TW201803938A - Resin composition including liquid-crystal polymer particles, molded object obtained using same, and production processes therefor - Google Patents

Abstract

An aspect of the present invention relates to a resin composition which comprises: at least one resin selected from the group consisting of thermosetting resins and thermoplastic resins; and liquid-crystal polymer particles.

Description

Liquid crystal polymer particle-containing resin composition, formed body using the same, and manufacturing method thereof

An embodiment of the present invention relates to a resin composition containing liquid crystal polymer particles. Furthermore, the embodiment of this invention is related with the manufacturing method of this resin composition, the molded object using this resin composition, and its manufacturing method.

For printed boards such as rigid substrates and flexible substrates, resin substrates such as epoxy resins or polyimide resins have become mainstream from the viewpoint of economics including insulation and manufacturability. For electrical equipment such as communications, high-speed processing of large-capacity data is required, and the radio frequency used is shifted to a high-frequency band, and the printed circuit board is also required to support high-frequency.

Based on such a background, as a resin used for a circuit board, a resin having excellent dielectric properties is examined. For example, in Patent Document 1, a partially split structure containing (a) a polyamino acid having an alicyclic structure in the main chain, and (b) a silsesquioxane having a silanol group and a cage shape is included. A polyimide film having a relative dielectric constant of 3 or less obtained by heating the polyamic acid composition. The polyfluorene imide film described in Patent Document 1 has a low dielectric constant by introducing a silanol group as a part of the polymer skeleton, but the reduction of the dielectric loss angle (dissipation factor) is not sufficient. Effect.

Because the liquid crystal polymer has excellent dimensional stability, heat resistance, It is chemically stable, has a low dielectric constant, and has a low water absorption. Therefore, it is reviewed for use in the electrical and electronic fields such as printed circuit boards.

For example, Patent Document 2 describes a method for producing a film comprising a polymer composition containing a thermoplastic liquid crystal polymer having a predetermined melt viscosity and activation energy, and a temperature-designed mold under predetermined conditions. Extruded and blow molded.

Further, Patent Document 3 describes a method for manufacturing a printed substrate in which a liquid crystal polymer film is pulverized with a cutter mill and then fibrillated to produce a fibrillated liquid crystal polymer powder. The liquid crystal polymer powder is heated and pressurized to manufacture a printed substrate.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2012-107121

[Patent Document 2] Japanese Patent Publication No. 2005-1376

[Patent Document 3] International Publication No. WO2014 / 188830

As described in Patent Document 2, when the liquid crystal polymer is formed into a film, it is generally necessary to heat-melt the liquid crystal polymer before molding. On the other hand, the liquid crystal polymer sheet produced by the method described in Patent Document 3 does not contain a resin component that can constitute a binder, and is composed only of a liquid crystal polymer powder, which has a problem of high cost.

The implementation form of the present invention has been made in view of the above-mentioned problems. The subject is to provide a resin composition capable of achieving both excellent electrical characteristics and economy and a method for producing the same. Moreover, the subject of the embodiment of this invention is providing the molded article which has excellent electrical characteristics and economy, and its manufacturing method.

One embodiment of the present invention relates to a resin composition containing at least one resin selected from the group consisting of a thermosetting resin and a thermoplastic resin, and liquid crystal polymer particles.

Another embodiment of the present invention relates to the resin composition described above, and the melting point of the liquid crystal polymer particles is 270 ° C or higher.

Another embodiment of the present invention relates to the resin composition described above, and the average particle diameter of the liquid crystal polymer particles is 0.1 to 200 μm.

Another embodiment of the present invention relates to the resin composition described above, and the bulk density of the liquid crystal polymer particles is 0.08 to 1.2 g / mL.

Still another embodiment of the present invention relates to the above-mentioned resin composition, and contains 5 to 80% by mass of liquid crystal polymer particles of the entire mass of the resin composition.

Another embodiment of the present invention relates to the above-mentioned resin composition. The resin includes an epoxy resin, a phenol resin, a polyimide resin, a bismaleimide triazine resin, a polyphenylene ether resin, and a polyimide resin. Groups of polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, and polybutylene naphthalate resin are selected from more than one resin.

According to another embodiment of the present invention, the method for manufacturing the resin composition includes selecting at least one resin selected from the group consisting of a thermosetting resin and a thermoplastic resin and the liquid crystal polymer particles, and the liquid crystal polymer particles are Mixing step at a temperature below the melting point.

Another embodiment of the present invention relates to a molded article using the above-mentioned resin composition.

Another embodiment of the present invention relates to a molded body obtained by curing the above-mentioned resin composition.

A further embodiment of the present invention relates to the above-mentioned formed body, which is in a film shape, a sheet shape, or a plate shape.

Another embodiment of the present invention relates to a method for producing a molded article, comprising: a step of preparing a liquid composition containing at least the resin composition; and a step of curing the liquid composition.

Another embodiment of the present invention relates to a method for producing a molded article, comprising: a step of impregnating a substrate with a liquid composition including at least a resin composition and an organic solvent; and impregnating the liquid composition with the liquid composition. Step of drying the substrate.

According to a further embodiment of the present invention, the method for manufacturing the molded article further includes a step of heating the dried substrate.

According to a further embodiment of the present invention, in the method for producing the above-mentioned formed body, the organic solvent includes acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and toluene , Xylene, N, N-dimethylformamide, dioxane, and tetrahydrofuran select one or more organic solvents.

Another embodiment of the present invention relates to an electronic circuit board, which is formed by using the above-mentioned resin composition or includes the above-mentioned molded body.

According to a further embodiment of the present invention, the electronic circuit substrate described above, It is a flexible circuit board.

The disclosure of this application is related to the subject matter described in Japanese Patent Application No. 2016-037525 filed on February 29, 2008 (2016), and the contents of these disclosures are incorporated herein by reference.

According to the embodiment of the present invention, it is possible to provide a resin composition capable of achieving both excellent electrical characteristics and economy and a method for producing the same. Furthermore, according to the embodiment of the present invention, it is possible to provide a molded article having excellent electrical characteristics and economy and a manufacturing method thereof.

[Resin composition]

A resin composition according to an embodiment includes a thermosetting resin and / or a thermoplastic resin, and liquid crystal polymer particles.

