesive for a circuit board of the sixth aspect of the present invention is impregnated.

In the tenth invention, the prepreg can be used as a constituent material such as a multilayer flexible printed wiring board, and is a dust-free, low-flow prepreg capable of impregnating the above-mentioned adhesive composition. The fiber is then supplied to a sheet which is semi-hardened by drying.

The fiber to be used in the prepreg is one or more types selected from the group consisting of carbon fibers, cellulose fibers, glass fibers, and aromatic polyamide fibers. In addition, one or more types of fibers selected from the group consisting of E glass fiber, D glass fiber, NE glass fiber, H glass fiber, T glass fiber, and aromatic polyamide fiber may be mentioned. In particular, in order to minimize the specific dielectric constant and dielectric loss coefficient of the prepreg, it is preferred to use NE glass fibers having a lower dielectric constant and dielectric loss coefficient than other glass fibers (specific dielectric ratio of about 4.8). The dielectric loss coefficient is about 0.0015).

The prepreg system has a thickness of 15 to 500 μm, and is preferably a thinner 15 to 50 μm for use in a circuit board.

The prepreg according to the tenth aspect of the present invention, which is used as an interlayer structural material which is also used as a multilayer flexible printed wiring board or the like, can provide a dielectric constant lower than a dielectric tangent and then A prepreg having excellent properties such as properties, heat resistance, dimensional stability, and flame retardancy.

[Examples]

Hereinafter, the present invention (the first invention to the tenth invention) will be described in detail with reference to the examples and comparative examples. Further, the present invention is not limited to the following examples and the like.

[First invention: Examples 1 to 6 and Comparative Examples 1 to 4, Reference Example 1]

A non-aqueous dispersion of each fluorine-based resin was prepared according to each method described below. Moreover, the nonaqueous solvents of Example 5 and Comparative Example 1 were adjusted and used by adding water. The blending compositions of Examples 1 to 6 and Comparative Examples 1 to 4 and Reference Example 1 are shown in Table 1 below.

(Example 1)

As the fine powder of the fluorine-based resin, a fine polytetrafluoroethylene powder having an average particle diameter of 0.3 μm was used. As the compound A represented by the above formula (I), S-LEC BL-10 [PVB) resin, manufactured by Sekisui Chemical Co., Ltd., hydroxyl group 28 mol%, butyral degree 71±3 Mo was used. Ear %, molecular weight 1.5 Million]. Further, as the nonaqueous solvent A, methyl ethyl ketone [MEK] was used.

Using the above materials, a non-aqueous dispersion of a fluorine-based resin using a fine powder of polytetrafluoroethylene was prepared in the formulation shown in Table 1 below. In the production, the compound A represented by the formula (I) is sufficiently dissolved in a non-aqueous solvent, and then a fine powder of polytetrafluoroethylene is added, and further stirred and mixed.

The mixed liquid of the polytetrafluoroethylene fine powder obtained as described above was dispersed in a transverse bead mill with zirconia beads having a particle diameter of 0.3 mm.

The obtained dispersion was subjected to filter filtration to remove coarse particles of 5 μm or more, thereby obtaining a non-aqueous dispersion of a fluorine-based resin.

(Example 2)

A dispersion was prepared in the same manner as in Example 1 except that N-methylpyrrolidone [NMP] was used as the nonaqueous solvent B.

(Example 3)

In addition to S-LEC BL-1 [polybutyraldehyde (PVB) resin, manufactured by Sekisui Chemical Co., Ltd., hydroxy 34 mol%, butyralization degree 65 ± 3 mol%, molecular weight 40,000] as formula (I) A dispersion of the compound B shown in the same manner as in Example 1 was carried out except that N,N-dimethylacetamide [DMAc] was used as the nonaqueous solvent C.

(Example 4)

In addition to the use of polytetrafluoroethylene micropowder with an average particle size of 0.5 μm as fluorine It is a fine powder of resin and is made of S-LEC BL-1 [PVB) resin, manufactured by Sekisui Chemical Co., Ltd., with a hydroxyl group of 34% by mole, a degree of butyralization of 65±3 mol%, and a molecular weight of 40,000. A dispersion was prepared in the same manner as in Example 1 except for the compound B represented by the formula (I).

(Example 5)

A dispersion was prepared in the same manner as in Example 2 except that the water was forcibly added to N-methylpyrrolidone and sufficiently stirred as a nonaqueous solvent.

(Example 6)

A dispersion was prepared in the same manner as in Example 2 except that the amounts of the compound A and the N-methylpyrrolidone represented by the formula (I) were changed.

(Comparative Example 1)

A dispersion was prepared in the same manner as in Example 5 except that more water than Example 5 was forcibly added to N-methylpyrrolidone and sufficiently stirred, and this was used as a nonaqueous solvent.

