TW202111025A - Non-aqueous dispersion of fluorine-based resin, fluorine-based resin-containing thermocurable resin composition using same, and cured product thereof - Google Patents

Abstract

To provide: a non-aqueous dispersion of a fluorine-based resin, which has a small particle diameter, low viscosity and excellent storage stability, and in which fluorine-based resin particles do not aggregate when mixed with various thermosetting resin solutions; a fluorine-containing resin thermosetting resin composition using the non-aqueous dispersion; and a cured product of the fluorine-containing resin thermosetting resin composition. A non-aqueous dispersion of a fluorine-based resin is characterized by containing at least: 5-70% by mass of fluorine-based resin particles; a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group and/or a compound represented by formula (I) in an amount of 0.1-50% by mass relative to the mass of the fluorine-based resin particles; a polymer having a urethane structure; and a non-aqueous solvent. In the formula (I), the l, m and n are positive integers.

Description

Non-aqueous dispersions of fluorine-based resins, thermosetting resin compositions using fluorine-containing resins and their cured products

The present invention relates to non-aqueous dispersions of fluorine resins with fine particle diameter, low viscosity, and excellent storage stability, which do not aggregate when mixed with resin solutions, and thermosetting resin compositions using fluorine-containing resins. And its hardened objects.

In recent years, with the advancement of high-speed and high-performance electronic devices, there is a demand for higher communication speeds. In this way, low dielectric constant and low dielectric tangent of various electronic equipment materials are required, and low dielectric constant and low dielectric tangent of thermosetting resins that can be used for insulating materials or substrate materials are also required.

As a material with low dielectric rate and low dielectric tangent, polytetrafluoroethylene (PTFE, specific dielectric rate 2.1, dielectric tangent 0.0002), which has the most excellent characteristics among resin materials, has attracted attention, and the proposal is for thermosetting A thermosetting resin composition of a fluorine-containing resin dispersed in a fluorine resin or a non-aqueous dispersion of a fluorine resin for mixing with a thermosetting resin solution (Patent Documents 1 and 2 proposed by the applicant).

However, even if the fine particles of fluorine resin such as PTFE are dispersed stably in a non-aqueous solvent, when mixed with a thermosetting resin solution, the fluorine resin particles still agglomerate with each other, and many become foreign matter in the final resin composition. Of several topics. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 6165307 (application scope, examples, etc.) [Patent Document 2] Japanese Patent No. 6283441 (application scope, examples, etc.)

[The problem to be solved by the invention]

The present invention was completed in order to eliminate the above-mentioned conventional problems. Its purpose is to provide fine particles with low viscosity and excellent storage stability. When mixed with various thermosetting resin solutions, the fluorine resin particles do not agglomerate and can achieve low dielectric. Non-aqueous dispersions of fluorine-based resins with low dielectric tangent and low-dielectric tangent, thermosetting resin compositions using fluorine-containing resins and their cured products. [Means to solve the problem]

The inventors of the present invention have actively reviewed the above-mentioned conventional problems and found that by the following first to seventh inventions, a non-aqueous dispersion of fluorine-based resin and a thermosetting resin using the above-mentioned fluorine-based resin can be obtained. The composition and its hardened product have thus completed the present invention.

[上述式(I)中，l、m、n為正整數]。That is, the first invention of the present invention is a non-aqueous dispersion of fluorine resin, which is characterized by containing at least 5 to 70% by mass of fluorine resin particles, and 0.1 to 50% by mass relative to the mass of fluorine resin particles. At least a fluorine-based additive containing a fluorine-containing group and a lipophilic group and/or a compound represented by the following formula (I), a polymer having a urethane structure, and a non-aqueous solvent,

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

The second invention is a non-aqueous dispersion of fluorine resin according to the first invention, wherein the fluorine resin particles are selected from polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, perfluoroalkoxy polymer, chlorine One or more fluorine resin particles from the group consisting of trifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, and polychlorotrifluoroethylene.

The third invention is a non-aqueous dispersion of a fluororesin of the first invention or the second invention, wherein the fluororesin in the non-aqueous dispersion has an average particle diameter of 1 μm or less after being dispersed.

The fourth invention is a non-aqueous dispersion of fluorine resin according to any one of the first invention to the third invention, and its viscosity at a shear rate of 19.2/s is 300 mPa･s or less.

The fifth invention is a non-aqueous dispersion of fluororesin according to any one of the first to fourth inventions, wherein the aforementioned polymer having a urethane structure is relative to the mass of the fluororesin particles. Contains 0.1-30% by mass.

The sixth invention is a thermosetting resin composition containing a fluorine-based resin, which is characterized by a non-aqueous dispersion containing at least a fluorine-based resin of any one of the first invention to the fifth invention and a thermosetting resin containing The resin composition.

The seventh invention is a cured thermosetting resin of a fluorine-containing resin, which is characterized by curing the thermosetting resin composition of the fluorine-containing resin of the sixth invention.

The non-aqueous dispersion of the fluorine resin of the present invention has a fine particle diameter, low viscosity, and excellent storage stability. When mixed with various thermosetting resin solutions, the fluorine resin particles do not agglomerate. The non-aqueous dispersion of the present invention is used for the fluorine-containing resin. The thermosetting resin composition of the resin and its cured product are free of foreign matter, and can achieve low dielectric constant and low dielectric tangent.

Hereinafter, embodiments of the present invention will be described in detail.

