CN108884325B - Resin composition containing liquid crystal polymer particles, molded article using the same, and method for producing the same - Google Patents

Abstract

The present invention provides a resin composition comprising at least one resin selected from thermosetting resins and thermoplastic resins and liquid crystal polymer particles.

Description

Resin composition containing liquid crystal polymer particles and composition using the same Shapes, and methods of making them

technical field

Embodiments of the present invention relate to a resin composition containing liquid crystal polymer particles. Moreover, embodiment of this invention also relates to the manufacturing method of this resin composition, the molded object using this resin composition, and its manufacturing method.

Background technique

From the viewpoints of insulating properties of printed boards such as rigid boards and flexible boards and economical efficiency including manufacturability, among printed boards such as rigid boards and flexible boards, resin boards such as epoxy resin or polyimide resin have become the mainstream. . The electrical equipment involved in communication needs to process large-capacity data at high speed, and the frequency of the radio waves used is shifted to a high frequency band, so the printed circuit board needs to be compatible with high frequencies.

Against such a background, resins having excellent dielectric properties are being examined as resins for circuit boards. For example, Patent Document 1 describes a polyamic acid containing (a) a polyamic acid having an alicyclic structure in the main chain and (b) a partially cleaved structure of a cage-like silsesquioxane having a silanol group by heating. A polyimide film having a relative dielectric constant of 3 or less obtained from an amic acid composition. The polyimide film described in Patent Document 1 achieves lower dielectric constant by introducing a silanol group as a part of the polymer backbone, but cannot obtain a sufficient effect on the reduction of the dielectric loss factor.

Since liquid crystal polymers are excellent in dimensional stability, heat resistance, chemical stability, etc., and have a low dielectric constant and a low water absorption rate, applications in the electrical and electronic fields such as printed circuit boards are being studied.

For example, Patent Document 2 describes the process of extruding a polymer composition containing a thermoplastic liquid crystal polymer having a predetermined melt viscosity and activation energy from a die set at a predetermined temperature, and performing bubble molding of a film. Manufacturing method.

In addition, Patent Document 3 describes that a thin film of a liquid crystal polymer is pulverized with a chopper and then fibrillated to produce a fibrillated liquid crystal polymer powder, and the fibrillated liquid crystal polymer powder is heated and pressurized, Thus, a method of manufacturing a printed circuit board.

prior art literature

Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2012-107121

Patent Document 2: Japanese Patent Laid-Open No. 2005-1376

Patent Document 3: International Publication No. WO2014/188830

SUMMARY OF THE INVENTION

The problem to be solved by the invention

As described in Patent Document 2, when a liquid crystal polymer is formed into a thin film, it is usually necessary to heat and melt the liquid crystal polymer and then perform 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 be used as a binder but is composed of only liquid crystal polymer powder, and therefore has a problem of being expensive.

The embodiments of the present invention have been made in view of the above-mentioned problems, and an object of the present invention is to provide a resin composition capable of realizing both excellent electrical properties and economical efficiency, and a method for producing the same. Moreover, the subject of embodiment of this invention is to provide the molded article which has excellent electrical characteristics and economical efficiency, and its manufacturing method.

methods for solving problems

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

A further embodiment of the present invention relates to the resin composition in which the melting point of the liquid crystal polymer particles is 270° C. or higher.

Still another embodiment of the present invention relates to the resin composition in which the average particle diameter of the liquid crystal polymer particles is 0.1 to 200 μm.

A further embodiment of the present invention relates to the resin composition having a bulk density of liquid crystal polymer particles of 0.08 to 1.2 g/mL.

Still another embodiment of the present invention relates to the resin composition containing the liquid crystal polymer particles in an amount of 5 to 80 mass % of the total mass of the resin composition.

A further embodiment of the present invention relates to resins containing resins selected from epoxy resins, phenolic resins, polyimide resins, bismaleimide triazine resins, polyphenylene ether resins, polyamide resins, and polyterephthalene resins. The resin combination of one or more resins selected from the group consisting of polyethylene formate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, and polybutylene naphthalate resin thing.

Another embodiment of the present invention relates to a method for producing the resin composition,

It includes the step of mixing at least one resin selected from the group consisting of the thermosetting resin and the thermoplastic resin and the liquid crystal polymer particles at a temperature lower than the melting point of the liquid crystal polymer particles.

Another embodiment of the present invention relates to a molded body using the resin composition.

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

A further embodiment of the present invention relates to the molded body in the form of a film, a sheet or a plate.

Another embodiment of the present invention relates to a method for producing a molded body,

Including: the process 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 body,

including: a step of immersing a base material in a liquid composition containing at least a resin composition and an organic solvent; and

A step of drying the substrate immersed in the liquid composition.

Another embodiment of this invention relates to the manufacturing method of the said molded object further including the process of heating the said dried base material.

A further embodiment of the present invention relates to a method for producing the molded body containing an organic solvent, wherein the organic solvent contains a compound selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether. One or more organic solvents selected from methyl ether, toluene, xylene, N,N-dimethylformamide, dioxane, and tetrahydrofuran.

Another embodiment of the present invention relates to an electronic circuit board obtained by using the resin composition or including the molded body.

A further embodiment of the present invention relates to the electronic circuit substrate which is a flexible circuit substrate.

The present application is related to the subject matter described in Japanese Patent Application No. 2016-037525 filed on February 29, 2016, the disclosure of which is incorporated herein by reference.

Invention effect

According to the embodiment of the present invention, it is possible to provide a resin composition capable of realizing both electrical properties and economical efficiency, and a method for producing the same. Furthermore, according to the embodiment of the present invention, a molded article having excellent electrical properties and economical efficiency, and a method for producing the same can be provided.

Detailed ways

[resin composition]

The resin composition according to one embodiment contains 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 crystalline polymer (also referred to as a "liquid crystalline polymer" or a "liquid crystalline resin") refers to a polymer exhibiting melt processability having a property of forming an optically anisotropic melt phase. The properties of the anisotropic melt phase can be confirmed by a common polarized light inspection method using crossed polarizers. More specifically, the confirmation of the anisotropic molten phase can be carried out by observing the particles placed on the heating stage of Linkam Corporation at a magnification of 40 times under a nitrogen atmosphere using a polarizing microscope manufactured by Olympus Corporation. molten sample. In one embodiment, when the liquid crystal polymer is inspected between crossed polarizers, even in a molten static state, polarized light is generally transmitted and exhibits optical anisotropy.

