Particles, compositions, molded articles, and low dielectric materials

Abstract

The present invention provides particles, compositions, molded articles, and low dielectric materials that can finely disperse fluororesin in a matrix resin. [Solution] Particles comprising a fluororesin, a compound (I) having multiple groups (A) represented by the following formula, and a compound (II) that can react with compound (I). [C1] JPEG2026094015000009.jpg31156 (In the formula, R 1 and R 2 These are either the same or different hydrogen atoms or organic groups, which may be bonded to each other to form a ring structure. Double lines, represented by solid and dashed lines, represent single or double bonds.

Description

Technical Field

[0001] The present disclosure relates to particles, compositions, molded articles, and low dielectric materials.

Background Art

[0002] In the development of low dielectric materials, a method of adding a fluororesin to a matrix resin such as polyimide has been studied (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, with the conventional method, it has been difficult to finely disperse the fluororesin in the matrix resin.

[0005] An object of the present disclosure is to provide particles, compositions, molded articles, and low dielectric materials capable of finely dispersing a fluororesin in a matrix resin.

Means for Solving the Problems

[0006] The present disclosure (1) is particles containing a fluororesin, a compound (I) having a plurality of groups (A) represented by the following formula, and a compound (II) capable of reacting with the compound (I).

Chemical Formula

[0007] Disclosure (2) is the particle according to Disclosure (1), wherein group (A) is an oxazoline group and compound (I) is an oxazoline compound.

[0008] Disclosure (3) is the particle according to Disclosure (2), wherein the oxazoline compound is an oxazoline group-containing polymer.

[0009] The present disclosure (4) is a particle according to the present disclosure (3) wherein the oxazoline group-containing polymer comprises at least one selected from the group consisting of repeating units derived from 2-vinyl-2-oxazoline and repeating units derived from 2-isopropenyl-2-oxazoline.

[0010] Disclosure (5) is a particle according to any one of Disclosures (1) to (4), wherein compound (II) is a compound having at least one selected from the group consisting of a carboxyl group, a mercapto group, and a hydroxyl group.

[0011] Disclosure (6) is a particle according to any one of Disclosures (1) to (5), wherein compound (II) is a compound having a carboxyl group.

[0012] Disclosure (7) is a particle according to any one of Disclosures (1) to (6), wherein compound (II) is at least one selected from the group consisting of polyamic acid, polyacrylic acid, and epoxy resin.

[0013] The present disclosure (8) is a particle according to any of the present disclosures (1) to (7), wherein the compound (II) is a polyamic acid.

[0014] Disclosure (9) is a particle according to any one of Disclosures (1) to (8), wherein the fluororesin is at least one selected from the group consisting of tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer, and polytetrafluoroethylene.

[0015] Disclosure (10) includes the particles described in any of Disclosures (1) to (9), The composition comprises compound (III), which is at least one compound selected from the group consisting of polyimide, liquid crystal polymer, polyphenylene ether, polycarbonate, polyphenylene sulfide, and epoxy resin.

[0016] Disclosure (11) is the composition according to Disclosure (10), wherein compound (III) is a polyimide.

[0017] Disclosure (12) is the composition according to Disclosure (10) or (11), wherein the particles form an island structure and the compound (III) forms a sea island structure.

[0018] Disclosure (13) is a composition according to any one of Disclosures (10) to (12), wherein the content of the particles is 0.1 to 50% by mass.

[0019] This disclosure (14) describes how, in image analysis by optical microscopy, five aggregates with large areas are selected from top to bottom, and the average area of ​​these aggregates is calculated as X μm. 2 The composition is one of the compositions according to any of (10) to (13) of this disclosure, wherein when the content of the particles is Y by mass%, X / Y is 250 or less.

[0020] Disclosure (15) is a molded article of the particles described in any of Disclosures (1) to (9) and / or the compositions described in any of Disclosures (10) to (14).

[0021] Disclosure (16) is a low-dielectric material comprising the particles described in any of Disclosures (1) to (9) and / or the compositions described in any of Disclosures (10) to (14). [Effects of the Invention]

[0022] According to this disclosure, it is possible to provide particles, compositions, molded articles, and low dielectric materials that can finely disperse fluororesin in a matrix resin. [Brief explanation of the drawing]

[0023] [Figure 1] Microscopic image of the composite film of Example 1. [Modes for carrying out the invention]

[0024] In this specification, "organic group" means a group containing one or more carbon atoms, or a group formed by removing one hydrogen atom from an organic compound. Examples of such "organic groups" are: Alkyl molecules which may have one or more substituents, An alkenyl group which may have one or more substituents, An alkynyl group which may have one or more substituents, A cycloalkyl group which may have one or more substituents, A cycloalkenyl group which may have one or more substituents, A cycloalkadienyl group which may have one or more substituents, An aryl group which may have one or more substituents, An aralkyl group which may have one or more substituents, A non-aromatic heterocyclic group which may have one or more substituents, A heteroaryl group which may have one or more substituents, Cyano group, formyl group, RaO-, RaCO-, RaSO2-, RaCOO-, RaNRaCO-, RaCONRa-, RaOCO-, RaOSO2-, and RaNRbSO2- (In these formulas, Ra is independent of, Alkyl molecules which may have one or more substituents, An alkenyl group which may have one or more substituents, An alkynyl group which may have one or more substituents, A cycloalkyl group which may have one or more substituents, A cycloalkenyl group which may have one or more substituents, A cycloalkadienyl group which may have one or more substituents, An aryl group which may have one or more substituents, An aralkyl group which may have one or more substituents, A non-aromatic heterocyclic group which may have one or more substituents, A heteroaryl group which may have one or more substituents, Rb is independently H or an alkyl group which may have one or more substituents. It includes. The above organic group is preferably an alkyl group which may have one or more substituents.

[0025] The following provides a detailed explanation of this disclosure.

[0026] <Particle> The particles of this disclosure include a fluororesin, a compound (I) having a plurality of groups (A) represented by the following formula, and a compound (II) that can react with compound (I). [ka] (In the formula, R 1 and R 2 These are either the same or different hydrogen atoms or organic groups, which may be bonded to each other to form a ring structure. Double lines, represented by solid and dashed lines, represent single or double bonds.

