CN108884325B - Resin composition containing liquid crystal polymer particles, molded article using the same, and method for producing the same - Google Patents
Resin composition containing liquid crystal polymer particles, molded article using the same, and method for producing the same Download PDFInfo
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- CN108884325B CN108884325B CN201780013885.0A CN201780013885A CN108884325B CN 108884325 B CN108884325 B CN 108884325B CN 201780013885 A CN201780013885 A CN 201780013885A CN 108884325 B CN108884325 B CN 108884325B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
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Abstract
The present invention provides a resin composition comprising at least 1 resin selected from thermosetting resins and thermoplastic resins, and liquid crystal polymer particles.
Description
Technical Field
Embodiments of the present invention relate to a resin composition containing liquid crystal polymer particles. Embodiments of the present invention also relate to a method for producing the resin composition, a molded article using the resin composition, and a method for producing the molded article.
Background
In terms of insulation properties of printed boards such as rigid boards and flexible boards and economy including manufacturability, substrates made of resins such as epoxy resins and polyimide resins are the mainstream of printed boards such as rigid boards and flexible boards. Electric devices for communication need to process large volumes of data at high speed, and the frequency of the radio wave used shifts to a high frequency band, so that printed boards need to be compatible with high frequencies.
Under such circumstances, a resin having excellent dielectric properties has been studied as a resin for a circuit board. For example, patent document 1 describes a polyimide film having a relative dielectric constant of 3 or less, which is obtained by heating a polyamic acid composition containing a partially cleaved structure of (a) a polyamic acid having an alicyclic structure in its main chain and (b) a caged silsesquioxane having a silanol group. The polyimide film described in patent document 1 has a low dielectric constant by introducing silanol groups as a part of the polymer skeleton, but cannot obtain a sufficient effect on the decrease of the dielectric loss tangent.
Liquid crystal polymers are excellent in dimensional stability, heat resistance, chemical stability, etc., have a low dielectric constant and a low water absorption rate, and thus applications of printed boards and the like in the electrical and electronic fields are being studied.
For example, patent document 2 describes a method for producing a film by 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 under predetermined conditions and carrying out bubble molding.
Patent document 3 describes a method of producing a printed circuit board by pulverizing a liquid crystal polymer film with a shredder, fibrillating the pulverized liquid crystal polymer film to produce a fibrillated liquid crystal polymer powder, and heating and pressing the fibrillated liquid crystal polymer powder.
Prior art documents
Patent document
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
Disclosure of Invention
Problems to be solved by the invention
As described in patent document 2, when a liquid crystal polymer is made into a thin film, it is generally necessary to heat and melt the liquid crystal polymer and then mold the liquid crystal polymer. On the other hand, the liquid crystal polymer sheet produced by the method described in patent document 3 is composed only of liquid crystal polymer powder without containing a resin component that can be a binder, and therefore has a problem of being expensive.
Embodiments of the present invention have been made in view of the above problems, and an object thereof is to provide a resin composition which can achieve both excellent electrical characteristics and economy, and a method for producing the same. Further, an object of an embodiment of the present invention is to provide a molded article having excellent electrical characteristics and economy, and a method for producing the same.
Means for solving the problems
One embodiment of the present invention relates to a resin composition containing at least 1 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, wherein the melting point of the liquid crystal polymer particles is 270 ℃ or higher.
A further embodiment of the present invention relates to the resin composition, wherein the liquid crystal polymer particles have an average particle diameter of 0.1 to 200 μm.
A further embodiment of the present invention relates to the resin composition, wherein the bulk density of the liquid crystal polymer particles is 0.08 to 1.2g/m L.
A further embodiment of the present invention relates to the resin composition containing 5 to 80 mass% of liquid crystal polymer particles based on the total mass of the resin composition.
A further embodiment of the present invention relates to the resin composition containing 1 or more resins selected from the group consisting of an epoxy resin, a phenol resin, a polyimide resin, a bismaleimide-triazine resin, a polyphenylene ether resin, a polyamide resin, a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polyethylene naphthalate resin, and a polybutylene naphthalate resin.
Another embodiment of the present invention relates to a method for producing the resin composition,
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.
Another embodiment of the present invention relates to a molded article using the resin composition.
Another embodiment of the present invention relates to a molded article obtained by curing the resin composition.
A further embodiment of the invention relates to the film-like, sheet-like or plate-like shaped body.
Another embodiment of the invention relates to a process for producing a shaped body,
the method comprises the following steps: a step for preparing a liquid composition containing at least the resin composition; and
and curing the liquid composition.
Another embodiment of the invention relates to a process for producing a shaped body,
the method comprises the following steps: a step of immersing the base material in a liquid composition containing at least a resin composition and an organic solvent; and
and drying the substrate impregnated with the liquid composition.
Another embodiment of the present invention relates to a method for producing the molded body, further comprising a step of heating the dried base material.
In a further embodiment of the present invention, the method for producing the molded article comprises an organic solvent, wherein the organic solvent comprises 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.
Another embodiment of the present invention relates to an electronic circuit board formed using the resin composition or including the molded article.
A further embodiment of the invention relates to the electronic circuit substrate being a flexible circuit substrate.
The present application is related to the subject matter described in Japanese patent application No. 2016-.
Effects of the invention
According to the embodiments of the present invention, it is possible to provide a resin composition which can realize both electrical characteristics and economy, and a method for producing the same. Further, according to the embodiment of the present invention, a molded article having excellent electrical characteristics and economical efficiency and a method for manufacturing the same can be provided.
Detailed Description
[ 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 crystal polymer" or a "liquid crystal resin") is a polymer exhibiting melt processability and having a property of forming an optically anisotropic melt phase, and the property of the anisotropic melt phase can be confirmed by a conventional polarized light inspection method using cross polarizers, more specifically, the confirmation of the anisotropic melt phase can be carried out by observing a melt sample placed on a heating stage made by L inkam under a nitrogen atmosphere using a polarizing microscope made by olympus under a magnification of 40 times.