The type of the liquid crystal polymer is not particularly limited, but an aromatic polyester and/or an aromatic polyester amide is preferable. In addition, polyesters partially containing an aromatic polyester and/or an aromatic polyester amide in the same molecular chain also fall within this range. As the liquid crystal polymer, when it is dissolved in pentafluorophenol at a concentration of 0.1 mass % at 60°C, it is preferable to use one having a logarithmic viscosity (I.V.) of at least about 2.0 dl/g, and more preferably one having a logarithmic viscosity (I.V.) of 2.0 to 10.0 dl/g. The logarithmic viscosity (I.V.) of the substance in g.

In particular, the aromatic polyester or aromatic polyester amide of the liquid crystal polymer preferably has a repeating unit derived from at least one compound selected from the group consisting of aromatic hydroxycarboxylic acid, aromatic hydroxyamine, and aromatic diamine as a structure Ingredient of aromatic polyester or aromatic polyester amide.

More specifically, one can list:

(1) polyesters mainly composed of one or more repeating units derived from aromatic hydroxycarboxylic acids and derivatives thereof;

(2) Mainly composed of (a) one or more repeating units derived from aromatic hydroxycarboxylic acids and derivatives thereof, (b) derived from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and these One or two or more repeating units derived from derivatives of (c) at least one or two or more repeating units derived from aromatic diols, alicyclic diols, aliphatic diols, and their derivatives unitary polyester;

(3) Mainly composed of (a) one or more repeating units derived from aromatic hydroxycarboxylic acids and derivatives thereof, (b) derived from aromatic hydroxyamines, aromatic diamines, and derivatives thereof Polyester amide consisting of one or more repeating units of (c) one or more repeating units derived from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and their derivatives ;

(4) Mainly composed of (a) one or more repeating units derived from aromatic hydroxycarboxylic acids and derivatives thereof, (b) derived from aromatic hydroxyamines, aromatic diamines, and derivatives thereof One or more repeating units of (c) one or more repeating units derived from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and their derivatives, and (d) Polyester amides etc. which consist of at least 1 type or 2 or more types of repeating units of aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof.

If necessary, a molecular weight regulator may be used together with the above-mentioned constituent components. In addition, arbitrary components may be contained.

In addition, in the above (1) to (4), the ratio of “one or two or more repeating units derived from aromatic hydroxycarboxylic acids and derivatives thereof” mainly contained is not particularly limited, but it is preferable to constitute 40 mol% or more in the repeating units of the liquid crystal polymer. Further, the total of the repeating units exemplified in the above (1) to (4) is preferably 80 mol% or more, and more preferably 90 mol% or more (including 100 mol%) of the repeating units constituting the liquid crystal polymer.

In one embodiment, preferable examples of specific monomer compounds constituting the liquid crystal polymer include aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; 2,6-dihydroxyl Naphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, hydroquinone, resorcinol, compounds represented by the following general formula (I), and compounds represented by the following general formula (II) Aromatic diols such as the compounds of Aromatic dicarboxylic acids such as compounds; aromatic amines such as p-aminophenol, p-phenylenediamine, and acetoxyaminophenol.

[hua 1]

(X is a group selected from alkylene (C ₁ -C ₄ ), alkylene, -O-, -SO-, -SO ₂ -, -S-, and -CO-)

[hua 2]

[hua 3]

(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 liquid crystal polymers can be carried out, for example, by the above-mentioned monomer compounds (or mixtures of monomer compounds) using direct polymerization method or transesterification method according to methods well known in the art, usually by melt polymerization method or slurry polymerization method, etc. . Compounds with ester-forming ability may be used for polymerization in their original form, or may be modified from precursors to derivatives with ester-forming ability in the early stage of polymerization. When these are polymerized, various catalysts can be used, and typical catalysts include dialkyltin oxides, diaryltin oxides, titanium dioxide, titanium alkoxides, silicates, titanium alkoxides, Alkali and alkaline earth metal salts of carboxylic acids, Lewis acid salts such as _BF3 , and the like. The usage-amount of a catalyst is about 0.001-1 mass % with respect to the total mass of a monomer compound normally, It is especially preferable that it is about 0.01-0.2 mass %. The liquid crystal polymer produced by these polymerization methods can further increase the molecular weight by solid-phase polymerization under reduced pressure or heating in an inert gas, if necessary.

The melt viscosity of the liquid crystal polymer obtained by the method as described above is not particularly limited. Usually, the melt viscosity at a temperature 10 to 30° C. higher than the melting point of the liquid crystal polymer is preferably a melt viscosity of 5 MPa or more and 600 MPa or less at a shear rate of 1000 sec ⁻¹ .

In addition, the liquid crystal polymer may be a mixture of two or more liquid crystal polymers.

(Liquid Crystal Polymer Particles)

According to one embodiment, the liquid crystal polymer particles contain the liquid crystal polymer as a main component. Containing the liquid crystal polymer as a main component means that 80 mass % or more, preferably 90 mass % or more, more preferably 95 mass % or more (including 100 mass %) of the mass of the liquid crystal polymer particles are used for the liquid crystal polymerization. thing.

In one embodiment, the liquid crystal polymer particles preferably have a melting point of 270°C or higher. The upper limit is not particularly limited, but from the viewpoint of productivity, it is preferably 400° C. or lower. When the melting point of the liquid crystal polymer particles is 270° C. or higher, it is preferable from the viewpoint of heat resistance in the reflow step of mounting a substrate. The melting point of the liquid crystal polymer particles is more preferably 300°C or higher, further preferably 330°C or higher. In addition, in this specification, "melting point (melting temperature)" of a liquid crystal polymer particle means the temperature measured according to JIS K 7121 by a differential scanning calorimeter. The measurement can use liquid crystal polymers (eg particles) or liquid crystal polymer particles.