<Liquid crystal polymer particles>

(Liquid crystal polymer)

In one embodiment, a liquid crystal polymer (also referred to as a "liquid crystalline polymer" or a "liquid crystalline resin") refers to a polymer that exhibits melt processing properties that can form an optically anisotropic melt phase. . The properties of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the anisotropic molten phase can be confirmed by using a polarizing microscope made by Olympus Corporation and observing the molten sample placed on a Linkam heating plate at a magnification of 40 times in a nitrogen gas environment. In one embodiment, the liquid crystal polymer When inspected between orthogonal polarizers, polarized light is transmitted normally even in a molten stationary state, showing optical anisotropy.

The type of the liquid crystal polymer is not particularly limited, but is preferably an aromatic polyester and / or an aromatic polyester amidamine. In addition, the aromatic polyester and / or the aromatic polyester amide containing a polyester in a part of the same molecular chain is also included in the scope. As the liquid crystal polymer, when it is dissolved in pentafluorophenol at a concentration of 0.1% by mass at 60 ° C, a logarithmic viscosity (IV) of at least about 2.0 dl / g is preferable, and a logarithmic viscosity of 2.0 to 10.0 dl / g is preferably used. (IV) is better.

As the aromatic polyester or aromatic polyester amide of the liquid crystal polymer, it is particularly preferred that the repeating unit has at least one compound selected from the group consisting of an aromatic hydroxycarboxylic acid, an aromatic hydroxyamine, and an aromatic diamine. Aromatic polyester or aromatic polyester amidine as a constituent.

More specifically, (1) a polyester mainly composed of one or two or more repeating units derived from an aromatic hydroxycarboxylic acid and a derivative thereof; (2) mainly derived from (a) One or two or more repeating units of aromatic hydroxycarboxylic acids and their derivatives, (b) One or two types derived from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof The above repeating units, and (c) a polyester composed of one or more repeating units derived from aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof; 3) It consists mainly of (a) one or two or more repeating units derived from aromatic hydroxycarboxylic acids and their derivatives, (b) aromatic aromatic amines, aromatic diamines, and derivatives thereof 1 or 2 or more repeating units, and (c) are derived from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof Polyesteramine composed of one or two or more repeating units of living organisms; (4) mainly consisting of (a) one or two or more repeating units derived from aromatic hydroxycarboxylic acids and their derivatives, ( b) one or more repeating units derived from aromatic hydroxyamines, aromatic diamines, and derivatives thereof; (c) derived from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and One or two or more kinds of repeating units of these derivatives, and (d) one or two kinds of derivatives derived from aromatic diols, alicyclic diols, aliphatic diols, and these derivatives Polyesteramide and the like composed of the above repeating units.

Furthermore, the said structural component may use a molecular weight modifier together as needed. Furthermore, it may contain other arbitrary components.

The ratio of "one or two or more repeating units derived from aromatic hydroxycarboxylic acids and their derivatives" contained in the above (1) to (4) is not particularly limited. The repeating unit of the polymer is preferably 40 mol% or more. In the repeating unit composed of the liquid crystal polymer, the total of the repeating units individually exemplified in the above (1) to (4) is preferably 80 mol% or more, and more preferably 90 mol% or more (including 100 mol). ear%).

In one embodiment, as preferable specific examples of the specific monomer compound constituting the liquid crystal polymer, aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and the like, 2, 6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, hydroquinone, resorcinol, a compound represented by the following general formula (I), and the following general formula Aromatic diols such as compounds represented by formula (II); terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and the following general formula Aromatic dicarboxylic acids such as compounds represented by (III); aromatic diamines such as p-aminophenol and p-phenyldiamine.

(X is a group selected from alkylene (C ₁ to C ₄ ), alkylene, -O-, -SO-, -SO _2- , -S-, and -CO-.)

(Y is a group selected from-(CH ₂ ) _n- (n = 1 to 4) and -O (CH ₂ ) _n O- (n = 1 to 4).)

The preparation of the liquid crystalline polymer can be performed by a method known in the technical field using the above-mentioned monomer compound (or a mixture of monomers) using a direct polymerization method or a transesterification method, but it is usually performed by a melt polymerization method or Slurry polymerization method. In the case of a compound having an ester-forming ability, it can also be used in polymerization in its original form, and it is also possible to use a precursor in which the precursor is modified to a derivative having the ester-forming ability. When these are aggregated, various catalysts can be used. Typical examples include dialkyltin oxides, diaryltin oxides, titanium dioxide, titanium alkoxides, silicates, titanium alkoxides, alkalis of carboxylic acids, and alkaline earth metal salts. Like BF ₃ 's Lewis acid salt and the like. The amount of the catalyst used is generally about 0.001 to 1% by mass, particularly about 0.01 to 0.2% by mass, relative to the total mass of the monomer compound. The polymer produced by these polymerization methods can be solid-phase polymerized by heating under reduced pressure or in an inert gas, if necessary, to increase the molecular weight.

The melt viscosity of the liquid crystal polymer obtained by the above method is not particularly limited. In general, it is preferable to use a melt viscosity at a temperature of 10 to 30 ° C higher than the melting point of the liquid crystal polymer and a shear rate of 1000 sec ^-1 to 5 MPa or more and 600 MPa or less.

The liquid crystal polymer may be a mixture of two or more liquid crystal polymers.

(Liquid crystal polymer particles)

According to an embodiment, the liquid crystal polymer particles contain the liquid crystal polymer as a main component. The inclusion of the main component means that the mass of the liquid crystal polymer particles of the liquid crystal polymer is 80% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass or more (including 100% by mass).

In one embodiment, the melting point of the liquid crystal polymer particles is preferably 270 ° C or higher. The upper limit is not particularly limited, but is preferably 400 ° C or lower from the viewpoint of productivity. The melting point of the liquid crystal polymer particles is 270 ° C. or higher, and it is preferable from the viewpoint of heat resistance of the reflow step of the substrate package. The melting point of the liquid crystal polymer particles is more preferably 300 ° C or more, and more preferably 330 ° C or more. In addition, in this specification, the "melting point (melting temperature)" of a liquid crystal polymer particle means the temperature measured using the differential scanning calorimeter and based on JIS K7121. For the measurement, a liquid crystal polymer (for example, a pellet) or liquid crystal polymer particles can be used.

The shape of the liquid crystal polymer particles is not particularly limited, and examples thereof include a spherical shape (including a slightly spherical shape), a spindle shape, an irregular particle shape, a fibril shape, a fibrous shape, and the like, but are not limited thereto. Here it is. Moreover, a spherical shape is preferable from the viewpoint of isotropic improvement of electrical characteristics, and a fibril shape is preferable from the viewpoint of improving mechanical physical properties.