The kind of the liquid crystal polymer is not particularly limited, and an aromatic polyester and/or an aromatic polyester amide is preferable. Further, a polyester partially containing an aromatic polyester and/or an aromatic polyester amide in the same molecular chain is also within the range. When the liquid crystal polymer is dissolved in pentafluorophenol at a concentration of 0.1 mass% at 60 ℃, it is preferable to use a substance having an logarithmic viscosity (I.V.) of at least about 2.0dl/g, and it is more preferable to use a substance having an logarithmic viscosity (I.V.) of 2.0 to 10.0 dl/g.
The aromatic polyester or aromatic polyester amide of the liquid crystal polymer is particularly preferably an aromatic polyester or aromatic polyester amide having a repeating unit derived from at least 1 compound selected from the group consisting of an aromatic hydroxycarboxylic acid, an aromatic hydroxylamine, and an aromatic diamine as a constituent component.
More specifically, there may be mentioned:
(1) a polyester mainly composed of 1 or 2 or more kinds of repeating units derived from an aromatic hydroxycarboxylic acid or a derivative thereof;
(2) a polyester mainly comprising (a) 1 or 2 or more kinds of repeating units derived from an aromatic hydroxycarboxylic acid or a derivative thereof, (b) 1 or 2 or more kinds of repeating units derived from an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, or a derivative thereof, and (c) at least 1 or 2 or more kinds of repeating units derived from an aromatic diol, an alicyclic diol, an aliphatic diol, or a derivative thereof;
(3) a polyesteramide mainly comprising (a) 1 or 2 or more kinds of repeating units derived from an aromatic hydroxycarboxylic acid or a derivative thereof, (b) 1 or 2 or more kinds of repeating units derived from an aromatic hydroxylamine, an aromatic diamine, or a derivative thereof, and (c) 1 or 2 or more kinds of repeating units derived from an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, or a derivative thereof;
(4) and polyesteramides mainly comprising (a) 1 or 2 or more kinds of repeating units derived from aromatic hydroxycarboxylic acids and derivatives thereof, (b) 1 or 2 or more kinds of repeating units derived from aromatic hydroxyamines, aromatic diamines, and derivatives thereof, (c) 1 or 2 or more kinds of repeating units derived from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof, and (d) at least 1 or 2 or more kinds of repeating units derived from aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof.
If necessary, a molecular weight modifier may be used in combination with the above-mentioned components. In addition, the composition may contain any component.
The ratio of "1 or 2 or more kinds of repeating units derived from the aromatic hydroxycarboxylic acid and the derivative thereof" mainly contained in the above-mentioned (1) to (4) is not particularly limited, but is preferably 40 mol% or more of the repeating units constituting the liquid crystal polymer. The total of the repeating units shown in (1) to (4) is preferably 80 mol% or more, more preferably 90 mol% or more (including 100 mol%) of the repeating units constituting the liquid crystal polymer.
In one embodiment, preferable examples of the specific monomer compound constituting the liquid crystal polymer include: aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; aromatic diols such as 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); aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 4' -diphenyldicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, and compounds represented by the following general formula (III); aromatic amines such as p-aminophenol, p-phenylenediamine and acetoxyaminophenol.
[ solution 1]
(X is selected from the group consisting of alkylene (C)1～C4) Alkylene, -O-, -SO-, -SO2Radicals in-S-, and-CO-)
[ solution 2]
[ solution 3]
(Y is selected from- (CH)2)n- (n-1-4) and-O (CH)2)nAnd (1-4) O- (n). )
The liquid crystal polymer can be produced, for example, from the monomer compound (or a mixture of monomer compounds) described above by a direct polymerization method or an ester exchange method according to a method well known in the art, and a melt polymerization method, a slurry polymerization method, or the like can be generally used. The compounds having an ester-forming ability may be used in the polymerization in their original form, or may be derivatives modified from precursors to have an ester-forming ability in an early stage of the polymerization. Various catalysts can be used in the polymerization, and typical catalysts include dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium, silicates, titanium alkoxides, alkali and alkaline earth metal salts of carboxylic acid, and BF3Such Lewis acid salts and the like. Catalytic converterThe amount of the oxidizing agent used is usually about 0.001 to 1% by mass, particularly preferably about 0.01 to 0.2% by mass, based on the total mass of the monomer compounds. The liquid crystal polymer produced by these polymerization methods can be further subjected to solid phase polymerization under reduced pressure or heated in an inert gas to increase the molecular weight, if necessary.
The melt viscosity of the liquid crystal polymer obtained by the method as described above is not particularly limited. In general, the melt viscosity at a temperature of 10to 30 ℃ higher than the melting point of the liquid crystal polymer is preferably 1000sec at the shear rate-1A melt viscosity of 5MPa to 600 MPa.
The liquid crystal polymer may be a mixture of 2 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. The liquid crystal polymer is contained as a main component, and the liquid crystal polymer is contained in an amount of 80 mass% or more, preferably 90 mass% or more, and more preferably 95 mass% or more (including 100 mass%) of the mass of the liquid crystal polymer particles.
In one embodiment, the liquid crystal polymer particles preferably have a melting point of 270 ℃ or higher. The upper limit is not particularly limited, but from the viewpoint of productivity, it is preferably 400 ℃ or lower. When the melting point of the liquid crystal polymer particles is 270 ℃ or higher, it is preferable from the viewpoint of heat resistance in the reflow step of substrate mounting. The melting point of the liquid crystal polymer particles is more preferably 300 ℃ or higher, and still more preferably 330 ℃ or higher. In the present specification, the "melting point (melting temperature)" of the liquid crystal polymer particles means a temperature measured by a differential scanning calorimeter in accordance with JIS K7121. The measurement may use liquid crystal polymers (e.g. particles) or liquid crystal polymer particles.