The shape of the liquid crystal polymer particles is not particularly limited, and examples include, but are not limited to, spherical (including substantially spherical), spindle-shaped, indefinite particle, fibrillar, fibrous, etc., and mixtures thereof . In addition, the spherical shape is preferable from the viewpoint of improving the isotropy of electrical properties, and the fibrillar shape is preferable from the viewpoint of improving the mechanical properties.

The average particle size of the liquid crystal polymer particles is not particularly limited, but in one embodiment, it is, for example, 0.1 μm or more and 250 μm or less, preferably 1 μm or more and 200 μm or less. When 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 molded body obtained by using the resin composition within an appropriate range. Moreover, it is preferable that it is 0.1 micrometer or more from a viewpoint of productivity of a liquid crystal polymer particle. In addition, from the viewpoint of improving dispersibility in the resin composition and surface properties, 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.

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

In addition, in this specification, the "average particle diameter" of a liquid crystal polymer particle means the volume-based arithmetic mean particle diameter based on the laser diffraction/scattering 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 HORIBA, Ltd.

In addition, in one embodiment, from the viewpoint of achieving homogenization of the dispersibility of the liquid crystal polymer particles and the properties 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, more preferably 0.1 to 300 μm. The range of 1 to 250 μm is more preferably 150 μm or less, and particularly preferably 100 μm or less. In this specification, the "peak particle size of the particle size distribution" of the liquid crystal polymer particles refers to the peak particle size in the volume-based particle size distribution measured using a laser diffraction/scattering distribution measuring apparatus. When there are two or more peaks in the particle size distribution, the peak particle diameter of the peak with the largest 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 particle size distribution measuring apparatus LA-920 manufactured by Horiba Corporation.

Further, in one embodiment, 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 in the range of 0.1 to 0.5 g/mL. When the bulk density of the liquid crystal polymer particles is 0.08 g/mL or more, it is preferable from the viewpoint of handling during production, and when it is 1.2 g/mL or less, it is preferable from the viewpoint of dispersibility of the particles. In addition, in this specification, the bulk density of the liquid crystal polymer particles can be calculated by using a funnel to remove the liquid crystal polymer particles from the outside of a measuring cylinder (outer diameter dimension 2.5 cm, outer diameter dimension height 21.5 cm) with a volume of 50 mL. The mass of the filled liquid crystal polymer particles was measured by falling naturally at a height of 15 cm from the bottom surface and filling it up to a scale of 50 mL.

The method for producing the liquid crystal polymer particles is not particularly limited, but after producing a sheet formed of a liquid crystalline thermoplastic resin and a non-liquid crystalline thermoplastic resin, the non-liquid crystalline thermoplastic resin is eluted with a solvent to form a sheet. A method of removing; a method of pulverizing an oligomer of a liquid crystalline thermoplastic resin followed by solid-phase polymerization; a method of pulverizing and fibrillating a flaky liquid crystalline resin; a method of pulverizing a particulate liquid crystalline resin, and the like.

Moreover, in one Embodiment, the method of grinding|pulverizing a liquid crystal polymer with a stone mortar type grinder is preferable. According to the method of pulverizing with a stone mortar type grinder, particles with a small average particle size can be easily and simply produced.

The content of the liquid crystal polymer particles in the resin composition is not particularly limited, but is preferably 5% by mass or more and 80% by mass or less of the total composition. When the content of the liquid crystal polymer particles is 5% by mass or more, the effect of improving electrical properties (lowering the dielectric constant) can be further enhanced, and when 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 more preferably 10% by mass or more, still more preferably 20% by mass or more, more preferably 70% by mass or less, and still more preferably 60% by mass or less of the total composition. When a resin composition contains a solvent, the said range is calculated|required based on the mass of the resin composition from which a solvent was removed.

＜Resin composition＞

The resin composition which concerns on one Embodiment contains at least 1 type of resin (henceforth "resin component") chosen from a thermoplastic resin and a thermosetting resin. The resin component is a resin other than the liquid crystal polymer.

The thermoplastic resin and the thermosetting resin are not particularly limited, and can be appropriately selected in consideration of the application and the like of the resin composition according to the embodiment.

For example, when the resin composition is used for a circuit board as described later, it is generally preferable to use a resin component with a low dielectric constant. However, since the resin composition according to one embodiment contains liquid crystal polymer particles, it has the advantage of being able to maintain excellent electrical properties (low dielectric constant) even when a resin with a high dielectric constant is used. . Specific examples of the resin having a relatively high dielectric constant include resins having a higher dielectric constant than liquid crystal polymers, for example, resins having a dielectric constant at 5 GHz of 3 or more, or 3.2 or more. Specifically, an epoxy resin, a phenol resin, a polyimide resin, a bismaleimide triazine resin (BT resin), etc. can be illustrated, but it is not limited to this. In addition, of course, a resin having a dielectric constant of less than 3 can also be appropriately used. Here, the dielectric constant is a value at 5 GHz measured at 23° C. by the cavity perturbation method.

In addition, since the resin composition according to one embodiment contains particles of a liquid crystal polymer, it is not necessary to heat and melt the liquid crystal polymer particles when the resin composition is produced, and the liquid crystal polymer particles are mixed at a temperature lower than the melting point of the liquid crystal polymer particles. In the case of the resin component and the liquid crystal polymer particles, a resin composition in which the liquid crystal polymer particles are dispersed can be obtained. Therefore, in one embodiment, as the resin component, a resin having a thermal decomposition temperature lower than the melting point of the liquid crystal polymer particles can be preferably used. In addition, of course, a resin whose thermal decomposition temperature is equal to or higher than the melting temperature of the liquid crystal polymer particles can also be appropriately used.

In addition, when the resin composition according to one 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 Specifically, it is preferably 300°C or higher, more preferably 330°C or higher, and further preferably 350°C or higher.

In addition, when it is described in this specification that "the glass transition temperature, melting point, and thermal decomposition temperature of the resin component are above a specific temperature", it means the lowest temperature among the glass transition temperature, melting point, and thermal decomposition temperature of the resin. above this specific temperature. Here, "melting point (melting temperature)" means a temperature measured by differential scanning calorimetry (DSC) in accordance with JIS K 7121, and "thermal decomposition temperature" means a temperature of 25°C from 25°C in an air flow by a thermogravimetric measuring device. The temperature at which the weight was reduced by 10% (10% weight reduction temperature) when the temperature was raised at 10°C/min, and "glass transition temperature" means the temperature measured according to JIS K 6240 by differential scanning calorimetry (DSC).