The average particle diameter of the liquid crystal polymer particles is not particularly limited. In one embodiment, it is, for example, 0.1 μm or more and 250 μm or less, and more preferably 1 μm or more and 200 μm or less. If the average particle diameter of the liquid crystal polymer particles is 250 μm or less, it is easy to maintain the surface roughness of the formed article obtained by using the resin composition in an appropriate range. Moreover, if it is 0.1 micrometer or more, it is preferable from a viewpoint of the productivity of a liquid crystal polymer particle. The average particle diameter of the liquid crystal polymer particles is more preferably 150 μm or less, still more preferably 100 μm or less, and particularly preferably 80 μm or less, from the viewpoint of improving dispersibility and surface characteristics in the resin composition.

Furthermore, in one embodiment, from the viewpoint of obtaining a molded body having uniform characteristics, the average particle diameter of the liquid crystal polymer particles is preferably 50 μm or less, and more preferably 30 μm or less.

In addition, in this specification, the "average particle diameter" of a liquid crystal polymer means the volume-based arithmetic average particle diameter obtained by the laser diffraction / scattering type particle size distribution measurement method. The average particle diameter can be measured using, for example, a laser diffraction / scattering particle size distribution measuring apparatus LA-920 manufactured by Kogyo Corporation.

Furthermore, in one embodiment, from the viewpoint of seeking to homogenize the dispersibility of the liquid crystal polymer particles and the characteristics of the molded body, the peak particle size of the particle size distribution of the liquid crystal polymer particles is preferably in the range of 0.1 to 300 μm, and more preferably The range is 1 to 250 μm, more preferably 150 μm or less, and particularly preferably 100 μm or less. In addition, in this specification, the "peak particle size distribution of a particle size distribution" of a liquid crystal polymer particle means the peak particle size distribution of the volume-based particle size distribution measured using the laser diffraction / scattering type particle size distribution measuring device. In the case where the particle size distribution has a peak of 2 or more, the peak particle diameter of the maximum peak at the peak height may exist within the above-mentioned particle diameter range. The peak particle size of the particle size distribution can be measured using, for example, a laser diffraction / scattering type particle size distribution measuring device LA-920 made by Kogyo Corporation.

Moreover, in an implementation form, the bulk density of the liquid crystal polymer particles is preferably in the range of 0.08 to 1.2 g / mL, more preferably in the range of 0.09 to 1.0 g / mL, and even more preferably 0.1 to 0.5 g / mL. range. If the bulk density of the liquid crystal polymer particles is 0.08 g / mL or more, it is preferable from the viewpoint of operability at the time of production, and if it is 1.2 g / mL or less, it is more preferable from the viewpoint of particle dispersibility. Furthermore, in this specification, a funnel is used to naturally drop the liquid crystal polymer particles from a 50-mL measuring cylinder (outer diameter 2.5 cm, outer dimension 21.5 cm) on the outer bottom surface 15 cm in height and fill until the inside of the graduated cylinder reaches the 50 mL mark. And determine the mass of the filled liquid crystal polymer particles to calculate the bulk density of the liquid crystal polymer.

There is no particular limitation on the method for producing the liquid crystal polymer particles. Examples include a method of producing a sheet composed of a liquid crystalline thermoplastic resin and a non-liquid crystalline thermoplastic resin, and then dissolving and removing the non-liquid crystalline thermoplastic resin with a solvent; pulverizing the oligomer of the liquid crystalline thermoplastic resin, followed by curing A method of phase polymerization; a method of pulverizing and fibrillating a sheet-shaped liquid crystalline resin; a method of pulverizing a liquid crystal resin in a pellet form; and the like.

Furthermore, in one embodiment, a method of pulverizing a liquid crystal polymer by a stone mortar mill is preferred. If the method is pulverized by a stone mortar mill, it is easy and simple to produce particles with a small average particle size.

The content of the liquid crystal polymer particles in the resin composition is not particularly limited, but it is preferably 5 mass% or more and 80 mass% or less of the entire composition. If the content of the liquid crystal polymer particles is 5% by mass or more, the effect of improving electrical characteristics (lower dielectric constant) can be further enhanced, and if it is 80% by mass or less, it is more advantageous from the viewpoint of economy. The content of the liquid crystal polymer particles is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 70% by mass or less, and still more preferably 60% by mass or less. When a resin composition contains a solvent, the said range is calculated | required based on the mass of the resin composition except a solvent.

<Resin composition>

One embodiment of the resin composition includes at least one resin selected from the group consisting of a thermosetting resin and a thermoplastic resin (hereinafter also referred to as "resin component"). The resin component is a resin other than a liquid crystal polymer.

The thermoplastic resin and the thermosetting resin are not particularly limited, and can be appropriately selected in consideration of the use of the resin composition of one embodiment.

For example, as described later, when a resin composition is used for a circuit board, it is generally desirable to use a resin component having a low dielectric constant. However, since the resin composition of one embodiment contains liquid crystal polymer particles, even when a resin having a high dielectric constant is used, it has the advantage of being able to maintain excellent electrical characteristics (low dielectric constant). Specific examples of the resin having a high dielectric constant include a resin having a higher dielectric constant than a liquid crystal polymer, and for example, a resin having a dielectric constant of 3 or more or 3.2 or more at 5 GHz. Specific examples include, but are not limited to, epoxy resin, phenol resin, polyfluorene imine resin, bismaleimide imine triazine resin (BT resin), and the like. It is needless to say that a resin having a dielectric constant of less than 3 can also be applied. Here, the dielectric constant is determined by the cavity resonator perturbation method at 23 A value of 5 GHz measured in ° C.

Furthermore, since the resin composition in one embodiment contains liquid crystal polymer particles, the liquid crystal polymer particles need not be heated and melted during the production of the resin composition, and the resin component and the liquid crystal polymer particles are added to the liquid crystal polymer particles. When the mixture is mixed at a temperature lower than the melting point, a resin composition in which liquid crystal particles are dispersed can be obtained. Therefore, in one embodiment, a resin whose thermal decomposition temperature is less than the melting point of the liquid crystal polymer particles can be preferably used. In addition, of course, a resin having a thermal decomposition temperature of at least the melting temperature of the liquid crystal polymer particles can be preferably used.