The shape of the liquid crystal polymer particles is not particularly limited, and examples thereof include spherical (including substantially spherical), spindle, amorphous particulate, fibril, fiber, and the like, and mixtures thereof, but the liquid crystal polymer particles are not limited to these shapes. In addition, the spherical shape is preferable from the viewpoint of improving isotropy of electrical characteristics, and the fibrillar 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, but in one embodiment, is, for example, 0.1 μm to 250 μm, and preferably 1 μm to 200 μm. When the average particle diameter of the liquid crystal polymer particles is 250 μm or less, the surface roughness of a molded article obtained by using the resin composition can be easily maintained within an appropriate range. In addition, 0.1 μm or more is preferable from the viewpoint of productivity of the liquid crystal polymer particles. From the viewpoint of improving dispersibility in the resin composition and surface characteristics, 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 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 article having uniform characteristics.
In the present specification, the term "average particle diameter" of the liquid crystal polymer particles means an arithmetic mean particle diameter based on a volume basis of a laser diffraction/scattering particle size distribution measurement method, and the average particle diameter can be measured, for example, using a laser diffraction/scattering particle size distribution measuring apparatus L A-920 manufactured by horiba, Ltd.
In one embodiment, 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 in the range of 1 to 250 μm, even more preferably 150 μm or less, and particularly preferably 100 μm or less, from the viewpoint of achieving the dispersibility of the liquid crystal polymer particles and the uniformity of the properties of the molded article, and in the present specification, "the peak particle size of the particle size distribution" of the liquid crystal polymer particles means that, when 2 or more peaks are present in the volume-based particle size distribution measured by a laser diffraction/scattering distribution measuring apparatus, the peak particle size of the peak having the largest peak height is present in the above-mentioned particle size range, and the peak particle size of the particle size distribution can be measured by, for example, a laser diffraction/scattering particle size distribution measuring apparatus L a-920 manufactured by horiba, kokai.
In one embodiment, the volume density of the liquid crystal polymer particles is preferably in the range of 0.08 to 1.2g/m L, more preferably in the range of 0.09 to 1.0g/m L, and even more preferably in the range of 0.1 to 0.5g/m L, and when the volume density of the liquid crystal polymer particles is 0.08g/m L or more, it is preferable from the viewpoint of handling at the time of production, and when 1.2g/m L or less, it is preferable from the viewpoint of dispersibility of the particles, and in the present specification, the volume density of the liquid crystal polymer particles is calculated by filling the liquid crystal polymer particles to a scale of 50m L by dropping naturally with a funnel from the outer bottom of a cylinder having a volume of 50m L (outer diameter of 2.5cm, outer diameter height of 21.5cm), and measuring the mass of the filled liquid crystal polymer particles.
The method for producing the liquid crystal polymer particles is not particularly limited, but includes a method in which a sheet comprising a liquid crystal thermoplastic resin and a non-liquid crystal thermoplastic resin is produced, and then the non-liquid crystal thermoplastic resin is dissolved out and removed with a solvent; a method of pulverizing an oligomer of a liquid crystal thermoplastic resin and then performing solid-phase polymerization; a method of pulverizing and fibrillating a flaky liquid crystalline resin; and a method of pulverizing the particulate liquid crystalline resin.
In one embodiment, the liquid crystal polymer is preferably pulverized by a stone mortar type grinder. According to the method of grinding by a stone mortar type grinder, particles having a small average particle diameter 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 to 80 mass% of the total composition. When the content of the liquid crystal polymer particles is 5% by mass or more, the effect of improving the electrical characteristics (lowering the dielectric constant) can be further improved, 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, further preferably 20% by mass or more, further preferably 70% by mass or less, further preferably 60% by mass or less of the total composition. When the resin composition contains a solvent, the above range is determined based on the mass of the resin composition from which the solvent has been removed.
< resin component >
The resin composition according to one embodiment includes at least 1 resin (hereinafter, also referred to as a "resin component") selected 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 may be appropriately selected in consideration of the use of the resin composition according to one 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 having a low dielectric constant. However, the resin composition according to one embodiment includes liquid crystal polymer particles, and thus has an advantage that excellent electrical characteristics (low dielectric constant) can be maintained even when a resin having a high dielectric constant is used. Specific examples of the resin having a high dielectric constant include resins having a higher dielectric constant than a liquid crystal polymer, for example, resins having a dielectric constant of 3 or more, or 3.2 or more at 5 GHz. Specifically, an epoxy resin, a phenol resin, a polyimide resin, a bismaleimide triazine resin (BT resin), and the like can be exemplified, but not limited thereto. Of course, a resin having a dielectric constant of less than 3 can be suitably used. Here, the dielectric constant is a value at 5GHz measured at 23 ℃ by a resonance cavity perturbation method.
Further, since the resin composition according to one embodiment includes the liquid crystal polymer particles, it is not necessary to heat and melt the liquid crystal polymer particles at the time of producing the resin composition, and a resin composition in which the liquid crystal polymer particles are dispersed can be obtained even when the resin component and the liquid crystal polymer particles are mixed at a temperature lower than the melting point of the liquid crystal polymer particles. Therefore, in one embodiment, a resin having a thermal decomposition temperature lower than the melting point of the liquid crystal polymer particles can be preferably used as the resin component. Further, it is needless to say that a resin having a thermal decomposition temperature equal to or higher than the melting temperature of the liquid crystal polymer particles can be suitably used.
When the resin composition according to one embodiment is used for a circuit board described later, the glass transition temperature, the melting point (melting temperature), and the 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, and more specifically, preferably equal to or higher than 300 ℃, more preferably equal to or higher than 330 ℃, and still more preferably equal to or higher than 350 ℃.