[0027] In the particles of this disclosure, group (A) in compound (I) reacts with the surface functional groups of the fluororesin, resulting in the fluororesin being coated with compound (I). Then, another group (A) in compound (I) reacts with compound (II), resulting in the outside of compound (I) being coated with compound (II). Therefore, by selecting compound (II), which has a high affinity for the matrix resin, aggregation of the fluororesin is suppressed, and the particles of this disclosure containing the fluororesin can be finely dispersed in the matrix resin. As a result, in compositions containing the particles of this disclosure, it is possible to obtain dielectric constant and dielectric loss tangent suitable for low dielectric materials, as well as good mechanical properties and appearance.

[0028] In the particles of this disclosure, it is generally believed that the above-mentioned coating structure (a structure in which the fluororesin is coated with compound (I) and the outside is coated with compound (II)) is formed by the reaction of group (A) with the surface functional groups of the fluororesin or compound (II) of the fluororesin. However, a reaction is not necessarily required, and the above-mentioned coating structure may be formed by physical actions such as adsorption. Furthermore, the structure does not necessarily have to consist solely of the coating structure described above; for example, there may be portions in which the fluororesin is directly coated with compound (II). Furthermore, in this specification, covering does not necessarily mean that the entire surface is covered; there may be exposed areas.

[0029] Examples of fluororesins include polytetrafluoroethylene [PTFE], tetrafluoroethylene [TFE] / perfluoro(alkyl vinyl ether) [PAVE] copolymer [PFA], TFE / hexafluoropropylene [HFP] copolymer [FEP], ethylene [Et] / TFE copolymer [ETFE], Et / TFE / HFP copolymer [EFEP], polychlorotrifluoroethylene [PCTFE], chlorotrifluoroethylene [CTFE] / TFE copolymer, CTFE / TFE / PAVE copolymer, Et / CTFE copolymer, and the like.

[0030] As the fluororesin, perfluororesin is preferred, and at least one selected from the group consisting of polytetrafluoroethylene [PTFE], tetrafluoroethylene [TFE] / perfluoro(alkyl vinyl ether) [PAVE] copolymer [PFA], and tetrafluoroethylene [TFE] / hexafluoropropylene [HFP] copolymer [FEP] is preferred, at least one selected from the group consisting of PFA and FEP is more preferred, and FEP is even more preferred.

[0031] PTFE may be a TFE homopolymer consisting only of tetrafluoroethylene (TFE) units, or it may be a modified PTFE containing TFE units and modified monomer units based on modified monomers copolymerizable with TFE.

[0032] The modified monomer is not particularly limited as long as it can copolymerize with TFE, and examples include perfluoroolefins such as hexafluoropropylene [HFP]; chlorofluoroolefins such as chlorotrifluoroethylene [CTFE]; hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride [VdF]; perfluorovinyl ethers; perfluoroalkyl allyl ethers; (perfluoroalkyl)ethylene; and ethylene. Furthermore, one or more modified monomers may be used.

[0033] The perfluorovinyl ether is not particularly limited; for example, the following general formula (1) CF2 = CF - ORf (1) Examples include perfluorounsaturated compounds represented by the formula (wherein Rf represents a perfluoroorganic group). In this specification, the term "perfluoroorganic group" means an organic group in which all hydrogen atoms bonded to a carbon atom are replaced with fluorine atoms. The perfluoroorganic group may have an ether oxygen.

[0034] Examples of perfluorovinyl ethers include perfluoro(alkyl vinyl ether) [PAVE], in which Rf in general formula (1) represents a perfluoroalkyl group having 1 to 10 carbon atoms. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 5.

[0035] Examples of perfluoroalkyl groups in PAVE include perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, and perfluorohexyl groups, but perfluoro(propyl vinyl ether) [PPVE] in which the perfluoroalkyl group is a perfluoropropyl group is preferred.

[0036] As perfluorovinyl ethers, in general formula (1), Rf is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, and Rf is given by the following formula:

[0037] [ka]

[0038] (In the formula, m represents an integer from 0 to 4.) The base is represented by the following formula, where Rf is:

[0039] [ka]

[0040] Examples include the base represented by (wherein n represents an integer from 1 to 4).

[0041] (Perfluoroalkyl)ethylene is not particularly limited and examples include (perfluorobutyl)ethylene [PFBE], (perfluorohexyl)ethylene [PFHE], and (perfluorooctyl)ethylene.

[0042] The modified monomer in modified PTFE is preferably at least one selected from the group consisting of HFP, CTFE, VdF, PPVE, PFBE, and ethylene. More preferably, it is at least one selected from the group consisting of PPVE, HFP, and CTFE.

[0043] In modified PTFE, the content of the above-mentioned modified monomer units is preferably in the range of 0.00001 to 1.0 mass%. The lower limit of the content of modified monomer units is more preferably 0.0001 mass%, even more preferably 0.001 mass%, even more preferably 0.005 mass%, especially preferably 0.010 mass%, and particularly preferably 0.030 mass%. The upper limit of the content of modified monomer units is preferably 0.90 mass%, more preferably 0.50 mass%, even more preferably 0.40 mass%, and even more preferably 0.30 mass%. In this specification, a modified monomer unit means a part of the molecular structure of modified PTFE that is derived from a modified monomer.

[0044] PTFE preferably has a melting point of 324 to 360°C. The melting point of PTFE refers to the first melting point. The above first melting point is the temperature corresponding to the maximum value in the heat of fusion curve when PTFE that has not been heated to a temperature above 300°C is heated at a rate of 10°C / min using a differential scanning calorimeter (DSC).

[0045] PTFE is preferably given a standard specific gravity (SSG) of 2.130 to 2.280. More preferably, the standard specific gravity is 2.220 or less, and even more preferably 2.200 or less. It is also preferably 2.140 or more, and even more preferably 2.150 or more. The SSG is measured using a sample molded in accordance with ASTM D 4895-89 and measured by the water displacement method in accordance with ASTM D-792.

[0046] PTFE preferably has non-melting secondary processability. The non-melting secondary processability means the property that the melt flow rate cannot be measured at a temperature higher than the crystallization melting point in accordance with ASTM D-1238 and D-2116.

[0047] Although PFA is not particularly limited, a copolymer in which the molar ratio of TFE units to PAVE units (TFE units / PAVE units) is 70 / 30 or more and less than 99 / 1 is preferable. A more preferable molar ratio is 70 / 30 or more and 98.9 / 1.1 or less, and an even more preferable molar ratio is 80 / 20 or more and 98.9 / 1.1 or less. The above PFA preferably has monomer units derived from monomers copolymerizable with TFE and PAVE in an amount of 0.1 to 10 mol% (a copolymer in which the total of TFE units and PAVE units is 90 to 99.9 mol%), more preferably 0.1 to 5 mol%, and particularly preferably 0.2 to 4 mol%.