(Comparative Example 2)

A dispersion was obtained in the same manner as in Example 1 except that a fine powder of polytetrafluoroethylene having an average particle diameter of 1.2 μm was used as the fine powder of the fluorine-based resin.

(Comparative Example 3)

The preparation of the dispersion was carried out in the same manner as in Example 1 except that the compound A represented by the formula (I) was used in an amount of 8 mass%.

(Comparative Example 4)

The preparation of the dispersion was carried out in the same manner as in Example 1 except that 65 mass% of the fine polytetrafluoroethylene powder was added.

(Reference example 1)

A dispersion was obtained in the same manner as in Example 1 except that a fluorine-based dispersant was used.

With respect to the non-aqueous dispersion of the fluorine-based resin obtained in the above Examples 1 to 6 and Comparative Examples 1 to 4 and Reference Example 1, the fluidity of the dispersion was stored at 25 ° C for one month according to the following evaluation methods. The subsequent redispersibility was assessed.

These results are shown in Table 1 below.

(Method for assessing the fluidity of the dispersion)

The degree of dispersion of the dispersion when the non-aqueous dispersion of each of the obtained fluorine-based resins is dropped on the PET film by a dropper, and the state of the dispersion when the dispersion is strongly inclined by 90 degrees from the standing state in the bottle. The evaluation was performed according to the following criteria based on the visual observation.

Rating basis:

◎: Flows smoothly.

○: It will flow.

△: Has structural viscous properties.

×: Almost no flow.

(Method for assessing redispersibility)

The non-aqueous dispersion of each of the obtained fluorine-based resins was placed in a glass container (30 ml, the same hereinafter) attached thereto, and the redispersibility after storage at 25 ° C for one month was evaluated according to the following criteria.

Rating basis:

◎: Easy to redisperse.

○: It will be dispersed again.

△: Gradually flow, but granules are visible.

×: It is not easy to redisperse.

As is apparent from the above Table 1, the dispersions of Examples 1 to 6 which are within the scope of the present invention have good fluidity, and have excellent storage stability and redispersibility.

In addition, it is known that the fluorine-based dispersing agent (MEGAFACE F-563: fluorinated group ‧ lipophilic group-containing oligomer, active component: 100% by weight) of the fluorine-based dispersing agent of the reference example 1 is used Dispersion, preservation stability.

On the other hand, in Comparative Example 1 and Comparative Example 2 which were outside the range of the present invention, the initial particle diameter was large, and the redispersibility after storage was also inferior.

Further, in Comparative Example 3, the compound represented by the formula (I) was added in a large amount, and the viscosity was improved, so that the dispersion was not easily achieved. Further, in Comparative Example 4 in which the amount of the fine polytetrafluoroethylene fine powder was 65% by mass, fluidity was not observed at all, and dispersion was difficult to be achieved.

[First Invention: Examples 7 to 13 and Comparative Example 5]

According to the formulation shown in Table 2 below, 8 kinds of PTFE (A~H) of each specific surface area were used, and S-LEC BL-10 [PVB) resin, manufactured by Sekisui Chemical Co., Ltd., hydroxyl 28 mol was used. %, a degree of butyralization of 71 ± 3 mol%, and a molecular weight of 15,000. As a compound represented by the above formula (I), a nonaqueous dispersion of a fluorine resin was prepared by using methyl ethyl ketone as a nonaqueous solvent. Further, G of the PTFE powder is the same as H, except that G is used to adjust the surface area of the PTFE powder by heating the PTFE powder at a temperature of 270 ° C to change the surface area.

Moreover, in the above-mentioned preparation, S-LEC BL-10 was sufficiently dissolved in a non-aqueous solvent, and then polytetrafluoroethylene was added, and further stirred and mixed.

The polytetrafluoroethylene mixture obtained in the above manner was dispersed in zirconia beads having a particle diameter of 0.3 mm using a transverse bead mill to obtain each of the polytetrafluoroethylenes of Examples 7 to 13 and Comparative Example 5. Non-aqueous dispersion. Further, as a result of measuring the water content of each of the nonaqueous dispersions of Examples 7 to 13 and Comparative Example 5 by the Karl Fischer method, it was confirmed to be 8000 ppm or less.

The evaluation of the average particle diameter and the viscosity of each of the obtained non-aqueous dispersions of Examples 7 to 13 and Comparative Example 5 was carried out by using FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.). The average particle diameter (nm) of the PTFE in the dispersion was measured for each viscosity (mPa‧s, 25 °C) by an E-type viscometer. These results are shown in Table 3 below.