In the present specification, the phrase "the glass transition temperature, the melting point, and the thermal decomposition temperature of the resin component are equal to or higher than a specific temperature" means that the lowest temperature among the glass transition temperature, the melting point, and the thermal decomposition temperature of the resin is equal to or higher than the specific temperature. Here, "melting point (melting temperature)" represents a temperature measured by Differential Scanning Calorimetry (DSC) in conformity with JIS K7121, "thermal decomposition temperature" represents a temperature (10% weight reduction temperature) reduced by 10% by weight when heated at 10 ℃/min from 25 ℃ in an air stream by a thermogravimetric device, and "glass transition temperature" represents a temperature measured by Differential Scanning Calorimetry (DSC) in conformity with JIS K6240.
In one embodiment, examples of the thermosetting resin that is preferably used include, but are not limited to, epoxy resins, phenol resins, polyimide resins, bismaleimide-triazine resins (BT resins), and the like.
(epoxy resin)
The epoxy resin is not particularly limited, and examples thereof include 2-functional epoxy resins such as bisphenol-a type epoxy resins, bisphenol-F type epoxy resins, bisphenol AD type epoxy resins, and the like, naphthalene type epoxy resins, glycidyl amine type epoxy resins, alicyclic epoxy resins, polyether modified epoxy resins, silicon modified epoxy resins, glycidyl ester type epoxy resins, and the like. In addition, polyfunctional epoxy resins such as phenol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, xylylene type epoxy resin, cresol novolac type epoxy resin, tetraphenylmethane type epoxy resin, and the like can be used. The epoxy resin may be used alone in 1 kind or in combination of 2 or more kinds.
(phenol resin)
Examples of the phenol resin include, but are not limited to, cresol novolak type phenol resins, phenol novolak resins, alkylphenol novolak resins, bisphenol a novolak resins, dicyclopentadiene novolak resins, silorac (ザイロック) type phenol resins, terpene-modified phenol resins, polyvinyl phenols, naphthol aralkyl type phenol resins, biphenyl aralkyl type phenol resins, naphthalene type phenol resins, aminotriazine novolak type phenol resins, and the like. The phenol resin may be used alone in 1 kind or in combination of 2 or more kinds.
(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, and examples thereof include 3, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, and the like, and the diamine is preferably an aromatic diamine, and examples thereof include, but are not limited to, p-phenylenediamine, 4, 4 ' -oxydianiline, and the like. Further, an imidization catalyst such as an amine compound, a dehydrating agent such as a carboxylic acid anhydride, and the like may be used together. When a polyimide resin is used as the resin component, it is preferable to use a polyamic acid obtained by polymerizing an acid anhydride and a diamine, and imidize the polyamic acid during or after molding. The polyimide resin may be used alone in 1 kind or in combination of 2 or more kinds.
(bismaleimide triazine resin)
As the bismaleimide triazine resin (BT resin), various bismaleimide triazine resins obtained by crosslinking bismaleimide and an aromatic cyanate can be used. 1 kind of bismaleimide triazine resin can be used alone, or more than 2 kinds can be used in combination.
In one embodiment, a thermoplastic resin is preferably used as the resin component. Specifically, polyphenylene ether, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like can be exemplified, but not limited thereto.
Among these, polyphenylene ether is preferably used in substrate applications described later from the viewpoint of electrical characteristics such as dielectric constant. Polyphenylene ether means a phenylene ether unit structure (-C)6H4-O-) as main component. The phenylene ether unit structure may have a substituent, and for example, 1 or more hydrogen atoms of 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 polyphenylene ethers include, but are not limited to, poly (2, 6-dimethyl-1, 4-phenylene ether), poly (2-methyl-6-ethyl-1, 4-phenylene ether), poly (2, 6-dichloro-1, 4-phenylene ether), and modified polyphenylene ethers (m-PPE).
The thermosetting resin and the thermoplastic resin may be used alone in 1 kind or in combination of 2 or more kinds. The content of the resin component in the resin composition is not particularly limited, but is preferably 20 mass% or more and 95 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 economy, and when it is 95% by mass or less, the effect of improving the electrical characteristics (lowering the dielectric constant) can be further improved. The content of the resin component is more preferably 30% by mass or more, further preferably 40% by mass or more, further preferably 90% by mass or less, further preferably 80% by mass or less of the total composition. When the resin composition contains a solvent, the above range is determined based on the mass of the resin composition from which the solvent has been removed. In the case where the resin composition contains a thermosetting resin as a resin component and further contains a curing agent and/or a curing accelerator, the range is the total content of the resin component, the curing agent, and the curing accelerator.
The resin composition according to an embodiment contains at least the liquid crystal polymer particles and the resin component, and if necessary, further contains a component other than the liquid crystal polymer particles and the resin component as described below.
< curing agent and curing accelerator >
When the resin composition according to one embodiment contains a thermosetting resin as a resin component, it is preferable that the resin composition further contains a curing agent. The curing agent is not particularly limited, and any curing agent known in the art can be used. Examples of the curing agent include dicyandiamide, hydrazide, imidazole compounds, amine adducts, sulfonium salts, onium salts, ketimine, acid anhydride, tertiary amine, and novolak-type phenol resin, but are not limited thereto.
The content of the curing agent is not particularly limited, and may be appropriately selected depending on the resin component to be used and the curing conditions, but is, for example, preferably 10to 100 parts by mass, and more preferably 20 to 90 parts by mass, based on 100 parts by mass of the thermosetting resin.
In addition, a curing accelerator may be used instead of the above curing agent, or in combination with the curing agent. The curing accelerator is not particularly limited, and examples thereof include diazabicycloundecene, derivatives thereof, and salts thereof; organic phosphine compounds, salts thereof, derivatives thereof, and the like. The content of the curing accelerator is not particularly limited, but is preferably 50 to 150 parts by mass, and more preferably 80 to 120 parts by mass, based on 100 parts by mass of the thermosetting resin.
< filling Material >
Further, the resin composition according to one embodiment may contain a filler, if necessary. The filler herein does not contain liquid crystal polymer particles.