[上述式(I)中，l、m、n為正整數]。[Non-aqueous dispersion of fluorine-based resin] The non-aqueous dispersion of fluorine-based resin of the present invention is characterized by containing at least 5 to 70% by mass of fluorine resin particles, with respect to the mass of fluorine resin particles being 0.1 to 50 The mass% of the fluorine-based additive containing at least a fluorine-containing group and a lipophilic group and/or a compound represented by the following formula (I), a polymer having a urethane structure, and a non-aqueous solvent.

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

Examples of fluorine resin particles that can be used in the present invention are selected from polytetrafluoroethylene (PTFE), fluorinated ethylene-propylene copolymer (FEP), perfluoroalkoxy polymer (PFA), and chlorotrifluoroethylene. (CTFE), tetrafluoroethylene-chlorotrifluoroethylene copolymer (TFE/CTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polychlorotrifluoroethylene (PCTFE) is one or more of the groups The fluorine-based resin particles preferably have a primary particle diameter of 1 μm or less. Among the above-mentioned fluorine resin particles, it is desirable to use polytetrafluoroethylene (PTFE, specific dielectric constant 2.1, dielectric tangent 0.0002), which has the most excellent characteristics among resin materials, especially as a material with low dielectric constant and low dielectric tangent.

These fluorine-based resin particles are obtained by the emulsion polymerization method, and can be obtained, for example, by the method described in the Fluorine Resin Handbook (edited by Takao Kurokawa, Nikkan Kogyo Shimbun) and other commonly used methods. Next, the fluorine-based resin particles obtained by the aforementioned emulsion polymerization are aggregated/dried, and the secondary particles aggregated as the primary particle size are recovered as fine powder. However, various generally used methods for producing fine powder can be used.

The particle diameter of the fluorine resin particles is preferably one having a primary particle diameter of 1 μm or less, and it is also preferably an average particle diameter of 1 μm or less in a non-aqueous dispersion. In terms of stable dispersion in a non-aqueous solvent, the primary particle size is preferably 0.5 μm or less, and more desirably 0.3 μm or less, to obtain a more uniform dispersion. In addition, when the average particle size of the fluorine resin particles in the non-aqueous dispersion exceeds 1 μm, it becomes easy to settle and it is difficult to stably disperse, which is not preferable. It is preferably 0.5 μm or less, more preferably 0.3 μm or less.

In the present invention, as a method for measuring the primary particle size, a volume-based average particle size (50% volume diameter, median diameter) measured by laser diffraction/scattering method, dynamic light scattering method, image imaging method, etc. can be used However, the fluorine-based resin particles dried into a powder state are likely to be difficult to measure the primary particle size by using laser diffraction/scattering methods or dynamic light scattering methods due to the strong cohesion of the primary particles. In this case, it may also indicate the value obtained by the image imaging method.

On the other hand, as a method for measuring the particle size of the fluorine-based resin in a non-aqueous dispersion, the volume-based average particle size measured by the laser diffraction/scattering method, dynamic light scattering method, image imaging method, etc. can be used (50% volume diameter, median diameter).

As the measurement device of the above-mentioned particle size, for example, a dynamic light scattering method using FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) or a laser diffraction/scattering method using MICROTRAC (manufactured by Nikkiso Co., Ltd.) can be exemplified. Or use Mac-View (manufactured by MOUNTECH Corporation) image imaging method, etc.

In the present invention, the fluorine-based resin particles contain 5 to 70% by mass, preferably 10 to 60% by mass with respect to the total amount of the non-aqueous dispersion. If the content is less than 5% by mass, a large amount of solvent is not economical for manufacturing or transportation. When mixing with thermosetting resin solutions and other materials, defects due to the large amount of solvent may occur, such as solvent removal changes. It takes time and bad things happen. On the other hand, when it exceeds 70% by mass in many cases, the viscosity becomes very large, and it is extremely difficult to maintain a fluid state, so it is not good.

The fluorine-based additive that can be used in the non-aqueous solvent-based dispersion of the present invention is not particularly limited as long as it contains at least a fluorine-containing group and a lipophilic group, and it may also contain a hydrophilic group. By using a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group, the surface tension of the non-aqueous solvent used as a dispersion medium can be reduced, the wettability to the surface of the fluorine-based resin particle can be improved, and the dispersibility of the fluorine-based resin particle can be improved And the fluorine-containing group is adsorbed on the surface of the fluorine-based resin particles, and the lipophilicity is based on extending in the non-aqueous solvent that becomes the dispersion medium. The steric obstacle of the lipophilic group prevents the agglomeration of the fluorine-based resin particles and improves the dispersion stability.

Examples of fluorine-containing groups include perfluoroalkyl groups and perfluoroalkenyl groups. Examples of lipophilic groups include one or more of alkyl groups, phenyl groups, and siloxyalkyl groups. Examples of hydrophilic groups include For example, one or two or more of ethylene oxide, amine group, ketone group, carboxyl group, sulfo group, and the like. As specific fluorine-based additives that can be used, SURFLON series (manufactured by AGC SEMICHEMICAL), such as SURFLON S-611 containing perfluoroalkyl groups, MEGA FAC F-555, MEGA FAC F-558, MEGA FAC F-563, etc. can be used. MEGA FAC series (manufactured by DIC Corporation), UNIDYNE series such as UNIDYNE DS-403N (manufactured by Daikin Industrial Co., Ltd.), FLOREN FD-420 (manufactured by Kyoeisha Chemical), FTERGENT 610FM, FTX-218, 215M, 710FM, 730LM, etc. FTERGENT series (manufactured by NEOS), etc. These fluorine-based additives are appropriately selected according to the types of fluorine-based resin particles and non-aqueous solvents used, but they can be used singly or in combination of two or more.