In one embodiment, epoxy resins, phenol resins, polyimide resins, bismaleimide triazine resins (BT resins), etc. are mentioned as thermosetting resins preferably used, but not limited to these .

(epoxy resin)

The epoxy resin is not particularly limited, and examples thereof include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, and naphthalene type epoxy resin. Resin, glycidylamine epoxy resin, alicyclic epoxy resin, polyether modified epoxy resin, silicon modified epoxy resin, glycidyl ester epoxy resin and other bifunctional epoxy resins. In addition, phenol novolac 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, tetraphenylmethane type epoxy resin and other multifunctional epoxy resins. One type of epoxy resin may be used alone, or two or more types may be used in combination.

(Phenolic Resin)

Examples of phenolic resins include cresol novolak resins, phenol novolak resins, alkylphenol novolak resins, bisphenol A novolak resins, dicyclopentadiene phenolic resins, zyloricザイロック)-type phenolic resin, terpene-modified phenolic resin, polyvinylphenols, naphthol aralkyl-type phenolic resin, biphenyl aralkyl-type phenolic resin, naphthalene-type phenolic resin, aminotriazine novolak-type phenolic resin etc., but not limited to this. One type of phenolic resin may be used alone, or two or more types may be used in combination.

(Polyimide resin)

As the polyimide resin, various polyimide resins obtained from acid anhydrides and diamines can be used. The acid anhydride is preferably an aromatic tetracarboxylic acid, for example, 3,3',4,4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, etc., and the diamine is preferably an aromatic diamine, and examples thereof include Examples include p-phenylenediamine, 4,4'-diaminodiphenyl ether, etc., but are not limited thereto. In addition, an imidization catalyst such as an amine compound, a dehydrating agent such as a carboxylic acid anhydride, and the like may be used together. Moreover, when using a polyimide resin as a resin component, it is preferable to use the polyamic acid obtained by polymerizing an acid anhydride and a diamine, and it is preferable to carry out imidation at the time of shaping|molding or after shaping|molding. One type of polyimide resin may be used alone, or two or more types may be used in combination.

(Bismaleimide triazine resin)

As the bismaleimide triazine resin (BT resin), various bismaleimide triazine resins obtained by crosslinking bismaleimide and an aromatic cyanate ester can be used. One type of bismaleimide triazine resin may be used alone, or two or more types may be used in combination.

In one embodiment, a thermoplastic resin can be preferably used as the resin component. Specifically, polyphenylene ether, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate can be exemplified. esters, etc., but not limited thereto.

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

One type of thermosetting resin and thermoplastic resin may be used alone, or two or more types may be used in combination. The content of the resin component in the resin composition is not particularly limited, but is preferably 20% by mass or more and 95% by mass or less of the total composition. When the content of the resin component is 20% by mass or more, it is more advantageous from the viewpoint of economical efficiency, and when it is 95% by mass or less, the effect of improving the electrical properties (lowering the 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, more preferably 90% by mass or less, and still more preferably 80% by mass or less of the total composition. When a resin composition contains a solvent, the said range is calculated|required based on the mass of the resin composition from which the solvent was removed. Moreover, when a resin composition contains a thermosetting resin as a resin component, and a hardening|curing agent and/or a hardening accelerator, the said range is the range of the total content of a resin component, a hardening|curing agent, and a hardening accelerator.

The resin composition according to one embodiment contains at least the above-mentioned liquid crystal polymer particles and the resin component, and as necessary, further contains components other than the above-mentioned liquid crystal polymer particles and the resin component as shown below.

<Curing agent and curing accelerator>

When the resin composition which concerns on one Embodiment contains a thermosetting resin as a resin component, it is preferable to further contain a hardening|curing agent. The curing agent is not particularly limited, and curing agents known in the technical field can be used. Examples of the curing agent include dicyandiamide, hydrazide, imidazole compounds, amine adducts, sulfonium salts, onium salts, ketimines, acid anhydrides, tertiary amines, novolak-type phenolic resins, and the like, but are not limited to this.

The content of the curing agent is not particularly limited, and can be appropriately selected according to the resin component used and curing conditions, but for example, it is preferably 10 to 100 parts by mass, more preferably 20 parts by mass relative to 100 parts by mass of the above-mentioned thermosetting resin. ~90 parts by mass.

In addition, a curing accelerator may be used instead of the above-mentioned curing agent, or may be used in combination with the curing agent. Although it does not specifically limit as a hardening accelerator, For example, diazabicycloundecene, its derivatives, and its salts; an organic phosphine compound, its salt, its derivatives, etc. are mentioned. Although content of a hardening accelerator is not specifically limited, It is preferable that it is 50-150 mass parts with respect to 100 mass parts of said thermosetting resins, and it is more preferable that it is 80-120 mass parts.

＜Filling material＞

Moreover, the resin composition which concerns on one Embodiment may contain a filler as needed. The filler material here does not contain liquid crystal polymer particles.

As filler material, glass fibers, ground glass fibers, glass beads, glass spheres, ceramic spheres, glass flakes, silica, alumina fibers, zirconia fibers, potassium titanate fibers, carbon fibers, graphite; calcium silicate, silicon Silicates such as aluminum oxide, kaolin, talc, and clay; 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; Silicon carbide, silicon nitride, boron nitride, etc. are exemplified as organic fillers, and high-melting fibers such as aromatic polyester fibers, aramid fibers, fluororesin fibers, and polyimide fibers are exemplified. Not limited to this.

When a filler is contained, 80 mass % or less is preferable in the total mass of the resin composition which concerns on one Embodiment, 10-60 mass % is more preferable, 30-50 mass % is further more preferable. When a resin composition contains a solvent, the said range is calculated|required based on the mass of the resin composition from which the solvent was removed.

＜Organic solvent＞

The resin composition according to one embodiment may further contain an organic solvent as necessary.

The organic solvent is preferably a compound that functions to improve the fluidity of the resin composition during molding and can be removed by drying and/or heating under the process conditions during molding.