As a filler, glass fiber, milled glass fiber, glass beads, glass spheres, ceramic spheres, glass flakes, silica, alumina fiber, zirconia fiber, potassium titanate fiber, carbon fiber, graphite; silicates such as calcium silicate, aluminum silicate, 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; examples of the organic filler include, but are not limited to, high-melting-point fibers such as aromatic polyester fibers, aromatic polyamide fibers, fluororesin fibers, and polyimide fibers.
When the filler is contained, the total mass of the resin composition according to one embodiment is preferably 80% by mass or less, more preferably 10to 60% by mass, and still more preferably 30 to 50% by mass. When the resin composition contains a solvent, the above range is determined based on the mass of the resin composition from which the solvent has been removed.
< organic solvent >
The resin composition according to an embodiment may further contain an organic solvent as needed.
The organic solvent is preferably a compound that functions to improve the fluidity of the resin composition according to one embodiment at the time of molding and is removable by drying and/or heating under the process conditions at the time of molding.
More preferably, the organic solvent is a removable compound that is dried and/or heated at a temperature less than the melting point of the liquid crystal polymer particles.
In one embodiment, the boiling point (normal boiling point) of the organic solvent is preferably 40 to 210 ℃, and more preferably 50 to 190 ℃ from the viewpoint of suppressing deterioration of the resin component or the like when the organic solvent is removed.
In one embodiment, examples of the organic solvent that can be preferably used include, but are not limited to, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, toluene, xylene, N-dimethylformamide, dioxane, tetrahydrofuran, and derivatives thereof. The organic solvent may be used alone in 1 kind, or may be used in combination with 2 or more kinds. When the 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 of the total mass of the resin composition. The total mass of the resin composition herein 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 at least a part of the resin component is preferably dissolved in the organic solvent.
< other ingredients >
The liquid crystal polymer particles of one embodiment may contain any other components than the above-described components as long as the resin composition does not inhibit the effect. Examples of the other components include various stabilizers (an antacid, an ultraviolet absorber, a near infrared absorber, a heat stabilizer, etc.), a flame retardant aid, a plasticizer, a mold release agent, a colorant such as a dye and a pigment, and a fluorescent whitening agent. More than 1 of them may be added as necessary.
< method for producing resin composition >
The resin composition according to one embodiment can be produced by using an apparatus and a method which are generally used as a conventional resin composition production method. A preferable method is, for example, a method of kneading (mixing) the respective components using a kneading apparatus such as a 1-axis or 2-axis extruder.
In one embodiment, the resin composition is preferably produced by mixing at least 1 resin component selected from the group consisting of a thermosetting resin and a thermoplastic resin with the liquid crystal polymer particles at a temperature lower than the melting point of the liquid crystal polymer particles.
The resin composition of one embodiment is a resin composition containing a resin component and liquid crystal polymer particles, and the resin component and the liquid crystal polymer particles are mixed at a temperature lower than the melting point of the liquid crystal polymer particles without heating and melting the liquid crystal polymer particles at the time of producing the resin composition, whereby a resin composition in which the liquid crystal polymer particles are dispersed in the resin component can be obtained. Therefore, a resin that is decomposed when heated and melted at a temperature equal to or higher than the melting point of the liquid crystal polymer particles may be used as the resin component.
The 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.
[ Molding product and Molding method ]
The shape of the molded article (molded article) of the resin composition according to the embodiment is not particularly limited, but examples thereof include film-like, sheet-like, plate-like, and three-dimensional molded articles. In the case of a film, a sheet, or a plate, the resin composition according to one embodiment can provide significant effects.
The molded article can be produced by various methods known as a method for molding a resin composition, such as extrusion molding, injection molding, press molding, and tape casting.
For example, the molded body of an embodiment can be produced by a method including:
a step of preparing a liquid composition containing the resin composition according to one embodiment; and
and curing the liquid composition.
The liquid composition containing a resin composition may be the resin composition according to one embodiment (for example, a case where a liquid resin is used as a resin component and/or a case where the resin composition according to one embodiment contains an organic solvent). If necessary, the resin composition may be heated and melted at a temperature lower than the melting point of the liquid crystal polymer particles to prepare a liquid composition.
The curing step of curing the liquid composition is not particularly limited, and a method known in the art can be used. Examples of the solidification 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, and a combination thereof. The drying step is preferably performed at a temperature ranging from room temperature to a temperature lower than the melting point of the liquid crystal polymer particles, for example, at 100 to 250 ℃. The heating step may be appropriately set in consideration of the curing conditions of the resin component used, but is preferably performed at a temperature lower than the melting point of the liquid crystal polymer particles, for example, at 120 to 220 ℃. The drying step may be performed as both the heating step and the heating step, or may be performed as both the drying step and the heating step.
In one embodiment, a molded article can be produced by a method including the steps of,
1. a step of pouring the resin composition into a mold; and
2. and a step (curing step) of heating the resin composition.
In one embodiment, the molded article preferably contains a base material, and the molded article can be produced by a method including, for example,
1. a step for preparing a liquid composition;
2. a step of impregnating a base material with the liquid composition; and
3. and a step of drying the base material impregnated with 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 article obtained by the above-described drying step is also referred to as a prepreg.
In one embodiment, a molded article can be produced by a method including the steps of,
1. a step for preparing a liquid composition;
2. a step of impregnating a base material with the liquid composition;
3. a step (semi-curing step) of drying the base material impregnated with the liquid composition; and
4. and a step (curing step) of heating the dried base material.
In one embodiment, the resin composition preferably contains a thermosetting resin. The molded body obtained by the semi-curing step is also referred to as a prepreg.