The content of the aforementioned fluorine-based additive is 0.1-50% by mass relative to the mass of the fluorine-based resin particles, but it is desirably 0.3-20% by mass, and more desirably 0.3-5% by mass. When the content is less than 0.1% by mass relative to the mass of the fluorine-based resin particles, the surface of the fluorine-based resin particles cannot be sufficiently wetted by the non-aqueous solvent. On the other hand, when the content exceeds 50% by mass, the dispersion may foam and become strongly dispersed. The efficiency is reduced, and the dispersant itself is treated or mixed with resin materials afterwards, and unsuitable situations may occur, so it is unsatisfactory. Moreover, even if there is no undesirable situation such as foaming, it is not economical to add a large amount of fluorine-based additives because they are expensive.

The compound represented by (I) used in the present invention is a compound that can uniformly and stably disperse fluorine resin particles in a non-aqueous solvent as fine particles. Its molecular structure is a ternary polymer composed of vinyl acetal/vinyl acetate/vinyl alcohol. It is a reaction of polyvinyl alcohol (PVA) with butyraldehyde (BA) and other aldehydes. It has an acetal group and ethyl acetate. The structure of the acyl group and the hydroxyl group can be controlled by changing the ratio of the three structures (the ratios of l, m, and n) and the type of acetal group to control the solubility to non-aqueous solvents. Chemical reactivity when adding non-aqueous dispersions of fluorine resin particles to various resin materials.

As the compound represented by (I) above, as commercially available products, S LEC B series, K(KS) series, SV series, and MOWITAL series manufactured by Kuraray Co., Ltd. can be used. Specific examples are the product names made by Sekisui Chemical Industry Co., Ltd.; S LEC BM-1, same as BH-3, same as BH-6, same as BX-1, same as BX-5, same as BM-2, same as BM-5, and same BL -1. Same BL-1H, same BL-2, same BL-2H, same BL-5, same BL-10, same KS-10, etc., or the product name made by KURARAY company; MOWITAL B14S, same B16H, same B20H , Same B30H, Same B45H, Same BX860, Same B60H, Same B75H, Same BL16, Same B30HH, Same B60HH, Same B30T, Same B45M, Same B60T, etc., or the trade name of Eastman Chemical; BUTVAR B-72, Same as B-74, same as B-76, same as B-79, same as B-90, same as B-98, etc. These can be used individually or in mixture of 2 or more types. In addition, if it is within the specified addition amount range, it can also be used in combination with the aforementioned fluorine-based additives.

The content of the compound represented by (I) above is 0.1-50% by mass relative to the mass of the fluorine-based resin particles. If the content of the compound is less than 0.1% by mass, the dispersion stability will deteriorate and the fluorine resin particles will easily settle, and if it exceeds 50% by mass, the viscosity will increase, and the fluidity of the dispersion will not be obtained, resulting in poor fluidity. Furthermore, considering the characteristics when adding a non-aqueous dispersion of fluorine-based resin particles to thermosetting resins, etc., the content of the above-mentioned compound is desirably 0.1-15% by mass relative to the mass of the fluorine-based resin particles. It is desirably 0.1 to 10% by mass, and particularly preferably 0.3 to 5% by mass.

Furthermore, in the present invention, when the above-mentioned fluorine-based additive containing at least a fluorine-containing group and a lipophilic group is used in combination with the compound represented by the above-mentioned formula (I), in order to maximize the combined effect, it is expected that it is better than the fluorine-based resin particle The mass of the fluorine-based additive is 0.1-5 mass%, and the compound represented by the above formula (I) is 0.3-5 mass%.

The polymer having a urethane structure that can be used in the non-aqueous solvent dispersion of the present invention can prevent the dispersion from becoming unstable when the thermosetting resin solution is mixed with the fluorine resin particle dispersion. The fluorine-based resin particles aggregate. If a dispersion of fluorine resin particles is mixed with a solution of different composition, the components in the solution move towards the dispersion phase, adsorb on the surface of the particles, and destroy the dispersion. The difference in the concentration of the various components causes the dispersion stabilizer or solvent. The non-uniformity causes the particles to agglomerate. The polymer having a urethane structure used in the present invention suppresses the movement of substances during mixing, so that rapid changes in the composition of the dispersion system can be alleviated and aggregation can be suppressed.

The polymer having a urethane structure used in the present invention is composed of a compound having more than one urethane bond (-NH-COO-) in one molecule. With the formula: R-NH-COO-R’ (In the above formula, R and R'are aliphatic, alicyclic or aromatic monovalent or multivalent organic groups, and the multivalent organic groups are further bonded to groups having other urethane bonds or other groups ) Means, In a polymer with a urethane structure, it may be present in a lipophilic group and/or a hydrophilic group, and these groups may be present in the main chain and/or side of the polymer with a urethane structure Furthermore, more than one chain may exist in the polymer which has a urethane structure. When there are two or more polymers having a urethane structure with a urethane bond, each urethane bond may be the same or different.