More preferably, the organic solvent is a compound that can be removed by drying and/or heating at a temperature lower than the melting point of the liquid crystal polymer particles.

In one embodiment, the boiling point (standard boiling point) of the organic solvent is preferably 40 to 210°C, more preferably 50 to 190°C, from the viewpoint of suppressing deterioration of the resin component and the like when the organic solvent is removed.

In one embodiment, 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, etc., but not limited thereto. One type of organic solvent may be used alone, or two or more types may be used in combination. When an organic solvent is contained, 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 in the total mass of the resin composition. The total mass of the resin composition here is the total mass including the 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 the organic solvent, and preferably at least a part of the resin component is dissolved in the organic solvent.

＜Other ingredients＞

The liquid crystal polymer particle-containing resin composition of one embodiment may optionally contain other components than the above-mentioned components as long as the effects are not inhibited. Examples of other components include various stabilizers (antacids, ultraviolet absorbers, near-infrared absorbers, heat stabilizers, etc.), flame retardants, flame retardant aids, plasticizers, mold release agents, dyes, and pigments and other colorants, fluorescent whitening agents, etc. One or more of them can be added as needed.

<Manufacturing method of resin composition>

The resin composition which concerns on one Embodiment can be manufactured by the equipment and method normally used as a conventional resin composition preparation method. As a preferable method, the method of kneading (mixing) each component using kneading apparatuses, such as a 1-screw or 2-screw extruder, is mentioned, for example.

In one embodiment, the resin composition is preferably prepared by mixing at least one resin component selected from thermosetting resins and thermoplastic resins and liquid crystal polymer particles at a temperature lower than the melting point of the liquid crystal polymer particles. manufacture.

The resin composition of one embodiment is a resin composition including a resin component and liquid crystal polymer particles, and it is not necessary to heat and melt the liquid crystal polymer particles at the time of production of the resin composition, and the temperature is lower than the melting point of the liquid crystal polymer particles. By mixing the resin component and the liquid crystal polymer particles at a temperature, a resin composition in which the liquid crystal polymer particles are dispersed in the resin component can be obtained. Therefore, a resin decomposed when heated and melted at a temperature equal to or higher than the melting point of the liquid crystal polymer particles can also be used as the resin component.

In addition, components other than the resin component and the liquid crystal polymer particles (hardener, 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 product and molding method]

The shape of the molded product (molded article) of the resin composition according to one embodiment is not particularly limited, and examples thereof include a film shape, a sheet shape, a plate shape, a three-dimensional molded product, and the like. When it is a film shape, a sheet shape, or a plate shape, the remarkable effect by the resin composition which concerns on one Embodiment can be acquired.

The molded body can be produced by various methods known as extrusion molding, injection molding, press molding, tape casting, and the like as a molding method of a resin composition.

For example, the molded body of one embodiment can be produced by a method including:

A step of preparing a liquid composition containing the resin composition according to one embodiment; and

The step of solidifying the liquid composition.

The liquid composition containing the resin composition may be the resin composition according to one embodiment (for example, when a liquid resin is used as a resin component and/or when the resin composition according to one embodiment contains an organic solvent, etc.) . Further, if necessary, a liquid composition may be prepared by heating and melting the resin composition at a temperature lower than the melting point of the liquid crystal polymer particles.

The curing process for curing the liquid composition is not particularly limited, and a method known in the technical field can be employed. As the curing step, 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 can be exemplified. The drying step is preferably performed in a temperature range from room temperature to a temperature lower than the melting point of the liquid crystal polymer particles, for example, in a range of 100°C to 250°C. The heating step can be appropriately set in consideration of the curing conditions of the resin component used and the like, but is preferably performed in a temperature range lower than the melting point of the liquid crystal polymer particles, for example, in a range of 120°C to 220°C. The drying step may also serve as a heating step or a heating step and also a drying step.

In one embodiment, a molded body can be produced by a method including the following steps:

1. the process of flowing the resin composition into the mold; and

2. The step of heating the resin composition (curing step).

Further, in one embodiment, it is preferable that the molded body contains a base material. For example, the molded body can be produced by a method including the following steps:

1. A process for preparing a liquid composition;

2. the process of impregnating the substrate with the liquid composition; and

3. A step of drying the substrate immersed in the liquid composition.

In one embodiment, the resin composition preferably contains a thermoplastic resin. In one embodiment, the resin composition preferably contains a thermosetting resin. The molded body obtained by the above-described drying process is also referred to as a prepreg.

In addition, in one embodiment, a molded body can be produced by a method including the steps of:

1. A process for preparing a liquid composition;

2. the process of impregnating the substrate with the liquid composition;

3. a step of drying the substrate impregnated with the liquid composition (semi-curing step); and

4. The step of heating the dried base material (curing step).

In one embodiment, the resin composition preferably contains a thermosetting resin. The molded body obtained by the semi-curing process is also referred to as a prepreg.

Although it does not specifically limit as a material of a base material, For example, the material which can be used as a reinforcement material of the insulating layer of a circuit board is mentioned. For example, inorganic fibers such as glass fibers, quartz glass fibers, carbon fibers, alumina fibers, silicon carbide fibers, asbestos, rock wool, slag wool, and gypsum whiskers, or wholly aromatic polyamide fibers, polyimide Fiber, polyester fiber and other organic fibers. The substrate can also be in the form of a film, non-woven or woven.

In addition, in one embodiment, it is preferable to manufacture a molded body by performing tape casting using a liquid composition containing a resin composition.

[circuit board]

In a film-like, sheet-like, or plate-like molded product formed using the resin composition according to one embodiment, the liquid crystal polymer particles are dispersed in the resin component. Therefore, the molded body is excellent in electrical properties (low dielectric constant) and also easy to obtain excellent surface properties (surface smoothness), and is preferably used for electronic circuit boards such as flexible circuit boards. Although the manufacturing method of an electronic circuit board is not particularly limited, it can be carried out by bonding the above-mentioned film-shaped, sheet-shaped, or plate-shaped molded body (semi-cured body or cured body) to metal foil such as copper foil. A method of heat molding to form a metal laminate. The conditions of the heat press are not particularly limited, but may be, for example, 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 by way of examples, but the present invention is not limited to the following examples.