The material of the base is not particularly limited, but for example, a material that can be used as a reinforcing material for an insulating layer of a circuit board is exemplified. For example, inorganic fibers such as glass fibers, quartz glass fibers, carbon fibers, alumina fibers, silicon carbide fibers, asbestos (アルベスト), rock wool, slag wool, and gypsum whiskers, and organic fibers such as wholly aromatic polyamide fibers, polyimide fibers, and polyester fibers. The substrate may be a film, a nonwoven fabric or a woven fabric.
In one embodiment, the molded article is preferably produced by casting using a liquid composition containing a resin composition.
[ Circuit Board ]
In a film-like, sheet-like, or plate-like molded article formed using the resin composition according to one embodiment, liquid crystal polymer particles are dispersed in a resin component. Therefore, the molded article is excellent in electrical characteristics (low dielectric constant) and also excellent in surface characteristics (surface smoothness), and is preferably used for an electronic circuit board such as a flexible circuit board. The method for producing the electronic circuit board is not particularly limited, but a method for forming a metal laminate by laminating the above-described film-like, sheet-like, or plate-like molded body (prepreg or cured body) with a metal foil such as a copper foil and heating and pressing the laminate is exemplified. The heating and pressing conditions are not particularly limited, but may be, for example, a heating temperature: 60-220 ℃, pressure: 0.1-10 MPa, time: 1 minute to 3 hours.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
< liquid Crystal Polymer >
Liquid crystalline polyester amide resin
After the following raw materials were charged into the polymerization vessel, the temperature of the reaction system was raised to 140 ℃ and the reaction was carried out at 140 ℃ for 1 hour. Then, the temperature was raised to 340 ℃ over 4.5 hours, and then reduced to 10Torr (i.e., 1330Pa) under a pressure of 15 minutes, thereby carrying out melt polymerization while distilling off acetic acid, excess acetic anhydride and other low-boiling components. After the stirring torque reached a predetermined value, nitrogen was introduced to increase the pressure from a reduced pressure state to a pressurized state through normal pressure, and the strand was discharged from the lower part of the polymerization vessel and granulated to obtain pellets. To the resulting particles, in nitrogenThe melting point of the obtained polymer was 334 ℃ and the melt viscosity was 14.0 pas. the melt viscosity of the polymer was measured according to JIS K7121 using a differential scanning calorimeter (DSC Q1000, manufactured by TA instruments Co., Ltd.) and according to ISO 11443, a cylinder temperature of 350 ℃ and a shear rate of 1000sec were measured according to a capillary rheometer (CAPI L OGRAPH 1D: 10mm in piston diameter, manufactured by Toyo Seiki Seisaku-Sho Ltd.) according to-1The apparent melt viscosity under the conditions of (1) was measured. The measurement was performed using an orifice having an inner diameter of 1mm and a length of 20 mm.
(I) 4-hydroxy benzoic acid; 188.4g (60 mol%)
(II) 2-hydroxy-6-naphthoic acid; 21.4g (5 mol%)
(III) terephthalic acid; 66.8g (17.7 mol%)
(IV)4, 4' -dihydroxybiphenyl; 52.2g (12.3 mol%)
(V) 4-acetoxyaminophenol; 17.2g (5 mol%)
Metal catalysts (potassium acetate catalysts); 15mg of
An acylating agent (acetic anhydride); 226.2g
< 1. production of liquid Crystal Polymer particles
(L CP particles 1)
Average particle diameter: 15 μm, peak particle size: 21 μm
Bulk density 0.10g/m L
The average particle diameter and the peak particle diameter of the obtained liquid crystal polymer particles were measured by a laser particle size analyzer (manufactured by horiba, Ltd., laser diffraction/scattering particle size distribution measuring device L A-920). the average particle diameter was an arithmetic average diameter expressed as calculation result data, and the liquid crystal polymer particles were naturally dropped from an outer bottom surface of a 50m L cylinder (manufactured by Kaita scientific Co., Ltd., cylinder custom A026500-501A, outer diameter size 2.5cm, outer diameter size height 21.5cm) to a scale of 50m L and their weights were measured to calculate the volume density of the liquid crystal polymer particles.
Raw materials: particles of liquid crystalline polymer (average particle diameter: 3mm)
Raw material input amount: 400g
And (3) crushing speed: 60g/hr
Water inflow (30L/min)
Void: 50 μm
Rotating speed: 1400rpm
(L CP particles 2)
Average particle diameter: 195 μm, peak particle size: 242 μm
Bulk density 0.12g/m L
The produced liquid crystal polymer particles were subjected to freeze-pulverization using a ball mill type freeze-pulverizer (JFC-1500, manufactured by Nippon analytical industries, Ltd.) under the following conditions to obtain substantially spherical liquid crystal polymer particles, and 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 L CP particle 1.
Raw materials: particles of liquid crystalline polymer (average particle diameter: 3mm)
Raw material input amount: 5g
Preparation freezing time: 30min
Freezing and crushing time: 20min
(L CP particles 3)
Average particle diameter: 211 μm, peak particle size: 281 μm
Bulk density 0.06g/m L
The produced liquid crystal polymer particles were pulverized using a screen mill type pulverizer (HA-2542, manufactured by Horai, Ltd.) under the following conditions to obtain fibrillar liquid crystal polymer particles, and 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 L CP particles 1.
Raw materials: particles of liquid crystalline polymer (average particle diameter: 3mm)
Raw material input amount: 10kg of
And (3) crushing speed: 10kg/hr
(L CP particles 4)
Average particle diameter: 5.3 μm, peak particle size: 6.9 μm
Bulk density 0.47g/m L
L CP particles 1 were classified by a semi-automatic turbo classifier (heiqing engineering corporation, NISSHIN ENGINEERING INC.) to obtain fine, substantially spherical liquid crystal polymer particles, and the average particle diameter, peak particle size, and bulk density of the obtained liquid crystal polymer particles were measured in the same manner as for L CP particles 1.