As is apparent from the above Tables 2 and 3, Examples 7 to 13 which are within the scope of the first invention can be dispersed, and Comparative Example 5 which is outside the scope of the first invention is gelled, and good dispersion cannot be obtained. body. Further, in Example 13, in which the specific surface area was close to 15 m ² /g, the dispersion was possible, but it was a non-aqueous dispersion having a slightly higher viscosity. Further, any of the nonaqueous dispersions is excellent in stability.

[2nd invention: Examples 14 to 23 and Comparative Examples 6 to 9]

(Preparation of non-aqueous dispersion of fluorine-based resin: dispersions 1 to 5)

The compound represented by the above formula (I) was sufficiently stirred and mixed in a non-aqueous solvent according to the formulation shown in the following Table 3, and then a fine powder of PTFE was added as a fine powder of a fluorine-based resin, and further stirred and mixed. Thereafter, the obtained PTFE mixed liquid was dispersed by zirconia beads having a particle diameter of 0.3 mm using a horizontal bead mill to obtain each of the dispersions 1 to 5. Further, in the case of the dispersion 4, the water content is adjusted by adding water at the time of blending.

The average particle diameter of PTFE in the obtained dispersions 1 to 5 (average particle diameter of the cumulative amount analysis under the scattering intensity distribution) was measured by a dynamic light scattering method using FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.). Further, the water content obtained by the Karl Fischer method for each of the dispersions 1 to 5 was measured.

The formulations of Dispersions 1 to 5 and the average particle diameter and water content of PTFE in the obtained dispersion are shown in Table 4 below.

(Examples 14 to 18 and Comparative Examples 6 to 7: Preparation of a thermosetting resin composition of a fluorine-containing resin)

Using the obtained dispersions 1 to 5, a thermosetting resin composition of a fluorine-containing resin was prepared according to the formulation shown in Table 5 below.

After mixing in the blending ratios shown in Examples 14 to 18 and Comparative Examples 6 to 7, the mixture was stirred with a disperser to uniformly blend the PTFE dispersion with the resin to obtain a thermosetting resin composition of a fluorine-containing resin. .

Here, Examples 14 to 18 which are thermosetting resin compositions of the respective fluorine-containing resins produced by the dispersions 1 to 5 showed extremely uniform state. Further, in Example 17 which used the thermosetting resin composition of the fluorine-containing resin produced in the dispersion 4, the aggregation of the PTFE particles was slightly observed, and the granular matter was observed slightly on the wall surface. Further, in Example 18, which is a thermosetting resin composition of a fluorine-containing resin produced by the dispersion 5, sedimentation separation of the particles was slightly observed when stored for a long period of time.

(Examples 19 to 23, Comparative Examples 8 to 9: Preparation of a cured product of a thermosetting resin of a fluorine-containing resin)

The thermosetting resin composition of the fluorine-containing resin obtained in Examples 14 to 18 and Comparative Examples 6 to 7 was applied to the one side of the polyimide film (thickness: 25 μm) by a coater. The thickness was made uniform so that the thickness after drying became about 25 μm, and after drying at about 120 ° C for about 10 minutes, it was heated at 180 ° C for 60 minutes to be hardened, and an evaluation sample was prepared.

(physical evaluation)

Using the evaluation samples of Examples 19 to 23 and Comparative Examples 8 to 9 obtained above, the physical property evaluation as described below was carried out.

(Method for evaluating electrical characteristics)

The specific dielectric constant and the dielectric dielectric tangent were measured in accordance with the test specifications of JIS C6481-1996 at 1 GHz using an impedance analyzer (Impedence Analyzer), and the results are shown in Table 6 below.

As shown in the above Table 6, the cured products of the thermosetting resin of the fluorine-containing resin of Examples 19 to 23 showed extremely low specific dielectric ratio and comparison with Comparative Examples 8 to 9 which did not contain the fluorine-based resin. Low dielectric tangent.

In Examples 22 and 23, the effects were slightly lower than those of Examples 19 to 21. However, since PTFE was contained, it was found that a more excellent effect was obtained as compared with Comparative Examples 8 to 9.

[Third invention: Examples 24 to 31 and Comparative Examples 10 to 15]

(Preparation of non-aqueous dispersion of fluorine-based resin: dispersion 6 to 9)

After the compound represented by the above formula (I) was sufficiently stirred and mixed and dissolved in a solvent, the PTFE fine powder was added as a fine powder of a fluorine-based resin, and further stirred and mixed. Thereafter, the obtained PTFE mixed liquid was dispersed by zirconia beads having a particle diameter of 0.3 mm using a horizontal bead mill to obtain respective dispersions 6 to 9.

The average particle diameter of the PTFE in the obtained dispersions 6 to 9 (average particle diameter of the cumulative amount analysis under the scattering intensity distribution) was measured by a dynamic light scattering method using FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).