＜Liquid crystal polymer＞

· Liquid crystal polyester amide resin

After the following raw materials were put into 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. Then, the temperature was raised to 340° C. over 4.5 hours, and the pressure was reduced to 10 Torr (ie, 1330 Pa) over 15 minutes, whereby melt polymerization was performed while distilling out acetic acid, excess acetic anhydride, and other low-boiling components. After the stirring torque reached a predetermined value, nitrogen was introduced to make the pressure change from a decompressed state to a pressurized state through normal pressure, the 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 gas stream to obtain the target polymer. The obtained polymer had a melting point of 334° C. and a melt viscosity of 14.0 Pa·s. In addition, the melting point of the polymer was measured according to JIS K 7121 using a differential scanning calorimeter (manufactured by TA Instruments, Inc., DSC Q1000). The melt viscosity of the polymer was measured using a capillary rheometer (manufactured by Toyo Seiki Co., Ltd., CAPILOGRAPH 1D: piston diameter 10 mm) under the conditions of a cylinder temperature of 350° C. and a shear rate of 1000 sec ⁻¹ in accordance with ISO 11443. The apparent melt viscosity was measured under. For the measurement, an orifice with an inner diameter of 1 mm and a length of 20 mm was used.

(I) 4-Hydroxybenzoic acid; 188.4 g (60 mol%)

(II) 2-Hydroxy-6-naphthoic acid; 21.4 g (5 mol %)

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

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

(V) 4-acetoxyaminophenol; 17.2 g (5 mol %)

Metal catalyst (potassium acetate catalyst); 15mg

Acylating agent (acetic anhydride); 226.2g

<1. Production of liquid crystal polymer particles>

(LCP particle 1)

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

Bulk density: 0.10g/mL

The produced liquid crystal polymer particles were pulverized under the following conditions using an attritor (manufactured by Masukyuki Sangyo Co., Ltd., MKZA10-15JP) to obtain substantially spherical liquid crystal polymer particles. The average particle diameter and peak particle size of the obtained liquid crystal polymer particles were measured with a laser particle size analyzer (a laser diffraction/scattering particle size distribution measuring apparatus LA-920, manufactured by Horiba, Ltd.). The average particle diameter is the arithmetic mean diameter expressed as calculation result data. In addition, the liquid crystal polymer particles were naturally dropped from a height of 15 cm from the outer bottom surface of a 50 mL measuring cylinder (manufactured by Shibata Science Co., Ltd., custom measuring cylinder A026500-501A, outer diameter dimension 2.5 cm, outer diameter dimension height 21.5 cm) using a funnel And it filled up to the mark of 50 mL, and the bulk density of the liquid crystal polymer particle was calculated by measuring the weight.

Raw material: Particles of liquid crystal polymer (average particle diameter: 3 mm)

Raw material input: 400g

Crushing speed: 60g/hr

Water inflow (30L/min)

Void: 50μm

Speed: 1400rpm

(LCP particles 2)

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

Bulk density: 0.12g/mL

The produced liquid crystal polymer particles were freeze pulverized under the following conditions using a ball mill-type freeze pulverizer (manufactured by Nippon Analytical Industries, Ltd., JFC-1500) to obtain substantially 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 particle 1.

Raw material: Particles of liquid crystal polymer (average particle diameter: 3 mm)

Amount of raw material input: 5g

Pre-freezing time: 30min

Freeze crushing time: 20min

(LCP particles 3)

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

Bulk density: 0.06g/mL

The produced liquid crystal polymer particles were pulverized under the following conditions using a mesh mill-type pulverizer (manufactured by Horai Co., Ltd., HA-2542) to obtain fibrillar 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 the LCP particle 1.

Raw material: Particles of liquid crystal polymer (average particle diameter: 3 mm)

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 by a semi-automatic turbo classifier (NISSHIN ENGINEERING INC.) to obtain fine substantially 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 the LCP particle 1 .

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

<Examples 1 to 3>

The produced liquid crystal polymer particles, liquid epoxy resin (XNR5002G manufactured by Nagase ChemteX Co., Ltd.), and tetrahydromethyl phthalate as a curing agent were mixed at room temperature (23° C.) in accordance with the mass ratios shown in Table 1. Formic anhydride (XNH5002G manufactured by Nagase ChemteX Co., Ltd.) was kneaded 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 the liquid crystal polymer particles were not used.

<3. Manufacture and evaluation of molded body>

<Examples 1 to 3, Comparative Example 1>

The mixed composition was poured into a polyethylene mold of 8 cm×3 cm×2 mm, heated at 100° C. for 1 hour, and then heated at 150° C. for 3 hours to obtain a test piece.

的圆柱状，并在23℃下使用微扰法谐振腔·介电常数测量装置(株式会社关东电子应用开发制Cavity Resornator)对5GHz下的介电常数及介质损耗因数进行测量。The obtained test piece was cut into

Columnar shape, and the dielectric constant and dielectric loss factor at 5GHz were measured at 23°C using a perturbation method resonator and dielectric constant measuring device (Cavity Resornator, manufactured by Kanto Electronics Co., Ltd.).

In addition, the surface of the obtained test piece was visually observed, and the test piece without cracks was marked with ⊚, the test piece with some cracks (less than 30% of the surface area) was marked with ◯, and about half (30% of the surface area) was marked with ◯. About ∼70%) of the test piece with cracks was denoted as Δ, and the test piece with cracks in the whole (over 70% of the surface area) was denoted as ×, and the dispersibility was evaluated.

Then, after the obtained test piece was ruptured, the rupture surface was visually observed, and the test piece without the aggregates of the liquid crystal polymer particles was marked with ⊚, the test piece with less than 5 aggregates was marked with ◯, and 5 A test piece with more than 10 agglomerates and less than 10 agglomerates was denoted as Δ, and a test piece with 10 or more agglomerates was denoted as ×, and the surface properties were evaluated.