Examples of such polymers having a urethane structure include, for example, the reaction of diisocyanates and/or triisocyanates with polyesters having hydroxyl groups at one end and/or polyesters having hydroxyl groups at both ends Product. Examples of the above-mentioned diisocyanates include benzene diisocyanates such as benzene-1,3-diisocyanate and benzene-1,4-diisocyanate; toluene-2,4-diisocyanate and toluene-2,5-diisocyanate , Toluene-2,6-diisocyanate, toluene-3,5-diisocyanate and other toluene diisocyanates; 1,2-xylene-3,5-diisocyanate, 1,2-xylene-3,6- Diisocyanate, 1,3-xylene-2,4-diisocyanate, 1,3-xylene-2,5-diisocyanate, 1,3-xylene-4,6-diisocyanate, 1,4-di Other aromatic diisocyanates such as xylene diisocyanates such as toluene-2,5-diisocyanate and 1,4-xylene-2,6-diisocyanate.

Examples of the above-mentioned triisocyanates include benzene-1,2,4-triisocyanate, benzene-1,2,5-triisocyanate, benzene-1,3,5-triisocyanate, and other benzene triisocyanates; toluene- Toluene triisocyanates such as 2,3,5-triisocyanate, toluene-2,3,6-triisocyanate, toluene-2,4,5-triisocyanate, toluene-2,4,6-triisocyanate; 1, 2-xylene-3,4,5-triisocyanate, 1,2-xylene-3,4,6-triisocyanate, 1,3-xylene-2,4,5-triisocyanate, 1,3- Xylene-2,4,6-triisocyanate, 1,3-xylene-4,5,6-triisocyanate, 1,4-xylene-2,3,5-triisocyanate, 1,4-xylene -2,3,6-triisocyanate and other aromatic triisocyanates such as xylene triisocyanate, etc. These diisocyanates and triisocyanates can be used individually or in mixture of 2 or more types, respectively.

As the above-mentioned polyesters having hydroxyl groups at one end and polyesters having hydroxyl groups at both ends, from the viewpoint of dispersibility, it is preferable to contain -(OR ^j CO) _n -(R ^j as carbon number 1 ~20 alkylene, n is an integer of 2 or more) represented by the compound of the polyester chain. Specific examples of polyester chains include polylactones such as polycaprolactone, polyvalerolactone, and polypropiolactone, and poly(ethylene terephthalate) and polybutylene terephthalate. Condensed polyester type. Among them, from the viewpoint of heat resistance, polylactones are preferably included, and among them, polycaprolactone is preferably included. Specifically, examples include polycaprolactone having hydroxyl groups at one or both ends, polyvalerolactone having hydroxyl groups at one or both ends, polypropiolactone having hydroxyl groups at one or both ends, etc. Polylactones with hydroxyl groups at one or both ends; polyethylene terephthalate with hydroxyl groups at one or both ends, polybutylene terephthalate with hydroxyl groups at one or both ends, etc. Polycondensation polyesters with hydroxyl groups at one end or both ends. The polyesters having hydroxyl groups at one end and the polyesters having hydroxyl groups at both ends can be used individually or in combination of two or more types.

As the polymer having a urethane structure of the present invention, it is preferably produced by the reaction of aromatic diisocyanates with polylactones having hydroxyl groups at one end and/or polylactones having hydroxyl groups at both ends The product is particularly preferably a reaction product of toluene diisocyanate and polycaprolactone having hydroxyl groups at one end and/or polycaprolactone having hydroxyl groups at both ends.

In addition, the polymer having a urethane structure preferably does not have an acidic functional group from the viewpoint of dispersibility. Examples of the acidic functional group include, for example, a carboxyl group, a sulfo group, a phosphoric acid group, etc., and the representative is a carboxyl group. Furthermore, from the viewpoint of heat resistance, the polymer having a urethane structure preferably does not contain a polyether chain that is easily cut by heating. The polyether chain here refers to a structure represented by -(OR ⁱ ) _n- (R ⁱ is an alkylene group with 1 to 10 carbon atoms, and n is an integer of 2 or more). Specific examples are -(O-CH ₂ CH ₂ ) _n -, -(O-CH ₂ CH ₂ CH ₂ ) _n -, -(O-CH ₂ CH ₂ CH ₂ CH ₂ ) _n -, -(O-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) _n -, -(O-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) _n -.

As the polymer having a urethane structure used in the present invention, commercially available products are the DISPERBYK series made by CYK Chemie, the Efka series made by BASF, the BURNOCK series made by DIC, and the Solsphere series made by Lubrizol. Specifically, based on the viewpoints of heat resistance, electrical reliability, and dispersion, examples are made by CYK Chemie; DISPERBYK-161, Same 162, Same 163, Same 164, Same 167, Same 168, Same 170, Same 174 , The same 180, the same 182, the same 184, the same 185, the same 2163, the same 2164, etc., or BASF company system; Efka PU4063, etc., or DIC company system; BURNOCK 16-411, the same 16-416, the same 16-472, the same DF-402, same DF-407, same ENL-659, etc., or manufactured by Lubrizol; Solsphere 71000, same 74000, same 75500, same 76400, same 76500, same 79000, etc. The weight average molecular weight (Mw) of the polymer having a urethane structure of the present invention is usually 5,000 to 50,000, preferably 7,000 to 20,000. The above-mentioned polymer having a urethane structure can be used singly or as a mixture of two or more kinds.

The content of the polymer having a urethane structure is preferably 0.1 to 30% by mass relative to the fluorine-based resin particles. If the content of the compound is less than 0.1% by mass, the agglutination inhibitory effect cannot be exhibited, and when it exceeds 30% by mass, the agglutination inhibitory effect also decreases, which is only excessive and uneconomical. Furthermore, when considering the properties when adding a non-aqueous dispersion of fluorine resin particles to a thermosetting resin, etc., it is desirably 0.1-20% by mass, further desirably 0.1-15% by mass, and particularly preferably 0.3 ~10% by mass.