The formulations of Dispersions 6 to 9 and the average particle diameter of PTFE in the obtained dispersion are shown in Table 7 below. Further, as a result of measuring the water content of the obtained dispersions 6 to 9, the respective water contents obtained by the Karl Fischer method were in the range of 800 to 1800 ppm.

[Examples 24 to 27 and Comparative Examples 10 to 12: Preparation of a thermosetting resin composition of a fluorine-containing resin]

Using the obtained dispersions 6 to 9, a thermosetting resin composition of a fluorine-containing resin was prepared according to the formulation shown in Table 8 below.

After blending at the mixing ratios shown in Examples 24 to 27 and Comparative Examples 10 to 12, the mixture was stirred with a disperser to uniformly blend the PTFE dispersion with the resin to obtain a thermosetting resin composition of a fluorine-containing resin. .

Here, in Examples 24 to 27, a state of extremely uniformity was observed, and no change in particle diameter was observed. On the other hand, in Comparative Examples 10 and 11, a plurality of granules of PTFE which are considered to be agglomerated were observed, and it was found that the particle diameter also became large.

Further, the average particle diameter of the dispersion 6 and the dispersion 7 in Table 7 was less than 0.3 μm, and it is considered that the particle diameter of the rubber particles belonging to the elastomer component was as small as about 0.1 μm, which was expressed as a numerical value on the measurement. It is caused by smaller.

(Examples 28 to 31, Comparative Examples 13 to 15: Preparation of a cured product of a thermosetting resin of a fluorine-containing resin)

The thermosetting resin composition of the fluorine-containing resin obtained in Examples 24 to 27 and Comparative Examples 10 to 12 was applied to the one side of the polyimide film (thickness: 25 μm) by a coater. The thickness was made uniform so that the thickness after drying became about 25 μm, and after drying at about 120 ° C for about 10 minutes, it was heated at 180 ° C for 60 minutes to be hardened, and an evaluation sample was prepared.

(physical evaluation)

Using the evaluation samples of Examples 28 to 31 and Comparative Examples 13 to 15 obtained above, the physical property evaluation as described below was carried out.

(Method for evaluating electrical characteristics)

The specific dielectric constant and the dielectric tangent were measured in accordance with the test specifications of JIS C6481-1996 at 1 GHz using an impedance analyzer (Impedence Analyzer), and the results are shown in Table 9 below.

As shown in the above Table 9, the cured thermosetting resin of the fluorine-containing resin of Examples 28 to 31 showed a lower specific dielectric ratio and lower than that of Comparative Example 15 which did not contain a fluorine-based resin. Dielectric tangent.

On the other hand, in Comparative Examples 13 and 14, since the PTFE was contained, the effect of lowering the specific dielectric constant and the dielectric tangent was superior to that of Comparative Example 15, but the surface of the cured product was slightly rough compared with Examples 28 to 31. The effect of sufficiently reducing the specific dielectric constant and dielectric tangent is less likely to be obtained.

[This fourth invention: Examples 32 to 37 and Comparative Examples 16 to 21]

(Preparation of non-aqueous dispersion of fluorine-based resin: dispersion 10 to 13]

The compound represented by the above formula (I) was sufficiently stirred and mixed in a non-aqueous solvent according to the formulation shown in the following Table 10, and then a fine powder of PTFE was added as a fine powder of a fluorine-based resin, and further stirred and mixed. Thereafter, the obtained PTFE mixed liquid was dispersed by zirconia beads having a particle diameter of 0.3 mm using a horizontal bead mill to obtain respective dispersions 10 to 13.

The average particle diameter of the PTFE in the obtained dispersions 10 to 13 (average particle diameter analyzed by the cumulative amount method under the scattering intensity distribution) was measured by a dynamic light scattering method using FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).

The formulations of Dispersions 10 to 13 and the average particle diameter of PTFE in the obtained dispersion are shown in Table 10 below. Further, as a result of measuring the water content of the obtained dispersions 10 to 13, the respective water contents obtained by the Karl Fischer method were in the range of 800 to 1800 ppm.

[Examples 32 to 34 and Comparative Examples 16 to 18: Preparation of a thermosetting resin composition of a fluorine-containing resin]

Using the obtained dispersions 10 to 13, a thermosetting resin composition of a fluorine-containing resin was prepared according to the formulation shown in Table 11 below.

After mixing in the blending ratios shown in Examples 32 to 34 and Comparative Examples 16 to 18, the mixture was stirred with a disperser to uniformly blend the PTFE dispersion with the resin to obtain a thermosetting resin composition of a fluorine-containing resin. .

Here, Examples 32 to 34 showed extremely uniform states, and no change in particle diameter was observed. On the other hand, in Comparative Example 18, a plurality of granules of PTFE which are considered to be agglomerated were observed, and it was found that the particle diameter also became large.