When a resin composition according to an embodiment is used for a circuit board described later, the glass transition temperature, melting point (melting temperature), and thermal decomposition temperature of the resin component are preferably equal to or higher than the process temperature at the time of manufacturing the circuit board. It is preferably 300 ° C or higher, more preferably 330 ° C or higher, and even more preferably 350 ° C or higher.

In addition, in this specification, when "the glass transition temperature, melting point, and thermal decomposition temperature of a resin component is above a specific temperature" is meant, the lowest temperature among the glass transition temperature, melting point, and thermal decomposition temperature of the resin is This specific temperature is above. Here, "melting point (melting temperature)" means a temperature measured using differential scanning calorimetry (DSC) and measured in accordance with JIS K7121, and "thermal decomposition temperature" means a thermogravimetric device in an air stream from 25 ° C to 10 ° C / min. The temperature at the time of 10% weight loss at the time of temperature increase (10% weight loss temperature), and the "glass transition temperature" is a temperature measured by differential scanning calorimetry (DSC) and measured in accordance with JIS K6240.

In one embodiment, epoxy resins, phenol resins, polyimide resins, bismaleimide triazine resins (BT resins), and the like are preferably used as the thermosetting resin, but are not limited thereto. some.

(Epoxy resin)

The epoxy resin is not particularly limited, and examples thereof include bisphenol epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, and bisphenol AD epoxy resin, and naphthalene epoxy resin. Resin, epoxypropylamine epoxy resin, alicyclic epoxy resin, polyether modified epoxy resin, silicone modified epoxy resin, epoxypropyl ester epoxy resin, etc. Resin. In addition, phenol novolak type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, xylene type epoxy resin, cresol novolac type epoxy resin can also be used. Resin, polyphenol epoxy resin, and other polyfunctional epoxy resins. The epoxy resin may be used alone or in combination of two or more.

(Phenol resin)

The phenol resin is not particularly limited, and examples thereof include a cresol novolac phenol resin, a phenol novolac resin, an alkylphenol novolac resin, a bisphenol A novolac resin, and a dicyclopentadiene phenol resin. , New phenol (xyloc) phenol resin, terpene modified phenol resin, polyvinyl phenols, naphthyl aralkyl phenol resin, biphenyl aralkyl phenol resin, naphthalene phenol resin, aminotriazine A phenol-type phenol resin and the like are not limited thereto. A phenol resin can be used individually by 1 type or in combination of 2 or more types.

(Polyimide resin)

As the polyimide resin, various polyimide resins obtained by using an acid anhydride and a diamine can be used. The acid anhydride is preferably an aromatic tetracarboxylic acid, such as 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, etc., and the diamine is preferably an aromatic diamine, such as P-phenylenediamine, 4,4'-diaminodiphenyl ether, and the like are not limited thereto. In addition, it is also possible to use a combination of sulfonium imidization catalysts such as amine compounds and carboxylic anhydrides. Dehydrating agent and so on. Furthermore, in the case of using polyfluorene imine as a resin component, it is preferable to use a polyfluorinated acid obtained by polymerizing an acid anhydride and a diamine, and to fluorinate the fluorene during or after molding. Polyimide resins can be used individually by 1 type or in combination of 2 or more types.

(Bismaleimide imine triazine resin)

As the bismaleimide imine triazine resin (BT resin), various bismaleimide imine triazine resins obtained by crosslinking the bismaleimide imine with an aromatic cyanate can be used. The bismaleimide imine triazine resin may be used singly or in combination of two or more kinds.

In one embodiment, a thermoplastic resin is preferably used as the resin component. Specific examples include polyphenylene ether, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. Not limited to this.

Among them, from the viewpoint of electrical characteristics such as dielectric constant, polyphenylene ether can be preferably used for substrate applications and the like described later. Polyphenylene ether refers to a polymer containing a phenyl ether group (-C ₆ H ₄ -O-) as a main component. The phenyl ether group unit structure may also have a substituent. For example, it is one or more phenyl ether group unit structures. The hydrogen atom may be independently substituted with a halogen atom, an alkyl group having 1 to 5 carbon atoms, and the like. Specific examples of the polyphenylene ether include poly (2,6-dimethyl-1,4-phenyl ether) and poly (2-methyl-6-ethyl-1,4-phenyl). Ether), poly (2,6-dichloro-1,4-phenyl ether), and further modified polyphenylene ether (m-PPE), but are not limited to these.

The thermosetting resin and the thermoplastic resin may be used singly or in combination of two or more kinds. The content of the resin component in the resin composition is not particularly limited, but it is preferably from 20% by mass to 95% by mass of the entire composition. If the content of the resin component is 20% by mass or more, it is more advantageous from the viewpoint of economy, and the effect of improving electrical characteristics (lower dielectric constant) can be further enhanced. The content of the resin component is more preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 90% by mass or less, and even more preferably 80% by mass or less. When a resin composition contains a solvent, the said range is calculated | required based on the mass of the resin composition except a solvent. When the resin composition contains a thermosetting resin as a resin component and further contains a curing agent and / or a curing accelerator, the aforementioned range is a range of the total content of the resin component, the curing agent, and the curing accelerator.

The resin composition according to one embodiment includes at least the above-mentioned liquid crystal polymer particles and resin components. However, as necessary, as shown in the following examples, the resin composition also includes components other than the above-mentioned liquid crystal polymer particles and resin components.

<Curing agent and curing accelerator>

In the case where the resin composition of the one embodiment type includes a thermosetting resin as a resin component, it is more preferable that the resin composition further contains a curing agent and / or a curing accelerator. The curing agent is not particularly limited, and curing agents known in the technical field can be used. Examples of the curing agent include, but are not limited to, dicyandiamide, hydrazine, imidazole compounds, amine adducts, sulfonates, onium salts, imines, acid anhydrides, tertiary amines, and novolac-type phenol resins. .

The content of the curing agent is not particularly limited, and may be appropriately selected according to the resin component and curing conditions to be used. For example, it is preferably 100 to 100 parts by mass, more preferably 20 to 90 parts by mass relative to the above-mentioned thermosetting resin. .

In addition, a curing accelerator may be used in place of or in combination with the curing agent. The curing accelerator is not particularly limited, and examples thereof include diazabicycloundecane, a derivative thereof, and a salt thereof; and an organic phosphine compound. The content of the hardening accelerator is not particularly limited, and it is, for example, relative to the above-mentioned thermosetting resin. 100 parts by mass, preferably 50 to 150 parts by mass, and more preferably 80 to 120 parts by mass.

<Filler>

In addition, the resin composition of one embodiment may contain a filler according to need, and the filler here does not include liquid crystal polymer particles.