The non-aqueous dispersion of fluorine resin particles of the present invention may also be combined with the above-mentioned fluorine-based additives, the compound represented by the above formula (I), and those having a urethane structure without impairing the effects of the present invention. The polymers are combined to use other surfactants or dispersants. For example, regardless of fluorine-based or non-fluorine-based surfactants, nonionic, anionic, and cationic surfactants or dispersants, nonionic, anionic, and cationic polymer surfactants or high The molecular dispersant and the like can be used without being limited to them.

The non-aqueous solvent used as the above-mentioned non-aqueous dispersion of the present invention can be exemplified, for example, from γ-butyrolactone, acetone, methyl ethyl ketone, hexane, heptane, octane, 2-heptanone, and cycloheptanone. , Cyclohexanone, cyclohexane, methylcyclohexane, ethylcyclohexane, methyl n-amyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, ethylene glycol, diethylene glycol , Propylene glycol, dipropylene glycol, ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diethyl ether, propylene glycol Monoacetate, dipropylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexyl acetate, 3-ethoxypropionic acid Ethyl acetate, dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl Ethyl oxypropionate, anisole, ethyl benzyl ether, cresol methyl ether, diphenyl ether, dibenzyl ether, phenethyl alcohol, butyl phenyl ether, benzene, ethylbenzene, di Ethylbenzene, amylbenzene, cumene, toluene, xylene, p-isopropyl toluene (cymene), mesitylene, methanol, ethanol, isopropanol, butanol, methyl monoglycidyl ether, ethyl Base monoglycidyl ether, butyl monoglycidyl ether, phenyl monoglycidyl ether, methyl diglycidyl ether, ethyl diglycidyl ether, butyl diglycidyl ether, phenyl diglycidyl ether, methyl Phenol monoglycidyl ether, ethyl phenol monoglycidyl ether, butylphenol monoglycidyl ether, mineral spirits, 2-hydroxyethyl acrylate, tetrahydrofurfuryl acrylate, 4-vinylpyridine, N-methyl- 2-pyrrolidone, 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, neopentyl glycol diacrylate, hexanediol diacrylate Ester, trimethylolpropane triacrylate, methacrylate, methyl methacrylate, styrene, perfluorocarbon, hydrofluoroether, hydrochlorofluorocarbon, hydrofluorocarbon, perfluoropolyether, N, N -Dimethylformamide, N,N-dimethylacetamide, dioxolane, cyclohexanol acetate, dipropylene glycol dimethyl ether, propylene glycol diacetate, dipropylene glycol methyl n-propyl Base ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, various silicones One solvent selected from the group of oils or containing two or more of these solvents. Among these solvents, it is preferable to vary according to the type of resin used, but examples are methyl ethyl ketone, cyclohexanone, toluene, xylene, N-methyl-2-pyrrolidone, N,N- Dimethylformamide, N,N-dimethylacetamide, dioxolane.

In the present invention, although the above-mentioned solvents are mainly used, they may be used in combination with other solvents or other solvents, and an appropriate one may be selected according to the application (various resin materials for circuit boards) and the like. In addition, depending on the polarity of the solvent used, it is considered that the compatibility with water is high. However, when the amount of water is large, the dispersibility of the fluororesin particles in the solvent may be hindered, and the viscosity may increase or the particles may agglomerate. In the present invention, the non-aqueous solvent used is preferably one whose water content measured by Karl Fischer method is 6000 ppm or less [0≦moisture content≦6000 ppm]. In the present invention (including the embodiments described below), the measurement of the moisture content by Karl Fischer method is based on JIS K 0068:2001, for example, it can be measured by MCU-610 (manufactured by Kyoto Electronics Industry Co., Ltd.). By making the water content in the solvent 6000ppm or less, it is possible to further suppress aggregation when the resin solution is mixed with the fluororesin particle dispersion. It is more preferably 5000ppm or less, still more preferably 3000ppm or less, particularly preferably 2500ppm or less . In addition, the above-mentioned adjustment of the water content can be performed using a solvent dehydration method such as a generally used non-aqueous solvent, but for example, molecular sieve can be used.

The non-aqueous dispersion of the fluorine resin of the present invention, based on the manufacturing aspect and the aspect after the thermosetting resin solution is mixed, the average particle diameter of the dispersion of the aforementioned fluorine resin in the non-aqueous dispersion is preferably 1 μm or less, and The viscosity at a temperature of 25°C and a shear rate of 19.2/s is 300mPa･s or less, more preferably 200mPa･s or less. The average particle size and viscosity after the dispersion can be appropriately combined with the fluorine-based resin particle species, fluorine-based additives, the compound represented by the above formula (I), the polymer with urethane structure, and the non-aqueous solvent. The various amounts, etc., are adjusted using appropriate mixing methods, etc. The non-aqueous dispersion of the fluorine-based resin of the present invention thus constituted by containing at least fluorine-based resin particles, a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group, and/or a compound represented by the above formula (I), has an amine Carbamate-structured polymers and non-aqueous solvents can achieve fine particle diameters with low viscosity and excellent storage stability. When mixed with various thermosetting resin solutions, fluorine resin particles do not agglomerate and have a low dielectric rate. , Non-aqueous dispersion of fluorine resin with low dielectric tangent.