(Examples 35 to 37, Comparative Examples 19 to 21: Preparation of a cured product of a thermosetting resin of a fluorine-containing resin)

The thermosetting resin composition of the fluorine-containing resin obtained in Examples 32 to 34 and Comparative Examples 16 to 18 was applied to the one side of the polyimide film (thickness: 25 μm) by a coater. The thickness was made uniform so that the thickness after drying became about 25 μm, and after drying at about 120 ° C for about 10 minutes, it was heated at 180 ° C for 60 minutes to be hardened, and an evaluation sample was prepared.

(physical evaluation)

Using the evaluation samples of Examples 35 to 37 and Comparative Examples 19 to 21 obtained above, the physical property evaluation as described below was carried out.

(Method for evaluating electrical characteristics)

The specific dielectric constant and the dielectric tangent were measured in accordance with the test specifications of JIS C6481-1996 at 1 GHz using an impedance analyzer (Impedence Analyzer), and the results are shown in Table 12 below.

As shown in the above Table 12, the cured products of the thermosetting resin of the fluorine-containing resin of Examples 35 to 37 showed a lower specific dielectric ratio and comparison with Comparative Examples 19 and 20 which did not contain the fluorine-based resin. Low dielectric tangent.

On the other hand, in Comparative Example 21, since it contained PTFE, the effect of lowering the specific dielectric constant and dielectric tangent was superior to Comparative Examples 19 and 20, but the surface of the cured product was slightly rough compared with Examples 35 to 37. The effect of sufficiently reducing the specific dielectric constant and dielectric tangent is less likely to be obtained.

[The fifth invention: Examples 38 to 43 and Comparative Examples 22 to 27]

(Preparation of non-aqueous dispersion of fluorine-based resin: dispersion 14 to 17)

The compound represented by the above formula (I) was sufficiently stirred and mixed in a non-aqueous solvent according to the following formula, and then a fine powder of PTFE was added as a fine powder of a fluorine-based resin, and further stirred and mixed. Thereafter, the obtained PTFE mixed liquid was dispersed by zirconia beads having a particle diameter of 0.3 mm using a horizontal bead mill to obtain each of the dispersions 14 to 17.

The average particle diameter of the PTFE in the obtained dispersions 14 to 17 (average particle diameter analyzed by the cumulative amount method under the scattering intensity distribution) was measured by a dynamic light scattering method using FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).

The formulations of Dispersions 14 to 17 and the average particle diameter of PTFE in the obtained dispersion are shown in Table 13 below. Further, as a result of measuring the water content of the obtained dispersions 14 to 17, the respective water contents obtained by the Karl Fischer method were in the range of 800 to 1800 ppm.

(Examples 38 to 40 and Comparative Examples 22 to 24: Preparation of a thermosetting resin composition of a fluorine-containing resin)

Using the obtained dispersions 14 to 17, a thermosetting resin composition of a fluorine-containing resin was prepared according to the formulation shown in Table 14 below.

After mixing in the blending ratios shown in Examples 38 to 40 and Comparative Examples 22 to 24, the mixture was stirred with a disperser to uniformly blend the PTFE dispersion with the resin to obtain a thermosetting resin composition of a fluorine-containing resin. .

Here, in Examples 38 to 40, a state of extremely uniformity was exhibited, and no change in particle diameter was observed. On the other hand, in Comparative Example 24, a plurality of granules of PTFE which are considered to be agglomerated were observed, and it was found that the particle diameter also became large.

(Examples 41 to 43 and Comparative Examples 25 to 27: Preparation of a cured product of a thermosetting resin of a fluorine-containing resin)

The thermosetting resin composition of the fluorine-containing resin obtained in Examples 38 to 40 and Comparative Examples 22 to 24 was applied to the one side of the polyimide film (thickness: 25 μm) by a coater. The thickness was made uniform so that the thickness after drying became about 25 μm, and after drying at about 120 ° C for about 10 minutes, it was heated at 180 ° C for 60 minutes to be hardened, and an evaluation sample was prepared.

(physical evaluation)

Using the evaluation samples of Examples 41 to 43 and Comparative Examples 25 to 27 obtained above, the physical property evaluation as described below was carried out.

(Method for evaluating electrical characteristics)

The specific dielectric constant and the dielectric dielectric tangent were measured in accordance with the test specifications of JIS C6481-1996 at 1 GHz using an impedance analyzer (Impedence Analyzer) and shown in Table 15 below.

As shown in the above Table 15, the cured products of the thermosetting resin of the fluorine-containing resin of Examples 41 to 43 showed lower specific dielectric ratio and comparison than Comparative Examples 25 and 26 which did not contain the fluorine-based resin. Low dielectric tangent.