< 2. production of a resin composition containing liquid-crystalline Polymer particles >
< examples 1 to 3 >
The liquid crystal polymer particles thus produced, a liquid epoxy resin (XNR 5002G, manufactured by Nagase ChemteX, Ltd.), and tetrahydromethylphthalic anhydride (XNH 5002G, manufactured by Nagase ChemteX, Ltd.) as a curing agent were kneaded at room temperature (23 ℃ C.) in the mass ratios shown in Table 1 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. production and evaluation of molded article >
< examples 1 to 3, comparative example 1 >)
The mixed composition was poured into a polyethylene mold 8cm × 3cm × 2mm, heated at 100 ℃ for 1 hour, and further heated at 150 ℃ for 3 hours to obtain a test piece.
The resulting test pieces were cut into
And a dielectric constant and a dielectric loss tangent at 5GHz were measured at 23 ℃ using a perturbation resonator/dielectric constant measuring apparatus (Cavity Resorcator, Kanto electronic applications, Inc.).
The surface of the obtained test piece was visually observed, and the dispersibility was evaluated by designating ◎ as a test piece having no cracks, ○ as a test piece having cracks in a part (less than 30% of the surface area), △ as a test piece having cracks in a half (about 30 to 70% of the surface area), and × as a test piece having cracks in the whole (more than 70% of the surface area).
After the obtained test piece was fractured, the fracture surface was visually observed, and the surface properties were evaluated by designating a test piece without aggregates of liquid crystal polymer particles as ◎, a test piece with less than 5 aggregates as ○, a test piece with 5 or more aggregates with less than 10 aggregates as △, and a test piece with 10 or more aggregates as ×.
The dispersibility and the surface property were both ◎ to △ in a practical range, and 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 |
| L CP particles 1 | 30 | |||
| L CP particles 2 | 30 | |||
| L CP particles 3 | 30 | |||
| Curing agent | 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 |
| Dispersibility | ◎ | ◎ | △ | - |
| Surface property | ○ | ◎ | △ | ◎ |
In examples 1 to 3 using a resin composition containing a resin component and liquid crystal polymer particles, a molded article having excellent economical efficiency was obtained by a simple production method.
As shown in table 1, the molded articles of examples 1 to 3 using the resin composition containing liquid crystal polymer particles obtained excellent electrical characteristics (dielectric constant and dielectric loss tangent) while maintaining surface properties suitable for practical use, in particular, the molded articles of examples 1 and 2 in which the average particle diameter of L CP particles was 200 μm or less had good dispersibility of L CP particles, and excellent surface properties and excellent electrical characteristics were obtained.
< 4. production and evaluation of prepreg
< examples 4 and 5, comparative example 2 >
(examples 4 and 5)
The liquid crystal polymer particles thus produced, cresol novolac-type epoxy resin (EPIC L ON N-690-75M, 75% methyl ethyl ketone solution, epoxy equivalent: 217g/eq, manufactured by DIC), and novolac-type phenol resin (TD-2090-60M, 60% methyl ethyl ketone solution, and water acid equivalent: 105g/eq, manufactured by DIC) as a curing agent were added to a mixed solvent of methyl ethyl ketone and ethylene glycol monomethyl ether at the mass ratios shown in Table 2, and stirred to obtain a uniform resin varnish, and the obtained resin varnish was impregnated with a glass fiber cloth (# 2116, 100 μ M thick, manufactured by Nidoku K., Ltd.) and treated with a hot air dryer at 150 ℃ for 10 minutes to obtain a prepreg.
The mass ratio shown in table 2 is the mass ratio of the solid component after the solvent was removed.
Comparative example 2
Preforms were 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 liquid crystal polymer particles thus produced, a dicyclopentadiene type epoxy resin (EPIC L ON HP-7200H-75M, 75% methyl ethyl ketone solution, epoxy equivalent: 279g/eq, manufactured by DIC Co., Ltd.), and a novolak type phenol resin (TD-2090-60M, 60% methyl ethyl ketone solution, and 105g/eq, manufactured by DIC Co., Ltd.) as a curing agent were added to a mixed solvent of methyl ethyl ketone and ethylene glycol monomethyl ether at the mass ratios shown in Table 2, and stirred 25785to obtain a uniform resin varnish, and the obtained resin varnish was impregnated with a glass fiber cloth (# 2116, 100 μ M thick, manufactured by Nidoku Co., Ltd.) and treated with a hot air dryer at 150 ℃ for 10 minutes to obtain a preform.
Comparative example 3
Preforms were obtained in the same manner as in examples 6 and 7, except that liquid crystal polymer particles were not used.
< examples 8 and 9, comparative example 4 >
(examples 8 and 9)
The liquid crystal polymer particles thus produced, a novolak type epoxy resin (EPIC L ON N-740-80M manufactured by DIC, 80% methyl ethyl ketone solution, epoxy equivalent: 182g/eq), and a novolak type phenol resin (TD-2090-60M manufactured by DIC, 60% methyl ethyl ketone solution, and water acid group equivalent: 105g/eq) as a curing agent were added to a mixed solvent of methyl ethyl ketone and ethylene glycol monomethyl ether at the mass ratios shown in Table 2, and stirred to obtain a uniform resin varnish, and the obtained resin varnish was impregnated with a glass fiber cloth (# 2116 manufactured by Nidoku corporation, thickness 100 μ M) and treated with a hot air dryer at 150 ℃ for 10 minutes to obtain a prepreg.
Comparative example 4
Preforms were 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 liquid crystal polymer particles thus produced, a bisphenol epoxy resin (EPICOAT 828 manufactured by Mitsubishi chemical corporation, epoxy equivalent: 190g/eq), and a novolak phenol resin (TD-2090-60M manufactured by DIC, 60% methyl ethyl ketone solution, water acid equivalent: 105g/eq) as a curing agent were added to a mixed solvent of methyl ethyl ketone and ethylene glycol monomethyl ether at the mass ratios shown in Table 2, followed by stirring to obtain a uniform resin varnish. The obtained resin varnish was impregnated with a glass fiber cloth (# 2116, thickness 100 μm, manufactured by Nidoku K.K.) and treated with a hot air dryer at 150 ℃ for 10 minutes to obtain a prepreg.