Examples of the filling material include glass fibers, fused glass fibers, glass beads, glass balls, ceramic balls, glass flakes, silica, alumina fibers, zirconia fibers, potassium titanate fibers, carbon fibers, graphite; calcium silicate , Silicates such as aluminum silicate, kaolin, talc, clay, etc .; metal oxides such as iron oxide, titanium oxide, zinc oxide, antimony oxide, and aluminum oxide; carbonates or sulfates of metals such as calcium, magnesium, and zinc Further, as the organic filler, silicon carbide, silicon nitride, boron nitride, and the like can be exemplified by high-melting fibers such as aromatic polyester fibers, aromatic polyamide fibers, fluororesin fibers, and polyimide fibers. , But not limited to these.

In the case where the filler is included, the total mass of the resin composition in one embodiment is preferably 80% by mass or less, more preferably 10 to 60% by mass, and even more preferably 30 to 50% by mass. When a resin composition contains a solvent, the said range is calculated | required based on the mass of the resin composition except a solvent.

<Organic solvents>

The resin composition according to an embodiment may further include an organic solvent as required.

The organic solvent is a compound having a function of improving fluidity during molding of the resin composition of one embodiment, and is preferably a compound that can be removed by drying and / or heating under process conditions during molding.

The organic solvent is more preferably a compound which can be removed by drying and / or heating at a temperature below the melting point of the liquid crystal polymer.

In an implementation form, from the viewpoint of suppressing deterioration of resin components and the like when removing the organic solvent, the boiling point (standard boiling point) of the organic solvent is preferably 40 to 210 ° C, and more preferably 50 to 190 ° C.

Examples of organic solvents that can be preferably used in one embodiment include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, toluene, Xylene, N, N-dimethylformamide, dioxane, tetrahydrofuran, and derivatives thereof are not limited thereto. The organic solvents may be used alone or in combination of two or more. When an organic solvent is included, the content of the organic solvent can be appropriately determined in consideration of moldability and the like. For example, the content of the organic solvent may be 90% by mass or less of the entire mass of the resin composition. The total mass of the resin composition here is the total mass including an organic solvent.

When the resin composition contains an organic solvent, the resin component and the liquid crystal polymer particles of the resin composition are preferably dissolved and / or dispersed in an organic solvent, and at least a part of the resin component is preferably dissolved in an organic solvent.

〈Other ingredients〉

The resin composition containing a liquid crystal polymer particle according to an embodiment may contain other components than the above components as long as the effect is not hindered. Examples of other ingredients include various stabilizers (antioxidants, ultraviolet absorbers, near-infrared absorbers, heat stabilizers, etc.), flame retardants, flame retardant additives, plasticizers, mold release agents, dyes, and pigments. Colorants, fluorescent brighteners, etc. One or more of these may be added as necessary.

<Manufacturing method of resin composition>

The resin composition of one embodiment can use equipment and methods generally used as a conventional method for preparing a resin composition. As a preferred method, for example A method of kneading (mixing) each component using a kneading device such as a uniaxial or biaxial extruder is given.

The resin composition of one embodiment is preferably produced by mixing at least one resin component and liquid crystal polymer particles in a group consisting of a thermosetting resin and a thermoplastic resin, and mixing the liquid crystal polymer particles at a temperature below the melting point of the liquid crystal polymer particles. .

The resin composition according to one embodiment is a resin composition including a resin component and liquid crystal polymer particles. The resin composition does not need to be heated and melted during the production of the resin composition. The resin particles are mixed at a temperature lower than the melting point of the object particles to obtain a resin composition in which liquid crystal polymer particles are dispersed in a resin component. Therefore, a resin that can be decomposed by heating and melting at a temperature higher than the melting point of the liquid crystal polymer particles can be used as the resin component.

Moreover, components other than the resin component and the liquid crystal polymer particles (curing agent, filler, organic solvent, etc.) may be added in the step of mixing the resin component and the liquid crystal polymer particles, or may be added during molding.

[Molded article and molding method]

The shape of the molded article (molded article) of the resin composition of one embodiment is not particularly limited, and examples thereof include film-like, sheet-like, plate-like, and three-dimensionally shaped articles. In the case of a film shape, a sheet shape, or a plate shape, a remarkable effect obtained by the resin composition of one embodiment is obtained.

The molded body can be produced by various methods known as a molding method of a resin composition such as extrusion molding, injection molding, extrusion molding, and cast molding.

For example, a shaped body of an implementation form can be manufactured by a method including the following steps: A step of preparing a liquid composition including the resin composition of one embodiment; and a step of curing the liquid composition.

The liquid composition containing the resin composition may be a resin composition of one embodiment (for example, when a liquid resin is used as a resin component, and / or the resin composition of one embodiment contains an organic solvent Situation, etc.). Further, if necessary, the resin composition may be heated and melted at a temperature below the melting point of the liquid crystal polymer particles to prepare a liquid composition.

The curing step for curing the liquid composition is not particularly limited, and a method known in the technical field can be used. Examples of the curing step include a cooling step of cooling the liquid composition, a drying step of drying the liquid composition, a heating step of heating the liquid composition, or a combination thereof. The drying step is preferably performed at a temperature ranging from room temperature to the melting point of the liquid crystal polymer particles, for example, it is preferably performed at a temperature ranging from 100 ° C to 250 ° C. The heating step can be appropriately set in consideration of the curing conditions and the like of the resin component to be used, and is preferably performed in a temperature range where the melting point of the liquid crystal polymer particles is less than, for example, 120 ° C to 220 ° C. The drying step may be a heating step, or the heating step may be a drying step.

In one embodiment, a molded body can be manufactured by a method including the following steps: 1. a step of flowing a resin composition into a mold; and 2. a step of heating the resin composition (curing step).

Moreover, in an implementation form, the formed body preferably includes a substrate, and the formed body can be manufactured by a method including the following steps: 1. a step of preparing a liquid composition; 2. a step of impregnating the liquid composition with a substrate; and 3. a step of drying the substrate impregnated with the liquid composition.

In one embodiment, the resin composition preferably includes a thermoplastic resin. In one embodiment, the resin composition preferably includes a thermosetting resin. The formed body obtained in the above drying step is also referred to as a prepreg.

In one embodiment, a formed body can be manufactured by a method including the following steps: 1. a step of preparing a liquid composition; 2. a step of impregnating the aforementioned liquid composition with a substrate; and 3. impregnation There is a step of drying the substrate of the liquid composition (semi-curing step); and 4. a step of heating the dried substrate (curing step).