On the other hand, in Comparative Example 27, since it contained PTFE, the effect of lowering the specific dielectric constant and dielectric tangent was superior to that of Comparative Examples 25 and 26, but the surface of the cured product was slightly rough compared with Examples 41 to 43. The effect of sufficiently reducing the specific dielectric constant and dielectric tangent is less likely to be obtained.

[This seventh invention: Examples 44 to 55 and Comparative Examples 28 to 35]

[Preparation of non-aqueous dispersion of fluorine-based resin: dispersion 18 to 22]

The compound (A, B) represented by the formula (I) is sufficiently stirred and mixed in a non-aqueous solvent according to the formulation shown in the following Table 16, and then a PTFE fine powder is added as a fine powder of a fluorine-based resin, and further Mix and mix. Thereafter, the obtained PTFE mixed liquid was dispersed by zirconia beads having a particle diameter of 0.3 mm using a horizontal bead mill to obtain respective dispersions 18 to 22. Further, in the case of the dispersion 21, the water content is adjusted by adding water at the time of blending.

The average particle diameter of the PTFE in the obtained dispersions 18 to 22 (average particle diameter analyzed by the cumulative amount method under the scattering intensity distribution) was measured by a dynamic light scattering method using FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.). Further, the water content obtained by the Karl Fischer method for each of the dispersions 18 to 22 was measured.

The formulations of the dispersions 18 to 22 and the average particle diameter and water content of the PTFE in the obtained dispersion are shown in Table 16 below.

(Examples 44 to 46 and Comparative Examples 28 to 29: Preparation of an adhesive composition for a circuit board)

Using the obtained dispersions 18 to 22, an adhesive composition for a circuit board was produced in accordance with the formulation shown in Table 17 below.

After mixing with the formulations shown in Examples 44 to 46 and Comparative Examples 28 to 29, the mixture was stirred with a disperser to uniformly blend the PTFE dispersion with the resin to obtain an adhesive composition for each circuit board.

Here, Examples 44 to 46 which are the respective adhesive composition for circuit boards produced by using the dispersions 18 to 22 are in a state of being extremely uniform, and are an adhesive composition for a circuit board produced by using the dispersion 21 . In Comparative Example 28, a granular material which was regarded as agglomeration of PTFE particles was observed on the wall surface. Further, in Comparative Example 29 using the adhesive composition for a circuit board produced by the dispersion 22, sedimentation separation of the particles was observed when stored for a long period of time.

(Ninth Invention: Examples 47 to 49, Comparative Examples 30 to 31: Production of Coating Film)

The adhesive composition obtained in Examples 44 to 46 and Comparative Examples 28 to 29 on the one side of the polyimide film (thickness: 25 μm) was applied to a uniform thickness using a coater to dry. After the thickness was about 25 μm and drying was carried out at about 120 ° C for about 10 minutes, a release film having a thickness of 125 μm which was subjected to release coating was laminated to form a coating film.

(10th invention: Examples 50 to 52, and Comparative Examples 32 to 33: Production of prepreg)

The adhesive compositions obtained in Examples 44 to 46 and Comparative Examples 28 to 29 were impregnated into a NE glass cloth having a thickness of about 100 μm, and then dried at about 120 ° C for about 10 minutes to form a total thickness of about 125 μm. Thermosetting prepreg.

(Eighth Invention: Examples 53 to 55, Comparative Examples 34 to 35: Production of Laminates for Circuit Boards)

The adhesive composition obtained in Examples 44 to 46 and Comparative Examples 28 to 29 on the one side of the polyimide film (thickness: 25 μm) was applied to a uniform thickness using a coater to dry. After the thickness was about 10 μm and the adhesive resin layer was formed, it was dried to be semi-hardened. Then, on the side opposite to the side of the polyimide film, the same adhesive resin layer was formed to form an adhesive sheet.

Next, the copper foil (thickness: about 12 μm, rough surface roughness (Rz): 1.6 μm) of the above-mentioned adhesive sheet was pressure-bonded at 170 ° C under a pressure of 40 kgf / cm ² , and at 170 After curing at ° C for 5 hours, a laminate for a circuit board was produced.

(production of evaluation sample of coating film)

The coating layers of Examples 47 to 49 and Comparative Examples 30 to 31 were laminated in the order of the coating layer of the polyimide film/coating layer of the coating layer/copper foil (12 μm), and then it was 180 ° C, 40 kgf / cm. The pressure of ² was subjected to hot pressing for 60 minutes to prepare a test sample.

(production of evaluation sample of prepreg)

The prepregs of Examples 50 to 52 and Comparative Examples 32 to 33 were laminated in the order of polyimine film (12.5 μm) / prepreg / polyimine (12.5 μm), and then 180 ° C, A pressure of 40 kgf/cm ² was subjected to hot pressing for 60 minutes to prepare an evaluation sample.