Comparative example 5
Preforms were 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, L ubron L-2 manufactured by Dajin industries, Ltd., average particle diameter: 10 μ M), cresol novolac-type epoxy resin (EPIC L ON N-690-75M manufactured by DIC, 75% methyl ethyl ketone solution, epoxy equivalent: 217g/eq), and novolac-type phenol resin as a curing agent (TD-2090-60M manufactured by DIC, 60% methyl ethyl ketone solution, water acid equivalent: 105g/eq) were added to a mixed solvent of methyl ethyl ketone and ethylene glycol monomethyl ether at the mass ratios shown in Table 2 and stirred to obtain a uniform resin varnish, and the obtained resin varnish was impregnated with a glass fiber cloth (# 2116 manufactured by Nidoku corporation, thickness 100 μ M) and treated with a hot air dryer at 150 ℃ for 10 minutes to obtain a prepreg.
< 5. production and evaluation of laminate
< examples 4 to 11, comparative examples 2 to 6 >
The laminate obtained was cut into a quadrangular prism of 1.5mm × 1.0.0 mm × 70mm, and the dielectric constant and the dielectric loss tangent at 5GHz were measured at 23 ℃ using a perturbation resonator/dielectric constant measuring apparatus (Cavity Resorcator, manufactured by Kanto electronics applications, Inc.) under a load of 5MPa at 200 ℃ for × 60 minutes of 6 sheets to obtain a laminate having a thickness of about 1 mm.
The obtained laminate was punched out into a dumbbell-shaped tensile test piece (JIS K7127Type5) to obtain a test piece, and a tensile test was conducted immediately after punching and after × 500 hours at 170 ℃ C.for 500 hours using the obtained test piece, and the ratio of the tensile strength immediately after punching after × 500 hours at 170 ℃ C.for 500 hours was taken as a tensile strength retention ratio.
Then, the obtained test piece was cooled with liquid nitrogen and cracked, and the cracked surface was observed with a scanning electron microscope, and the test piece in which no peeling was observed at the boundary between the liquid crystal polymer particles (or polytetrafluoroethylene particles) and the epoxy resin was designated ○, and the test piece in which peeling was observed was designated ×, to evaluate the boundary adhesion.
The results are shown in Table 2.
[ Table 2]
In examples 4 to 11 using the resin composition containing the resin component and the liquid crystal polymer particles, a prepreg having excellent economical efficiency can be obtained by a simple production method.
As shown in table 2, the prepregs of examples 4 to 11 using the resin composition containing liquid crystal polymer particles were able to obtain excellent electrical characteristics (dielectric constant and dielectric loss tangent) while maintaining tensile strength retention and boundary adhesion suitable for practical use.
Industrial applicability
The resin composition containing the liquid crystal polymer particles according to one embodiment of the present invention and the molded article thereof can be widely used in various applications using high frequencies, such as an electronic component having a high-frequency circuit, for example, an internal antenna of a mobile phone, an antenna of a car radar, and 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.
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| JP2016-037525 | 2016-02-29 | ||
| JP2016037525 | 2016-02-29 | ||
| PCT/JP2017/006862 WO2017150336A1 (en) | 2016-02-29 | 2017-02-23 | Resin composition including liquid-crystal polymer particles, molded object obtained using same, and production processes therefor |
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| JP6788150B2 (en) * | 2018-12-06 | 2020-11-18 | ポリプラスチックス株式会社 | Powdered liquid crystal resin for press-molded products, press-molded products and their manufacturing methods |
| US11637365B2 (en) | 2019-08-21 | 2023-04-25 | Ticona Llc | Polymer composition for use in an antenna system |
| US11258184B2 (en) | 2019-08-21 | 2022-02-22 | Ticona Llc | Antenna system including a polymer composition having a low dissipation factor |
| EP4019569A4 (en) * | 2019-08-22 | 2023-09-13 | ENEOS Corporation | Liquid-crystal polymer particles, thermally curable resin composition, and molded object |
| US11555113B2 (en) | 2019-09-10 | 2023-01-17 | Ticona Llc | Liquid crystalline polymer composition |
| US11912817B2 (en) | 2019-09-10 | 2024-02-27 | Ticona Llc | Polymer composition for laser direct structuring |
| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
| US11646760B2 (en) | 2019-09-23 | 2023-05-09 | Ticona Llc | RF filter for use at 5G frequencies |
| CN110591063B (en) * | 2019-09-24 | 2022-06-07 | 沈阳建筑大学 | Modified polyethylene naphthalate containing imide structure and preparation method thereof |
| CN114450328A (en) | 2019-09-25 | 2022-05-06 | 株式会社村田制作所 | Liquid crystal polymer powder and method for producing same |
| WO2021085329A1 (en) * | 2019-10-29 | 2021-05-06 | 日鉄ケミカル＆マテリアル株式会社 | Resin composition, resin film, layered body, coverlay film, copper foil with resin, metal-clad layered board and circuit board |
| JP7410716B2 (en) * | 2019-12-27 | 2024-01-10 | 日鉄ケミカル＆マテリアル株式会社 | Resin composition and resin film |
| JP7398277B2 (en) * | 2019-12-27 | 2023-12-14 | 日鉄ケミカル＆マテリアル株式会社 | Resin composition and resin film |
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| TWI712642B (en) | 2020-12-11 |
| JP6295013B2 (en) | 2018-03-14 |
| WO2017150336A1 (en) | 2017-09-08 |
| JPWO2017150336A1 (en) | 2018-03-15 |
| CN108884325A (en) | 2018-11-23 |
| TW201803938A (en) | 2018-02-01 |
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