[0048] Monomers copolymerizable with TFE and PAVE include HFP, formula (I): CZ 1 Z 2 =CZ 3 (CF2) n Z 4 (where Z 1 , Z 2 and Z 3 are the same or different and represent a hydrogen atom or a fluorine atom, and Z 4 represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 2 to 10.) vinyl monomers represented by, and formula (II): CF2=CF-OCH2-Rf 1 (where Rf 1 represents a perfluoroalkyl group having 1 to 5 carbon atoms.) alkyl perfluorovinyl ether derivatives represented by, formula (X): CZ 5 Z 6 =CZ 7 -CZ 8 Z 9 -O-Rf 4 (where Z 5 , Z 6 and Z 7 are the same or different and represent a hydrogen atom, a chlorine atom or a fluorine atom, and Z 8and Z 9 Rf represents a hydrogen atom or a fluorine atom. 4 CH2=CFCF2-O-Rf 4 CF2 = CFCF2 - O - Rf 4 (Perfluoroalkyl allyl ether), CF2=CFCH2-O-Rf 4 CH2=CHCF2-O-Rf 4 (In the formula, Rf 4 Examples of which are the same as in formula (X) above include: Furthermore, monomers copolymerizable with TFE and PAVE include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and acid anhydrides of unsaturated dicarboxylic acids such as itaconic acid, itaconic anhydride, citraconic anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride.

[0049] PFA preferably has a melting point of 180 to less than 324°C, more preferably 230 to 320°C, and even more preferably 280 to 320°C. The melting point of PFA is the temperature corresponding to the maximum value in the heat of fusion curve when the temperature is increased at a rate of 10°C / min using a differential scanning calorimeter (DSC).

[0050] While not particularly limited, copolymers with a molar ratio of TFE units to HFP units (TFE units / HFP units) of 70 / 30 or more and less than 99 / 1 are preferred. A more preferred molar ratio is 70 / 30 or more and 98.9 / 1.1 or less, and an even more preferred molar ratio is 80 / 20 or more and 98.9 / 1.1 or less. The above FEP preferably contains 0.1 to 10 mol% monomer units derived from monomers copolymerizable with TFE and HFP (a copolymer in which TFE units and HFP units total 90 to 99.9 mol%), more preferably 0.1 to 5 mol%, and particularly preferably 0.2 to 4 mol%.

[0051] Monomers copolymerizable with TFE and HFP include PAVE, monomers represented by formula (X), and alkyl perfluorovinyl ether derivatives represented by formula (II). Furthermore, monomers copolymerizable with TFE and HFP include unsaturated monocarboxylic acids such as itaconic acid, itaconic anhydride, citraconic anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride, as well as unsaturated dicarboxylic acids and acid anhydrides of unsaturated dicarboxylic acids.

[0052] The melting point of FEP is preferably 150 to less than 324°C, more preferably 200 to 320°C, and even more preferably 240 to 320°C. The melting point of FEP is the temperature corresponding to the maximum value in the heat of fusion curve when the temperature is increased at a rate of 10°C / min using a differential scanning calorimeter (DSC).

[0053] As for ETFE, copolymers in which the molar ratio of TFE units to ethylene units (TFE units / ethylene units) is 20 / 80 or more and 90 / 10 or less are preferred. A more preferred molar ratio is 37 / 63 or more and 85 / 15 or less, and an even more preferred molar ratio is 38 / 62 or more and 80 / 20 or less. ETFE may also be a copolymer consisting of TFE, ethylene, and monomers copolymerizable with TFE and ethylene. The above ETFE preferably contains 0.1 to 10 mol% monomer units derived from monomers copolymerizable with TFE and ethylene (a copolymer in which the total of TFE units and ethylene units is 90 to 99.9 mol%), more preferably 0.1 to 5 mol%, and particularly preferably 0.2 to 4 mol%.

[0054] Monomers copolymerizable with TFE and ethylene include the following formula CH2=CX 1 Rf 2 CF2=CFRf 2 CF2 = CFORf 2 CH2=C(Rf 2 )2(where, X 1 is a hydrogen atom or a fluorine atom, Rf 2represents a fluoroalkyl group which may contain an ether bond. Examples include monomers represented by ) and monomers represented by formula (X), among which CF2=CFRf 2 CF2 = CFORf 2 and CH2=CX 1 Rf 2 A fluorine-containing vinyl monomer represented by formula (X) is preferred, and HFP, CF2=CF-ORf 3 (In the formula, Rf 3 ) represents a perfluoroalkyl group with 1 to 5 carbon atoms. Perfluoro(alkyl vinyl ether), represented as CF2=CF-CF2-O-Rf 4 (In the formula, Rf 4 represents a perfluoroalkyl group having 1 to 5 carbon atoms. ) represents perfluoroalkyl allyl ethers and Rf 2 CH2=CX is a fluoroalkyl group with 1 to 8 carbon atoms. 1 Rf 2 More preferably, a fluorine-containing vinyl monomer represented by is preferred. Other monomers copolymerizable with TFE and ethylene include unsaturated monocarboxylic acids such as itaconic acid, itaconic anhydride, citraconic anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride, as well as unsaturated dicarboxylic acids and acid anhydrides of unsaturated dicarboxylic acids.

[0055] ETFE preferably has a melting point of 140 to less than 324°C, more preferably 160 to 320°C, and even more preferably 195 to 320°C. The melting point of ETFE is the temperature corresponding to the maximum value in the heat of fusion curve when the temperature is increased at a rate of 10°C / min using a differential scanning calorimeter (DSC).

[0056] The content of each monomer unit of the polymer described above can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis depending on the type of monomer.

[0057] Fluororesins have a main chain with 10 carbon atoms. 6Each molecule may have 100 to 2000 terminal groups. Typical terminal groups include -COF and -COOH, and the above number represents the total number of these groups.