(Production of Evaluation Sample for Laminates for Circuit Boards)

The laminates for circuit boards of Examples 53 to 55 and Comparative Examples 34 to 35 were used as evaluation samples.

(physical evaluation)

Using the evaluation samples of Examples 47 to 55 and Comparative Examples 30 to 35 obtained above, the physical property evaluation as described below was carried out.

(Method for evaluating electrical characteristics)

The specific dielectric constant and the dielectric dielectric tangent were measured at 1 MHz using an impedance analyzer (Impedence Analyzer) in accordance with the test specifications of JIS C6481-1996.

(Method for evaluating heat resistance)

A sample having a size of 50 mm × 50 mm was prepared, and subjected to a moisture absorption treatment at 120 ° C, 0.22 MPa, and 12 hours, and then floated in a solder bath at 260 ° C for 1 minute to visually observe the state of the sample. As a basis for evaluation, if there is no abnormality such as peeling, deformation, and expansion, it is rated as "○"; if there is abnormality such as peeling, deformation, or expansion, it is rated as "X".

(following the method of assessing the strength)

A sample cut into 100 mm × 10 mm was prepared, and the adhesion strength of the adhesive layer formed using Tensilon was measured.

The results of the evaluation of the coating film are shown in the following Table 18. The evaluation results of the prepreg are shown in Table 19 below, and the evaluation results of the laminate for a circuit board are shown in Table 20 below.

As shown in the above Tables 18 to 20, the adhesive compositions of Examples 44 to 46 used the coating films of Examples 47 to 49 which were produced because of their low specific dielectric ratio and low dielectric tangent. The prepreg of Examples 50 to 52 and the laminate for a circuit board of Examples 53 to 55 were confirmed as compared with the laminate film of Comparative Examples 30 to 35, the prepreg, and the laminate for a circuit board. Although the heat resistance and the bonding strength are the same, they exhibit further improved electrical characteristics.

[Industrial availability]

The non-aqueous dispersion of the fluorine-based resin in the present invention can be uniformly added to various resin materials (resist materials) or rubbers, adhesives, lubricants or greases, printing inks, paints, and the like to enhance product characteristics. Use, can be used in electronic equipment, sliding materials, cars, kitchen supplies Wait. Moreover, the thermosetting resin composition of the fluorine-containing resin using the non-aqueous dispersion of the fluorine-based resin and the cured product thereof have a lower dielectric constant and dielectric tangent, and are excellent in adhesion, heat resistance, dimensional stability, and difficulty. The flammability and the like are excellent, and can be applied to an adhesive composition for a circuit board used in the production of a circuit board, and a multilayer printed wiring for a circuit board laminate, a coating film, a prepreg, or an electronic device using the same. The insulation of the board, etc. In addition, the adhesive composition for a circuit board using the non-aqueous dispersion of the fluorine-based resin has a lower dielectric constant and dielectric tangent, and is excellent in adhesion, heat resistance, dimensional stability, flame retardancy, and the like. The characteristics can be applied to a laminate for a circuit board, a coating film, a prepreg, or the like.

10‧‧‧Insulating film

20‧‧‧A layer of adhesive for circuit board

30‧‧‧metal foil

Claims (20)