In one embodiment, the resin composition preferably includes a thermosetting resin. The formed body obtained in the aforementioned semi-curing step is also referred to as a prepreg.

The material of the base material is not particularly limited, and examples thereof include materials that can be used as a reinforcing material for an insulating layer of a circuit board. Examples include inorganic fibers such as glass fibers, quartz glass fibers, carbon fibers, alumina fibers, silicon carbide fibers, asbestos, rock wool, slag wool, gypsum whiskers, or wholly aromatic polyamide fibers, polystyrene Organic fibers such as iminium fiber and polyester fiber. The substrate may be a film, a non-woven fabric, or a woven fabric.

Furthermore, in one embodiment, it is preferable to use a liquid composition containing a resin composition to perform cast molding, thereby manufacturing a molded body.

[Circuit Board]

Film, sheet or plate formed using the resin composition of one embodiment In the shaped body, liquid crystal polymer particles are dispersed in a resin component. Therefore, the molded article is excellent in electrical characteristics (low dielectric constant), and is easy to obtain excellent surface characteristics (surface smoothness), and can be applied to electronic circuit boards and the like such as flexible circuit boards. The manufacturing method of the electronic circuit board is not particularly limited, and examples include a film-like, sheet-like, or plate-like formed body (semi-cured body or cured body) and a metal foil such as a copper foil, followed by heating and pressing. A method for forming a metal laminate. The conditions for heating and pressing are not particularly limited, and examples include heating temperature: 60 to 220 ° C, pressure: 0.1 to 10 MPa, and time: 1 minute to 3 hours.

[Example]

The present invention will be described in more detail with examples, but the present invention is not limited to the following examples.

<Liquid crystal polymer>

‧Liquid-crystalline polyester amide resin

After placing the following raw materials in the polymerization vessel, the temperature of the reaction system was raised to 140 ° C, and the reaction was carried out at 140 ° C for 1 hour. Thereafter, the temperature was raised to 340 ° C. over 4.5 hours, and the pressure was reduced to 10 Torr (that is, 1330 Pa) over 15 minutes. The acetic acid, excess acetic anhydride, and other low-boiling components were distilled off and melt-polymerized. After the stirring torque reached a predetermined value, nitrogen was introduced, and the pressure was changed from a reduced pressure state to a pressurized state through normal pressure. Strands were discharged from the lower part of the polymerization vessel, and the strands were pelletized to obtain pellets. The obtained pellets were heat-treated at 300 ° C. for 2 hours under a nitrogen stream to obtain the target polymer. The melting point of the obtained polymer was 334 ° C, and the melt viscosity was 14.0 Pa. s. The melting point of the polymer was measured using a differential scanning calorimeter (manufactured by TA Instruments, DSC Q1000) in accordance with JIS K7121. The melt viscosity of the above polymers was measured by using a capillary rheometer (CAPILOGRAPH 1D: Piston diameter 10mm) manufactured by Toyo Seiki Seisakusho Co., Ltd. and measuring the conditions of a cylinder temperature of 350 ° C and a shear rate of 1000sec ^-1 according to ISO 11443 Observed melt viscosity. For the measurement, an orifice having an inner diameter of 1 mm and a length of 20 mm was used.

(I) 4-hydroxybenzoic acid; 188.4 g (60 mole%)

(II) 2-hydroxy-6-naphthoic acid; 21.4g (5 mole%)

(III) terephthalic acid; 66.8g (17.7 mole%)

(IV) 4,4'-dihydroxybiphenyl; 52.2g (12.3 mole%)

(V) 4-Ethyloxyaminophenol; 17.2 g (5 mole%)

Metal catalyst (potassium acetate catalyst); 15mg

Chelating agent (acetic anhydride); 226.2g

<1. Production of liquid crystal polymer particles>

(LCP Particle 1)

Average particle size: 15 μm, peak particle size: 21 μm

Bulk density: 0.10g / mL

The produced liquid crystal polymer pellets were pulverized under the following conditions using a mass colloder (manufactured by Masuki Kogyo Co., Ltd., MKZA10-15JP) to obtain slightly spherical liquid crystal polymer particles. The average particle diameter and peak particle size of the obtained liquid crystal polymer particles were measured using a laser particle size meter (Laser Diffraction / Scattering Particle Size Distribution Measurement Apparatus LA-920, manufactured by Kogyo Co., Ltd.). The average particle diameter is an arithmetic mean diameter shown as a calculation result. Furthermore, the funnel was used to naturally drop the liquid crystal polymer particles from a 50-mL measuring cylinder (made by Shibata Scientific Co., Ltd. measuring cylinder Custom A 026500-501A, outer diameter 2.5cm, outer diameter 21.5cm), and the natural bottom was dropped 15 cm high. Fill the graduated cylinder to reach 50mL. And measuring its weight to calculate the bulk density of the liquid crystal polymer particles.

Material: Liquid crystal polymer pellets (average particle size: 3mm)

Raw material input: 400g

Crushing speed: 60g / hr

Water inflow (30L / min)

Gap: 50μm

Number of rotations: 1400rpm

(LCP Particle 2)

Average particle size: 195 μm, peak particle size: 242 μm

Bulk density: 0.12g / mL

The produced liquid crystal polymer pellets were freeze-pulverized using a ball mill type freeze pulverizer (manufactured by Analytical Industries, Inc., JFC-1500) under the following conditions to obtain liquid crystal polymer particles having a substantially spherical shape. The average particle diameter, peak particle size, and bulk density of the obtained liquid crystal polymer particles were measured in the same manner as in the LCP particles 1.

Material: Liquid crystal polymer pellets (average particle size: 3mm)

Raw material input: 5g

Freezing time: 30min

Freeze crushing time: 20min

(LCP Particle 3)

Average particle size: 211 μm, peak particle size: 281 μm

Bulk density: 0.06g / mL

The produced liquid crystal polymer pellets were pulverized using a mesh mill type pulverizer (manufactured by Horai Co., Ltd., HA-2542) under the following conditions to obtain fibrillar liquid crystal polymer particles. The average particle diameter of the obtained liquid crystal polymer particles, The peak particle size and the overall density were measured in the same manner as in the LCP particles 1.