[Thermosetting resin composition of fluorine-containing resin] The fluorine-containing resin-containing thermosetting resin composition of the present invention is characterized by at least a non-aqueous dispersion of fluorine-containing resin and a resin composition containing thermosetting resin. The content of the non-aqueous dispersion of the fluorine resin is expressed by the fluorine resin particles such as PTFE contained in the dispersion, the fluorine additive containing at least a fluorine-containing group and a lipophilic group, and/or the above formula (I) The amount of the compound, the polymer with the urethane structure, and the non-aqueous solvent varies according to the use of the composition of the thermosetting resin, etc. The non-aqueous solvent in the resin composition is finally prepared to contain After the composition of the thermosetting resin is removed during curing, it is desirable that the content of fluorine resin particles such as PTFE is preferably 1 to 120 parts by mass in the end relative to 100 parts by mass of the resin. The dispersion is used for the adjustment of 5-100 parts by mass. By setting the content of fluorine resin particles such as PTFE to 1 part by mass or more with respect to 100 parts by mass of the resin, the electrical characteristics of low specific permittivity and low dielectric tangent can be exhibited. On the other hand, by By setting it as 120 parts by mass or less, the adhesiveness or heat resistance of the thermosetting resin will not be impaired, and the effect of the present invention can be exhibited.

As the resin composition used in the present invention, one containing at least a thermosetting resin is exemplified. Examples of thermosetting resins include epoxy resins, polyimide resins, polyimide resins, triazine resins, phenol resins, melamine resins, polyester resins, cyanate ester resins, and bismaleic resins. For amine resins and modified resins of these resins, these resins may be used singly, or two or more of them may be used in combination. These resins are used as the base resin of the thermosetting resin composition, and they can be used without particular limitation as long as they are suitable for users such as insulation or insulation in electronic devices. The preferred resin composition is at least exemplified by cyanate ester resin and/or epoxy resin. These resins become the preferred base resin especially for thermosetting resin compositions, which are suitable for insulating or insulating properties in electronic equipment. By. As the cyanate ester resin that can be used in the present invention, for example, at least 2-functional aliphatic cyanate ester, at least 2-functional aromatic cyanate ester, or a mixture of these, for example, From 1,3,5-tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8 -Dicyanatonaphthalene, 2,6-dicyanatonaphthalene and 2,7-dicyanatonaphthalene selected from at least one polyfunctional cyanate polymer, bisphenol A cyanate Resin or hydrogenated in these, bisphenol F cyanate resin or hydrogenated in these, 6F bisphenol A dicyanate resin, bisphenol E dicyanate resin, tetramethyl At least one of bisphenol F dicyanate resin, bisphenol M dicyanate resin, dicyclopentadiene bisphenol dicyanate resin, or cyanate novolak resin. In addition, commercial products of these cyanate ester resins can also be used.

Examples of usable epoxy resins are, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, tertiary butylcatechol type epoxy resin, and naphthalene type epoxy resin. Resin, naphthyl ether type epoxy resin, glycidyl amine type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, chain aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic ring Formula epoxy resin, epoxy resin containing spiro ring, cyclohexane dimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, etc. One type of these epoxy resins can be used, or two or more types can be used in combination. The epoxy resin that can be used in the present invention is not limited to the above-mentioned resin as long as it has one or more epoxy groups in one molecule, but it is preferably bisphenol A, hydrogenated bisphenol A, cresol novolac and the like. In the present invention, the above-mentioned cyanate ester resin and epoxy resin can be used alone or in combination. In the case of combined use, it can be used together in the range of 1:10-10:1 in terms of mass ratio.

When the above-mentioned cyanate ester resin and epoxy resin are used in the present invention, active ester compounds can also be used as additives based on the viewpoints of reactivity, curability, and moldability. The active ester compound that can be used is generally preferably a compound having two or more active ester groups in one molecule, and examples thereof include carboxylic acid compounds, phenol compounds, or naphthol compounds. Examples of carboxylic acid compounds include acetic acid, benzoic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methyl Bisphenol S, phenol, o-cresol, meta-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxyl Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadienyl diphenol, phenol Novolac, etc. These active ester compounds may be used singly or in combination of two or more kinds. Examples of commercially available active ester compounds include EXB-9451, EXB-9460, HPC-8000-65T (manufactured by DIC Co., Ltd.), DC808, YLH1030 (manufactured by Nippon Epoxy Co., Ltd.), and the like. The amount of the active ester compound used is determined according to the base resin of the thermosetting resin composition used and the type of the active ester compound used. Furthermore, among the above-mentioned active ester compounds, an active ester compound hardening accelerator can also be used as needed. As the active ester compound hardening accelerator, an organometallic salt or organometallic complex is used. For example, an organometallic salt or organometallic complex containing iron, copper, zinc, cobalt, nickel, manganese, tin, etc. is used. Specifically, the aforementioned cyanate ester hardening accelerator is exemplified by manganese naphthenate, iron naphthenate, copper naphthenate, zinc naphthenate, cobalt naphthenate, iron octoate, copper octoate, zinc octoate, cobalt octoate, etc. The organic metal salt; lead acetopyruvate, cobalt acetopyruvate and other organic metal complexes. These active ester compound hardening accelerators are based on the metal concentration and based on the viewpoints of reactivity, hardenability, and formability, and contain 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the resin used above. Mass parts.