[0058] The number of end groups can be measured by infrared spectroscopy. Specifically, first, a film with a thickness of 0.25 to 0.3 mm is produced by melt extrusion molding of fluororesin. This film is analyzed by Fourier transform infrared spectroscopy to obtain the infrared absorption spectrum of the fluororesin, and a difference spectrum is obtained from this spectrum to the base spectrum where no end groups are present due to complete fluorination. From the absorption peaks of specific end groups appearing in this difference spectrum, the number of carbon atoms in the fluororesin can be determined according to the following formula (A). 6 Calculate the terminal base N per unit. N = I × K / t (A) I: Absorbance K: Correction coefficient t: Film thickness (mm)

[0059] In the particles of this disclosure, the fluororesin content is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and also preferably 99.98% by mass or less, more preferably 99.90% by mass or less, and even more preferably 99.80% by mass or less.

[0060] Compound (I) is not particularly limited as long as it has multiple groups (A), and may be a polymer, an oligomer, or any other low-molecular-weight compound.

[0061] The low molecular weight compound (I) is preferably a compound containing a benzene ring and a naphthalene ring. The structure of the polymer or oligomer compound (I) is not particularly limited and may or may not contain a benzene ring and a naphthalene ring.

[0062] In base (A), R 1 and R 2 The organic groups are as described above.

[0063] R1 and R 2 Examples of ring structures formed by the bonding of these elements include cyclohexane rings and benzene rings.

[0064] Because it can react with carboxyl groups present on the surface of many fluororesins and form stable amide ester bonds, R 1 and R 2 It is preferable that the group is hydrogen, and the double lines, represented by solid and dashed lines, are preferably single bonds. That is, it is preferable that group (A) is an oxazoline group and compound (I) is an oxazoline compound.

[0065] Specific examples of oxazoline compounds include low molecular weight oxazoline compounds such as 2-vinyl-2-oxazoline, 4-methyl-2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4-ethyl-2-vinyl-2-oxazoline, 5-ethyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 4,4-diethyl-2-vinyl-2-oxazoline, 4,5-dimethyl-2-vinyl-2-oxazoline, 4,5-diethyl-2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 4-methyl-2-isopropenyl-2-oxazoline, 5-methyl-2-isopropenyl-2-oxazoline, 4-ethyl- Examples include 2-isopropenyl-2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline, 4,4-diethyl-2-isopropenyl-2-oxazoline, 4,5-dimethyl-2-isopropenyl-2-oxazoline, 4,5-diethyl-2-isopropenyl-2-oxazoline, 1,3-phenylbisoxazoline [1,3-PBO], 1,4-phenylbisoxazoline [1,4-PBO], etc. Examples of polymer oxazoline compounds include homopolymers of the oxazoline compounds of the low molecular weight compounds mentioned above, such as poly-2-vinyl-2-oxazoline [Pvozo] and poly-2-isopropenyl-2-oxazoline [Pipovo], as well as copolymers of the oxazoline compounds of the low molecular weight compounds mentioned above with other monomers. These may be used alone or in combination of two or more.

[0066] From the standpoint of readily reacting with fluororesins and compound (II), the oxazoline compound is preferably an oxazoline group-containing polymer. From a similar viewpoint, the oxazoline group-containing polymer preferably contains at least one selected from the group consisting of repeating units derived from 2-vinyl-2-oxazoline and repeating units derived from 2-isopropenyl-2-oxazoline, more preferably at least one selected from the group consisting of Pvozo and Pipovo, and even more preferably Pvozo. The oxazoline group-containing polymer is also preferably a copolymer of 2-vinyl-2-oxazoline or 2-isopropenyl-2-oxazoline with another monomer, more preferably a copolymer of 2-vinyl-2-oxazoline or 2-isopropenyl-2-oxazoline with an acrylic monomer, and even more preferably a copolymer of 2-isopropenyl-2-oxazoline with an acrylic monomer.

[0067] In an oxazoline group-containing polymer, the oxazoline group may be introduced at the terminal, introduced in the side chain, or introduced in both the terminal and the side chain, but it is preferable that it is introduced at least at the terminal.

[0068] The oxazoline group-containing polymer may have a branched structure. When the oxazoline group-containing polymer has a branched structure, the oxazoline group may be present in the main chain, in the branched chain, or in both the main chain and the branched chain, but it is preferable that it is present in at least the main chain, and more preferably at the ends of the main chain.

[0069] The number-average molecular weight (Mn) of the oxazoline group-containing polymer is preferably 2,000 or more, more preferably 5,000 or more, even more preferably 10,000 or more, and also preferably 400,000 or less, more preferably 300,000 or less, and even more preferably 200,000 or less. The weight-average molecular weight (Mw) of the oxazoline group-containing polymer is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 50,000 or more, and also preferably 400,000 or less, more preferably 300,000 or less, and even more preferably 200,000 or less. The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of oxazoline group-containing polymers can be determined in accordance with the PS-converted average molecular weight obtained by GPC measurement.

[0070] Specific examples of compounds other than oxazoline compounds (I) include 1,4-bis(benzoxazole-2-yl)naphthalene [1,4-BBN].

[0071] In compound (I), there may be multiple groups (2 or more) of group (A), but preferably there are 10 or more, and more preferably 100 or more, in order to facilitate reaction with fluororesin and compound (II). There is no particular upper limit, but it is usually 1000 or less.

[0072] In the particles of this disclosure, the content of compound (I) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and also preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0073] Compound (II) can be any compound that can react with compound (I), and can be appropriately selected according to the matrix resin used. However, from the standpoint of readily reacting with compound (I), it is preferable that compound (II) has at least one selected from the group consisting of a carboxyl group, a mercapto group, and a hydroxyl group, more preferably a compound having at least one selected from the group consisting of a carboxyl group and a hydroxyl group, and even more preferably a compound having a carboxyl group. Furthermore, the hydroxyl group is preferably a phenolic hydroxyl group such as a phenol group, a catechol group, or a gallol group. Compound (II) may be used alone or in combination of two or more compounds.

[0074] The compound having a carboxyl group may be a compound having one carboxyl group (such as a carboxylic acid) or a compound having multiple carboxyl groups (such as a dicarboxylic acid or tricarboxylic acid). Examples of compounds having a carboxyl group include polyamic acid, polyacrylic acid, formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, phthalic acid, citric acid, isocitric acid, aconitic acid, trimellitic acid, citraconic acid, melitic acid, and ethylenediaminetetraacetic acid. Also, saturated fatty acids (e.g., caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid) and unsaturated fatty acids (e.g., oleic acid, linoleic acid, linolenic acid) are also examples. Furthermore, the compound having a carboxyl group may be a liquid crystal polymer having a carboxyl group or an epoxy resin having a carboxyl group. Among these, polymers having a carboxyl group (carboxyl group-containing polymers) are preferred, polyamic acid, polyacrylic acid, and liquid crystal polymers having a carboxyl group are more preferred, and polyamic acid is even more preferred.