Material: Liquid crystal polymer pellets (average particle size: 3mm)

Raw material input: 10kg

Crushing speed: 10kg / hr

(LCP Particle 4)

Average particle size: 5.3 μm, peak particle size: 6.9 μm

Bulk density: 0.47g / mL

The LCP particles 1 were classified with a semi-free vortex classifier (Nissin Engineering Co., Ltd.) to obtain finely-spherical liquid crystal polymer particles. The average particle diameter, peak particle size, and bulk density of the obtained liquid crystal polymer particles were measured in the same manner as in the LCP particles 1.

<2. Production of liquid crystal polymer particle-containing resin composition>

<Examples 1 to 3>

The produced liquid crystal particles, liquid epoxy resin (XNR5002G manufactured by Nagase Chemtech), and tetrahydroxymethyl phthalic anhydride (XNH5002G manufactured by Nagase Chemtech) as a curing agent were divided into The mass ratios shown in Table 1 were kneaded at room temperature (23 ° C) to obtain a uniform mixed composition.

<Comparative Example 1>

A mixed composition was obtained in the same manner as in Examples 1 to 3 except that liquid crystal polymer particles were not used.

<3. Production and Evaluation of Molded Body>

<Examples 1 to 3 and Comparative Example 1>

The mixed composition was put into a polyethylene mold of 8 cm × 3 cm × 2 mm, and after heating at 100 ° C. for 1 hour, it was further heated at 150 ° C. for 3 hours. Inspection film.

1.5mm×8cm的圓柱狀，5GHz的介電常數以及介質損耗角使用微擾法空腔共振器‧介電常數測定裝置(股份有限公司關東電子應用開發製Cavity Resornator)，於23℃測定。 The obtained test piece was cut into

A 1.5mm × 8cm cylindrical, 5GHz dielectric constant and dielectric loss angle were measured at 23 ° C using a perturbation cavity resonator and dielectric constant measuring device (Cavity Resornator, manufactured by Kanto Electronics Application Development Co., Ltd.).

In addition, the surface of the obtained test piece was visually inspected. The uncracked ones were ◎, a part of them (30% of the non-full surface area) had cracks, and the half (about 30 to 70% of the surface area) had cracks. The whole was △. (Over 70% of the surface area), the number of cracks was ×, and the dispersibility was evaluated.

Furthermore, after the obtained test piece was fractured, the fracture surface was visually observed. Those who had no aggregate of liquid crystal polymer particles were ◎, those with less than 5 aggregates were ○, and those with 5 or more aggregates and less than 10 were (Triangle | delta), and the thing with 10 or more aggregates was x, and evaluated the surface property by this.

Both the dispersibility and surface properties are in a range suitable for practical use. The results are shown in Table 1.

Using Examples 1 to 3 of the resin composition containing a resin component and liquid crystal polymer particles, an economical molded body was obtained by a simple production method.

In addition, as shown in Table 1, the molded articles of Examples 1 to 3 using the resin composition of the liquid crystal polymer particles maintained good practical surface properties and obtained excellent electrical characteristics (dielectric constant and dielectric loss angle). ). In particular, in the molded bodies of Examples 1 and 2 in which the average particle diameter of the LCP particles was 200 μm or less, the dispersibility of the LCP particles was good, and excellent surface properties and excellent electrical characteristics were obtained.

<4. Production and evaluation of prepregs>

<Examples 4 and 5, Comparative Example 2>

(Examples 4 and 5)

The produced liquid crystal polymer particles, cresol novolac novolac epoxy resin (EPICLON N-690-75M, manufactured by DIC Corporation, 75% methyl ethyl ketone solution, epoxy equivalent weight: 217 g / eq) were used as Novolak-type phenol resin (TD-2090-60M, produced by DIC Corporation, 60% methyl ethyl ketone solution, hydroxyl equivalent: 105 g / eq) as a curing agent, methyl ethyl ketone was added at a mass ratio of Table 2 A mixed solvent with ethylene glycol monomethyl ether and stirred to obtain a uniform resin varnish. The obtained resin varnish was impregnated with glass cloth (# 2116, manufactured by Nittobo Industries Ltd., thickness 100 μm), and treated with a hot air dryer at 150 ° C. for 10 minutes to obtain a prepreg.

The mass ratios shown in Table 2 are the mass ratios of the solid components other than the solvent.

(Comparative example 2)

A prepreg was obtained in the same manner as in Examples 4 and 5 except that liquid crystal polymer particles were not used.

<Examples 6 and 7, Comparative Example 3>

(Examples 6 and 7)

The produced liquid crystal polymer particles, dicyclopentadiene-type epoxy resin (EPICLON HP-7200H-75M, manufactured by DIC Corporation, 75% methyl ethyl ketone solution, epoxy equivalent weight: 279 g / eq) were used as Novolak-type phenol resin (TD-2090-60M, produced by DIC Corporation, 60% methyl ethyl ketone solution, hydroxyl equivalent: 105 g / eq) as a curing agent, methyl ethyl ketone was added at a mass ratio of Table 2 A mixed solvent with ethylene glycol monomethyl ether and stirred to obtain a uniform resin varnish. The obtained resin varnish was impregnated with glass cloth (# 2116, manufactured by Nittobo Industries Ltd., thickness 100 μm), and treated with a hot air dryer at 150 ° C. for 10 minutes to obtain a prepreg.

(Comparative example 3)

A prepreg was obtained in the same manner as in Examples 6 and 7 except that liquid crystal polymer particles were not used.

<Examples 8 and 9 and Comparative Example 4>

(Examples 8 and 9)

The produced liquid crystal polymer particles, phenol novolak epoxy resin (EPICLON N-740-80M, manufactured by DIC Corporation, 80% methyl ethyl ketone solution, epoxy equivalent weight: 182 g / eq) were used as a curing agent. Novolak phenol resin (TD-2090-60M, manufactured by DIC Corporation, 60% methyl ethyl ketone solution, hydroxyl equivalent weight: 105 g / eq), methyl ethyl ketone and ethyl acetate were added at a mass ratio of Table 2 A mixed solvent of glycol monomethyl ether was stirred to obtain a uniform resin varnish. The obtained resin varnish was impregnated with glass cloth (# 2116, manufactured by Nittobo Industries Ltd., thickness 100 μm), and treated with a hot air dryer at 150 ° C. for 10 minutes to obtain a prepreg.

(Comparative Example 4)

A prepreg was obtained in the same manner as in Examples 8 and 9 except that liquid crystal polymer particles were not used.