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

[Table 1]

Example 1 Example 2 Example 3 Comparative Example 1 Liquid epoxy resin 37 37 37 53 LCP particle 1 30 LCP particle 2 30 LCP particle 3 30 Hardener 33 33 33 47 Dielectric Constant (5GHz) 2.9 3.0 3.1 3.3 Dielectric Loss Factor (5GHz) 0.008 0.009 0.01 0.01 dispersion ◎ ◎ △ - superficial ○ ◎ △ ◎

In Examples 1 to 3 in which the resin composition containing the resin component and the liquid crystal polymer particles was used, a molded body excellent in economical efficiency was obtained by a simple manufacturing method.

In addition, as shown in Table 1, the molded bodies of Examples 1 to 3 using the resin composition containing liquid crystal polymer particles obtained excellent electrical properties (dielectric constant and dielectric loss factor). 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 properties were obtained.

<4. Production and evaluation of preforms>

<Examples 4 and 5, Comparative Example 2>

(Examples 4 and 5)

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

The mass ratio shown in Table 2 is the mass ratio of the solid component after removing the solvent.

(Comparative Example 2)

A prepreg was obtained in the same manner as in Examples 4 and 5 except that the 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 epoxy resin (EPICLON HP-7200H-75M manufactured by DIC Corporation, 75% methyl ethyl ketone solution, epoxy equivalent: 279 g/ eq), as a curing agent, novolak-type phenolic resin (TD-2090-60M manufactured by DIC Corporation, 60% methyl ethyl ketone solution, water acid base equivalent: 105 g/eq) was added to the mixed solvent of methyl ethyl ketone and ethylene glycol monomethyl ether and Agitate to obtain a uniform resinous varnish. The obtained resin varnish was impregnated with glass fiber cloth (#2116 manufactured by Nittobo Co., Ltd., thickness 100 μm), and was 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 the liquid crystal polymer particles were not used.

<Examples 8 and 9, Comparative Example 4>

(Examples 8 and 9)

The produced liquid crystal polymer particles and novolak-type epoxy resin (EPICLON N-740-80M, 80% methyl ethyl ketone solution by DIC Corporation, epoxy equivalent: 182 g/eq) were prepared in the mass ratios shown in Table 2. , Novolak-type phenolic resin (TD-2090-60M manufactured by DIC Corporation, 60% methyl ethyl ketone solution, water acid base equivalent: 105 g/eq) as a curing agent was added to the mixed solvent of methyl ethyl ketone and ethylene glycol monomethyl ether and stirred , so as to obtain a uniform resin varnish. The obtained resin varnish was impregnated with glass fiber cloth (#2116 manufactured by Nittobo Co., Ltd., thickness 100 μm), and was 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 the liquid crystal polymer particles were not used.

<Examples 10 and 11, Comparative Example 5>

(Examples 10 and 11)

The produced liquid crystal polymer particles, bisphenol-type epoxy resin (EPICOAT 828 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 190 g/eq), and novolak-type novolac as a curing agent were prepared in the mass ratios shown in Table 2. Resin (TD-2090-60M manufactured by DIC Corporation, 60% methyl ethyl ketone solution, aqueous acid group equivalent: 105 g/eq) was added to a mixed solvent of methyl ethyl ketone and ethylene glycol monomethyl ether and stirred to obtain a uniform resin varnish. The obtained resin varnish was impregnated with glass fiber cloth (#2116 manufactured by Nittobo Co., Ltd., thickness 100 μm), and was 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 the liquid crystal polymer particles were not used.

<Comparative Example 6>

Polytetrafluoroethylene particles (PTFE particles, Lubron L-2 manufactured by Daikin Industries, Ltd., average particle size: 10 μm) and cresol novolac epoxy resin (EPICLON N- 690-75M, 75% methyl ethyl ketone solution, epoxy equivalent: 217 g/eq), novolak-type phenolic resin as curing agent (TD-2090-60M, 60% methyl ethyl ketone solution, water acid equivalent: 105 g/eq) It was added to a mixed solvent of methyl ethyl ketone and ethylene glycol monomethyl ether and stirred to obtain a uniform resin varnish. The obtained resin varnish was impregnated with glass fiber cloth (#2116 manufactured by Nittobo Co., Ltd., thickness 100 μm), and was treated with a hot air dryer at 150° C. for 10 minutes to obtain a prepreg.

<5. Production and Evaluation of Laminates>

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

Six sheets of the preform were heated at 200° C.×60 minutes under a load of 5 Mpa to obtain a laminate having a thickness of about 1 mm. The obtained laminate was cut into a quadrangular prism shape of 1.5 mm × 1.0 mm × 70 mm, and was measured at 5 GHz at 23°C using a perturbation method resonator/dielectric constant measuring device (Cavity Resornator, manufactured by Kanto Electronics Co., Ltd.). The dielectric constant and dielectric loss factor are measured.

Further, the obtained laminate was punched into the shape of a dumbbell-shaped tensile test piece (JIS K7127Type5) to obtain a test piece. Using the obtained test piece, a tensile test was performed immediately after punching and after 170°C × 500 hours, and the ratio of the tensile strength after 170°C × 500 hours to the tensile strength immediately after punching was maintained as the tensile strength. Rate.

Then, after cooling the obtained test piece with liquid nitrogen and cracking, the cracked surface was observed with a scanning electron microscope, and no peeling was found at the boundary between the liquid crystal polymer particles (or polytetrafluoroethylene particles) and the epoxy resin. The sheet was marked with ○, and the test piece in which peeling was found was marked with ×, and the boundary adhesion was evaluated.

The results are shown in Table 2.

[Table 2]

In Examples 4 to 11 in which the resin composition containing the resin component and the liquid crystal polymer particles was used, a prepreg excellent in economical efficiency was obtained by a simple manufacturing method.

In addition, as shown in Table 2, the prepregs of Examples 4 to 11 using the resin composition containing the liquid crystal polymer particles were such that, while maintaining the retention of tensile strength and boundary adhesion suitable for practical use, Excellent electrical properties (dielectric constant and dielectric dissipation factor) can be obtained.

Industrial Availability

A resin composition containing the liquid crystal polymer particles according to an embodiment of the present invention, and a molded product thereof can be widely used in electronic parts having high-frequency circuits, for example, built-in antennas of mobile phones, antennas of in-vehicle radars of automobiles, Various applications using high frequency, such as high-speed wireless communication for home use.