[0075] When the compound having a carboxyl group is a carboxyl group-containing polymer, its number-average molecular weight (Mn) is preferably 2,000 or more, more preferably 5,000 or more, even more preferably 10,000 or more, and also preferably 400,000 or less, more preferably 300,000 or less, and even more preferably 200,000 or less. The number-average molecular weight (Mn) of carboxyl group-containing polymers can be determined according to the PS-converted average molecular weight obtained by GPC measurement.

[0076] Compounds having a mercapto group may have one mercapto group or multiple mercapto groups. Examples of compounds having a mercapto group include thiophenol, methanethiol, ethanethiol, and propanethol. Among these, aromatic compounds having a mercapto group are preferred, and thiophenol is more preferred.

[0077] Compounds having a hydroxyl group (preferably a phenolic hydroxyl group) may have one hydroxyl group or multiple hydroxyl groups. Examples of compounds having a hydroxyl group include compounds having at least one selected from the group consisting of a phenol group, a catechol group, and a gallol group, polymers having a hydroxyl group (hydroxyl group-containing polymers), phenol, methanol, ethanol, and the like. Compounds having a hydroxyl group may also be epoxy resins having a hydroxyl group or epoxy resins having a hydroxyl group and an aromatic ring. Among these, aromatic compounds having a hydroxyl group are preferred, and epoxy resins having a hydroxyl group and an aromatic ring, phenolic resins, polyphenylene ethers, and phenol are more preferred.

[0078] When the compound having a hydroxyl group is a hydroxyl group-containing polymer, its number-average molecular weight (Mn) is preferably 2,000 or more, more preferably 5,000 or more, even more preferably 10,000 or more, and also preferably 400,000 or less, more preferably 300,000 or less, and even more preferably 200,000 or less. The number-average molecular weight (Mn) of hydroxyl group-containing polymers can be determined according to the PS-converted average molecular weight obtained by GPC measurement.

[0079] Compound (II) may be a compound having a carboxyl group and a mercapto group, such as 4-mercaptobenzoic acid; a compound having a carboxyl group and a hydroxyl group, such as lactic acid; a compound having a mercapto group and a hydroxyl group, such as p-mercaptophenol; or a compound having a carboxyl group, a mercapto group, and a hydroxyl group, such as 3-mercapto-2-hydroxypropanoic acid.

[0080] The liquid crystal polymer and epoxy resin of compound (II) can be the same as those used for compound (III) described later.

[0081] Compound (II) is preferably at least one selected from the group consisting of polyamic acid, polyacrylic acid, and epoxy resin, and more preferably polyamic acid.

[0082] In the particles of this disclosure, the content of compound (II) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and also preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0083] The particles of this disclosure may further contain additives. Common additives used in resins include crosslinking agents, antistatic agents, heat stabilizers, foaming agents, foaming nucleating agents, antioxidants, surfactants, photopolymerization initiators, anti-abrasion agents, and surface modifiers.

[0084] The method for producing the particles of this disclosure is not particularly limited, and they can be produced by mixing a fluororesin and compound (I), then adding compound (II) and mixing further.

[0085] <Composition> The compositions of the present disclosure comprise the particles of the present disclosure and compound (III), which is at least one selected from the group consisting of polyimide, liquid crystal polymer, polyphenylene ether, polycarbonate, polyphenylene sulfide, and epoxy resin.

[0086] In the composition of the present disclosure, the particles of the present disclosure are finely dispersed in compound (III), which is a matrix resin. Therefore, it is possible to obtain a dielectric constant and dielectric loss tangent suitable for a low dielectric material, as well as good mechanical properties and appearance.

[0087] The compositions of the present disclosure may form a sea-island structure in which the particles of the present disclosure form islands and compound (III) form a sea. When such a sea-island structure is formed, the content of the particles of the present disclosure in the compositions of the present disclosure is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, and also preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. From a similar viewpoint, in the compositions of the present disclosure, the content of compound (III) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and also preferably 99.9% by mass or less, more preferably 99% by mass or less, and even more preferably 97% by mass or less.

[0088] As compound (III), at least one selected from the group consisting of polyimide, liquid crystal polymer, polyphenylene ether, polycarbonate, polyphenylene sulfide, and epoxy resin can be used. Among these, polyimide is preferred. The liquid crystal polymer and epoxy resin of compound (III) may be the same as or different from those of compound (II).

[0089] It is preferable that compound (III) is produced from compound (II), that is, that compound (II) is a precursor of compound (III). This ensures good compatibility between the particles of this disclosure and compound (III). Examples of such combinations include a form in which compound (II) is a polyamic acid and compound (III) is a polyimide. In addition, in the composition of the Disclosure, compound (II) in the particles of the Disclosure may be partially or entirely replaced by compound (III).

[0090] The polyimide is not particularly limited as long as it has imide bonds in its molecule, and any general type can be used, but aromatic polyimides are preferred. Furthermore, the polyimide may be thermoplastic or thermosetting.

[0091] The glass transition temperature of polyimide is preferably 210°C or higher, more preferably 280°C or higher, and also preferably 430°C or lower, more preferably 360°C or lower.

[0092] The liquid crystal polymer is not particularly limited, but it may be a polymer with a liquid crystal temperature (i.e., melting point) of 180°C to 380°C, and a thermotropic liquid crystal polymer that becomes a liquid crystal state such as a nematic when heated is preferred, for example, Type I liquid crystal polymers (such as biphenol / benzoic acid / parahydroxybenzoic acid (POB) copolymers) Type II liquid crystal polymers (such as hydroxynaphthoate (HNA) / POB copolymers) Type III liquid crystal polymers (such as POB / ethylene terephthalate copolymers) These are some examples. In particular, from the viewpoint of mixing temperature and liquid crystal transition temperature, at least one selected from the group consisting of type I liquid crystal polymers and type II liquid crystal polymers is preferred, and type II liquid crystal polymers are more preferred.

[0093] The melting point of the liquid crystal polymer is preferably 280°C or higher, more preferably 310°C or higher, and also preferably 380°C or lower, more preferably 350°C or lower.

[0094] The polyphenylene ether is not particularly limited as long as it is polymerized using 2,6-xylenol as a raw material, and any common type can be used. The polyphenylene ether may also be a modified polyphenylene ether.