<Examples 10 and 11 and Comparative Example 5>

(Examples 10 and 11)

The produced liquid crystal polymer particles, a bisphenol epoxy resin (EPICOAT 828 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 190 g / eq), and a novolac phenol resin (TD manufactured by DIC Corporation) as a curing agent were prepared. -2090-60M, 60% methyl ethyl ketone solution, hydroxyl equivalent weight: 105 g / eq), add a mixed solvent of methyl ethyl ketone and ethylene glycol monomethyl ether in a mass ratio of Table 2 and stir to obtain Uniform resin varnish. The obtained resin varnish was impregnated with glass cloth (# 2116, manufactured by Nittobo Industries Ltd., thickness 100 μm), and treated with a hot air dryer at 150 ° C. for 10 minutes to obtain a prepreg.

(Comparative example 5)

A prepreg was obtained in the same manner as in Examples 10 and 11 except that liquid crystal polymer particles were not used.

<Comparative Example 6>

Polytetrafluoroethylene particles (PTFE particles, Ruburon L-2 manufactured by Daikin Industry Co., Ltd., average particle size: 10 μm), cresol novolac novolac epoxy resin (EPICLON N-690-75M manufactured by DIC Corporation) 75% methyl ethyl ketone solution, epoxy equivalent: 217 g / eq), novolac-type phenol resin (TD-2090-60M, manufactured by DIC Corporation, 60% methyl ethyl ketone solution, hydroxyl group) Equivalent: 105g / eq), add a mixed solvent of methyl ethyl ketone and ethylene glycol monomethyl ether in the mass ratio of Table 2 and stir to obtain a uniform Resin varnish. The obtained resin varnish was impregnated with glass cloth (# 2116, manufactured by Nittobo Industries Ltd., thickness 100 μm), and treated with a hot air dryer at 150 ° C. for 10 minutes to obtain a prepreg.

<5. Manufacturing and Evaluation of Laminates>

<Examples 4 to 11, Comparative Examples 2 to 6>

Six sheets of the aforementioned prepregs were heated under a load of 5 MPa at 200 ° C. for 60 minutes to obtain a laminated body having a thickness of about 1 mm. The obtained laminated body was cut into a rectangular prism of 1.5 mm × 1.0 mm × 70 mm, and measured at 5 GHz by a perturbation cavity resonator and dielectric constant measuring device (Cavity Resornator, manufactured by Kanto Electronics Application Development Co., Ltd.) at 23 ° C. Dielectric constant and dielectric loss angle.

Then, the obtained laminated body was punched into the shape of a dumbbell-type tensile test piece (JIS K7127 Type5) to obtain a test piece. Using the obtained test piece, a tensile test was performed after punching and after 170 ° C. × 500 hours, and the ratio of the tensile strength at 170 ° C. × 500 hours to the tensile strength after punching was the tensile strength retention ratio.

Furthermore, after the obtained test piece was cooled and fractured with liquid nitrogen, the fracture surface was observed with a scanning electron microscope, and no peeling was found at the interface between the liquid crystal polymer particles (or polytetrafluoroethylene particles) and the epoxy resin. The peeler was found to be X, and thereby the interface adhesion was evaluated.

Using Examples 4 to 11 of the resin composition containing a resin component and liquid crystal polymer particles, an economical prepreg was obtained by a simple manufacturing method.

Further, as shown in Table 2, the prepregs of Examples 4 to 11 using the resin composition containing liquid crystal polymer particles maintained excellent tensile strength retention ratio and interface adhesiveness, and obtained excellent results. Electrical characteristics (dielectric constant and dielectric loss angle).

[Industrial availability]

A resin composition containing liquid crystal polymer particles and a molded body thereof according to an embodiment of the present invention can be widely applied to electronic components having a high-frequency circuit, such as a built-in antenna of a mobile phone, and an antenna of an on-board radar of an automobile. Various applications such as high-speed wireless communication for home use and high frequency.

Claims (16)

A resin composition containing at least one resin selected from the group consisting of a thermosetting resin and a thermoplastic resin, and liquid crystal polymer particles. The resin composition according to item 1 of the patent application range, wherein the melting point of the liquid crystal polymer particles is 270 ° C or higher. The resin composition according to item 1 or 2 of the patent application range, wherein the average particle diameter of the liquid crystal polymer particles is 0.1 to 200 μm. The resin composition according to any one of claims 1 to 3, wherein the entire density of the aforementioned liquid crystal polymer particles is 0.08 to 1.2 g / mL. The resin composition according to any one of claims 1 to 4, wherein the liquid crystal polymer particles are contained in an amount of 5 to 80% by mass based on the total mass of the resin composition. The resin composition according to any one of claims 1 to 5, wherein the aforementioned resin comprises an epoxy resin, a phenol resin, a polyimide resin, a bismaleimide triazine resin, and a polybenzene Groups of ether resins, polyamide resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polyethylene naphthalate resins, and polybutylene naphthalate resins Select more than one resin. A method for manufacturing a resin composition, which is the method for manufacturing a resin composition according to any one of claims 1 to 6, including: selecting at least the aforementioned group consisting of a thermosetting resin and a thermoplastic resin. A step of mixing one resin and the liquid crystal polymer particles at a temperature below the melting point of the liquid crystal polymer particles. A shaped body using any of the patent application scopes 1 to 6 The resin composition described above. A formed body is obtained by curing the resin composition according to any one of claims 1 to 6 of the scope of patent application. The formed body according to item 8 or 9 of the scope of application for a patent, which is film-like, sheet-like, or plate-like. A method for producing a molded article, comprising: a step of preparing a liquid composition including at least the resin composition according to any one of claims 1 to 6 of the scope of patent application; and a step of curing the liquid composition. A method for manufacturing a molded article, comprising the steps of impregnating a substrate with a liquid composition containing at least the resin composition according to any one of claims 1 to 6 and an organic solvent, and impregnating the substrate; and There is a step of drying the substrate of the liquid composition. The method for manufacturing a molded article according to claim 12 of the application, further comprising the step of heating the dried substrate. The method for manufacturing a molded article according to claim 12 or claim 13, wherein the organic solvent includes acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, and propylene glycol monomethyl The group consisting of methyl ether, toluene, xylene, N, N-dimethylformamide, dioxane, and tetrahydrofuran is selected from one or more organic solvents. An electronic circuit board is formed using the resin composition according to any one of claims 1 to 6, or includes a molded body according to any one of claims 8 to 10. The electronic circuit board according to item 15 of the scope of patent application, which is a flexible circuit board.