Claims (15)

1. A thermosetting resin composition which comprises at least a thermosetting resin and liquid crystal polymer particles and, if necessary, at least 1 selected from the group consisting of a curing agent and a curing accelerator,

the content of the thermosetting resin and the total of at least 1 selected from the curing agent and the curing accelerator, which are contained as necessary, is 20 to 95 mass% of the thermosetting resin composition, wherein the mass of the thermosetting resin composition from which the solvent is removed when the thermosetting resin composition contains the solvent is taken as a reference,

the melting point of the liquid crystal polymer particles is 270 ℃ or higher,

the liquid crystal polymer particles contain at least 1 liquid crystal polymer selected from the following (1) to (4),

(1) is a liquid crystal polymer of an aromatic polyester containing 1 or 2 or more kinds of repeating units derived from an aromatic hydroxycarboxylic acid,

the ratio of the repeating units is 80 mol% or more of the repeating units constituting the liquid crystal polymer,

(2) a liquid crystal polymer comprising an aromatic polyester comprising (a) 1 or 2 or more kinds of repeating units derived from an aromatic hydroxycarboxylic acid, (b) 1 or 2 or more kinds of repeating units derived from an aromatic dicarboxylic acid, and (c) 1 or 2 or more kinds of repeating units derived from an aromatic diol,

the ratio of the repeating unit (a) is 40 mol% or more of the repeating units constituting the liquid crystal polymer,

the ratio of the total of the repeating units (a) to (c) is 80 mol% or more of the repeating units constituting the liquid crystal polymer,

(3) a liquid crystal polymer comprising an aromatic polyesteramide comprising (a) 1 or 2 or more kinds of repeating units derived from an aromatic hydroxycarboxylic acid, (b) 1 or 2 or more kinds of repeating units derived from an aromatic hydroxylamine and an aromatic diamine, and (c) 1 or 2 or more kinds of repeating units derived from an aromatic dicarboxylic acid,

the ratio of the repeating unit (a) is 40 mol% or more of the repeating units constituting the liquid crystal polymer,

the ratio of the total of the repeating units (a) to (c) is 80 mol% or more of the repeating units constituting the liquid crystal polymer,

(4) a liquid crystal polymer comprising an aromatic polyesteramide comprising (a) 1 or 2 or more kinds of repeating units derived from an aromatic hydroxycarboxylic acid, (b) 1 or 2 or more kinds of repeating units derived from an aromatic hydroxylamine and an aromatic diamine, (c) 1 or 2 or more kinds of repeating units derived from an aromatic dicarboxylic acid, and (d) 1 or 2 or more kinds of repeating units derived from an aromatic diol,

the ratio of the repeating unit (a) is 40 mol% or more of the repeating units constituting the liquid crystal polymer,

the ratio of the total of the repeating units (a) to (d) is 80 mol% or more of the repeating units constituting the liquid crystal polymer,

the average particle diameter of the liquid crystal polymer particles is 0.1 to 200 μm.

2. The thermosetting resin composition according to claim 1,

in the liquid crystal polymers of (1) to (4),

the aromatic hydroxycarboxylic acid comprises a compound selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid,

the aromatic diol comprises a compound selected from the group consisting of 2, 6-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 4' -dihydroxybiphenyl, hydroquinone, resorcinol, a compound represented by the following general formula (I), and a compound represented by the following general formula (II),

the aromatic dicarboxylic acid comprises a compound selected from terephthalic acid, isophthalic acid, 4' -diphenyldicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, and a compound represented by the following general formula (III),

the aromatic hydroxylamine and the aromatic diamine comprise a compound selected from the group consisting of p-aminophenol, p-phenylenediamine, and acetoxyaminophenol,

[ solution 1]

Wherein X is selected from C₁～C₄Alkylene, alkylidene, -O-, -SO₂A group of-S-, and-CO-,

[ solution 2]

[ solution 3]

Wherein Y is selected from- (CH)₂)_n- (n-1-4) and-O (CH)₂)_nAnd (1-4) O- (n).

3. The thermosetting resin composition according to claim 1 or 2,

the volume density of the liquid crystal polymer particles is 0.08-1.2 g/m L.

4. The thermosetting resin composition according to claim 1 or 2,

the liquid crystal polymer particles are contained in an amount of 5 to 80 mass% based on the total mass of the thermosetting resin composition, wherein the mass of the thermosetting resin composition from which the solvent is removed is defined as the reference mass when the thermosetting resin composition contains the solvent.

5. The thermosetting resin composition according to claim 1 or 2,

the resin contains more than 1 resin selected from epoxy resin, phenolic resin, polyimide resin and bismaleimide triazine resin.

6. A method for producing a thermosetting resin composition according to any one of claims 1 to 5,

the method comprises the following steps: and a step of mixing at least 1 resin selected from the thermosetting resin and the thermoplastic resin with the liquid crystal polymer particles at a temperature lower than the melting point of the liquid crystal polymer particles.

7. A molded article obtained by using the thermosetting resin composition according to any one of claims 1 to 5.

8. A molded article obtained by curing the thermosetting resin composition according to any one of claims 1 to 5.

9. The molded body according to claim 7 or 8,

the molded article is in the form of a film, a sheet or a plate.

10. A method of manufacturing a molded body, comprising:

a step of preparing a liquid composition containing at least the thermosetting resin composition according to any one of claims 1 to 5; and

and curing the liquid composition.

11. A method of manufacturing a molded body, comprising:

a step of impregnating a substrate with a liquid composition containing at least the thermosetting resin composition according to any one of claims 1 to 5 and an organic solvent; and

and drying the substrate impregnated with the liquid composition.

12. The method for producing a molded body according to claim 11,

further comprising a step of heating the dried base material.

13. The method for producing a molded body according to claim 11 or 12,

the organic solvent contains 1 or more organic solvents selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, toluene, xylene, N-dimethylformamide, dioxane, and tetrahydrofuran.

14. An electronic circuit board comprising the thermosetting resin composition according to any one of claims 1 to 5 or a molded article according to any one of claims 7 to 9.

15. The electronic circuit substrate of claim 14,

the electronic circuit substrate is a flexible circuit substrate.