[0095] The glass transition temperature of polyphenylene ether is preferably 210°C or higher, more preferably 270°C or higher, and also preferably 430°C or lower, more preferably 370°C or lower.

[0096] As for the polycarbonate, there are no particular limitations as long as it has carbonate groups in its molecule; general types can be used.

[0097] The glass transition temperature of polycarbonate is preferably 120°C or higher, more preferably 150°C or higher, and also preferably 300°C or lower, more preferably 270°C or lower.

[0098] As the polyphenylene sulfide, for example, a resin having structural units represented by the following formula can be used. The proportion of these structural units is preferably 70 mol% or more. -(Ph-S)- In the formula, Ph represents a phenylene group, and examples of such phenylene groups include p-phenylene, m-phenylene, o-phenylene, alkyl-substituted phenylene, phenyl-substituted phenylene, halogen-substituted phenylene, amino-substituted phenylene, amide-substituted phenylene, p,p'-diphenylene sulfone, p,p'-biphenylene, and p,p'-biphenylene ether. Among these, p-phenylene is preferred.

[0099] The melting point of polyphenylene sulfide is preferably 240°C or higher, more preferably 270°C or higher, and also preferably 380°C or lower, more preferably 350°C or lower.

[0100] Common epoxy resins can be used, including phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin, bisphenol novolac type epoxy resin, biphenol novolac type epoxy resin, bisphenol type epoxy resin, biphenyl type epoxy resin, triphenolmethane type epoxy resin, tetraphenolethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, and others.

[0101] The glass transition temperature of the epoxy resin is preferably 100°C or higher, more preferably 120°C or higher, and also preferably 300°C or lower, more preferably 270°C or lower.

[0102] The glass transition temperatures of polyimide, polyphenylene ether, polycarbonate, and epoxy resin can be determined using a differential scanning calorimeter (Mettler-Toledo, DSC822e). A DSC curve is obtained by heating 10 mg of the sample at 10°C / min, and the temperature is found at the midpoint of the intersection of the baseline extensions of the DSC curve before and after the second-order transition and the tangent line at the inflection point of the DSC curve. The melting point of liquid crystal polymers, polyphenylene sulfide, is the temperature corresponding to the maximum value in the heat of fusion curve when the temperature is increased at a rate of 10°C / min using a differential scanning calorimeter (DSC).

[0103] The compositions of this disclosure may further contain additives. These additives may be those described in relation to the particles of this disclosure.

[0104] The compositions of this disclosure may be solid or liquid at 25°C, but are preferably solid.

[0105] The compositions of this disclosure may be dispersions comprising particles of this disclosure and a solvent. The solvent is not particularly limited and may be water, or organic solvents such as alcohols, ethers, or pyrrolidones. In this case, the content of the particles of the Dispersion of the Disclosure is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 10% by mass or more, and also preferably 99% by mass or less, more preferably 80% by mass or less, and even more preferably 50% by mass or less.

[0106] In the image analysis of the composition observed with an optical microscope, five aggregates with large areas are selected from the top and their average area is X μm. 2 When the content of the particles is Y by mass%, the value of X / Y, i.e., X divided by Y, is preferably 250 or less, more preferably 200 or less, and even more preferably 150 or less. The lower limit of X / Y is not particularly limited, and the smaller the better, but it is usually around 10. The area of ​​the aggregated mass is measured by the method described in the examples below.

[0107] The compositions disclosed herein are not particularly limited in their applications. For example, electrical and electronic components such as connectors, sockets, relay components, coil bobbins, optical pickups, oscillators, printed circuit boards, and computer-related components; semiconductor manufacturing process-related components such as IC trays and wafer carriers; household electrical appliance components such as VTRs, televisions, irons, air conditioners, stereos, vacuum cleaners, refrigerators, rice cookers, and lighting fixtures; lighting fixture components such as lamp reflectors and lamp holders; audio product components such as compact discs and speakers; communication equipment components such as optical cable ferrules, telephone components, facsimile components, and modems; copier-related components such as separation claws and heater holders; and impellers. It can be used in a wide range of applications, including mechanical parts such as fans, gears, bearings, motor parts and cases, automotive mechanical parts, engine parts, engine compartment parts, electrical parts, interior parts, cooking utensils such as microwave cooking pots and heat-resistant tableware, thermal insulation and soundproofing materials such as flooring and wall materials, building materials such as beams and columns, roofing materials, or civil engineering and construction materials, aircraft, spacecraft and space equipment parts, radiation facility components such as nuclear reactors, marine facility components, cleaning jigs, optical instrument parts, valves, pipes, nozzles, filters, membranes, medical equipment parts and medical materials, sensor parts, sanitary fixtures, and more.

[0108] <Molded body> The molded articles of this disclosure are obtained by molding the particles and / or compositions of this disclosure. The molding method is not particularly limited, and conventional methods such as injection molding, blow molding, inflation molding, and vacuum / pressure molding can be used.

[0109] The molded articles of this disclosure are suitably used as dielectric materials, particularly low-dielectric substrate materials (e.g., insulating materials). In this specification, "low dielectric substrate material" means a material having a relative permittivity of 5.0 or less at 25°C and 20GHz, and a dielectric loss tangent of 0.020 or less at 25°C and 20GHz. A material having a relative permittivity of 4.0 or less at 25°C and 20GHz, and a dielectric loss tangent of 0.015 or less at 25°C and 20GHz is more preferred, and a material having a relative permittivity of 3.6 or less at 25°C and 20GHz, and a dielectric loss tangent of 0.010 or less at 25°C and 20GHz is even more preferred.

[0110] When the molded article of this disclosure is used as a dielectric material, there are no particular limitations on its application, and it can be used in a wide range of applications similar to those described in the composition of this disclosure.

[0111] The molded body of this disclosure may be laminated with a metal foil to form a laminate. Such a laminate is suitably used as a circuit board, particularly a printed circuit board, a multilayer circuit board (multilayer substrate), or a high-frequency circuit board.

[0112] A high-frequency circuit board is a circuit board capable of operating in the high-frequency band. The high-frequency band may be 1 GHz or higher, preferably 3 GHz or higher, and more preferably 5 GHz or higher. There is no particular upper limit, but it may be 100 GHz or lower.