In addition, when the above-mentioned epoxy resin is used in the present invention, a curing agent can also be used as an additive from the viewpoint of reactivity, curability, and moldability. Examples of hardeners that can be used include ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid-modified ethylenediamine, N-ethylaminopiperidine, and isophorone diamine. Aliphatic amines such as amines, meta-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4,4'-diamine Aromatic amines such as aminodiphenylmethane, 4,4'-diaminodiphenyl ether, mercaptans such as mercaptopropionate, epoxy terminal mercapto compounds, polyazalea, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, Bornane-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, methyl-norbornane-2,3-dicarboxylic anhydride and other alicyclic anhydrides, Aromatic anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc., imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, etc. Salts, amine adducts derived from the reaction of the aliphatic amines, aromatic amines and/or imidazoles with epoxy resins, hydrazines such as hydrazine adipate, dimethylbenzylamine, 1 At least one of tertiary amines such as 8-diazabicyclo[5.4.0]undecene-7, organic phosphines such as triphenylphosphine, and dicyanodiamide. The usage amount of these hardeners can be determined by the epoxy resin used and the type of hardener used. In the resin composition of the present invention, inorganic fillers, thermoplastic resin components, rubber components, flame retardants, colorants, tackifiers, defoamers, leveling agents, coupling agents, and adhesion-imparting materials can be used in combination. It is a material that is generally used in thermosetting resin compositions of electronic devices.

In the present invention, by adjusting the total resin concentration of the thermosetting resin necessary for the final thermosetting resin composition of the fluorine-containing resin, the fluorine resin particles can exist uniformly without agglomeration, and the specific permittivity can be obtained. Those with low dielectric tangent, no foreign matter obstructing the wiring pattern or interlayer adhesion, and capable of exhibiting excellent characteristics.

[Cured thermosetting resin of fluorine-containing resin] In the present invention, the thermosetting resin composition of the fluorine-containing resin of each of the above-mentioned constitutions can be molded and cured into a cured product by the same method as the thermosetting resin composition such as a conventional epoxy resin composition. The molding method and curing method can use the same methods as conventional thermosetting resin compositions such as epoxy resin compositions, and the specific method of the fluorine-containing resin thermosetting resin composition of the present invention is not required, and is not particularly limited. The cured product formed by curing the thermosetting resin composition of the fluorine-containing resin of the present invention can be in the form of a laminate, a molded product, an adhesive, a coating film, a film, and the like. The thermosetting resin composition of the fluorine-containing resin and its cured product of the present invention do not impair the adhesiveness or heat resistance of thermosetting resins such as epoxy resins, and are of low specific permittivity and low dielectric tangent. Excellent electrical properties, and by containing a polymer with a urethane structure, foreign matter caused by the aggregation of fluorine-based resin particles can be suppressed, so it can be used as electronic substrate materials, insulating materials, adhesive materials, etc., for example It can be preferably used in materials such as sealing materials, copper-clad laminates, insulating coatings, composite materials, insulating adhesives, etc. used in electronic parts, and is particularly preferably used in the formation of insulating layers of multilayer printed wiring boards for electronic equipment, Laminates for circuit boards, protective films, prepregs, etc. [Example]

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, the present invention is not limited to the following examples and the like.

[Examples 1 to 14 and Comparative Examples 1 to 8] [Preparation of non-aqueous dispersion of fluorine resin] According to the formulation shown in Table 1 below, use PTFE fine powder as fluorine resin particles, fluorine additives containing fluorine-containing groups and lipophilic groups, compounds represented by formula (I), and urethane structure Polymers and non-aqueous solvents are used to prepare non-aqueous dispersions of fluorine-based resins. In the above preparation, a fluorine-based additive, a compound represented by formula (I), and a polymer having a urethane structure are mixed and dissolved in a non-aqueous solvent, and then PTFE fine powder as fluorine-based resin particles is added, and then Stir and mix. Subsequently, the obtained PTFE mixture was batch-processed using a disperser: Dyno Mill Multilab type, dispersion conditions: zirconia beads φ0.3mm, filling rate 50%, and peripheral speed of 10m/s. After batch processing for 1 hour, the beads were separated and prepared ( Recycling) Non-aqueous dispersions of fluorine-based resins. The average particle size of PTFE in the non-aqueous dispersion of each fluorine-based resin (average particle size analyzed by the cumulative method in the scattering intensity distribution) was measured by the dynamic light scattering method using FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) . In addition, the viscosity of the non-aqueous dispersion (25°C) of each fluorine-based resin was measured using an E-type viscometer (shear rate 19.2/s). The redispersibility after storage at 25°C for 1 month was evaluated as follows: ○: easy to redisperse, △: redispersion, ×: sufficient stirring is required for redispersion. The formulation of the non-aqueous dispersion of each fluororesin in Table 1 below indicates the average particle size of PTFE in the resulting dispersion. In addition, the water content of the non-aqueous dispersion of each fluorine-based resin was measured by Karl Fischer method, and it was confirmed that it was in the range of 400 to 2500 ppm.

[Preparation of thermosetting resin solution (mixing)] Using the obtained non-aqueous dispersions of the above-mentioned fluorine-based resins, use the formula shown in Table 1 below (modified phenol novolac type epoxy resin: 20% by mass toluene solution, modified polyamide resin solution: 15 Mass% N-methyl-2-pyrrolidone solution) prepare a thermosetting resin solution (mixed) of fluorine-containing resin.