A non-aqueous dispersion of a fluorine-based resin, which comprises at least a fine powder of a fluorine-based resin, a compound represented by the following formula (I), and a non-aqueous solvent. [In the above formula (I), l, m, n are positive integers]. The non-aqueous dispersion of the fluorine-based resin of claim 1, wherein the compound represented by the above formula (I) is contained in an amount of 0.1 to 15% by mass based on the mass of the fine powder of the fluorine-based resin. The fluorine-based non-aqueous dispersion according to claim 1 or 2, wherein in the non-aqueous dispersion of the fluorine-based resin, the average particle diameter of the fine powder of the fluorine-based resin in a dispersed state (accumulation under the scattering intensity distribution) The average particle diameter of the quantitative analysis is 1 μm or less. A thermosetting resin composition containing a fluorine-containing resin, characterized in that it contains at least a non-aqueous dispersion of a fluorine-based resin containing at least a fine powder of a fluorine-based resin and a compound represented by the following formula (I) and a non-aqueous solvent; And a resin composition comprising a cyanate resin and/or an epoxy resin, [In the above formula (I), l, m, n are positive integers]. A thermosetting resin composition of a fluorine-containing resin characterized in that at least a fine powder containing a fluorine-based resin, a compound represented by the following formula (I), an elastomer component, and a fluorine-based resin of a non-aqueous solvent are contained. a non-aqueous dispersion and a resin composition comprising a cyanate resin and/or an epoxy resin, [In the above formula (I), l, m, n are positive integers]. A thermosetting resin composition containing a fluorine-containing resin, characterized in that it is at least blended: a fine powder containing at least a fluorine-based resin, a compound represented by the following formula (I), and a cyanate-containing resin and/or an epoxy resin. a resin composition and a non-aqueous dispersion of a fluorine-based resin of a non-aqueous solvent, and an elastomer component. [In the above formula (I), l, m, n are positive integers]. A thermosetting resin composition containing a fluorine-containing resin, characterized in that it is at least blended: a fine powder containing at least a fluorine-based resin, a compound represented by the following formula (I), and a cyanate-containing resin and/or an epoxy resin. a resin composition, a non-aqueous dispersion of a fluorine-based resin of a non-aqueous solvent, and a resin composition containing a cyanate resin and/or an epoxy resin. [In the above formula (I), l, m, n are positive integers]. The thermosetting resin composition of the fluorine-containing resin according to any one of claims 4 to 7, wherein the fine powder of the fluorine-based resin is selected from the group consisting of polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, and perfluoroalkane. Oxygen polymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, ethylene-chlorotrifluoroethylene A fine powder of one or more fluorine-based resins in a group of copolymers and polychlorotrifluoroethylene. The thermosetting resin composition of the fluorine-containing resin according to any one of claims 4 to 7, wherein the compound represented by the above formula (I) contains 0.1 to 15 masses based on the mass of the fine powder of the fluorine-based resin. %. The thermosetting resin composition of the fluorine-containing resin according to any one of claims 4 to 7, wherein the average particle diameter of the fine powder of the fluorine-based resin in a dispersed state in the non-aqueous dispersion of the fluorine-based resin (The average particle diameter of the condensed matter analysis under the scattering intensity distribution) is 1 μm or less. A thermosetting resin cured product of a fluorine-containing resin, which is characterized in that the thermosetting resin composition of the fluorine-containing resin according to any one of claims 4 to 7 is cured. An adhesive composition for a circuit board, comprising: a non-aqueous dispersion containing at least a fine powder of a fluorine-based resin, a compound represented by the following formula (I), and a fluorine-based resin of a non-aqueous solvent, and a resin composition of a cyanate resin and/or an epoxy resin, [In the above formula (I), l, m, n are positive integers]. An adhesive composition for a circuit board according to claim 12, wherein The compound represented by the above formula (I) is contained in an amount of 0.1 to 15% by mass based on the mass of the fine powder of the fluorine-based resin, and the water content of the non-aqueous dispersion of the fluorine-based resin measured by the Karl Fischer method is 8000ppm or less. The adhesive composition for a circuit board according to claim 12 or 13, wherein the fine powder of the fluorine-based resin is selected from the group consisting of polytetrafluoroethylene, a fluorinated ethylene-propylene copolymer, a perfluoroalkoxy polymer, and a chlorine trichloride. A fine powder of one or more fluorine-based resins in a group of fluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, and polychlorotrifluoroethylene. The adhesive composition for a circuit board according to claim 12 or 13, wherein the average particle diameter (scattering intensity) of the fine powder of the fluorine-based resin in a dispersed state in the non-aqueous dispersion of the fine powder of the fluorine-based resin The average particle diameter analyzed by the cumulative amount method under distribution is 1 μm or less. A laminate for a circuit board, comprising a laminate for a circuit board comprising at least an insulating film, a metal foil, and an adhesive layer interposed between the insulating film and the metal foil, wherein the adhesive is characterized by the adhesive The layer is an adhesive composition for a circuit board as claimed in claim 12. The laminate for a circuit board according to claim 16, wherein the insulating film is selected from the group consisting of polyimine (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), and polynaphthalene dicarboxylic acid. Ethylene diester (PEN), polyphenylene sulfide (PPS), polyether phthalimide (PEI), polyphenylene ether (modified PPE), polyester, para-aromatic polyamine, polylactic acid, nylon, poly One or more films selected from the group consisting of grass ureia and polyether ether ketone (PEEK). A coating film which is an insulating film and a coating film in which an adhesive layer is formed on at least one surface of the insulating film, The adhesive layer is the adhesive composition for a circuit board according to claim 12. The coated film of claim 18, wherein the insulating film is selected from the group consisting of polyimine (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), and polyethylene naphthalate Diester (PEN), polyphenylene sulfide (PPS), polyether phthalimide (PEI), polyphenylene ether (modified PPE), polyester, para-aromatic polyamine, polylactic acid, nylon, polygrass One or more films selected from the group consisting of guanidine and polyether ether ketone (PEEK). A prepreg characterized by being composed of one or more fibers selected from the group consisting of carbon fibers, cellulose fibers, glass fibers, or aromatic polyamide fibers. And at least impregnating the adhesive composition for a circuit board of claim 12 or 13.