[0113] Examples of metals used for metal foil include aluminum, iron, silver, gold, and ruthenium. Alloys of these metals can also be used. Among these, copper is preferred. Rolled copper, electrolytic copper, and other types of copper can be used.

[0114] The thickness of the laminate is preferably 10 μm to 1000 μm. Furthermore, in the laminate, the thickness of the molded article of this disclosure is preferably 1 μm to 100 μm. Furthermore, while it is preferable that the laminate and molded body be in the form of a sheet with a substantially uniform thickness, if there are parts with different thicknesses, the thickness should be measured at 10 equally spaced points along the longitudinal direction and the average of these measurements should be used.

[0115] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Examples]

[0116] The present disclosure will now be further described with reference to examples, but the present disclosure is not limited to these examples.

[0117] The materials used in the examples are as follows. Note that compound (II), PAA, was used not only for coating the fluororesin but also as a raw material for compound (III), PI. (Fluororesin) FEP (TFE units / HFP units (molar ratio) = 88.0 / 12.0, melting point: 260℃) PFA (TFE units / PPVE units (molar ratio) = 97.9 / 2.1, melting point: 300℃) (Compound (I) (Oxazoline compound)) Pvozo (poly-2-vinyl-2-oxazoline, number-average molecular weight: 48,000, weight-average molecular weight: 110,000) WS300 (Epocross WS300, manufactured by Nippon Shokubai Co., Ltd., a copolymer of 2-isopropenyl-2-oxazoline and acrylic acid ester, number average molecular weight: 40,000, weight average molecular weight: 120,000) (Compound (II)) PAA (Polyamic Acid) (Poly(3,3′,4,4′-biphenyltetracarboxylic dianhydride-co-1,4-phenylenediamine), number-average molecular weight: 50,000) (Compound (III)) PI (Polyimide) (Prepared from PAA)

[0118] <Example 1> 3 g of FEP aggregates were placed in a 50 cc sample vial, and 30 g of PGME (propylene glycol monomethyl ether) was added. The aggregates were crushed into small pieces with a spatula, and the mixture was ultrasonically homogenized for 15 minutes. Pvozo was added from a concentrated Pvozo / PGME solution to a concentration of 4% by mass relative to the FEP. The mixture was ultrasonically homogenized at room temperature for 10 minutes using a bath-type ultrasonic device. A stirring bar was added, and the mixture was reacted in an oil bath at 100°C for 3 hours. After 3 hours, the sample was removed from the oil bath. The mixture was separated using a centrifuge at 4000 rpm for 5 minutes. The supernatant PGME was removed, 10 g of methanol was added, and the mixture was stirred with a spatula and washed with methanol. The mixture was separated using a centrifuge at 4000 rpm for 5 minutes, and the methanol was removed. This methanol washing procedure (adding methanol, centrifugation, and removal of methanol) was repeated 5 times. Using a vacuum dryer, the material was dried at 40°C for 3 hours under a vacuum pressure of 1.33 kPa to obtain FEP / Pvozo powder.

[0119] 2 g of a mixture of PAA and NMP (N-methyl-2-pyrrolidone) (mass ratio PAA / NMP = 0.4 / 99.6) was placed in a 50 cc sample vial, and 0.2 g of FEP / Pvozo powder was added. Ultrasonics were applied for 10 minutes using a bath-type ultrasonic device. A stirring bar was added, and the mixture was reacted in an oil bath at 100°C for 3 hours to obtain a FEP / Pvozo / PAA complex. After 3 hours, the sample was removed from the oil bath.

[0120] The mixture was separated using a centrifuge at 4000 rpm for 5 minutes. The supernatant NMP was removed, 10 g of methanol was added, and the mixture was stirred with a spatula and washed with methanol. The same washing procedure (adding DMF, centrifugation, and removal of DMF) was repeated five times using DMF (dimethylformamide) instead of methanol. The mixture was dried in a vacuum dryer at 40°C for 3 hours under a vacuum pressure of 1.33 kPa to obtain FEP / Pvozo / PAA composite particles.

[0121] 1.98 g of a mixture of PAA and NMP (N-methyl-2-pyrrolidone) (mass ratio PAA / NMP = 20 / 80) was placed in a 50 cc sample vial, and 0.2 g of FEP / Pvozo / PAA composite particles were added and mixed with a spatula. Ultrasonics were applied for 10 minutes using a bath-type ultrasonic device. The mixture was then degassed using a rotary-orbit mixer at 2200 rpm for 3 minutes, and then further mixed at 2000 rpm for 5 minutes.

[0122] The mixed dispersion was dropped onto a glass plate using a dropper, and then spin-coated using a spin coater at 400 rpm for 100 seconds. Degassing was performed for 15 minutes under a vacuum pressure of 1.33 kPa. The PAA was imidized by heating in an oven at 100°C for 1 hour, 200°C for 1 hour, and 250°C for 2 hours in that order, to obtain a composition (composite film (thickness: approximately 20 μm)) containing FEP / Pvozo / PAA composite particles and PI.

[0123] <Examples 2, 3 and Comparative Examples 1-3> Particles, dispersions, and composite films were prepared in the same manner as in Example 1, except that the sample and compositional conditions were changed as shown in Table 1.

[0124] The particles and composite film obtained above were evaluated using the following method.

[0125] <ft-ir> When the particles were measured using FT-IR, the carboxyl group peak was found at 1710 cm⁻¹ in the particles of Examples 1-3. -1 From 1718cm -1 It had shifted to 1515cm. -1 An aromatic ring peak derived from compound (II) was observed. On the other hand, no such peak shift or peak was observed in the particles of Comparative Examples 1 to 3. Therefore, it is considered that in the particles of Examples 1 to 3, ester bonds are formed by the reaction between the fluororesin and compound (I), and between compound (I) and compound (II), thereby forming a structure in which the fluororesin is coated with compound (I) and the outside is coated with compound (II).