The mixture of the obtained thermosetting resin solution was evaluated by the following evaluation method. Evaluation method of thermosetting resin solution mixing: The thermosetting resins (modified phenol novolak type epoxy resin, modified polyamide resin solution) were mixed and stirred so that the solid content ratio of the PTFE in the thermosetting resin solution (mixed) became 50% by mass. After mixing and stirring, let it stand for 1 day, and evaluate the amount of agglomerates at the bottom of the bottle according to the following evaluation criteria. These results are shown in Table 1 below. Evaluation criteria: ○: No agglomerates ×: There is agglomerate

[Preparation of thermosetting resin cured product of fluorine-containing resin] Film formation evaluation (make a 1 mil coating film on glass and dry it at 150°C for 10 minutes, then evaluate the film state) The modified phenol novolac type epoxy resin is cured at 200°C for 1 hour, and the modified polyamide is cured at 350°C for 30 minutes. Evaluation criteria: ○: Peelable from glass (thin film) ×: Unable to peel from glass (thin film)

(Evaluation of electrical characteristics) On the entire surface of one side of the polyimide film (thickness: 25μm), use an applicator to coat the mixture of the thermosetting resin solution (a fluorine-containing resin with a uniform thickness) so that the thickness after drying becomes about 25μm. The thermosetting resin composition) was dried at about 120°C for about 10 minutes, and then heated at 180°C for 60 minutes to harden, thereby preparing an evaluation sample. Using each evaluation sample obtained above, the evaluation of electrical properties (specific permittivity and permittivity tangent) was performed by the test method shown below. Specific permittivity and permittivity tangent are measured at 10 GHz using a vector network analyzer (Vector network analyzer) and a resonator in accordance with the test specifications of JIS C6481-1996. In addition, the modified phenol novolak type epoxy resin cured product (resin only) has a specific dielectric rate of 3.8 and a dielectric tangent of 0.050, and the modified polyamide acid cured product (resin only) has a specific dielectric rate of 3.2, The electric tangent is 0.020. These results are shown in Table 1 below.

As can be understood from the results in Table 1 above, compared with Comparative Examples 1 to 8 outside the scope of the present invention, the non-aqueous dispersion system of fluorine resin has a fine particle diameter, low viscosity, and storage stability in comparison with the comparative examples 1 to 8 outside the scope of the present invention. Excellent. When mixed with various resin materials (modified phenol novolak type epoxy resin, modified polyamide resin), the fluorine resin particles do not agglomerate, and the fluorine-containing resin of the non-aqueous dispersion of the present invention is used. The thermosetting resin composition and its cured products have been confirmed to exhibit low dielectric constant and low dielectric tangent. However, in Example 14, the measurement deviation of the specific dielectric constant and the dielectric tangent became large. It is considered that the film thickness of the thin film is not uniform. In contrast, if we look at Comparative Examples 1 to 8 outside the scope of the present invention, the content of fluorine resin particles in Comparative Examples 1 and 2 is relatively large and when the content of fluorine resin particles is relatively small. Comparative Examples 3 and 5 are fluorine-based additives or When the content of the compound represented by the formula (I) is large, the comparative example 4 does not contain fluorine-based additives or the compound represented by the formula (I), and the comparative examples 6 to 8 contain no amino formic acid In the case of ester structure polymers, it was confirmed that gelation or dispersibility was caused in these cases, and the effects of the present invention could not be exhibited. [Industrial availability]

The non-aqueous dispersion system of the fluorine resin of the present invention has a fine particle diameter, low viscosity, and excellent storage stability. When mixed with various resin materials, the fluorine resin particles do not agglomerate. The fluorine-containing resin of the non-aqueous dispersion of the present invention is used. The thermosetting resin composition and its cured product can achieve low dielectric constant and low dielectric tangent, and can suppress foreign matter that will hinder the wiring pattern or interlayer adhesion, so it can be preferably used in multilayer printed wiring boards. Insulating layers, adhesives for circuit boards, laminates for circuit boards, protective films, prepregs, etc.

Claims (7)

A non-aqueous dispersion of fluorine resin, characterized by containing at least 5 to 70% by mass of fluorine resin particles, 0.1 to 50% by mass relative to the mass of fluorine resin particles, containing at least fluorine-containing groups and lipophilicity Fluorine-based additives and/or compounds represented by the following formula (I), polymers with urethane structure, and non-aqueous solvents,

[In the above formula (I), l, m, and n are positive integers]. The non-aqueous dispersion of fluorine-based resin according to claim 1, wherein the aforementioned fluorine-based resin particles are selected from polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene, tetrafluoroethylene One or more fluorine resin particles from the group consisting of fluoroethylene-chlorotrifluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, and polychlorotrifluoroethylene. The non-aqueous dispersion of fluorine-based resin according to claim 1 or 2, wherein the average particle diameter of the fluorine-based resin in the non-aqueous dispersion after dispersion is 1 μm or less. For example, the non-aqueous dispersion of fluorine resin in any one of claims 1 to 3 has a viscosity of less than 300 mPa･s at a shear rate of 19.2/s. The non-aqueous dispersion of a fluorine-based resin according to any one of claims 1 to 4, wherein the aforementioned polymer having a urethane structure contains 0.1-30% by mass relative to the mass of the fluorine-based resin particles. A thermosetting resin composition containing a fluorine-based resin, which is characterized by containing at least a non-aqueous dispersion of fluorine-based resin particles according to any one of claims 1 to 5 and a resin composition containing a thermosetting resin. A fluorine-containing resin thermosetting resin cured product characterized by hardening the fluorine-containing resin thermosetting resin composition of claim 6.