[0126] <Particle composition (coverage)> The amount (mass%) of compound (I) and (II) covering the particles in Examples 1-3 was determined using the following method. • Coverage of compound (I) Compound (I)(Pvozo) was dissolved in PGME at concentrations of 0.5% by mass, 1.0% by mass, 2.0% by mass, 2.5% by mass, and 3.0% by mass relative to fluoropolymer (FEP) to prepare PGME / Pvozo solutions. After mixing these solutions with FEP and drying, a powder containing FEP mixed with Pvozo was obtained. This powder was analyzed using FT-IR, and the peak at 1670 cm, which represents the oxazoline group derived from Pvozo, was identified. -1 The absorbance was read. This procedure was performed three times for each concentration, and the average value was plotted on a graph with absorbance on the y-axis and coating amount on the x-axis. A calibration curve was created by drawing an approximation line from these plotted points, and the coating amount of compound (I) on the fluororesin was calculated to be 0.88% by mass. • Coverage of compound (II) Compound (II)(PAA) was mixed in powder form with fluoropolymer (FEP) at concentrations of 0.5% by mass, 1.5% by mass, and 2.5% by mass, respectively, and then this powder was analyzed using FT-IR to identify the aromatic ring peak derived from PAA at 1515 cm⁻¹. -1 The absorbance was read. This procedure was performed three times for each concentration, and the average value was plotted on a graph with absorbance on the y-axis and coating amount on the x-axis. A calibration curve was created by drawing an approximation line from these plotted points, and the coating amount of compound (II) on the fluororesin was calculated to be 0.83% by mass. • Proportion of compounds (I) and (II) in the particles Based on the above results, the proportions (content) of compounds (I) and (II) in the particles were calculated to be 0.86% by mass and 0.82% by mass, respectively.

[0127] <Dielectric properties> The composite film was cut into strips 3 cm wide and 4 cm long, and the relative permittivity and dielectric loss tangent were measured at 25°C and 20 GHz using the cavity resonator perturbation method (network analyzer). The results are shown in Table 1.

[0128] <Distributed state> The composite film was observed with an optical microscope, and the obtained image was binarized to calculate the area of ​​the filler (particle) portion. As a representative example, Figure 1 shows a micrograph of the composite film of Example 1. Five aggregates with large areas were selected from top to bottom, and the average area was calculated, and X(average area (μm)) was calculated. 2 The particle content (mass %) was calculated as )) / Y. The results are shown in Table 1. Furthermore, microscopic images revealed that in both the example and comparative example, the composite films showed a sea-island structure where particles were islands and PI was the ocean.

[0129] [Table 1]

[0130] <Reference example 4> Particles, dispersions, and composite films were prepared in the same manner as in Example 1, except that the sample and compositional conditions were changed as shown in Table 2. The coating amounts (mass%) of compounds (I) and (II) on the fluororesin were 0.86% by mass and 0.82% by mass, respectively.

[0131] <Comparative Example 4> Particles, dispersions, and composite films were prepared in the same manner as in Example 1, except that the sample and compositional conditions were changed as shown in Table 2.

[0132] <Tensile Test> A 60mm x 10mm strip was cut from a composite film prepared using the same method as in Example 1. Notches were then made at both ends. A benchtop tensile and compression testing machine, MCT-2150 (manufactured by A&D Co., Ltd.), was used to test the tensile strength and tensile modulus at a test speed of 10mm / min and a chuck distance of 20mm. The results are shown in Table 2.

[0133] <Peel test> A composite film was prepared in the same manner as in Example 1, except that it was spin-coated onto copper foil, and strips measuring 200 mm x 10 mm were cut out. The peel strength at 180° was measured using a benchtop tensile and compression testing machine MCT-2150 (manufactured by A&D Co., Ltd.) at a test speed of 300 mm / min. The results are shown in Table 2.

[0134] [Table 2]

[0135] <Example 5> Particles, dispersions, and composite films were prepared in the same manner as in Example 1, except that water was used as the solvent, WS300 (Nippon Shokubai: Epocross) was used as compound (I), and the coating reaction of compound (I) was carried out for 24 hours. The coating amounts (mass%) of compounds (I) and (II) on the fluororesin were 0.86 mass% and 0.61 mass%, respectively.

[0136] <Comparative Example 5> Particles, dispersions, and composite films were prepared in the same manner as in Example 1, except that the sample and compositional conditions were changed as shown in Table 3.

[0137] <Distributed state> The dispersion state was evaluated using the same method as in Example 1. The results are shown in Table 3. Furthermore, microscopic images revealed that in both the example and comparative example, the composite films showed a sea-island structure where particles were islands and PI was the ocean.

[0138] [Table 3]

Claims

1. Particles comprising a fluororesin, a compound (I) having multiple groups (A) represented by the following formula, and a compound (II) that can react with compound (I). 【Chemistry 1】 (In the formula, R １ and R ２ These are either the same or different hydrogen atoms or organic groups, which may be bonded to each other to form a ring structure. Double lines, represented by solid and dashed lines, represent single or double bonds.

2. The particle according to claim 1, wherein the group (A) is an oxazoline group and the compound (I) is an oxazoline compound.

3. The particle according to claim 2, wherein the oxazoline compound is an oxazoline group-containing polymer.

4. The particles according to claim 3, wherein the oxazoline group-containing polymer comprises at least one selected from the group consisting of repeating units derived from 2-vinyl-2-oxazoline and repeating units derived from 2-isopropenyl-2-oxazoline.

5. The particle according to claim 1 or 2, wherein the compound (II) is a compound having at least one selected from the group consisting of a carboxyl group, a mercapto group, and a hydroxyl group.

6. The particle according to claim 1 or 2, wherein the compound (II) is a compound having a carboxyl group.

7. The particles according to claim 1 or 2, wherein the compound (II) is at least one selected from the group consisting of polyamic acid, polyacrylic acid, and epoxy resin.

8. The particle according to claim 1 or 2, wherein the compound (II) is a polyamic acid.

9. The particles according to claim 1 or 2, wherein the fluororesin is at least one selected from the group consisting of tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer, and polytetrafluoroethylene.

10. The particles according to claim 1, A composition comprising a compound (III) selected from the group consisting of polyimide, liquid crystal polymer, polyphenylene ether, polycarbonate, polyphenylene sulfide, and epoxy resin.

11. The composition according to claim 10, wherein the compound (III) is polyimide.

12. The composition according to claim 10 or 11, wherein the particles form an island and the compound (III) forms a sea island structure in the ocean.

13. The composition according to claim 10 or 11, wherein the content of the particles is 0.1 to 50% by mass.

14. In image analysis using an optical microscope, five aggregates with large areas are selected from top to bottom, and their average area is calculated as X μm. ２ The composition according to claim 10 or 11, wherein when the content of the particles is Y by mass%, X / Y is 250 or less.

15. A molded article of the particles according to claim 1 and / or the composition according to claim 10.

16. A low dielectric material comprising the particles according to claim 1 and / or the composition according to claim 10.

Images